3,658,836 United States Patent Office Patented Apr. 25, 1972 1. 2 the mol ratio of boric acid to amine and therefore if a 3,658,836 . mol ratio of less than 5:1, respectively, is used unreacted HYDROXYBOROXN-AMNE SALTS . . . amine will remain. Billy Dale Vineyard, St. Louis, Mo. assignor to Conveniently the preparation of the above-described Monsanto Company, St. Louis, Mo. - salts is conducted using a reaction medium which may No Drawing. Filed Apr. 16, 1964, Ser. No. 360,411 form a homogeneous or heterogeneous reaction mass. Int, C. C07d 49/34 Suitable reaction media are aromatic hydrocarbons such U.S. C. 260-309.7 6 Claims as benzene, toluene and xylene, alone or with water. Also an excess of the amine reactant will suffice as a reaction ABSTRACT OF THE DISCLOSURE O medium. The use of benzene is preferred since its use allows removal of water by azeotropic distillation at a This invention relates to hydroxyboroxin-amine Salts relatively low temperature after completing the reaction. which are prepared by reacting boric acid with an amine Typical materials which can be used to form the salts as described hereinafter. The compounds are useful inter of this invention are the mono-, di- and trialkyl amines alia as fungicides and additives for lubricating oils. 15 in which each alkyl group has from 1 to 20 carbons, such as methylamine, ethylamine, n-propylamine, isopropyl amine, n-butylamine, isobutylamine, sec-butylamine, amyl This invention relates to new hydroxyboroxin-amine amine, n-heptylamine, n-hexylamine, 1,1,3,3-tetramethyl salts which can be represented by the structure butylamine, n-octylamine, 2-ethylhexylamine, isooctyl C 20 amine, nonylamine, 2,2,4,4-tetramethylpentylamine, n-dec g EO - YB - Ois Y4 ylamine, isodecylamine, dodecylamine, 1,1,3,3,5,5-hexa Ba. e On 1. (Zy4. methylhexylamine, tridecylamine, pentadecylamine, ste N-ye and -Bag s arylamine, and the like; dimethylamine, diethylamine, 0 a So in OH Yy f Ye methylethylamine, diisopropylamine, di-n-butylamine, di 3. to - BN1 - ot 25 isoamylamine, dioctylamine, didecylamine, methyldecyl (I) (II) amine, distearylamine and the like; and trimethylamine, where Y is selected from hydrogen, alkyl, cycloalkyl and triethylamine, methyldiethylamine, tri-n-propylamine, di aralkyl and Y and Y are hydrogen, except that Y1, Y2 methylbutylamine, methyl-di-tert-butylamine, tri-n-hexyl and Y can, together with the nitrogen atom, form a amine, tri-2-ethylhexylamine, n-propyldioctylamine, tri group having a quinuclidine-type structure, that is, a 30 laurylamine, dimethyldodecylamine, dimethylstearyl quinuclidine compound, pyridine or a picoline; and Y4, amine, tristearylamine and the like. There can also be Ys and Ys are each selected from hydrogen, alkyl, cyclo used cycloalkyl amines of 3 to 10 carbon atoms, such alkyl and aralkyl, except that when Y is hydrogen Ys as cyclopropylamine, cyclohexylamine, dicyclohexylamine, and Y can, together with the nitrogen atom, form a methylcyclohexylamine, tricyclohexylamine, cyclooctyl heterocyclic ring selected from (i) 6-membered carbon 35 amine and cyclodecylamine. Also alkylenediamines such and nitrogen-containing rings, (ii) 6-membered carbon-ni as ethylenediamine, propylenediamine, trimethylenedi trogen- and oxygen-containing rings and (iii) 5-membered amine, tetramethylenediamine, hexamethylenediamine and rings selected from pyrrolidine, pyrroline, imidazole and the like can be used. Furthermore aralkyl amines can be thiazolidine, and further excepted that Y4, Ys and Ys can, used such as amines containing only aralkyl groups such together with the nitrogen atom, form a group having a 40 as benzylamines, phenethylamine, dibenzylamine and tri quinuclidine-type structure, that is, a quinuclidine com benzylamine, but there can also be used mixed alkyl pound. ' ' - aralkyl amines such as methylbenzylamine, dibenzyl In preparing the compounds of this invention, boric methylamine, methylpropylbenzylamine, decylbenzyl acid is reacted with a suitable amine, that is, an amine amine, stearylbenzylamine and the like. which will form a hydroxyboroxin-amine salt as de 45 The heterocyclic secondary amines which can be used scribed above, by heating a mixture of boric acid and to form the monoammonium pentaborates (II) are, for amine at temperatures of the order of 25-100° C. How example, piperidine, piperazine, pyrrolidine, the oxazines ever, steric requirements of the amine and mol ratio of (such as morpholine and 1,4-isoxazine), pyrroline, imid reactants dictates which product is formed as more fully azole, and thiazolidine, and their alkyl-substituted deriva explained below. 50 tives such as 2-methylpyrrolidine, and the like. Thus, the compounds represented by (I) which are The tertiary amines having a quinuclidine-type struc monoammonium salts of 1,3,5-trihydroxyboroxin (meta ture suitable for preparing the compounds of this inven boric acid), can be formed by reacting an amine YNH2 tion include, in addition to quinuclidine itself, triethylene and boric acid in a mol ratio of three or less mols of diamine, and alkyl-substituted derivatives thereof, such as boric acid per mol of amine. In the case of the com 55 3 - methylquinuclidine, 4-ethylcquinuclidine, 5-methyltri pounds containing a quinuclidine group, or pyridine or ethylenediamine, N-ethyltriethylenediamine and the like. a picoline, the mol ratio of boric acid to amine, as with Tertiary amines such as pyridine and the picolines can the primary amines, YNH2, is three or less to one, respec also be used. tively. - The preparation of typical examples of the salts The compounds represented by (II), which are mono 60 described above are given below in which parts are parts ammonium salts of spiro (3,5-dihydroxyboroxin) - 1,1'- by weight unless otherwise stated. (3',5' - dihydroxyboroxin)), but which can also be de scribed as monoammonium pentaborates, can be formed EXAMPLE 1. (1) from primary amines, YaNH2, and amines having a Triethylenediamine (16.8 parts-0.15 mol) in 50 ml. quinuclidine structure, by reacting boric acid with such 65 of benzene was added to a slurry of 18.6 parts of boric amines in mol ratios of three to five mols of boric acid acid (0.3 mol), 10 ml. of water, and 150 ml. of benzene. per mol of amine; (2) from secondary amines, YYNH, The mixture was then stirred for 5 minutes at room tem and the heterocyclic secondary amines, and tertiary perature. A sample of the reaction mixture was removed; amines, YYYsN, provided such amines have a dissocia the solid removed by filtration, washed with diethyl ether tion constant greater than about 1x10, by reacting such 70 and dried. The remaining reaction mixture was refluxed amines with boric acid. When using such secondary, and (70-80°. C.) until theory water (15-16 ml.) had been tertiary amines, the spiro compounds form regardless of . removed. The benzene insoluble product was then col 8,658,836 3 4. lected on a filter, washed with diethyl ether and dried. In the manner of the foregoing examples additional Infrared spectrum and elemental analysis of the final monoammonium salts of 1,3,5-trihydroxyboroxin, meet product was identical to the product obtained from the ing the above definition, can be prepared. Examples of sample removed after 5 minutes. The product, obtained in such salts are the following: 98% yield, was the monotriethylenediamine salt of 1,3,5- monomethylammonium salt of 1,3,5-trihydroxyboroxin. trihydroxyboroxin. Analysis of this product showed the monoethylammonium salt of 1,3,5-trihydroxyboroxin presence of 13.02% boron and 11.20% nitrogen. mono-n-butylammonium sait of 1,3,5-trihydroxyboroxin. EXAMPLE 2. mono-n-pentylammonium salt of 1,3,5-trihydroxyboroxin mono-n-hexylammonium salt of 1,3,5-trihydroxyboroxin. n-Octylamine (25.8 parts-0.2 mol) was added rapidly O mono-n-decylammonium salt of 1,3,5-trihydroxyboroxin to a mixture of 12.4 parts of boric acid (0.2 mol), 7 ml. monododecylammonium salt of 1,3,5-trihydroxyboroxin. of water and 100 ml. of benzene. The mixture was then monotridecylammonium salt of 1,3,5-trihydroxyboroxin refluxed (70-80 C.) until theory water (10.6 ml.) was monopentadecylammonium salt of 1,3,5-trihydroxy removed by azeotropic distillation. The solid product, the boroxin mono-n-octylammonium salt of 1,3,5-trihydroxyboroxin, 5 monostearylammonium salt of 1,3,5-trihydroxyboroxin was filtered from the cooled reaction mixture, washed with mono-a-picolinium salt of 1,3,5-trihydroxyboroxin diethyl ether and dried. The yield was 90%. The infrared monothiazolidinium salt of 1,3,5-trihydroxyboroxin spectrum showed bands at 714 cm.-1 and 1640 cm. 1 monoquinuclidinium salt of 1,3,5-trihydroxyboroxin (boroxin ring and amine salt, respectively). Analysis of monobenzylammonium salt of 1,3,5-trihydroxyboroxin the product showed the presence of 12.26% boron and 20 5.25% nitrogen. monophenethylammonium salt of 1,3,5-trihydroxy EXAMPLE 3 boroxin Four parts of 1,3,5-trihydroxyboroxin (metaboric acid) The preparation of monoammonium salt of spiro (3,5- (0.031 mol) was added to 11.4 parts of n-octylamine dihydroxyboroxin)-1,1-(3',5'-dihydroxyboroxin) (II) is (0.088 mol). The mixture was stirred at 40-60° C. for 25 illustrated in the following examples. 40 minutes, and then at 80 C. for 20 minutes. Diethyl EXAMPLE 8 ether (50 ml.) was added to the thick mass, and the in soluble solid isolated by filtration. The prdouct was n-Octylamine (10.3 parts, 0.08 mol) was added to a obtained in essentially quantitative yield. Infrared and slurry of 24.8 parts (0.4 mol) of boric acid, 15 ml. of elemental analyses as well as X-ray powder diffraction 30 water and 100 ml. of benzene. The mixture was stirred showed that this material was identical to the boric acid at 25-30 C. for 0.5 hour and then heated to reflux (70 n-octylamine reaction product obtained in Example 2. 80 C.). Water (22 ml.) was removed by azeotropic dis Analysis of the product showed the presence of 12.50% tillation. Acetonitrile (50 ml.) was then added and the boron and 5.68% nitrogen. white solid, mono n-octylammonium salt of spiro-I(3,5- 35 dihydroxyboroxin)-1,1'(3',5' - dihydroxyboroxin) col EXAMPLE 4 lected on a filter. The yield was quantitative. The infra n-Propylamine (11.8 parts-0.2 mol) was added to a red spectrum of the product showed bands at 700 cm. slurry of 12.4 parts of boric acid (0.2 mol), 10 ml. of and 1630 cm. (boroxin ring and the amine salt) re water, and 100 ml. of benzene. The mixture was stirred spectively. This salt contained 15.3% boron and 4.06% at 25-30 C. for 30 minutes. Theory water (13.6 ml.) 40 nitrogen. was removed by azeotropic distillation and the benzene EXAMPLE 9 insoluble product collected on a filter. The product was n-Propylamine (4.7 parts, 0.08 mol) was added rapid the mono-n-propylammonium salt of 1,3,5-trihydroxy ly to a mixture of 24.8 parts (0.4 mol) of boric acid, 15 boroxin. The product analyzed 16.8% boron and 7.54% ml. of water and 100 ml. of benzene. The mixture was nitrogen. 45 stirred at 50° C. for 40 minutes. Approximately 13 ml. EXAMPLE 5 of water was removed by azeotropic distillation. Aceto 14.4 parts of n-propylamine (0.238 mol) was added to nitrile (70 mi.) was then added to the cooled mixture 4 parts of freshly prepared 1,3,5-trihydroxyboroxin (0.035 and the mono n-propylammonium salt of spiro (3,5- mol). A twenty degree temperature increase was noted. dihydroxyboroxin)-1,1-(3',5' - dihydroxyboroxin) col The resulting solution was then stirred at 40-50 C. for 50 lected on a filter in a yield of 97%. The infrared spec 1.5 hours. Diethyl ether (60 mi.) was added to the cooled trum showed bands at 709 cm. and 1640 cm. (borox solution and the precipitated product isolated by filtra in ring and amine salt, respectively). This salt contained tion. The product was obtained in essentially quantitative 19.5% boron and 5.28% nitrogen. yield. Conductance, X-ray powder diffraction, and ele 55 EXAMPLE 10 mental analyses indicated that this material was identical According to the procedure followed in Example 8, the to the boric acid-n-propylamine reaction product obtained mono di-n-butylammonium salt of spiro (3,5-dihydroxy in Example 4. boroxin)-1,1'-(3',5'-dihydroxyboroxin) was prepared. EXAMPLE 6 The infrared spectrum showed bands at 716 cm., 1600 In the manner of Example 4, 7.3 parts of tert-butyl 60 cm., and 3300-3400 cm. i. (boroxin, amine salt, and amine and 6.2 parts of boric acid were reacted to provide, hydroxy groups, respectively). This salt contained 15.0% in quantitative yield, the mono-tert-butylammonium salts boron and 3.60% nitrogen. of 1,3,5-trihydroxyboroxin which analyzed 16.0% boron and 6.68% nitrogen. EXAMPLE 11 EXAMPLE 7 65 This example shows the formation of a salt of this invention by displacement of the amine portion of a salt Boric acid (18.6 parts-0.3 mol) was added to 90 parts with a more basic amine. of pyridine and the mixture was stirred at 25-30 C. for A solution of 1.5 parts (0.0054 mol) of the mono tri one hour. The mixture was then filtered (4 parts of prod methylammonium salt of spiro (3,5-dihydroxyboroxin)- uct recovered) after which excess pyridine was stripped O 1,1'-(3,5'-dihydroxyboroxin) and 2.0 parts (0.023 mol) (70° C. at 40 mm. Hg) to provide 15 additional parts of piperidine in 30 ml. of water was stirred for 2 hours of solid product which was combined with the 4 parts at room temperature and 200 mm. Hg vacuum. Benzene obtained previously. The product, the monopyridinium (100 ml.) was added and 80-90% of the water removed salt of 1,3,5-trihydroxyboroxin, analyzed 16.0% boron by azeotropic distillation. Acetonitrile (50 ml.) was then and 6.27% nitrogen. 75 added and the remaining water removed. The solvent was 5 8,658,836 6 decanted and the residual product isolated and dried to Screening of chemicals as soil fungicides is against the give a quantitative yield of desired product. Infrared and pathogen Pythium ultimum incorporated in sterile soil acid titration confirmed that the product was the mono which is placed in 1 ounce cups. The chemicals to be piperidiniumP is is salt of spiro (3,5-dihydroxyboroxin)-1,1'-o tested are drenched at 30 p.p.m. (on a soil weight basis) E2, E, was found to contain 5 over the surface of the soil in the cups. The treated The preparation of other spiro salts of this invention soil is incubated for 56-60 hours at 65-70 F. in a 100 is summarized in Table I below. All yields were 98-100%. percent relative humidity chamber. TABLE I Percent Percent boron nitrogen Ex. armer-man amal No. Amine Product Calc. Found Calc. Found 12.---- Isopropylamine------Mono isopropylammonium salt of spiro (3,5-dihydroxyboroxin)- 19.5 20. 5.04 5.2 1,1'-(3',5'-dihydroxyboroxin). 13----- tert-Butylamine------Mono tert-butylammonium salt of spiro (3,5-dihydroxyboroxin)- 18.5 17.7 4,80 5,40 1,1'-(3',5'-dihydroxyboroxin)). 14----- Dimethylamine------Mono dimethylammonium salt of spiro (3,5-dihydroxyboroxin)- 20.5 20,1 5.30 5.30 1,1-(3',5'-dihydroxyboroxin). - 15.----- Diethylamine------...--Mono diethylammonium salt of Spiro (3,5-dihydroxyboroxin)-1,1- 18.5 18.5 4.80 4.89 (3,5-dihydroxyboroxin). 16----- Dibutylamine------Monodibutylammonium salt of spiro (3,5-dihydroxyboroxin)-1,1'- . 15.5 5.2 4.02 3.80 (3',5'-dihydroxyboroxin)). ... . 17----- Trimethylamine------Mono trimethylammonium salt of spiro (3,5-dihydroxyboroxin)- 19.5 19.0 5.04 4,93 18----- Triethylamine------Monotriethylammonium1,1'-(3',5'-dihydroxyboroxin)). salt of Spiro (3,5-dihydroxyboroxin)-1,1'-. . . 16.9 16.8 4.38 4.59 (3,5-dihydroxyboroxin)). - 19..... N,N'-dimethylethylenediamine. Mono N,N-dimethylethylenediamine salt of spiro (3,5-dihydroxy- 17.6 17.7 910 9.00 boroxin)-1,1'-(3,5-dihydroxyboroxin). . The following two examples illustrate the preparation The fungicidal activity of the test compound is based of spiro hydroxyboroxin-amine salts (II) from hydroxy- on the degree of mycelial growth inhibition on the sur boroxin-amine salts (I). face of the soil. The amount of mycelial growth on the Surface. of the soil is rated 1 through 5 as follows: EXAMPLE 20 80 1=no growth, 2=growth from corn meal only, 3=some • growth in soil away from corn meal particles, 4-surface A solution of 1.9 parts of the mono-n-propylammonium covered, but little aerial growth, 5=surface covered, much salt of 1,3,5-trihydroxyboroxin (0.01 mol) as prepared aerial growth, (growth equivalent to that on untreated in Example10 p of 4water and was1.23 partsEa ofat boric40-50° acid C. for(0.02 1 hour.mol) 35 soil).Utilizing the above-described procedure the spiro hy Benzene (75 ml) was added and the water removed droxyboroxin-amine salts previously described were found by azeotropic distillation. When approximatey 80% of to possess good fungicidal activity. Representative results the water was removed, acetonitrile (50 ml.) was added are given in Table II below. and the remaining water distilled. The product was iso ated in essentially quantitative' '. . . . . yield. 40 TABLE II Infrared and elemental analyses, X-ray powder diffrac- Test Sompound Compound of Example- Rating tion, and base number showed that this product WaS ------2 identical to the boric acid-n-propylamine reaction product ------2 obtained in Example 9. 14"------m a weam an in a - - - -l...... EXAMPLE 21 is 18------2 ...... , w In addition to the foregoing, it has been found that saltA ofsolution 1,3,5-trihydroxyboroxin of 4.04 parts of the (0.015 Riyadi mol) as prepare formnot only the doSpiro relatively hydroxyboroxin-amine simple amines, assalts discussed (monoammo above, in Example 2 and 1.86 parts of boric acid (0.93 to 50 nium pentaborates) bit also that certain complex amines in 35 ml of water was stirred at 40-50 C. for 0.5 hour, or simple amines containing complex substituents will Benzene (100 ml) was then added and the water removed also react with boric acid to form spiro hydroxyboroxin by azeotropic distillation. After approximately 90% of amine salts. In more complex amines whose structure the water had been removed, the distillation was stopped may not be precisely known, the presence of a reactable becausenitrile (50 Solid, ml.) Was was Caking added the to sidethe stirredof the mixture.fast Act The 55 nitrogenamines with atom perchloric can be acid.determined by iration of solid product (5.3 parts) was collected on a filter. The Thus, it has been found that a large group of complex infra-red spectrum, equivalent conductance, and elemen- nitrogen-containing compounds, which are useful in lubri tal analysis of the product were identical to those of the cating oil compositions as non-metallic or ashless deter boric acid-n-octylamine reaction product obtained in Ex 60 gents or dispersants, can be improved with regard to ample 8. S.,vn s . their usefulness in such compositions, by reacting them The compounds represented by (I) and (II) are ther- with boric acid to form monoammonium salts of spiro mally stable. The monoammonium pentaborates (II) are (3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin). usefulcompounds as fungicides (I) and against(I) can Pythium be used ultimumas fine andretardant both 65 Thesecomplex salts, nitrogen-containing in addition to retaining compounds the function as detergents, of said coatings for paper and paper products. When used as also impart antirust protection and provide improved bear a flame retardant, these compounds can be applied from ing protection (anti-corrosion protection) in lubricating aqueous solution usually just preceding the final drying oil compositions. Also these spiro hydroxyboroxin-amine operation. The monoammonium salts of 1,3,5-trihydroxy- salts have better detergent qualities than do the nitrogen boroxiexamples, (I) in arepreparing also useful, the monoammonium as is evident from pentaborates the above 70 containingincorporated compounds into lubricating from which oils used they in are high prepared temperate Wien (II). ... ', " ... s...... applications such as in diesel engines especially where The fungicidal utility of the monoammonium penta- high sulfur content fuels are used. These spiro salts can borates is readily demonstrated by a screening test, the also be used in burner fuels and gasolines wherein they procedure for which is as follows: 75 function as detergents and rust preventives. 8,658,836 7 8 ...... , , . The new salts referred to above can be represented (g) A monoalkenylsuccinimide of an N-alkylpipera by the structure zine, represented by the structure

3-dep- Oef. --B O se Yo RaCH-C - Cia CHa -0, Yo-1 CHa- X-Rio-NC- CHa-CH2^ N-R. OH OH O 0 (h) An N-dialkylaminoalkyl monoalkenyl succinimide, where Q can be - . . . (a) An imidazolidine, represented by the structure represented by the structure.

R 15 .238ts 2 O R - CH-d' R R. CeeCar. CHaEl-R- Wo Ria R is tra-Yt -cis-3-(E-cha-3). R. R. R2Ys (i) A Schiff base represented by the structure

o, (b) A bis-imidazolidine, represented by the structure R. . . . Wr - R. R R-CH- C i4 R. 25 MCH-C-CH) eNH7 a CHaeca (CHNeC O A 2. ( te): E7 2"; (c ex YRis R. s R R R. CHanC-R. O R as H-cs CH, st R. R V (j) An imine represented by the structure O I 30

(c) An alkenylsuccinimide, represented by the struc R - CH-C ture . Cha- X-Ra-li-kYRis O 9. N. NH RCH- C Rs (k) A 2-substituted imidazolidine represented by the CH2- N-(NH)-C-(NH-C), N. Res 40 structure . . . . O (d) A bis(alkenylsuccinimide), represented by the i. structure 45 R--- . . . . H2--R.

O O i-CH2--(iii-CH2-), Rut s ... So R. R. R-CH- C C-SH as R. 50 CH2- N a Re - N G-CH2 O d (1) An imidazoline represented by the structure (e) An N,N'-azaalkylene-bis(alkenylsuccinimide), rep resented by the structure 55 . O. . . 4. ... O st- B. R. Re--R. 9. R -ch-r GHe-Ca-CH-C). RCH e-C re-id 60 w2-cha-chi-CH2-)-N2 O R R. CH2-C1"N-Cha-C-(CH2).-NH-CH2-C-(CH2).-NC s 2 YC-CH - Rs R. R. O o y and (f) A 3,5-dialkyl-4-hydroxybenzylamine, represented 65 (m) A bis-imidazoline represented by the structure by the structure ''" . . . .

70 . . He's is-c -cis--(E-cha-)-Qe. - w ... R. R. N T 75 3,658,836 O In the foregoing and hereinafter the various repre action thereof with boric acid using five mols of boric sentative letters have the following meanings: acid per mol of such complex. The use of lesser amounts R is a polyalkenyl radical having a molecular weight of of boric acid merely results in forming a mixture of the from about 700 to about 2500, preferably about 900 to compounds of the invention and intermediate nitrogen about 1500; containing product. However, such mixtures are also use R1 is hydrogen or alkyl of 1 to 3 carbon atoms; ful as detergent additives in lubricating oils and are there Ra and R3 are hydrogen, alkyl, alkenyl or haloalkyl of 1 fore contemplated herein. to 20 carbon atoms; The imidazolidine and bis-imidazolidine derived salts R4 is hydrogen or alkyl of 1 to 20 carbon atoms; can be prepared by forming (a) or (b) by reacting R5 is alkyl or cycloalkyl; 10 (i) an alkylenylsuccinic anhyride, represented by the Rs is hydrogen, alkyl or cycloalkyl of 1 to 20 carbon Structure atoms; R is a secondary or tertiary alkyl of 3 to 12 carbon atoms; R8 is hydrogen, alkyl of 1 to 12 carbons, cycloalkyl of 5 5 to 6 carbons, aralkyl of 7 to 11 carbons, aryl of 6 to 10 carbons, alkaryl of 7 to 15 carbons or S O 20 or the acid thereof, (ii) a polyethyleneamine, represented by the structure R R. HN-CH- b- NH-CH-C )et- CH l, and (iii) a carbonyl-containing compound, that is, 30 (1) an aldehyde or ketone represented by the structure R is hydrogen, alkyl of 1 to 12 carbons, cycloalkyl of 5 to 6 carbons, aralkyl of 7 to 11 carbons, ary of 6 to O 10 carbons or alkaryl of 7 to 15 carbons, Ro is alkylene radical containing from 1 to 3 carbon R.--R, atoms; 35 O R11 is an alkylene radical of 1 to 4 carbon atoms; R1a and R1s are each alkyl of 1 to 10 carbons; (2) a dialdehyde or diketone represented by the struc R4 is hydrogen, alkyl of 1 to 20 carbon atoms, a thienyl, ture a phenyl, a naphthyl or a furyl radical; Ris is a thienyl, a phenyl, a naphthyl or a furyl radical; 40 R1s is selected from NH where R, R, R2, R3, R., x and T have their aforedescribed (NH) --(NH) significance and then reacting the thus prepared imidazoli 45 dine or bis-imidazolidine with boric acid. The mol ratios of (i): (ii): (iii) used will be about 1:1:1, respectively, to prepare monoimidazolidines and about 2:2:1, respec m is 0 or 1, n is 0 or 1, and the sum of m--n is 1 to 2 tively, to prepare bis-imidazolidines. In this preparation and (ii) and (iii) are reacted to prepare an intermediate 50 imidazolidine which is then reacted with (i), or (i) can N NE be first reacted with (ii) followed by reaction with (iii). 8-NH-5 To provide a reaction medium an inert solvent can be used, e.g., a hydrocarbon such as toluene, xylene, cyclo hexane or mineral oil. Suitable temperatures for the re R1 and R1s are each hydrogen, an alkyl, alkenyl or halo 55 action of anhydride, polyethyleneamine and carbonyl alkyl of 1 to 20 carbon atoms, a thienyl, a phenyl, a containing compound at atmospheric pressure are of the naphthyl or a furyl radical or together can form a order of 100-175 C. and vacuum can be used in the carbocyclic ring of 5 to 10 carbon atoms; case of a mineral oil reaction medium to operate at about R19 is hydrogen, an alkyl, substituted alkyl, cycloalkyl, the same temperatures. The reaction involving boric acid alkenyl, substituted alkenyl, aryl, substituted aryl of 1 60 can be effected merely by mixing the reactants at tempera to 20 carbon atoms or heterocyclic radical of 5 to 6 tures of the order of 25-150° C. Preferably a tempera atoms; ture of about 60-110° C. is used, since such tempera A is oxygen, sulfur or NH; tures provide good reaction rates. T is alkylene of 1 to 20 and alkenylene of 2 to 20 carbon The alkenylsuccinic anhydrides useful in preparing the atOnS; 65 imidazolidines and bis-imidazolidines can be prepared d and e are each whole numbers from 0 to 1 but the from an olefin or olefin polymer and maleic anhydride. sum of d--e is from 0 to 1; Preferably a polymer of a lower olefin, or copolymer of it is a whole number from 0 to 3; lower olefins, is used, for example, polymers of ethylene, y is a whole number from 1 to 4; and propylene, butylene, isobutylene and mixtures thereof. z is a whole number from 0 to 3 except that when A is 70 Since the reaction between the olefin and maleic anhy oxygen or sulfur z cannot be 0. dride may not go to completion, the resulting alkenylsuc cinic anhydride can contain some unreacted olefin which The aforedescribed spiro hydroxyboroxin-amine salts can be allowed to remain as a diluent with no harmful (III) can be prepared from the various complex nitro effects upon the performance of the compounds of this gen-containing compounds (a) through (m) by the re 75 invention. 3,658,836 The polyethyleneamines useful in preparing the imi dehyde, azelaldehyde, sebacaldehyde, brassylaldehyde, dazolidines are available commercially, but can also be rocellaldehyde, and the like. prepared from alkylene dichlorides and ammonia; rep (b) Ketones: diacetyl, acetylacetone, acetonylacetone, resentative examples are diethylenetriamine, 2,5-dimethyl 2,3-hexanedione, 2,4-heptanedione, 3-methyl-2,4-hex 3-aza-pentamethylene-1,5-diamine, 2,5-diethyl-3-aza-pen- 5 anedione, 2,5-hexanedione, 2,3-octanedione, and the tamethylene-1,5-diamine, 2,2,5,5-tetramethyl-3-aza-penta- like. methylene - 1,5 - diamine, triethylenetetramine, 2,5,8-tri- a methyl-3,6-diaza-octamethylene - 1.8- diamine, tetraethyl- The preparation of illustrative salts within the above enepentamine, pentaethylenehexamine, and the like. . . . definition is given in the following non-limiting exam In the case of the carobonyl and dicarbonyl-contain, 10 ples wherein parts are parts by weight. ing compounds useful in preparing the imidazolidines and bis-imidazolidines of this invention, the following are rep- EXAMPLE 22 resentative. . . . Mono-carbonyl containing: Into a conventional reactor fitted with an agitator, raw (a) Aldehydes: formaldehyde, acetaldehyde, propional- 5 Sail l product tell condenser, Dean dehyde, n-butyraldehyde, isobutyraldehyde, n-valeralde- E. eating means and thernometer, there was dhyecaroadeyde,hyde, isovaleraldehyde, pivaldehyde,33 dimethylbutylaldehyde, or-methylbutyral- chargeddyiPolybulenysuitimide(prepared 240 parts (0.159 mol) of-N-(3,6,9,12-tetraazado frontetraethy heptaldehyde, pelagonaldehyde, nonanal, 2-ethylhex- 20 ene pentamine and polybutenylsuccinic anhydride in which anal, caprylaldehyde, lauraldehyde, tridecanal, myrist- the polybutenyl group shad an average molecular weight aldehyde, pentadecanal, palmitaldedehyde, heptadeca- of 980) and about 80 ml. toluene. With the agitator run na, Stearaidehyde, brassaldehyde and the like sub- ng 15 grims of n-butyraldehyde (0.159 rol) was stituted aldehydes such as chloroacetaldehyde, chloral, then slowly charged and the resulting mixture heated at butylchloral, trifluoroacetaldehyde, aldol, and the like; 25 s for about two hours while removing water formed and unsaturated aldehydes, such as acrolein, meth- y the reaction by azeotropic distillation. 3 : tra. acrolein, crotonaldehyde, 3-butena, 3- and 4-pentenal, After cooling, the reaction mixture, from above, 49.2 3-, 4-, and 5-hexenal, 4-octenal, 2-ethyl-3-hexenal, 3- parts of boc acid (0.795 mol), were charged, after which decenal, and the like. re- the resulting mixture was heated at 70-80 C. for 15-30 (b) Ketones: acetone, methyl ethyl ketone, methyl propyl 80 "Island. then heated at reflux for about two hours ketone,methyl isobutylmethyl isopropylketon methyscoutyiketoe, ketone, methyl butyl ketone,methyl whilethreation removing assis water filtered. formed The by filtrate the reaction. was disildoe Thereafter tert-butyl ketone, methyl cyclobutyl ketone, methyi neo- move the solvent leaving 275 parts of the 18-(poly pentylamylketone, ketone, methylhexy methyl tert-amyl ketone, ketone,methyl cyclohexy.methyl n- 85 byto E.E9E. -3,6-diazaoctyl)-2-propylimidazol St. Spot 3. dihydroxy. ketone, methyl n-hepty ketone, methyl n-octyl ketone, boroxin)-1,1-(3',5'-dihydroxyboroxin) which analyzed methyl nonyl ketone, methyl decyl ketone, diethyl ke- 3.3%itrogen and 2.77% boron, tone, di-n-propyl ketone, ethyl isopropyl ketone, ethyl Additional examples of other polyalkenylsuccinimido

n-propylktonpropy ketone, ethylisotopykeonen-propyler tert-butyl ketone, ethyl n-buty buy 40 azaalkylimidazolineoxin salts of this invention monoammonium and the materials spiro usedhydroxybor for their ketone, 3- and 4-methyl-2-hexanone, 3,4-dimethyl-2-pen- preparation (other than boric acid) are given in Table tanone, 3-ethyl-2-pentanone, 2-decanone, 2- and 3-meth- III, below. In the table only the alkenyl, or polyalkenyl, yl-1-penten-4-one, 1-hepten-4-one, 3-methyl-1-hexen-5- portion of the polyalkenylsuccinic anhydride and the one, 5-methyl-5-hexen-2-one, and the like. average molecular weight of such portion are given, DETA . Di-carbonyl containing: 45 means diethylenetriamine and TEPA means tetraethylene (a) Aldehydes: glyoxal, malonaldehyde, succinaldehyde, pentamine. In each case five mols...of boric acid are re glutaraldehyde, adipaldehyde, pimelaldehyde, suberal- acted per mol of amine...... ' ..." . . . . ' , TABLE III Alkenyl portion of 2 alkenylsuccinic v anhydride Poly- Carbonyl (no.wt. of ethylene containing E alkenyl group) amine compound . Molar ratio X. & No. (a) (b) (c) (a); (b); (c) Product - ...... 23-...- Polybutenyl (980).----- TEPA Formaldehyde.--- 1:1: The 1-(8:(polybitenylsuccinimido-3,6-diazaoctyl)imidazolidine mono . . sing: salt of spiro (3,5-dihydroxyboroxin)-1,1-(3',5'-dihydroxy 24.------do------TEPA Acetaldehyde...-- 1:1:1. The fis(polybutenylsuccinimido-2,6-diazaoctyl-2-methylimidazoline v'., " ... -- ES salt of spiro-i(8,5-dihydroxyboroxin)-1,1-(3',5'-di 25.------do a as as a a a as as TEPA Isodecylaldehyde. 1:1. TE i-3-(polybitenylsuccinimido)-3,6-diazaoctyl-2-nonyltraigazigine . . . agains, salt of spiro (3,5-dihydroxyboro.in)-L-3',5'-di 26..... Polybutenyl (1,350). DETA Glutaraldehyde.-- 2:2:1 Ttrimethylene bis(1-(8-polybutenylsuccinimido)-3,6-diazoctyl)-2-mid azolidine monoammonium salt of spiro (3,5-dihydroxyboroxin)-1,1- 27--- Polybutenyl (980).----- TEPA Acetone------S. . . . . 1:1:1.. The(3,5-dihydroxyboroxin).-- 1-8-(polybutenylsuccinimido)-3,6-diazaoctyl-2-dimethylimidazoli . . . : ... - dine monoammonium salt of spiro-C3,5-dihydroxyboroxin)-,-(3',5'- a v '. dihydroxyboroxin): v...... - ...... -- 28------do------TEPA Cycloaexanola--- i:1:1. The 1-8-(polybuitenylsuccinimido)-3,6-diazaoctyl-1,4-diazaspirp4.5dec . . .'; . :...... are monoammonium salt of spirot (3,5-dihydroxyboroxin)-1,1-(3',5'- ''. dihydroxyboroxin)...... 29.------do------DETA Acetylacetone...- 2:2:1. The 2,2'-methylene... bis-(8-polybutenylsuccinimido)-3,6-diazaoctyl)- - - imidazolidine monoammonium salt of spiro (3,5-dihydroxyboroxin)- s i,'-(35-dihydroxyboroxin) ...... ; 30----- Polyeutenyl (135). DEA Glutaraldehyde- 2:2:1. The trimethylene bis-(2-polybutenylsugeinimido)ethyl)-2-imidazoli ...... dine) monoammonium salt of spiro (3,5-dihydroxyboroxin)-1,1'-(3',5'- dihydroxyboroxin). - ...... - is : ...... 31------do------TEPA ra-Butyraldehyde 1:1:1. The 1-(8-(polybutenylsuccinimido)-3,6-diazaoctyl-2-propylimidazolidine ...... agains salt of spirot, dihydroxyberoin)-(3',5'-di 32..... Polybutenyl (980).---- DETA ----do----.------:: Ti 3-(polybitenylsuccinimido)ethyl)-2-propylimidazolidine mono ammonium salt of spiro (3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy boroxin)...... 3,658,836 13 14 The alkenylsuccinimide (c) derived monoammonium (2) cyanamide and an acid salt of an alkylguanidine, salts of spiro (3,5 - dihydroxyboroxin)-1,1-(3',5'-dihy droxyboroxin) can be prepared by heating an alkenyl R NH NE-CEN -- N-C-NH2 AC --> succinic anhydride as aforedescribed with an alkyl-substi / tuted nitrogen derivative of carbonic acid (hereinafter de R scribed) followed by reaction with boric acid. The prepara R5 N N tion of the alkenylsuccinimide can be conveniently car N ried out at temperatures in the range of about 75° C. to N-C-NH-C-NH.AC about 175 C., but at or above the dehydration tempera R ture of the reaction system (that is, under dehydration or 0. (3) biguanide and an amine salt, cyclization conditions) using substantially equal mols of each reactant, preferably while continuously removing, as NH NH R NH-C-NH-C-NH -- NH.AC - by distillation, water formed by the reaction. For the re / action with boric acid the temperatures are those previ R6 ously discussed, namely 25-150° C. but preferably 60° 110° C. RY-5-NH-5-NHAC NH NH It is preferred to conduct the preparation of the instant / compounds in an inert solvent, since the products are usu R6 ally very viscous and difficult to handle. Suitable solvents The basic salts of alkylguanidines and alkylbiguanides are hydrocarbons such as benzene, toluene, xylene, cyclo 20 can also be reacted with the alkenylsuccinic anhydrides to hexane or mineral oil. A synthetic oil can also be used, prepare the alkenylsuccinimides used in making the penta e.g., the alkylene polymers, alkylene oxide polymers, ole borate salts of this invention. Such basic salts are those fin-chlorinated hydrocarbon polymers, dicarboxylic acid of weak acids which, when dissolved in water, give a esters, alkylated benzenes, chlorinated biphenyl, silicate solution having a pH of at least about 7. Examples of such esters, silicon polymers and the like. No solvent is neces 25 basic salts are the carbonate salts, bicarbonate salts, and Sary, however. aliphatic acid salts; e.g., alkylguanidine carbonate, alkyl The alkyl-substituted (which includes cyclic alkyl) ni guanidine bicarbonate, alkylguanidine acetate, alkylguan trogen derivatives of carbonic acid useful in preparing the idine propionate, alkylguanidine stearate, alkylbiguanide alkenylsuccinimides are mono- and dialkyl-substituted carbonate, alkylbiguanide acetate, alkylbiguanide octoate, guanidine, aminoguanidine and biguanide. Such alkyl de 30 alkylbiguanide stearate, and the like. rivatives can be prepared by means known to the art, of The preparation of typical alkenylsuccinimide mono which the following is illustrative. In each illustration, AC ammonium salts of spiro (3,5-dihydroxyboroxin)-1,1-(3, represents an organic acid. 5'-dihydroxyboroxin) is illustrated in the following non Alkylguanidines limiting examples wherein parts are parts by weight. Alkylguanidines, EXAMPLE 33 Into a suitable reaction vessel fitted with a Dean-Stark N. R. / trap and conventional accessories containing 19.2 parts of NH-C-N cyclohexylamine and 30 cc. of water, there is slowly 40 R charged 12 parts of acetic acid. After completing addi tion of the acetic acid, there is charged an additional can be prepared from cyanimide and an amine, 2 parts of cyclohexylamine. The resulting mixture is then heated to about 90-95 C., and 16.8 parts of a 50% aque Rs NH R. ous solution of cyanamide is slowly charged (approxi / AC / 45 mately 2 hours). The reaction mixture is then heated at NH - NBI-CN - NE-C-N AC about 95 C. for about 30 minutes, 50 cc. of toluene was R6 R added, and the water was removed by azeotropic distilla Alkylaminoguanidines tion. The cooled mixture was then filtered to give cyclo hexylguanidine acetate. Alkylaminoguanidines, 50 Thereafter a mixture of 8.2 parts of cyclohexylguani dine acetate, 60 parts of polybutenylsuccinic anhydride NH Rs (the average molecular weight of the polybutenyl group NH-NH-5-N1 is about 900), and 50 cc. of toluene are heated for about Yu, 10 hours at about 130 C, while azeotropically removing 55 water... form in the reaction. The reaction mass is then can be prepared by the reduction of alkylnitroguanidines, cooled and 12.5 grams of boric acid are then charged and the reaction mass heated at reflux for one to two hours Rs NH Rs NE while azeotropically removing water as it is formed. The Y.-C-NH-NO - Y. -C-NH-NH. product is then filtered and the toluene stripped to yield 60 the N - cyclohexyl-1-polybutenylsuccinimidoformamidine monoammonium salt of spiro[(3,5-dihydroxyboroxin)-1, Alkylbiguanides 1, (3',5'-dihydroxyboroxin). Alkylbiguanides, EXAMPLE 34. N NH R. I / 65 NEI-C-NC-N Into a suitable reaction vessel, as described above, there N is slowly charged, over about 3% hours, a solution of 42 Rs parts of cyanamide in 84 cc. of water to a solution of can be prepared from 76.7 parts of n-butylamine and 60 parts of acetic acid in 75 cc. of water at 95-100° C. Thereafter the resulting (1) guanidine and alkylcyanamide, 70 reaction mixture is heated for an additional 4 hour. After the reaction mass is cooled, ammonia is added in a quanti R NH N ty Sufficient to make the reaction mass slightly alkaline. NH-C-NH -- . -CEN --> Carbon dioxide is then passed into and through the reac / tion mixture which is maintained at a temperature of 25 R 8 35 C., until all of the free n-butylguanidine prepared 3,658,836 15 16 above is converted to n-butylguanidine bicarbonate, which tions, using a mol ratio of amine to alkenylsuccinic an precipitates during the CO2 addition. The n-butylguanidine hydride of about 0.5:1, respectively, preferably while bicarbonate is then recovered by filtration and dried. continuously removing, as by distillation, water formed To the reaction vessel there is charged 17.4 parts of n by the reaction. Basic salt has the same meaning as de butylguanidine bicarbonate, 125 parts of polybutenylsuc scribed above. It is preferred to conduct the reaction in cinic anhydride (the average molecular weight of the poly a hydrocarbon solvent such as those previously described butenyl group is about 1000) and 90 cc. of toluene. The but the use of a solvent is not necessary. The resulting reaction mixture is then heated in the range of about 140 bis-imide is then reacted with boric acid under the same C. to about 150 C. for about 12 hours, during which time conditions described for the preparation of the salts based carbon dioxide evolves and water of reaction is azeo 0. on alkenylsuccinimides. tropically removed. 28.9 parts of boric acid are then The preparation of a typical bis-imide derived spiro charged and the resulting mixture heated at reflux for one hydroxyboroxin-amine salt is illustrated in the following to two hours while removing water of reaction. The prod non-limiting examples wherein parts are parts by weight. uct is filtered and the toluene is then stripped to give the N-butyl-1-polybutenylsuccinimidoformamidine mono 5 EXAMPLE 35 ammonium salt of spiro (3,5-dihydroxyboroxin)-1,1'-(3, Into a suitable reaction vessel, -as previously described, 5'-dihydroxyboroxin). there is charged 13.6 parts of aminoguanidine bicar Generally following the procedures of the foregoing bonate, 200 parts of polybutenylsuccinic anhydride (the examples, other similar salts can be prepared, examples average molecular weight of the polybutenyl group is of which are as listed below. The number in parentheses 20 about 1350) and 150 ml. of toluene. The resulting mix is the average molecular weight of the polyalkenyl group. ture is then heated at 140-150° C. for about 10-12 hours The N-(tert-dodecyl)-1-polybutenyl(1000)succinimido during which time carbon dioxide evolves and water of formamidine monoammonium salt of spiro (3,5-dihy reaction is azeotropically distilled. The reaction mass is droxyboroxin)-1,1-(3',5'-dihydroxyboroxin), then cooled, 31.0 parts of boric acid is charged and the The N,N'(dicyclohexyl)-1-polybutenyl (700) succinimi 25 reaction mass heated at reflux for one to two hours doformamidine amonoammonium salt of spiro (3,5- while removing water of reaction by azeotropic distil dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), lation. The reaction mass is then filtered and the toluene The N,N-(dibutyl)-1-polybutenyi (900) succinimidoform stripped to provide the 1,N-bis(polybutenylsuccinimido) amidine monoammonium salt of spiro (3,5-dihydroxy formamidine monoammonium salt of spiro[3.5 - dihy boroxin)-1,1'-(3',5'-dihydroxyboroxin), 30 droxyboroxin)-1,1'-(3',5'-dihydroxyboroxin)). The N-(tert-butyl)-1-polypropenyl (1200) succinimido formamidine monoammonium salt of spiro (3,5- EXAMPLE 36 dihydroxyboroxin)-1,1-(3',5'-dihydroxyboroxin), The 1-dodecyl-3-polybutenyl (1300) succinimidoguanidine In the manner of Example 35, 13.2 parts of biguanide monoammonium salt of spiro (3,5-dihydroxy 35 bicarbonate, 200 parts of the same polybutenylsuccinic boroxin)-1,1'-(3',5'-dihydroxyboroxin), anhydride and 31.0 parts of boric acid are reacted to The 1-(3-butylguanidino)-1-polybutenyl(1000) succin provide the bis(imino(polybutenylsuccinimido) methyl) imidomethyleneimine monoammonium salt of spiro amine monoammonium salt of spiro[(3,5-dihydroxy I(3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy 40 boroxin)-1,1'-(3',5'-dihydroxyboroxin). boroxin), Generally following the procedures of the foregoing The N-olleyl-1-polybutenyl (900) succinimidoformamidine examples, other boroxin salts based on the compounds monoammonium salt of spiro (3,5-dihydroxy of class (d) can be prepared, examples of which are as boroxin)-1,1'-(3',5'-dihydroxyboroxin), follows: The 1-IN,N-(dibutyl)-3-polybutenyl (1200) succinimi doguanidine monoammonium salt of spiro (3,5-dihy 45 the 1,N'-bis(polybutenyl (900) succinimido) formamidine droxyboroxin)-1,1-(3',5'-dihydroxyboroxin), monoammonium salt of spiro'3,5-dihydroxyboroxin)- The 1-butyl-3-polybutenyl (900) succinimidoguanidine 1,1-(3',5'-dihydroxyboroxin)), . monoammonium salt of spiro (3,5-dihydroxy the bisimino(polybutenyl(1315) succinimido)methyl) boroxin)-1,1'-(3',5'-dihydroxyboroxin), amino monoammonium salt of spiro (3,5-dihydroxy The 1-stearyl-3-polybutenyl (700) succinimidoguanidine 50 boroxin)-1,1'-(3',5'-dihydroxyboroxin)l, and monoammonium salt of spiro (3,5-dihydroxy the 1,3-bis(polybutenyl (1350) succinimido)guanidine boroxin)-1,1-(3',5'-dihydroxyboroxin), monoammonium salt of spiro[(3,5-dihydroxyboroxin)- The 1-N,N-(diethyl)-3-polybutenyl (900) succinimido 1,1-(3',5'-dihydroxyboroxin)). guanidine monoammonium salt of spiro (3,5-dihy droxyboroxin)-1,1'-3',5'-dihydroxyboroxin), 55 The spiro hydroxyboroxin-amine salts of this invention The 1-(3-dodecylguanidino)-1-polybutenyl (900) succin based upon the compounds of class (e) can be prepared imidomethyleneimine monoammonium salt of spiro by heating a toluene, or other hydrocarbon solution of (3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy an alkenylsuccinic anhydride (as aforedescribed) and an boroxin), azaalkylenediamine at temperatures of about 100° C. to The 1-(3-oleylguanidino)-1-polybutenyl (700) succinimi 60 175° C. using mol ratios of anhydride to amine of from domethyleneimine monoammonium salt of spiro about 2:1 to about 2.5:1, respectively, while continuously I(3,5-dihydroxyboroxin) 1, 1'-(3',5'-dihydroxy removing, as by distillation, the water formed from the boroxin), and - reaction. Thereafter boric acid is added and the resulting The 1-(3,3-dibutylguanidino)-1-polybutenyl (900) succin mass heated at 25°-150 C. as previously described. imidomethyleneimine monoammonium salt of spiro 65 The azaalkylenediamines which are used can be repre (3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy sented by the structure boroxin). ------The bis(alkenylsuccinimides) (d) used in preparing the spiro hydroxyboroxin-amine salts of this invention based 70 thereon can be prepared by heating an alkenylsuccinic anhydride (as aforedescribed) and 1,3-diaminoguanidine, aminoguanidine or biguanide or their basic salts attem peratures in the range of about 75° C. to about 175° C., but at or above the dehydration or cyclization condi. 75 y 8,658,836 17 18 where R, x and y have their aforedescribed significance. droxyboroxin)-1,1-(3',5'-dihydroxyboroxin) can be pre The azaalkylenediamines are available commercially, but pared, such as: can also be prepared from alkylene dichlorides and am monia. Examples of azaalkylenediamines useful in pre the N,N'-(3,69-triazaundecamethylene)-bispolyethenyl paring the bis-imides are diethylenetriamine, dipropylene 5 triamine, di(trimethylene) triamine, di(1,2-butylene) tri (1500)3,5-dihydroxyboroxin)-1,1-(3',5'-dihydroxy succinimide monoammonium salt of spiro amine, 2,2,5,5-tetramethyl-3-aza-pentamethylene-1,5-di boroxin)), amine, dipentamethylenetriamine, triethylenetetramine, the N,N'-(3-azapentamethylene)-bispolybutenyl (800) tripropylenetetramine, tetraethylenepentamine, pentaeth succinimide monoammonium salt of spiro (3,5-di ylenehexamine, and the like, and mixtures thereof. O hydroxyboroxin)-1,1-(3',5'-dihydroxyboroxin), The preparation of typical N,N'-azaalkylene-bis(alken the N,N'-(3-azapentamethylene)-bispolypropenyl(850) ylsuccinimide) monoammonium salts of spiro (3,5-dihy - succinimide) monoammonium salt of spiro (3,5-dihy droxyboroxin) - 1,1- (3',5'-dihydroxyboroxin)) is illus droxyboroxin)-1,1-(3',5'-dihydroxyboroxin), trated in the following nonlimiting examples wherein parts the N,N'-(3-azapentamethylene)-bis(polyethenyl(1000) are parts by weight. 5 succinimide) monoammonium salt of spiro[3,5-dihy 'droxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), EXAMPLE 37 the N,N'-(3,6-diazaoctamethylene)-bis(polypropenyl Seven hundred two parts of polybutenyl(935) succinic (1300) Succinimide monoammonium salt of spiro (3,5- anhydride and 200 ml. of toluene are charged into a dihydroxyboroxin)-1,1'-(3,5-dihydroxyboroxin), suitable vessel fitted with a Dean-Stark tube and other. 20 the N,N'-(3,6-diazaoctamethylene-bis(polybutenyl (1800). conventional accessories. After the resulting mixture is succinimide monoammonium salt of spiro (3,5-dihy warmed to about 50 C., 47.6 parts of tetraethylenepent droxyboroxin)-1,1-(3',5'-dihydroxyboroxin), amine are slowly added over about 30 minutes. The mix the N(N'-(3,6,9,12-tetraazatetradecamethylene)-bispoly ture is then heated with agitation at temperatures in the ethenyl (1800) succinimide monoammonium salt of range of about 120-140° C. for about 3 hours, during 25 Spiro (3,5-dihydroxyboroxin) - 1,1'-(3',5'-dihydroxy which time water of reaction is removed by azeotropic boroxin), distillation. Seventy-eight parts of boric acid are then the N,N'-(3,6,9,12-tetraazatetradecamethylene)-bis(poly charged and the resulting mixture heated at reflux to butenyl(2000) succinimide monoammonium salt of azeotropically remove water of reaction. Thereafter the Spiro (3,5-dihydroxyboroxin) - 1,1'-(3',5'-dihydroxy toluene is stripped to leave the N,N'-(3,6,9-triazaundeca 30 boroxin), methylene)-bispolybutenyl (935) succinimidel monoam the N,N'-(3,6,9,12-tetraazatetradecamethylene)-bis(poly monium salt of spiro (3,5-dihydroxyboroxin)-1,1'-(3',5'- pentenyl(2000) Succinimide monoammonium salt of dihydroxyboroxin). ' , ...... " spiro[(3,5-dihydroxyboroxin) - 1,1'-(3',5'-dihydroxy boroxin), EXAMPLE 38 the N,N'- (4azaheptamethylene)-bis polypropenyl(1500) Succinimidel monoammonium salt of spiro (3,5-dihy In the manner of Example 37, 1100 parts of poly droxyboroxin)-1,1'-(3,5 '-dihydroxyboroxin), butenyl (700) succinic anhydride and 300 ml. of toluene the N,N'-(4-azaheptamethylene) -bis(polybutenyl(1300) are charged into a suitable reaction vessel and the re Succinimidel monoammonium salt of spiro (3,5-dihy sulting mixture is warmed to about 50 C. 72.8 parts of 40 droxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), tetraethylenepentamine are then added dropwise and the the N,N'-(4,8-diazaundecamethylene)-bis polyethenyl reaction mixture heated at reflux until the amount of water collected equals the theoretical. 119.3 parts of boric dihydroxyboroxin)1,1'-(3,5(1200) succinimide monoammonium '-dihydroxyboroxin), salt of spiro (3,5- acid are then charged and the reaction mixture heated the N,N'-(4,8. diazaundecamethylene)-bis(polybutenyl at reflux to azeotropically remove water of reaction. 45 ( 1200) succinimide monoammonium salt of spiro (3,5- Thereafter the toluene is stripped to leave the N,N'- dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), (3,69 - triazaundecamethylene)-bis(polybutenyl(700) suc the N,N'-(4,8,12-triazapentadecamethylene )-bis(polypro cinimide monoamonium salt of spiro (3,5-dihydroxy penyl(900) Succinimide monoammonium salt of spiro boroxin)-1,1-(3',5'-dihydroxyboroxin). . . . S. - dihydroxyboroxin)-1,1'-(3',5'-dihydroxyborox 50 IIl EXAMPLE 39 the NN'-(4,8,12-triazapentadecamethylene)-bis(polybu In the manner of Example 37, the N,N'-(3,69-triazaun tenyl(1500) succinimide monoammonium salt of spiro decamethylene)-bispolybutenyl(1500) succinimide mon (3. - dihydroxyboroxin)-1,1'-(3',5'-dihydroxyborox oammonium salt of spiro (3,5-dihydroxyboroxin)-1,1'- lil), (3',5'-dihydroxyboroxin) is prepared from 220 parts of 55 the N,N' (5-azanonamethylene)-bis(polybutenyl(1800) polybutenyl(1500) succinic anhydride, 6.5 parts of tetra ... droxyboroxin)-1,1'-(3',5'-dihydroxyboroxin),Succinimide monoammonium salt of spiro (3,5-dihy ethylenepentamine and 10.7 parts of boric acid...... the N,N'- (3-aza-2,5-dimethylpentamethylene)-bis(poly propenyl(1800) succinimide monoammonium salt of EXAMPLE 40 60 Spiro (3,5-dihydroxyboroxin) - 1,1'- (3',5'-dihydroxy Into a suitable reaction vessel, there is charged 43.3 boroxin), parts of polybutenyl (1330) succinic anhydride, process oil the N,N'-(3-aza-2,5-dimethylpentamethylene)-bispoly and 1.8 parts of di(trimethylene) triamine. The resulting butenyl(1300) succinimide monoammonium salt of reaction mixture is then heated at about 150° C. and 65 Spiro[(3,5-dihydroxyboroxin) - 1,1'-(3',5'-dihydroxy under Vacuum until the amount of water collected is boroxin), about equal to the theoretical. 4.3 parts of boric acid the N,N'-(3,6-diaza-2,5,8-trimethyloctamethylene)-bis are then added and the reaction mass heated at 90° C. polybutenyl(1200) succinimide monoammonium salt for about one hour, and then at about 150° C. and a of spiro[(3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy pressure of 35 mm. Hg for one hour to yield the N,N'- boroxin), (4-azaheptamethylene) bis(polybutenyl(1330)succinimide 70 the N,N'-(4-aza-3,7-dimethylheptamethylene)-bis(poly. monoammonium salt of spiro (3,5-dihydroxyboroxin)- butenyl (800) succinimidel monoammonium salt of 1,1-(3',5'-dihydroxyboroxin). - spiro[(3,5-dihydroxyboroxin) - 1,1'-(3',5'-dihydroxy In a similar manner, other N,N-azaalkylene-bis(alken boroxin), ylsuccinimide) monoammonium salts of spiro (3,5-dihy 75 and the like.

19 2 o ... The monoammonium spiro salts made from 3,5-dialkyl-.... Other typical compounds which can be used to prepare 4-hydroxybenzylamines (f) can be prepared by reacting a the salts of this invention include: 2,6-dialkyl phenol in which the alkyl groups contain from N-benzyl-3,5-di-tert-butyl-4-hydroxybenzylamine, 3 to 12 carbon atoms, formaldehyde, and a primary or N-(3,5-xylyl)-3,5-di-tert-amyl-4-hydroxybenzylamine, secondary amine in which the hydrocarbon portion there N-(p-butylbenzyl)-bis-(3,5-di-tert-butyl-4-hydroxy of is in conformity with the groups designated herein benzyl)amine, . above as Rs and R9, and then reacting the resulting prod N-o-naphthyl-bis(3,5-diisopropyl-4-hydroxybenzyl) . uct with boric acid. In conducting the process a mono hydric, alcohol containing from 1 to 6 carbon atoms is N-p-tolyl-bis(3,5-di(2-dodecyl)-4-hydroxybenzyl... anille, ; ...... 3, ... . . preferably used as the reaction solvent for preparing the O amine, ...... intermediate. For the reaction with boric acid benzene, N,N-diphenyl-3,5-di(2-hexyl)-4-hydroxybenzylamine, toluene, mineral oil or other hydrocarbon is used as the N-phenyl-N-p-tolyl-3,5-di(2-amyl)-4-hydroxy is reaction solvent. The reaction temperature throughout the process is of the order of about 25°C. to about N-p-octylphenyl-3-ethyl-5-tert-butyl-4-hydroxybenzylamine, --: ... - - - ... --- ...... 5 benzylamine, In conducting the process to prepare the intermediate N-(2-dodecyl)-3,5-di(2-hexyl)-4-hydroxybenzyl 3,5-dialkyl-4-hydroxybenzylamine, the relative propor tions of the three reactants, phenol, formaldehyde and N-methyl-N-ethyl-3,5-di(2-octyl)-4-hydroxy... amine, . . . . - - - anine, are. Varied depending upon the particular type of benzylamine, * -- ...... " ... 3,5-dialkyl-4-hydroxybenzylamine being prepared. Thus, 20 N-nonyl-3-tert-butyl-5-tert-amyl-4-hydroxybenzylamine, when preparing the N,N-dihydrocarbon substituted 3,5- N,N-diisobutyl-3,5-di-tert-amyl-4-hydroxybenzylamine, dialkyl-4-hydroxybenzylamines, one mol of formaldehyde N,N-dioctyl-3,5-di(1,1,3,3-tetramethylbutyl)-4- and one mol, of dihydrocarbon Substituted: amine, i.e., . hydroxybenzylamine, secondary amine, are employed permol of appropriate-2,6- N-methyl-bis(3,5-di-tert-amyl-4-hydroxyzenzyl) - dialkyl phenol. When preparing N-hydrocarbon-N,N-bis 25 - amine, ...... ( 3,5-dialkyl-4-hydroxybenzyl)amine, one mol of formal N-heptyl-bis(3,5-di-tert-amyl-4-hydroxybenzyl)amine, dehyde and one-half of a mol of monohydrocarbon sub N-ethyl-3,5-di-tert-butyl-4-hydroxybenzylamine; stituted amine, i.e., primary amine, are reacted permol of -N-isohexyl-3,5-di-tert-butyl-4-hydroxybenzylamine, appropriately Substituted 2,6-dialkyl phenol used. When N,N-dipropyl-3,5-di-tert-butyl-4-hydroxybenzylamine, . Preparing the compounds which contain one hydrogen N-ethyl-bis(3,5-di-tert-butyl-4-hydroxybenzyl)amine, atom and one hydrocarbon group on the nitrogen atom, N-butyl-bis(3,5-di-tert-butyl-4-hydroxybenzyl)amine, one mol of a formaldehyde and a large excess of primary and the like. anine are employed per mol of 2,6-dialkyl phenol used. The compounds just described (f) are soluble in various This substantial excess of primary amine is of the order organic solvents, and in gasolines, diesel fuels, lubricating of about 8 to about 10 mols per mol of phenol used. This 35 oils, particularly hydrocarbon oils and the like, wherein particular reaction is conducted in a large amount of they function as antioxidants and rust inhibitors. Usual monohydric alcohol solvent in order to achieve dilution concentrations are of the order of 0.1% to 10% by of the reactants. weight. a ', s The new 3,5-dialkyl-4-hydroxybenzylammonium salts The spiro hydroxyboroxin-amine salts of mono of spiro (3,5- dihydroxyboroxin)-1,1'-(3',5'-dihydroxy 40 alkenylsuccinimides of N-alkylpiperazines (g) can be boroxin)) and a method for their preparation are illus prepared by reacting an alkenylsuccinic anhydride (as trated by the following examples wherein parts are by aforedescribed) with an N-(aminoalkyl)piperazine to weight...... prepare an intermediate which is then reacted with boric EXAMPLE 41 acid to prepare the compounds of this invention. Typi cal piperazines which can be used are: N-methyl-N'-2- In a suitable reaction vessel equipped with stirring (aminoethyl)piperazine, N - isopropyl - N - (2-amino means, reflux means, thermometer and reagent introducing ethyl)piperazine, N-(2-amino-1-methylethyl)piperazine, means are placed 89 parts of 2,6-diisopropylphenol, 248 and the like.s...... : ...... parts of 25 percent aqueous dimethylamine solution and . . The reaction of alkenylsuccinic anhydride and a sub 500 parts of ethanol. To this solution is added 75 parts 50 stituted piperazine can be at from about 100', C. to of 37 percent formalin solution at reom temperature and 200°C., preferably from 125° C. to 175 C. The alkenyl the mixture refluxed for 4 hours at 83° C. The reaction ... succinic anhydride and the piperazine derivative are re mixture is then hydrolyzed with excess cold water and acted in about equal molar quantities. The reaction of the solid product, N,N-dimethyl-3,5-diisopropyl-4-hydroxy the intermediate with: ; boric acid is conducted in the benzylamine, filtered off. The amine intermediate is then 55 usual: manner at temperatures of .25-150° C. : : returned to the reaction vessel to which a Dean-Stark trap The preparation of the new ammonium salts based has been added, with toluene and 155 parts of boric acid is 5 upon such alkenylsuccinimides is illustrated in the fol charged. The resulting mixture is then heated at reflux lowing example wherein parts are parts by weight. while removing water of reaction by azeotropic distilla 60 s: EXAMPLE 43 tion. The toluene is then stripped to leave the desired . . A mixture of 18 parts (0.14 mol) or N-(2-aminoethyl) product, which is the N,N-dimethyl-3,5-diisopropyl-4-hy piperazine and 200 parts (0.13 mol) of polybutenyl droxybenzylammonium salt of spiro (3,5-dihydroxy succinic anhydride, in which the alkenyl group has an average, molecular weight of about 1000, are blended

boroxin)-1,1'-(3,5-dihydroxyboroxin). 65 with agitation in a suitable vessel and heated to a tem EXAMPLE 42 perature of 150 C., after which the absolute pressure is reduced to about 50 mm. Hg to remove excess amine In the manner of Example 41, 159 parts of 2,6-di-(1,1- and water. The reaction mixture is then allowed to reach 3,3-tetramethylbutyl)phenol, 45 parts of 37 percent aque room-temperature at the reduced pressure. Thereafter O toluene and 40.4 parts of boric acid are charged and ous formalin solution, 29 parts of 40 percent aqueous the resulting mixture heated at reflux while continuously ethyl amine solution and 77.5 parts of boric acid are re removing water of reaction. After stripping the toluene acted to provide the N-ethyl-bis-(3,5-di-(1,1,3,3-tetra is there remains the N-2-(polybutenylsuccinimido)ethyl methylbutyl)-4-hydroxybenzyl ammonium salts of spiro piperazinium salt of spiro[(3,5-dihydroxyboroxin)-1,1- (3,5-dihydroxyboroxin)-1,1-(3',5'-dihydroxyboroxin). 75 (3',5'-dihydroxyboroxin). ; : . . . ' ' 3,658,836 21 22 The preparation of the salts of N-dialkylaminoalkyl (iii) a carbonyl-containing aromatic or heterocyclic com monoalkenylsuccinimides (h) can be effected by reacting pound represented by the structure a monoalkenylsuccinic anhydride with a dialkylamino alkylamine to form a monoalkenylsuccinimide which is then reacted with boric acid to form the desired am 5 R15-C-R1. monium salt. . . . where R, R1, R14, Ris, x and y have their aforedescribed The reaction between alkenylsuccinic anhydride and significance. The mol ratios of (i): (ii): (iii) reacted will amine can be made at from above 100° C. to 200 C, be about 1:1:1, respectively. The Schiff base is then preferably from 125 C-175° C. The alkenylsuccinic reacted with boric acid in the usual manner at tempera anhydride and the amine are reacted in about equal O molar quantities. An excess of the amine can be used, tures of 25-150° C. in a ratio of five mols of boric acid and the unreacted amine removed by distillation. The per mol of azaalkylenediamine. reaction with boric acid is conducted in the same manner The alkenylsuccinic anhydrides or acids useful in pre as hereinbefore described. paring the Schiff bases can be prepared from an olefin or Amine reactants include dimethylaminomethylamine, olefin polymer and maleic anhydride as previously de dimethylaminoethylamine, dimethylaminopropylamine, scribed. The azaalkylenediamines useful in preparing the dimethylaminobutylamine, diethylaminomethylamine, di Schiff bases are the azaalkylenediamines as described ethylaminopropylamine, dipropylaminopropylamine, above. methylpropylaminopropylamine, propylbutylaminoethyl As is evident from the foregoing, the carbonyl-con amine, and the like. Thus, R11 includes the methylene, taining compound can be an aldehyde or ketone. The alde ethylene, trimethylene, propylene, butylene and tetra 20 hydes can be of an aromatic or heterocyclic nature. Rep resentative examples of such aldehydes where R4 is a methylene and R12 and R can be an alkyl radical, such phenyl radical and Ris is hydrogen are benzaldehyde; as methyl, ethyl, propyl, octyl, etc. ,. alkyl-substituted benzaldehyde, e.g., 2-, 3- and 4-methyl The preparation of the N-dialkylaminoalkyl alkenylsuc benzaldehyde, 2,6- and 3,5-dimethylbenzaldehyde, 2-, 3 cinimide monoammonium salts of spiro (3,5-dihydroxy and 4-ethylbenzaldehyde, 4-isopropylbenzaldehyde, 2-iso boroxin)-1,1'-(3',5'-dihydroxyboroxin) is illustrated in butylbenzaldehyde; 4-octylbenzaldehyde, 2,3,6- and 2,4,5- the following example wherein parts are parts by weight. trimethylbenzaldehyde, 2,3,5,6- tetramethylbenzaldehyde; EXAMPLE 44. halogen-substituted benzaldehyde, e.g., 2-fluorobenzalde Using a suitable reaction vessel, a mixture of 9.2 parts hyde, 2-, 3- and 4-chlorobenzaldehyde, 2-, 3- and 4-bro (0.09 mol) of 3-(dimethylamino)propylamine and 150 30 mobenzaldehyde, 2-iodobenzaldehyde, 3,4-dichlorobenz parts (0.09 mol) of polybutenylsuccinic anhydride in aldehyde, 2,3,5-trichlorobenzaldehyde, pentachlorobenzal which the alkenyl group has an average molecular weight dehyde, 2-(trifluoromethyl)benzaldehyde; alkoxy-substi of about 1000, is blended with agitation and the resulting tuted benzaldehyde, e.g., 2- and 3-methoxybenzaldehyde, mixture is heated at 175 C. for a period of one hour, 4-methoxybenzaldehyde (anisaldehyde), 2-, 3- and 4 after which the absolute pressure is reduced to about ethoxybenzaldehyde, 2,3- and 3,4-dimethoxybenzalde 50 mm. Hg at this temperature for a period of 60 hyde. Other substituents can include nitro, as in 2-nitro minutes to facilitate the removal of water. The reaction benzaldehyde; amino, as in 2-aminobenzaldehyde and 4 mixture is then allowed to reach room temperature at (diethylamino) benzaldehyde; benzyloxy, as in 3-(benzyl the reduced pressure. Thereafter, toluene, and 28 parts 40 oxy)benzaldehyde; carboxyl, as in benzaldehyde-2-car of boric acid are charged and the resulting mixture heated boxylic acid; phenoxy, as in 2-phenoxybenzaldehyde; at reflux while azeotropically removing water formed in vinyl, as in 2-vinylbenzaldehyde; and cyano, as in 2-cyano the reaction. The toluene is then stripped to leave the benzaldehyde. N - 3 - (dimethylamino)propyl)polybutenylsuccinimide In the case where R1a is a naphthyl radical and Rs is monoammonium salt of spiro (3,5-dihydroxyboroxin)-1, hydrogen typical starting aldehydes are for example 1- and 1'-(3',5'-dihydroxyboroxin). 45 2-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 4-phen The monoammonium salts of this invention based upon yl-2-naphthaldehyde, and the like. Where R is a furyl the Schiff bases (i) can be prepared by first preparing w radical and R1s is hydrogen starting aldehydes include 2 a Schiff base by reacting ------. . . . . ------Y - as '' - - - and 3-furfuraldehyde, 4-methyl-2-furfuraldehyde, and the (i) an alkenylsuccinic anhydride represented by the like. Structure 50 When R15 is not hydrogen the carbonyl-containing aro O matic or heterocyclic compound is a ketone, which can 2 be of an aromatic, heterocyclic or mixed structure. - - R–H–C The ketones which are useful are illustrated by aceto . o phenone, propiophenone, butyrophenone, pelargonophe C-C 55 none, capriphenone, hendecanophenone, acetonaphthone, S capronaphthone, arachidophenone, stearonaphthone, O methyl 2-naphthyl ketone, benzophenone, 4,4'-bis(di or the acid thereof, with . methylamino)benzophenone, 4-methylbenzophenone, 4,4'- dimethyl benzophenone, di-1-naphthyl ketone, 4-methyl (ii) an azaalkylenediamine represented by the structure 60 1-naphthyl 1-naphthyl ketone, 4-methoxy-1-naphthyi 1 R R S. naphthyl ketone, 4-amino-1-naphthyl 1-naphthyl ketone, NH-CH - (-(CH) -NH-CH--(CH.) -NH2 1-naphthyl phenyl ketone, difuryl ketone, methyl furyl R R. ketone, phenyl furyl ketone, 1-naphthyl furyl ketone. to produce ...... The intermediate imides described above can be pre an intermediate product, an imide (which is an 65 pared by heating a toluene or other hydrocarbon solution alkenylsuccinimidoazaalkylamine), represented by of an alkenylsuccinic anhydride and an azaalkylenedi the structure amine at temperatures of the order of about 100° C. to about 200 C., using mol ratios of anhydride to polyamine e' of about 1:1 while at the same time continuously remov R-CH-C R R 70 ing the water formed from the reaction. The imides are then reacted with a carbonyl-contain CH-C N-(CH--(CH-NH-CH-C-(CH-NH,R1 R ing aromatic or heterocyclic compound while continuously Sn removing the water formed from the reaction to provide r O the Schiff bases. To provide a reaction medium and to which is in turn reacted with 75 facilitate the removal of the water of reaction, the prep 3,658,836 23 24 aration of the Schiff bases is generally carried out in a the N-benzylidene-7-polybutenyl (980) succinimido-. hydrocarbon solvent, e.g., toluene, Xylene or mineral oil. 4-azaheptylamine monoamonium salt of Spiro (3,5- Likewise, the preparation of the Schiff bases used to pre dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), i. pare the salts of the present invention can be carried out the N-furfurylidene-7-polybutenyl(900) succinimido in a mineral oil solution or dispersion. The mineral oil 5, 4-azaheptylamine monoammonium salt of spiro (3,5- can be used alone or in combination with a solvent. Suit- dihydroxyboroxin)-1,1-(3',5'-dihydroxyboroxin), sr. . able temperatures for preparng the Schiff bases at at- the N-benzylidene-8-polybutenyl(1,350) succinimido mospheric pressure are of the order of 50 to 200 C. 3,6-diazaoctylamine monoammonium salt of spiro (3,5- Thereafter the Schiff base is reacted with boric acid at dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), temperatures of the order of 25-150 C. using toluene 10 the N-(3-isopropylbenzylidene)-8-polybutenyl (1300): or other hydrocarbon as a reaction medium or a combina- succinimido-3,6-diazaoctylamine monoammonium tion of mineral oil and toluene. salt of spiro (3,5-dihydroxyboroxin) 1,1'-(3',5'-dihy The preparation of a monoammonium pentaborate de- droxyboroxin), - . . . . . rived from such Schiff bases is illustrated in the following the N-benzylidene-1-polybutenyl (900) succinimido - . non-limiting detailed example, wherein parts are parts 15 3,6,9-triazaundecylamine monoammonium salt of ... by weight. m spiro (3,5-dihydroxyboroxin)-1,1-(3,5-dihydroxy Example 45 boroxin), ...... the N-(1-naphthylmethylene)-11-polybutenyl (900) Into a suitable reaction vessel fitted with a mechanical succinimido-3,6,9-triazaundecylamine monoammo stirrer, heating mantle, thermometer, Dean-Stark trap and 20 nium Salt of Spiro (3,5-dihydroxyboroxin)-1,1'- condenser, containing 300 ml. of toluene and 74.3 parts of 3',5'-dihydroxyboroxin)...... diethylenetriamine, there is charged 917 parts of poly- the N-furfurylidene-1-polybutenyl(980) succinimido-... butenyl (980) succinic anhydride. The resulting mixture is 3,6,9-triazaundecylamine monoammonium salt of: - then heated, with stirring, to reflux and maintained at spirot (3,5-dihydroxyboroxin)-1,1-(3',5'-dihydroxy reflux until the evolution and collection of water ceases. 25 boroxin). . . . . The reaction mixture is then cooled to about 70° C., 76.4 the N-(2-chlorobenzylidene)-11-polybutenyl(980) parts of benzaldehyde is charged, and heating at reflux succinimido)-3,6,9-triazaundecylamine monoammo ceases.is continued 223 parts until ofthe boric evolution acid are and added collection and the of result-water. y rainyaroxE. of Eihydroxyboro.in)-1,1- XII), s ing mixture E. at reflux while removing water of re- 30 the N-(diphenylmethylene)-5-[polybutenyl(9 80) suc actionstripped by to azeotropicprovide thedistillation. N-benzylidene-5-(polybutenyl- The toluene is , then SEE. 5. iny roxyboroxin)- 1'-(Age, 5'-dihydroxy salt of succinimido)-3-azapentylamine monoammonium salt of a : oxin) J, - oxin).spiro (3,5-dihydroxyboroxin) - 1,1 - (3',5'-dihydroxybor. the risingiyi,N-(phenylethylmethylene)-7-polybutenyl(1000) yet salt Additional examples of other Schiff base derived mono- E5. ya xyboroxin)-1,1'-3', y ammonium pentaborates and the materials for their prep- the N-(2-naphthylpropylmethylene)-5-polypropenyl aration other than boric acid are given in Table IV, be- (1200) succinigidol 3-azapentylamine monoammonium low. In the table only the alkenyl, or polyalkenyl, portion salt of spiro (3,5-dihydroxyboroxin)-1,1-(3',5'- of the alkenylsuccinic anhydride and the average molec- dihydroxyboroxin), - ular weight of such portion are given, DETA means di- the N-(1-naphthylphenylmethylene)-7-polybutenyl ethylenetriamine, TETA means triethylenetetramine and (1100) succinimidol-4-azaheptylamine monoammo TEPAmols of meansboric acid tetraethylenepentamine. are used per mol of azaalkylenediamine In all cases five nium(3',5'-dihydroxyboroxin), salt of spiroI(3,5-dihydroxyboroxin)-1,1- (b). and the like... TABLE V: . . . . . Alkenyl portion of alkerylsuccinic Azaalkyl anhydride (mol wit. e- Carbonyl-contain-- E. of alkenyl group) diamine ing compound Molar ratio K. No. (a (b) (c) (a): (b); (c) Product 46----- Polybuttenyl (1,315)--. DETA Benzaldehyde------:: The N-benzylidene-5-polybutenyl (1315) succinimido-3-azapentyla FileIgnoarmoniu salt of spiro (3,5-dihydroxyboroxin)-l-,1-(3, 47.----- PolybutteryPolybuttenyl (980(980)----- TETA ----- 0------l:l: The5'-dihydroxyboroxin). N-benzylidene-8-polybutenyl(980)succinimido-3,6-diazaocyya 5'-dihydroxyboroxin)).i monoannonium salt of spiro (3,5-dihydroxyboroxin)-1,1-(3', 48------do------TEPA -----do------ll:l The, N-benzylidene-li-polybutenyl(980)succinimido-3,6,9-triazaunde cylamine monoammonium salt of spiro (3,5-dihydroxyboroxin)-1,1- (3',5'-dihydroxyboroxin). 49------do------DETA Acetophenone.------1:1:1 The N-(a methylbenzyiidene)-5-polybutenyl(980)succinimido-8-aza Petyanine monoammonium salt of spiro (3,5-dihydroxybotoxin). 50------do------TETA Benzophenone.------1:1:1. The1,1-(3,5-dihydroxyboroxin). N-(diphenylmethylene)-3-polybutenyl(980)succinimido-3,6-di Zaoyannermonoammonium salt of spiro(3,5-dihydroxyborosin 1,'-(3',5'-dihydroxyboroxin). 51----- Polybutenyl (1350). TEPA Butyronaphthonie- 1:1:1 The N-butylnaphthymethylene)-11-polybutenyl(1350)succinimido : . . . 3:5:33;Eliasm salt of spiro (3,5-dihydrox 52----- Polybutenyl (980).---- TEPA Furfural------lil: TheYoroxii)-il'-(3, .N-firfirylideneel-polyibutenyl(980)succinimido-3,6,9-triazaun ydroxyboroxin)...... decylanine monoamnioium salt of spiro (3,5-dihydroxyboroxin)-1,1- 53----- Polybutenyl (1,350). TETA 1-naphthaldehyde... l:1:1. The(3,5-dihydroxybproxin).: N-(l-haphthylmethylene)-1-polybutenyl-(1350)succinimido-3,6, - 9-tria.Zaladecylamine monoammonium salt of spiro (3,5-dihydroxy boroxin)-1,1'-(3',5'-dihydroxyboroxin). p (3, y y Typical examples of other Schiff base derived mono ammonium pentaborate salts of this invention are:- the N-benzylidene-5-polypropenyl(15 00) succinimido). The monoammonium spiro hydroxyboroxin, salts of 3-azapentylamine monoamonium salt of spiro (3,5- this invention based upon the imines (j) can be prepared dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), 5 by reacting 8,658,836 25 26 (i) an alkenylsuccinic anhydride represented by the In the case where R is a naphthyl radical and R18 structure is hydrogen, typical starting aldehydes are, for example, 1- and 2-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 20 4-phenyl-2-naphthaldehyde, and the like. Where R1 is R-II a furyl radical and R1s is hydrogen starting aldehydes Chas s include 2- and 3-furfuraldehyde, 5-methylfurfuraldehyde, and the like. or the acid thereof, with Typical examples of aliphatic ketones, that is, where (ii) a polyamine represented by the structure R1 and R1s are alkyl, alkenyl or haloalkyl are acetone, O methyl ethyl ketone, methyl propyl. ketone, methyl iso NH-R s-NH2 propyl ketone, methyl butyl ketone, methyl isobutyl to produce ketone, methyl sec-butyl ketone, methyl tert-butyl ketone, an intermediate product, an imide, represented by methyl cyclobutyl ketone, cyclohexanone, methyl neo the structure pentyl ketone, methyl tert.-amyl ketone, methyl n-amyl ketone, methyl hexyl ketone, methyl cyclohexyl ketone, . R-E-CX O methyl n-heptyl ketone, methyl n-octyl ketone, methyl N-Re-NH2 nonyl ketone, methyl decyl ketone, diethyl ketone, di-n- propyl ketone, diisopropyl ketone, ethyl isopropyl ketone, No ethyl isobutyl ketone, ethyl n-propyl ketone, ethyl tert which is then reacted with O 20 butyl ketone, ethyl n-butyl ketone, tert-butyl isopropyl (iii) a carbonyl-containing compound, that is, an alde ketone, n-propyl isopropyl ketone, diisobutyl ketone, hen hyde or a ketone, represented by the structure decyl pentyl ketone, dodecyl pentyl ketone, tetradecyl hexyl ketone, tetradecyl isobutyl ketone, hexadecyl octyl 9 ketone, 2- and 3-methyl-1-penten-4-one, 1-hepten-4-one R7 a C m Rie ketone, dinonadecyl ketone, dioctadecyl ketone, 3- and 4-methyl-2-hexanone, 3,4-dimethyl-2-pentanone, 3-ethyl where R, Re, R1 and R1s have their aforedescribed 2-pentanone, 2-ethyl-2 - decanone, 6-methyl-7-octadec significance, to produce an imine (j). The mol ratios of anone 5,7-dimethyl-9-heneicosanone, and the like; sub (i): (ii): (iii) which are used are about 1:1:1, respec stituted ketones such as 1-chloro-2-propanone, 1-chloro tively. Thereafter the imine (j) and boric acid are reacted 30 2-pentanone, 1,2-dichloro-3-pentanone, 1-bromo-7-nitro in the usual manner in mol ratios of 1:5, respectively, 4-heptanone, 1-chloro-7-octadecanone, and the like; un and temperatures of 25-150° C., preferably 60-110 C., saturated ketones such as vinyl methyl ketone, vinyl ethyl to(3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin)). produce imine-based monoammonium salts of spiro ketone, 2- and 3-methyl-1-penten 4-one, 1-hepten-4-one The alkenylsuccinic anhydride or acids which are useful 3-methyl-1-hexen-5-one, 4-methyl-5-hexen-2-one, 5-meth are those previously described. The polyamines which can 35 yl-6-nonadecen-2-one, and the like. be used to provide the radical R16 are aminoguanidine, In the case where R1 is a phenyl radical and R is 1,3-diaminoguanidine and biguanide. an alkyl, alkenyl or haloalkyl typical starting ketones are The carbonyl-containing compounds useful in prepar acetophenone, propiophenone, arachidophenone, acrylo ing the imine-based spiro hydroxyboroxin-amine salts can phenone, crotonophenone, chalcone, p-bromo-aceto be an aldehyde or a ketone, as mentioned above, and 40 phenone, p-chloro-acetophenone, p-bromo-or-chloroaceto they can be of an aliphatic or aromatic nature. Typical phenone, and the like. Where R1 and R1s are each a examples of aliphatic aldehydes, where R17 is hydrogen, phenyl radical starting ketones include benzophenone, an alkyl, alkenyl or haloalkyl radical and R1s is hydro 4,4'-bis(dimethylamino)benzophenone, 4-methylbenzo gen, are formaldehyde, acetaldehyde, propionaldehyde, phenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzo n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, iso 45 phenone, 2-, 3- and 4-chlorobenzophenone, 2-, 3- and 4 valeraldehyde, pivaldehyde, caproaldehyde, pelagonalde bromobenzophenone, and the like. Where R1 is a phenyl hyde, capraldehyde, lauraldehyde, myristaldehyde, Stear radical and R1s is a naphthyl radical typical starting aldehyde, and the like; substituted aldehydes such as ketones are 1- and 2-maphthyl phenyl ketone, 1-methyl-2- chloroacetaldehyde, chloral, butylchloral, trifluoroacetal naphthyl phenyl ketone, 3-methyl-2-naphthyl phenyl dehyde, aldol, and the like; and unsaturated aldehydes 50 ketone, 2,3-dimethyl-1-naphthyl phenyl ketone, 1-naph such as 2- and 3-butenal, 2-propenal, 2-methyl, 2-pro thyl ortho-tolyl ketone, 1-naphthyl 2-chlorophenyl ketone, penal, 3- and 4-pentenal, 3-, 4- and 5-hexenal, 2-ethyl-3- and the like. Where R is a phenyl radical and Ra is hexenal, 3-decenal and the like. a furyl radical starting ketones are ortho-tolyl furyl Representative examples of aromatic aldehydes where ketone, 2,3-dimethylphenyl furyl ketone, and the like. R is a phenyl radical and R1s is hydrogen are benzal 55 When R1 is a naphthyl radical and R1s is an alkyl, dehyde; alkyl-substituted benzaldehyde, e.g. 2-, 3- and 4 alkenyl or haloalkyl radical typical starting ketones are methylbenzaldehyde, 2,6- and 3,5-dimethylbenzaldehyde, 1-naphthyl methyl ketone, 1-naphthyl ethyl ketone, 2 2-, 3- and 4-ethylbenzaldehyde, 4-isopropylbenzaldehyde, naphthyl propyl ketone, 2-naphthyl octyl ketone, 1-naph 2-isobutylbenzaldehyde; 4-octylbenzaldehyde, 2,3,6-, 2,4, thyl nonyl ketone, 1-naphthyl octadecyl ketone, 1-naph 6- and 2,4,5-trimethylbenzaldehyde, 2,3,5,6-tetramethyl 60 thyl 2-chlorooctyl ketone, 1-naphthyl 2-butenyl ketone, benzaldehyde; halogen-substituted benzaldehyde, e.g., 2 1-naphthyl 3-pentenyl ketone, 1-naphthyl 4-octadecenyl fluorobenzaldehyde, 2-, 3- and 4-chlorobenzaldehyde, 2-, ketone, 2-chloro-1-naphthyl decyl ketone, 2,3-dibromo 3- and 4-bromobanzaldehyde, 3-iodobenzaldehyde, 3,4-di 1-naphthyl dodecyl ketone, and the like. Where R and chlorobenzaldehyde, 2,3,5-trichlorobenzaldehyde, penta R18 are each a naphthyl radical typical ketones are di(1- chlorobenzaldehyde, 2-trifluoromethylbenzaldehyde; alk 65 naphthyl) ketone, di(2-naphthyl) ketone, 2-methyl-1- oxy-substituted benzaldehyde, e.g., 2- and 3-methoxy naphthyl 1-naphthyl ketone, 4-methoxy-1-naphthyl 1 benzaldehyde, 4-methoxybenzaldehyde (anisaldehyde), naphthyl ketone, 2-chloro-1-naphthyl 3-chloro-1-naphthyl 2-, 3- and 4-ethoxybenzaldehyde, 2,3- and 3,4-dimethoxy ketone, and the like. Where R1 is a naphthyl radical benzaldehyde. Other substituents can include nitro, as and R1s is a furyl radical typical starting ketones are in 2-nitrobenzaldehyde; amino, as in 2-aminobenzalde 70 1-naphthyl furyl ketone, 2-methyl-1-naphthyl furyl hyde and 4-diethylaminobenzaldehyde; benzyloxy, as in ketone, 3-chloro-1-naphthyl furyl ketone, 4-methoxy-1- 3-benzyloxybenzaldehyde; carboxyl, as in benzaldehyde naphthyl furyl ketone, and the like. 2-carboxylic acid; phenoxy, as in 2-phenoxybenzaldehyde; In the case where R1 is a furyl radical and R1s is an vinyl, as in 2-vinylbenzaldehyde; and cyano, as in 2 alkyl, alkenyl or haloalkyl radical typical ketones are cyanobenzaldehyde. 75 furyl methyl ketone, furyl octyl ketone, furyl dodecyl 3,658,836 27 28 ketone, furyl 2-butenyl ketone, furyl 4-dodecyl ketone, the resulting mixture is heated at about 80°C. for one furyl 2-butenyl ketone, furyl 4-dodecenyl ketone, furyl hour. Water is then removed by azeotropic distillation chloroethyl-ketone, and the like. Where both R. and after which the reaction mass is filtered. Upon removal of R1s are a furyl radical, an example of a starting ketone the toluene by stripping, there remains the 1-(benzyl is difuryl ketone...... "... . idene)-3-(polybutenylsuccinimido)guanidine monoammo The various imides resulting from the first step in the nium salt of spiro (3,5-dihydroxyboroxin)-1,1-(3',5'-di preparation of the instant compounds can be prepared by hydroxyboroxin). heating a mineral oil, toluene or other hydrocarbon solution of an alkenylsuccinic anhydride and a polyamine EXAMPLE:55. - attemperatures of the order of about 50° C. to about O 200 C., using mol ratios of anhydride to polyamine of Following the procedure of Example 54 15.0 parts about 1:1 while at the same time continuously removing of 1,3-diaminoguanidine bicarbonate, 133 parts of poly the water formed from the reaction. butenylsuccinic anhydride in which the polybutenyl group It is thus evident that suitable imides prepared as has an average molecular weight of 980, .44 parts of heretofore... explained are 1-(polyalkenylsuccinimido) acetaldehyde and 31.0 parts of boric acid are utilized guanidines, 1-amino-3 - (polyalkenylsuccinimido)guani 5 to prepare 1-(aminoethylidene)-3-(polybutenylsuccin dines, or 1-guanyl-N-(polyalkenylsuccinimido)form imido)guanidine monoammonium salt of spiro[(3,5-dihy amidines. droxyboroxin)-1,1-(3',5'-dihydroxyboroxin). The imides, as described above, are then reacted with a carbonyl-containing compound in mineral oil or other 20 EXAMPLE 56 . inert hydrocarbon solvents at temperatures of the order of about 50 C. to about 200 C., using mol ratios of Again following the procedure of Example 54, but ulti imide to carbonyl-containing compound of about 1:1, lizing 13.1 parts of biguanide carbonate, 200 parts of respectively, while continuously removing the water polybutenylsuccinic anhydride in which the polybutenyl formed from the reaction. The thus prepared imine is 25 group has an average molecular weight of 1350, 9.4 parts then reacted with boric acid, using a 1:5. molar ratio, of benzaldehyde and 31.0 parts of boric acid, there is respectively, at temperatures of about 25-150° C., prefer prepared 1-(benzylidene)-3-(imino (polybutenylsuccinimi ably 60-110° C., while continuously removing the water do)methyl)guanidine monoammonium salt of spiro (3,5- of reaction. Typical examples of the instant salts are dihydroxyboroxin)-1,1-(3,5-dihydroxyboroxin). therefore: 30 The imidazolidine portion (k) of the 2-substituted imidazolidine monoammonium salts of spiro[(3,5-dihy 1 - (benzylidene) - 3 - polypropenyl (1500) succinimido droxyboroxin)-1,1-(3',5'-dihydroxyboroxin) can be rep guanidine monoammonium salt of spiro (3,5-dihy droxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), resented by the structure . . . 1 - (benzylidene) - 3 - polybutenyl(1500) succinimido guanidine monoammonium salt of spiro (3,5-dihy droxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), 1 - (aminobenzylidene) - 3 - polybutenyl(1300) succin imidoguanidine monoammonium salt of spiro (3,5- - R dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), 40 - : B. Gita--R. 1 - (aminopropylidene) - 3 - polypropenyl(1000) succin - CH-C1 N-CHa-C-(NH-CHa-C)2- ( i-vna 2. -N-Nit imidoguanidine monoammonium salt of spiro (3,5-di hydroxyboroxin)-1,1-(3',5'-dihydroxyboroxin), R. R. 1 - (aminodecylidene) - 3 - polybutenyl (900) succinimi doguanidine monoammonium salt of spiro (3,5-dihy droxyboroxin)-1,1'-(3',5'-dihydroxyboroxin)), 45 1 - (benzylidene)-3-(imino (polypropenyl(1300) succin imido) methylguanidine monoammonium salt of spiro and can be prepared by reacting (3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy boroxin), (i) a polyalkenylsuccinic anhydride represented by the 1 - (benzylidene) - 3 - Limino (polybutenyl(850) succin 50 structure - ...... imido)methyl)guanidine monoammonium salt of spiro I(3,5-dihydroxyboroxin)-1,1-(3',5'-dihydroxy boroxin), and 1 - (butylidene) - 3 - (imino(polybutenyl(1350) succin imido)methylguanidine monoammonium salt of Spiro (3,5-dihydroxyboroxin)-1,1-(3',5'-dihydroxy boroxin). a O. . The preparation of the salts presently under discussion is illustrated in the following non-limiting detailed ex amples, wherein parts are parts by weight. 60 EXAMPLE 54. (ii)or athe polyethyleneamine. acid thereof, with represented by the...A structure ... To a suitable reaction vessel there is charged 13.6 parts of aminoguanidine bicarbonate (0.1 mol) and 200 parts of 65 polybutenylsuccinic anhydride (the polybutenyl group has an average molecular weight of 1350) in 100 ml. of tolu ene. The resulting mixture is heated at reflux until the , evolution of carbon dioxide ceases and all water of reac NHa-CH2--(NE-Cita-)-NH-CH2--NHe- ' ' ' ' ' ... tion has been removed. After the reaction mass is filtered 9.4 parts of benzaldehyde (0.1 mol) is added and the R. R. Rios: reaction mass is then heated at reflux for about two hours while continuously removing water of reaction by azeo tropic distillation. The reaction mass is then cooled slightly, 31 parts of boric acid (0.5 mol) is charged and 75 to produce 3,658,836 29 30 an intermediate product, an imide, represented by the 1-8-(polybutenyl(1200) succinimido) - 3,6 - diaza the structure octyl)-2-imidazolidinone monoammonium salt of spiro (3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy O boroxin), R. R. R 5 the 1-11 - (polybutenyl (1350) succinimido)-3,6,9-triaza R-CH-C undecyl)-2-imidazolidinone monoammonium salt of N-CH2-C-(NH-CH2-C)-NH-CH2-C-NH2 spiro[3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy Cia-C1 2. boroxin, - 6 Rl. R. R. the 1-11 - (polyisobutenyl (1000) succinimido)-3,6,9-tri 10 azaundecyl-2-imidazolidinone monoammonium salt of which is then reacted with spiro[3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy boroXin), (iii) urea, thiourea or guanidine, represented by the the 1-11 - (polybutenyl(1900) succinimido)-3,6,9-triaza Structure undecyl)-2-imidazolidinone monoammonium salt of A 5 spiro[3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy boroxin, NHe a C - NHe the 1 - 8 - (polybutenyl (900)succinimido) - 3,6 - diaza octyl)-2-imidazolidinethione monoammonium salt of where R, R, A and z have their aforedescribed signifi-a u 20 ES5-dihydr ly oxyboroxin)-1,1-(3',5'-dihydroxy in)-1,1-(3',5'-di - 1:1:1E. respectively.E.E.E.E.E.E. Thereafter the imidazolidine is re- theundecyl-2-imidazolidinethione 11:polybutenyl(509) succinimido)-3,6,9-triaza. monoammonum salt of acted in the usual manner with boric acid at temperatures spiro (3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxy of 25-150° C. using five mols of boric acid per mol of boroxi?), s 9 polyethyleneamine to form the desired monoammonium the 2-imino-1-(2-(polyisobutenyl (1000) succinimido)eth pentaborate. yl)imidazolidine monoammonium salt of spiro (3,5- The polyalkenylsuccinic anhydrides useful in prepar- dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin), ing the 2-substituted imidazolidines can be pist f the 2-imino-1-8-(polyethenyl (1500) succinimido)-3,6-di an olefin a polymer of a lower olefin or a copolymer o aZaoctyl)imidazolidine monoammonium salt of spiro lower olefins and maleic anhydride as described above. -?i whorrxin. 11-?35 The polyethyleneamines which can be used are those 30 boroxin)3,5-dihydroxyboroxin)-11-(3',5'-dihydroxy described above with respect to the imidazolidines (a). s As is evident from the above description where A is oxy- and the like. gen reactant (iii) is urea, when A is sulfur reactant (iii) The preparation of typical 2-substituted imidazolidine is thiourea and when A is NH retactant (iii) is guanidine. monoammonium salts of spiro (3,5-dihydroxyboroxin)- The various imides resulting from the first step in the 1,1'-(3',5'-dihydroxyboroxin) is illustrated in the follow preparation of the instant salts can be prepaerd by heat- ing non-limiting detailed example, wherein parts are parts ing a polyalkenylsuccinic anhydride and a polyethylene- by weight. amine at temperatures of the order of about 75° C. to EXAMPLE 57 about 175 C., using mol ratios of anhydride to polyeth- 40 Into a suitable reaction vessel fitted with a mechanical se E. '". their E".E. stirrer, heating mantle, thermometer, Dean-Stark trap E. y y s be reacted With le i al or and condenser, containing 900 parts of polybutenyl (980) e e iii. y ten att the succinic anhydride in process oil, there is charged 103 guan1dine, Y g p . parts of triethylenetetramine. The resulting solution is order of 120°-200 C., while continuously removing the 45 heated at 140 C., and 30 mm. of Hg for about five REE",'Gai Y it. hours as the water evolving from the reaction is removed. d im th. boric acid, in the usual 1:5 molar ratio, b When the evolution of water ceases, 42.8 parts of urea in Wii, attemperatures of the order of 35 By are added and the mixture heated to about 185° C. and and thereafter E. the water formed from kept at about that temperature for about 3 hours until the reaction 9. 50 the evoluion of ammonia has ceased. 218 parts of boric . acid is then charged and the mixture heated at about To provide a reaction medium and to facilitate the 85-90 C. for one hour and then at 150° C. and 20 removal of the Water of reaction, the preparation of the mm. of Hg for one hour. The reaction is then filtered to intermediate, imide and imidazolidine is generally carried provide an oil solution of 1-(5-(polybutenylsuccinimido). out in a hydrocarbon Solyent. The reaction of the imid- 55 3-azapentyl-2-imidazolidinone monoammonium salt of azolidine with boric acid can also be conducted in a spiro (3,5-dihydroxyboroxin) - 1,1' - (3',5' - dihydroxy hydrocarbon, such as benzene or toluene. boroxin). Typical examples of the 2-substituted imidazoline-based Additional examples of other 2-substituted imidazoli salts of this invention are: dine monoammonium salts of spiro (3,5 - dihydroxy the 1-(5- (polybutenyl(1350) succinimido)-3-azapentyl)- 60 boroxin)-1,1'-(3',5'-dihydroxyboroxin)) of this invention 2-imidazolidinone monoammonium salt of spiro (3,5- and the materials used for their preparation (except boric dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin)), acid) are given in Table VI, below. In the table only the the 1-8-(polypropenyl(700)succinimido)-3,6-diazaoctyl- alkenyl, or polyalkenyl, portion of the polyalkenylsuc 2-imidazolidinone monoammonium salt of spiro (3,5- cinic anhydride and the average molecular weight of such dihydroxyboroxin)-1,1-(3',5'-dihydroxyboroxin), 65 portion are given, TEPA means tetraethylenepentamine.

TABLE VI Alkenyl portion of of aikenylsuccinic Ex. anhydride (mol wt. of Poly Urea type No. of alkenyl group) amine compound Product 58----- Polybutenyl (1,190). TEPA Urea------The 18:Cpslyterylsuccinimido)-3,629ty2-inidazolidinone monoammonium salt - of spiro (3,5-dihydroxybproxin)-1,1-(3',5'-dihydroxyboroxin). 59----- Polybutenyl (1,350). TEPA -----do.----- Theof spiro(3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin).1-8-(polybutenylsuccinimido)-3,6-diazaoctyl)-2-imidazolidinone monoammonium salt Guanidine- The 2-imino-1-8-(polybutenylsuccinimido)-3,6-diazaoctyl)imidazolidine monoammonium 60------sdo------TEPA salt of spiro(3,5-dihydroxyboroxin)-1,1'-(3',5'-dihydroxyboroxin). 3,658,836 31 32 The imidazoline portion of the salts of the present in of the carboxylic acid the mol of (i): (i): (iii). will be vention based upon mono-imidazolines (1) can be rep about 1:1:0.5, respectively, in the case of mono-imidazo resented by the structure , 2. lines and 2:2:0.5, respectively, in the case of the bis imidazolines. The imidazoline product is then reacted with ------...... :...... 5 .. R. boric acid using five mols of boric acid per mol of mono imidazoline orbis-imidazoline. . 20 R. R. CHa-C-R . . . The polyalkenylsuccinic anhydrides useful in preparing ; : ... R-CHas CS .:* - ". . . the imidazolines of this invention can be prepared from -cha-chi-clap.'' an olefin, a polymer of a lower olefin or a copolymer of '': i. O R. R. . . . ." IO lower olefins and maleic anhydride as aforedescribed. The ...... Ris: polyethyleneamines which can be used are those described above with respect to the imidazolidines (a). and based upon bis-imidazolines. (m) "can be represented In the case of the monocarboxylic acids useful in prepar by the structure . . . .''...... i ing the mono-imidazoline (1) based salts of this inven is 5

tion, the following are representative: k R is (a) Aliphatic monocarboxylic acids ... * (i) Where Rig is hydrogen, an alkyl or substituted alkyl it-it-é R. R. Ha--R. radical.--Formic acid, acetic acid, fluoroacetic acid, pro Cha-k -CH2--(NH-CH2-)-na- 20 pionic acid, (3-chloropropionic acid, butyric acid, isobutyric So R. R. N. acid, 2 - nitroisobutyric acid, valeric acid, "isovaleric acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic acid, non anoic acid, decanoic acid, dodecanoic acid, undecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic where R, R1, R19, x and T have their aforedescribed 25 acid, octadecanoic acid, eicosanoic acid, docosanoic acid significance. For convenience imidazoline, as used herein, and triacontanoic acid. is intended to include both the mono- and bis-imidazo (ii), Where R1 is an alkenyl or substituted alkenyl lines. The imidazolines can be prepared by reacting radical.-3-butenoic acid, 72-pentenoic acid, 2-hexenoic acid, teracrylic acid, hypogaeic acid, oleic acid, elaidic (i) a polyalkenylsuccinic anhydride, represented by the 30 acid, linoleic acid, a-eleostearic acid, 6-eleostearic acid, Structure c-linolenic acid, acrylic acid, g-chloroacrylic acid, meth O acrylic acid, crotonic acid, isocrotonic acid, angelic acid, R-h-c. senecioic acid and 4-tetradecenoic acid. C O s (b) Alicyclic monocarboxylic acids as & 35 Cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, hydnocarpic acid, chaul or the acid thereof, with noogric acid, naphthenic acids, 2,3,4,5-tetrahydrobenzoic (ii) a polyethyleneamine represented by the structure acid and cyclodecanecarboxylic acid. s : 40 (c) Aromatic monocarboxylic acids R. R. is Benzoic acid, 1-naphthoic acid, 2-naphthoic acid, o H2N-CH2 -- (NH-CH2 -: ) -NH-CH2--NHe s toluic acid, m-toluic acid, p-toluic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, 2,3-di R. R. Ri - " - bromobenzoic acid, 3,4-dichlorobenzoic acid, o-nitroben to produce .. ... Zoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, 2,3- an intermediate product, an imide, represented by the . . .9dinitrobenzoic 1 acid, anisic acid, phenylactic acid and b Structure ii. phenylpropionic acid. O ra. (d) Heterocyclic monocarboxylic acids R-CH- c 1. 1. : 50 Picolinic acid, nicotinic acid, furylacrylic acid, piperic CH2-C. X-CH2--(NH-CH2-)-Ni-CH2 = x : - acid, 3-indoleacetic 'acid, cinchoninic acid, furoic acid, 2 So R. R thiophenecarboxylic acid, 2-pyrrollecarboxylic acid, 9 acridancarboxylic acid, quinaldic acid and pyrazinoic acid. which is then reacted with 55 In the case of the dicarboxylic acids useful in prepar (iii) a carboxylic acid, that is, ------ing the bis-imidazoline based salts of this invention, the (1) a monocarboxylic acid represented by the struct following are representative: ... tre ...... ; ...... ". . . . (a) Aliphatic dicarboxylic acids 60 (i) Where T is an alkylene radical-Oxalic acid, Rae - C - OH ...... malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, and thapsic acid. or the anhydride thereof, or . . . . . (ii) Where T is an alkenylene radical-Maleic acid, (2) a dicarboxylic acid represented by the structure fumaric acid, glutaconic acid, citraconic acid, itaconic 65 acid, ethylidenenalonic acid, mesaconic acid, allylmalonic O to acid, teraconic acid and cetylmalonic acid. It is also contemplated herein to employ dimeric and O-C-T-C-OH, trimeric polycarboxylic acids to produce the bis-imidazo line based salts of the present invention. When two like or or the anhydride thereof, its fo unlike molecules of a polyethenoid monocarboxylic fatty Where R, R1, R19, X and T have their aforedescribed acid condense to form a dicarboxylic acid, the product by significance. The mol ratios of (i): (ii): (iii) will be about definition is a dimer acid, or the carboxylic acid is said 1:1:1, respectively, to prepare mono-imidazolines and to be dinerized. In general, the dimer acids suitable for about 2:2:1, respectively, to prepare bis-imidazolines. use in this invention are produced by the condensation of However, where the acid anhydride (iii) is used in place 7 5 two like or unlike unsaturated aliphatic monocarboxylic 3,658,836 33 34 acids having between about 16 and about 18 carbon atoms The reaction mass is cooled to 80° C. and 149 parts of per molecule, examples of which comprise boric acid is added. The mixture is then heated at about 90-110° C. for about one hour while continuously re A9,ll-hexadecadienoic acid moving water of reaction. The toluene is then stripped A9, 12-heptadecadienoic acid to leave the 1 - 8-(polybutenylsuccinimido)-3,6-diaza A8, 12-octadecadienoic acid octyl - 2 - naphthenyl - 2 - imidazoline monoammonium A9,11-octadecadienoic acid salt of spiro (3,5 - dihydroxyboroxin)-1,1'-(3',5'-dihy A9,12-octadecadienoic acid (linoleic acid) droxyboroxin). A9, 13-octadecadienoic acid A9,11,13-octadecatrienoic acid EXAMPLE 63 A9,12,15-octadecatrienoic acid (linolenic acid) 0 In the manner of Example 61, 810 parts of poly butenyl(980) succinic anhydride (0.64 mol) is reacted To provide a reaction medium and to facilitate the re with 65.9 parts of diethylenetriamine (0.64 mol), 181 moval of the water of reaction in the preparation of both parts of oleic acid (0.64 mol) and 198 parts of boric acid of the intermediate products, an inert hydrocarbon solvent (3.2 mols) to provide the 1-2-(polybutenylsuccinimido) can be used. Suitable temperatures for preparing the in 15 ethyl) - 2 - (heptadec - 8 - enyl)-2-imidazoline monoam termediate products at atmospheric pressure are of the monium salt of spiro (3,5-dihydroxyboroxin)-1,1'-(3', order of 80° C. to 220 C., preferably 125 C. to 200° C. 5'-dihydroxyboroxin). The reaction of boric acid and imidazoline can be con ducted as previously described using benzene, toluene or EXAMPLE 64 hydrocarbon oil as a solvent if desired, at temperatures of the order of 25-150° C. In the manner of Example 61, 1600 parts of poly A detailed general procedure for preparing the imidazo butenyl (980) succinic anhydride, 175 parts of triethylene line-based salts of this invention is as follows: tetramine, 59.2 parts of acetic acid and 372 parts of borie Into a conventional glass reactor fitted with an agitator, acid are reacted to provide 2 - methyl-1-(5-(polybutenyl raw material inlet, product outlet, reflux condenser, Dean 25 succinimide) - 3 - azapentyll - 2 - imidazoline monoam Stark trap, heating means and thermometer, containing a monium salt of spiro (3,5-dihydroxyboroxin)-1,1'-(3',5'- polyethyleneamine in a solvent, and with the agitator run dihydroxyboroxin). ning, polyalkenylsuccinic anhydride, or acid, is slowly EXAMPLE 65 added: The resulting mixture is then heated (125-200 In the manner of Example 61, 169.7 parts of poly C.) for about two to three hours while removing water 30 butenyl (1368) succinic anhydride is reacted with 18.9 formed by the reaction to produce an imide as described parts of tetraethylenepentamine in toluene. After suf above. The reaction mass is then cooled and a carboxylic . . -ficient reflux with the collection of all the by-product acid is added. The resulting mixture is heated (125 water, the reaction mixture is cooled and 6.0 parts of 200° C.) for a sufficient time to complete the reaction acetic acid is slowly added. Refluxing is continued until while simultaneously removing water formed by the re 35 the evolution and collection of water has ceased. The action. Thereafter boric acid is added and the resulting intermediate imidazoline is then reacted with 31 parts mixture is heated at 25-150° C. for one hour. Water of boric acid. After stripping the toluene there remains formed by the reaction can be removed during the heating the 1 - 8 - (polybutenylsuccinimido)-3,6-diazaoctyl period or thereafter. Thereafter if benzene or toluene or 2 - methyl - 2 - imidazoline monoammonium salt of other volatile solvent is used, it is stripped to leave the 40 spiro (3,5 - dihydroxyboroxin) - 1,1'-(3',5'-dihydroxy desired salt. boroxin). A variation of the above preparation can be practiced EXAMPLE 66 by adding the polyalkenylsuccinic anhydride, or acid, slowly to the polyamine with mixing and then following An 0.117 mol preparation of 11-polybutenyl (980) the latter addition with a charge of carboxylic acid. A sub 45 succinimidol-3,6,9-triazaundecylamine is carried out in sequent mixing and heating of the mixture and remov the usual manner by refluxing a reaction mixture of tetra ing the water formed by the reaction results in the pro ethylenepentamine (0.117 mol) in toluene and poly duction of the corresponding imidazoline. butenyl (980) succinic anhydride (0.117 mol) and remov Still another variation is to add the polyalkenylsuccinic ing the by-product water as it is formed. After cooling anhydride, or acid, and the polyamine to the reactor slow 50 the reaction mixture, 0.117 mol of oleic acid is added ly and in carefully regulated stochiometric quantities and the resulting solution is refluxed with further col (that is, in a mol ratio of essentially 1:1, respectively). lection of water being effected until the water has ceased The mixture can then be heated and the water which is to evolve. The intermediate imidazoline is then reacted formed then removed. Subsequently the carboxylic acid with 0.58 mol of boric acid to give the 1-3-(polybutenyl can be charged to the mixture and heating continued un 55 Succinimido)-3,6-diazaoctyl - 2 - (heptadec - 8 - enyl)- till evolution of water has ceased leaving an imidazoline. 2 - imidazoline monoammonium salt of spiro (3,5-di The preparation of specific imidazoline based salts of hydroxyboroxin) -1,1'-(3',5'-dihydroxyboroxin). this invention is illustrated in the following non-limiting Another embodiment of the present invention is to examples, wherein parts are parts by weight. use tall oil and other similar mixtures of acids in place 60 of the carboxylic acid reactant described above. Tall oil EXAMPLE 61 is a natural mixture of rosin acids, fatty acids and non acidic bodies. It is contemplated by the present disclosure Into a conventional glass reactor fitted as described to use said tall oil in its more refined form, that is to say, above, there is charged 14.5 parts of diethylenetriamine having only the unsaturated fatty acids present while all (0.1412 mol) in 50 ml. of toluene. With the agitator 65 other substituents have been substantially removed from running 188.6 parts of polybutenylsuccinic anhydride in the tall oil, thus making it suitable for the preparation 50 mi. of toluene, in which the polyalkenyl group has an of imidazolines and, therefore, the monammonium salts average molecular weight of about 980, (0.1412 mol) is of the present invention. slowly charged after which the resulting mixture is heated The following is an example of the use of tall oil in to about 125 C. (reflux) for about two hours. The by 70 the aforementioned manner. product water is removed as it is formed by the reaction. After cooling the reaction mixture from above to about EXAMPLE 67 70° C., 8.5 parts of acetic acid (0.1412 mol) is added. Into a suitable reaction vessel, fitted as described above, Refluxing is then continued until the evolution of water which contains 170 parts of tetraethylenepentamine in and its collection has ceased. 75 100 ml. of xylene is charged 1200 parts of polybutenyl 35 8,658,836. 36 (980) succinic anhydride in 500 ml. of xylene. This re- - - - . (2) dialdehydess and diketones represented by action mixture is heated to reflux, and maintained at re the structure - flux for about three hours with stirring until the evolu o O tion and collection of water has ceased. The reaction mixture is then cooled and 253 parts of refined tall oil is 5 - - - - - added. The refined tall oil had a total fatty acid content (b) a carbonyl-containing aromatic or heterocyclic of 96.8% by weight; its composition was 48% linoleic compound, represented by the structure acid and 52% oleic acid. The resulting solution is heated . . . and maintained at reflux until further evolution and col- O lection of water has ceased. 278 parts of boric acid is 10 R--Rs charged and the reaction mass is then heated at about ... - - 90° C. for one hour. Water formed in the reaction is (c) urea, thiourea or guanidine represented by the then removed by azeotropic distillation. Thereafter, the structure xylene is removed to leave the 2 - (heptadec - 8-enyl, - - - - . A heptadec - 8, 11 - dienyl) - 1-8-(polybutenylsuccinimido)- 5 NH (-NH 3,6 - diazaoctyl - 2 - imidazoline monoammonium salt 2- 2 of spiro (3,5 - dihydroxyboroxin)-1,1'-(3',5'-dihydroxy- and - - boroxin)). . (d) a carboxylic acid, that is, Additional examples of other salts of this invention (1) a monocarboxylic acid represented by the based upon imidazolines and the materials used for their 20 Structure preparation (other than boric acid) are given in Table VII, below. In the table only the alkenyl, or polyalkenyl, g “. . . portion of the polyalkenylsuccinic anhydride and the aver- R1-C-OH age molecular weight of such portion are given, TEPA . . . . " means tetraethylenepentamine. - . . . 25 or the anhydride thereof, or TABLE VII Alkenylportion of Polyeth alkenylsuccinican- ylene hydride (mol wt. of poly E alkenyl group) amine Carboxylic acid Molar ratio . No. (a) (b) (c) (a): (b); (c) Product - - 68----- Polybutenyl(1,368).---- TEPA Picolinic acid- 1:1:1. The 1-8-(polybutenylsuccinimido)-3,6-diazaoctyl-2-(2-pyridyl)-2-imidazol line monoammonium salt of spiro (3,5-dihydroxyboroxin)-1,1'-(3',5'- dihydroxyboroxin). -: 69------do------TEPA Benzoic acid---- i:1:1. The 1-8-(polybutenylsuccinimido)-3,6-diazaoctyl 2-phenyl-2-imidazoline Higging." salt of spiro (3,5-dihydroxyboroxin)-1,1'-(3',5'-dihy roxyboroXin), . . . . . " 70. Polybutenyl (980).----- TEPA Adipic acid....., 2:2:1. The 2,2-tetramethylene-1,1-bis(3-(polybutenylsuccinimido)-3,6-diazaoctyl 2-imidazoline)1,1-(3',5'-dihydroxyboroxin) monoammonium salt of spiro(3,5-dihydroxyboroxin). 7------do------TEPA Sebaclic acid--- 2:2:1. The 2,2'-octamethylene-1,1'-bis(8-(polybutenylsuccinimido)-3,6-diazaoctyl 2-imidazoline1,1-(3',5'-dihydroxyboroxin). monoammonium salt of spiro (3,5-dihydroxyboroxin)- . . 72----- Polybutenyl(1,368).--- TEPA Dimer acid .2:2:1. The 6-hexyl-5-pentyl-4-10-1-(8-polybutenylsuccinimido-3,6-diazaoctyl)-2- (containing inidazolin-2-yl)dec-2-enyl-3-7-1-(8-polybutenylsuccinimido-3,6-diaz 36 carbons). spiroagctyl)-2-imidazolin-2-ylheptyicyclohexenemonoammonium (3,5-dihydroxyboroxin) -1,1'-(3',5'-dihydroxyboroxin)). salt of . Additional groups of materials which are also useful (2) a dicarboxylic acid represented by the in lubricating oils, fuel oils and gasoline compositions as structure

ashless or non-metallic detergents, rust inhibitors and antioxidants are obtained by reacting boric acid, or a compound which gives boric acid in the presence of water, such as boric oxide, or other boron acids, e.g., metaboric Ho-5-T-8-OH acid, moron halides and esters of boron acids, with inter mediate reaction products formed by the interaction of or the anhydride thereof, (i) an alkenylsuccinic anhydride, represented by the ... where R, R1, R2, R3, R4, R14, R15, R19, T, A and z have stricte their aforedescribed significance, in mol ratios of (i): (ii) O of about 1:1 to about 1.6:1 preferably about 1.1:1 to 2 55 about 1.4:1, respectively, mol ratios of (ii): (iii) of from about 1:0.8 to 1:1.2, preferably about 1:1, respectively, R–H–C and mol ratios of boron compound to (ii) of from about o 0.1:1 to about 25:1, respectively. The maximum amount CH-C n of a boron compound used can also be expressed as five O 60 mols per gram atom of basic nitrogen in the intermediate or the acid thereof, , , reaction product. The number of gram atoms of basic (ii) a polyethyleneamine, represented by the structure nitrogen can be determined by a standard perchloric acid titration of such intermediate using a crystal violet indi f / \ . . cator. The products containing 1 to 10 mols of boron 65 compound per mol of (ii), which in the case of products NH-CH- g- NH-CH- -NH-CH-i-NH formed from a dicarboxylic acid is 0.5 to 5 mols per moi R R1/ R. of (ii), are preferred. For convenience boric acid will and generally be referred to as the boron compound used. It (iii) a compound selected from is to be noted that the mol ratios of reactants (i), (ii) (a) a carbonyl-containing compound selected from 70 and (iii) expressed above represent total quantities of (1) aldehydes and ketones represented by the such reactants and that in preparing the contemplated structure - ...... reaction products the order of reaction is not critical O and the reactants can be utilized in portions, that is, por tions of the total quantity of reactants (i), (ii) and (iii) R-C-Rs 75 to be used can be reacted together in any order. Also an 3,658,836 37 38 inert hydrocarbon can be used as a reaction medium. It EXAMPLE 75 is also preferred to conduct the process with agitation. All of the reactants designated (i), (ii) and (iii), (a), Into a suitable reaction vessel there is charged 12.2 (b), (c) and (d) have been described above and accord parts of triethylenetetramine (0.0834 mol), 80.4 parts ingly need no further description. process oil and 6.0 parts of butyraldehyde (0.0834 mol). The amount of excess alkenylsuccinic anhydride used During the addition of the butyraldehyde the reaction mass (relative to the polyethyleneamine) in preparing such temperature is kept below 30° C. Thereafter there is add products is important since large excesses above about ed 145 parts of polybutenylsuccinic anhydride (0.1 mol) 60% cause an increase in lacquer deposits resulting in a in which the polybutenyl group has an average molecular product which is less acceptable. Accordingly, the amount O weight of 980 and the resulting mixture is heated to and of excess alkenylsuccinic anhydride should range from held at 150° C. with a system pressure of 35 mm. of more than 0% up to about 60%. Engine test experience mercury for one hour while continuously removing water with the various products encompassed by this invention of reaction. 30.0 parts of boric acid (0.487 mol) is then has shown that the amount of such excess is preferably added along with 1.5 ml. of water and the reaction mass from about 10% to about 40%. 15 heated at 90° C. for 45 minutes followed by heating for The amount of excess or deficiency of reactant (iii) one hour at 150 C. and a pressure of 35 mm. of mer relative to the polyethyleneamine (ii) can vary from a cury during which by-product water is removed. The re mol ratio of 1:1.2 to 1:0.8, respectively. In the case of Sulting product is then filtered to provide the desired reac acid anhydrides (iii) (d) one-half mol of anhydride is tion product which analyzes 1.68% nitrogen and 1.45% equivalent to one mol of acid. However, mol ratios of 20 boron. The B/N atom ratio is 1.12. about 1:1 are preferred. In preparing the reaction products of this invention, EXAMPLE 76 the temperatures of reaction before addition of boric acid Into a reaction vessel containing 22.8 parts of tetra can be in the range of 0-200 C., preferably 100-190° C., ethylenepentamine in toluene (0.1205 mol) there is slow at atmospheric, superatmospheric or reduced pressure. The 25 ly charged 12.1 parts of glutaraldehyde (0.0301 mol) raw materials (i), (ii) and (iii) can be reacted in in followed by the addition of 245 parts of polybutenylsuc different order and in portions as is more fully illustrated cinic anhydride (0.1447 mol: the alkenyl group has an in the following examples. Thereafter boric acid is added average molecular weight of 1368) in toluene and then an and the resulting mixture heated at temperatures of 25 additional 12.1 parts of glutaraldehyde. The resulting mix 200° C., thereby forming the desired reaction products. 30 ture is then heated at reflux for three hours, while remov. The preparation of the reaction products of this invention ing water formed in the reaction. Thereafter 37.4 parts using (i) an alkenylsuccinic anhydride, (ii) a polyethyl of boric acid are chaged and the reaction mixture is heat eneamine, a compound of class (iii) and a boron com ed at about 85 C. for about forty-five minutes. The water pound is illustrated in the following non-limiting examples is then removed by azeotropic distillation, toluene is wherein parts are parts by weight. 35 Stripped under vacuum, process oil is added and the re Sulting mixture is filtered to leave the desired product. EXAMPLE 73 EXAMPLE 77 Into a reaction vessel containing, at 5 C., 16.1 parts of triethylenetetramine (0.11 mol) in process oil, there is 40 Into a suitable reaction vessel containing 14.2 parts slowly charged 4.85 parts of acetaldehyde (0.11 mol) of tetraethylenepentamine (0.0749 mol) in 70 ml. of tolu causing the temperature to rise to 14 C. followed by the ene, there is added, with stirring, 4.35 parts of acetone addition of 220 parts of polybutenylsuccinic anhydride (0.0749 mol). After heating the resulting mixture to about (0.1321 mol) having a polybutenyl group with an av 100 C, 150 parts of polybutenylsuccinic anhydride (0.09 erage molecular weight of about 1350. The resulting mix mol: the alkenyl group has an average molecular weight ture is then heated, under vacuum, to about 150 C. and 45 of 1368) in toluene is added. The resulting mixture is held at that temperature for about forty minutes at a pres refluxed for about two and one-half hours while removing sure of 35 mm. of Hg during which time the water of Water formed in the reaction. The intermediate reaction reaction is removed. After allowing the reaction mass to product is then reacted with 23.2 parts of boric acid (0.37 cool to about 70° C., 34 parts of boric acid (0.55 mol) mol) in the usual manner to provide the desired reaction and 3 ml. of water is added and the resulting mixture is 50 product. heated, with agitation, at 90° C. for about one hour foll EXAMPLE 78 lowed by heating at 150° C. and 35 mm. of Hg for forty five minutes. The reaction mass is then filtered to provide Into a suitable reaction vessel containing 10.85 parts the desired reaction product which analyzes 1.38% total of chloral (0.0738 mol) there is added 13.98 parts of 55 tetraethylenepentamine (0.0738 mol) in toluene, which nitrogen and 1.35% boron. The B/N atom ratio is 1.26. is followed by the addition of 148 parts of the same poly butenylsuccinic anhydride used in Example 77 (0.0885 EXAMPLE 74 mol) in toluene and the resulting mixture is heated at Into the reaction vessel containing 28.3 parts of tetra 60 reflux until no additional water of reaction can be re ethylenepentamine (0.1493 mol) in toluene is slowly add moved. The toluene is then stripped under vacuum and ed 3.28 parts of acetaldehyde (0.0746 mol), followed by the product diluted with oil. The diluted product is then 309 parts of polybutenylsuccinic anhydride (0.1792 mol: reacted with 23 parts (0.37 mol) of boric acid in the the average molecular weight of the alkenyl group is 1315) usual manner to provide the desired reaction product. in toluene and then an additional 3.28 parts of acetalde 65 hyde. The resulting mixture is then heated at reflux (123 EXAMPLE 79 C.) for three hours while removing water formed in the In the manner of Example 75, 37.2 parts of tetra reaction. Thereafter the toluene is removed to leave 337 ethylenepentamine (0.197 mol), 14.2 parts of butyralde parts of a reaction product which is diluted with mineral hyde (0.197 mol) and 500 parts of polybutenylsuccinic oil. Water and 19.1 parts of boric acid (0.309 mol) are 70 anhydride (0.275 mol) having an alkenyl group of aver then charged and the reaction mass heated at about 90 age molecular weight 1350, are reacted in 243 parts of C. for one hour. Thereafter the water is removed as in process oil to yield an intermediate reaction product which Example 73 to leave the desired reaction product which is in turn reacted with 60.8 parts of boric acid (0.982 analyzes 0.54% boron and 1.72% nitrogen. The B/N mol) in the usual manner to provide the desired reaction atom ratio is 0.4. 75 product having good detergent properties. 8,658,836 39 40 - - EXAMPLE 80 is then heated at 170-180° C. until the evolution of am monia has ceased. - * ; : : -. In the manner of the previous example 32.5 parts of The reaction mass is then cooled to 70° C. and 157.3 tetraethylenepentamine (0.172 mol), 12.4 parts of butyr parts of boric acid (2.5 mol) is charged. The resulting aldehyde (0.172 mol), 500 parts of polybuteneylsuccinic mixture, is then heated at 90° C. for about one-hour and anhydride (0.275 mol) and 53.4 parts of boric acid (0.86 then at 150° C. and a total pressure of 30 mm, of Hg mol) are reacted to provide the desired reaction product for one hour. The reaction mass is then filtered to leave having good detergent properties. an oil solution of the desired reaction product. EXAMPLE 81 EXAMPLE '86 In the general manner of Example 75, 4.33 parts of O Into a suitable reaction vessel containing 171 parts of tetraethylenepentamine (0.229 mol), 21.1 parts of fur polybutenylsuccinic anhydride having an alkenyl group fural (0.229 mol) and 500 parts of polybutenylsuccinic of an average molecular weight of about 980 and about anhydride (0.275 mol) in which the alkenyl group. has 40 ml. of toluene, at 40° C., there is added 18.9 parts an average molecular weight of 1350 are reacted, in oil, of tetraethylenepentamine and 8.9 parts of guanidine, car to provide an intermediate reaction product which is then 5 bonate. The temperature of the reaction mixture, is then reacted with 709 parts of boric acid (1.14 mol) in the increased to about 130° C. and held at 130-150° C. for presence of 10 ml. of water to provide the desired product about twelve hours while continuously removing water which analyzes 1.85% nitrogen and 1.4% boron and as it is formed. (The evolution of carbon dioxide occurs has good detergent properties. when the guanidine carbonate is added and during the EXAMPLE 82. 20 heat-up period.). The reaction mass is then cooled to Into a suitable reaction vessel, fitted as previously de about 70° C. and 17.4 parts of boric oxide and 7 ml...of scribed, and containing 26.3 parts of tetraethylenepent water are charged. The resulting mixture is then heated amine (0.1387 mol) in toluene, there is charged 7.36 parts . at 80° C. for about one and one-half hours, and then the of benzaldehyde (0.0693 mol). A slight temperature rise is 25 water is removed by azeotropic distillation. The toluene noted. Then 287 parts of polybutenylsuccinic anhydride is then stripped and the remaining mass diluted with oil (0.1665 mol: the average molecular weight of the alkenyl and filtered to provide an oil solution of the desired group is 1315) in toluene is slowly added. Again some product...... heat evolution is noted. After completing the anhydride - EXAMPLE 87 . . . . addition, an additional 7.36 parts of benzaldehyde is 30 Into a suitable reaction vessel, fitted as previously de charged and the resulting mixture is heated at reflux scribed, and containing 73 parts of triethylenetetramine (about 125 C.) for about three hours while continuously (0.5 mol) in toluene there is charged 1080 parts of poly removing water formed in the reaction. - butenylsuccinic anhydride (0.6 mol: the average molecu After cooling the reaction mass to about 85 C., 43 lar weight of the alkenyl group is 1350). The reaction parts of boric acid is added and the resulting mixture is mixture is refluxed until the evolution and collection of heated at 95-110 C. for about two hours while removing water has ceased and then the toluene is stripped. 30 parts water as it is formed. The toluene is then stripped and of urea (0.5 mol) along with 570 parts of process oil are the product diluted with oil. . added followed by heating the mixture at 180-190° C. EXAMPLE 83 40 until the evolution of ammonia has ceased. The reaction Into a suitable reaction vessel, fitted as previously de mass is cooled to 70° C. and 157.3 parts-of boric acid scribed, and containing 1520 parts of polybuteneylsuc (2.5 mol) is then charged. The resulting mixture is heated cinic anhydride (1.2 mol: the average molecular weight at 90° C. for about one hour and then 150° C. and 30 of the alkenyl group is 980) in toluene, there is charged mm. of Hg total pressure for one hour. The product is 189 parts of tetraethylenepentamine (1.0 mol) and the then filtered to leave the desired reaction product in oil. mixture is refluxed until the evolution and collection of 45 EXAMPLE 88 water ceases. The toluene is then stripped and 60 parts Into a suitable reaction vessel containing 22.9 parts of of urea (1.0 mol) along with 858 parts of process oil tetraethylenepentamine (0.1208 mol) and 75 ml. of tol are charged to the reaction mixture. Heating is continued uene, there is slowly added 17.0 parts of oleic acid at 180-190° C. until the evolution of ammonia has ceased 50 (0.0604 mol). After completing the addition of the oleic to provide the desired intermediate product. . acid there is added rapidly 250 parts of polybutenylsuc After cooling the reaction mixture 310 parts of boric cinic anhydride in which the polybutenyl group has an acid (5.0 mol) is charged and the resulting mixture heated average molecular weight of 1350 (0.145 mol) followed at 90° C. for about one hour. The pressure is reduced by the addition of 17.1 parts of oleic acid. The reaction to 30 mm. of Hg and the reaction mass heated at 150 C. 55 mass is then heated to 150° C. and held at 150 C. for for one hour while the water of reaction is removed. three hours, after which the toluene is removed. The re The mixture is then filtered to leave an oil solution of sulting product is diluted with oil and is heated with 18.7 the desired reaction product. parts of boric acid (0.302 mol), and 4 ml. of water at EXAMPLE 84 90° C. for about 30 minutes. Thereafter the system pres 6 sure is reduced to 35 mm. of mercury and the reaction Example 83 is repeated except that only 1.1 mol of mass is heated at 150 C. until the flow of by-product polybutenylsuccinic anhydride is employed and 1.0 mol water has ceased. The reaction mass is then filtered to of thiourea is used in place of the urea. The product is provide the desired reaction product, which analyzes a good detergent for use in lubricating oils. 0.62% boron and 1.46% nitrogen. The B/N atom ratio EXAMPLE 85 is 0.55...... " Into a suitable reaction vessel, fitted as previously, de ...... EXAMPLE 89. scribed, containing 94.5 parts of tetraethylenepentamine : To a suitable reaction vessel containing 17.33 parts of (0.5 mol) in toluene there is charged 895 parts of poly- . tetraethylenepentamine (0.0916 mol) in process oil there buteneylsuccinic anhydride (0.7 mol: the average molecu 70 is rapidly added 9.71 parts of benzaldehyde (0.0916 mol), lar weight of the alkenyl group is 980). The reaction mix followed by the addition of 183 parts of polybutenylsuc ture is refluxed until the evolution and collection of water cinic anhydride (0.1098 mol: the polybutenyl group has has ceased and then the toluene is stripped off. Subse an average molecular weight of 1350) in process oil. The quently, 30 parts of urea (0.5 mol) and 488 parts of resulting mixture is heated to 110°C. and then cooled to process oil is added to the reaction mixture. The mixture 75 about 85°C. Then 20.3 parts of boric acid (0.328 mol) 3,658,836 41 42 is charged and the resulting mixture heated to and main 2424 parts of the reaction product prepared above is com tained at 90° C. for about 10 minutes at a slight vacuum, bined with 320.5 parts of boric acid (5.19 mol) and 24 after which the reaction mass is heated at 150° C. with ml. of water and the resulting mixture heated at 90° C. a system pressure of 35 mm. of mercury for approxi for about 30 minutes. The system is then evacuated to a mately one hour. The reaction mass is then filtered to total pressure of 35 mm. of mercury. The reaction mass yield the desired reaction product which analyzes 0.61% is then heated at 150° C. for about one hour while re boron and 1.32% nitrogen. The B/N atom ratio is 0.60. moving water of reaction. The resulting product is then filtered to yield the desired reaction product which anal EXAMPLE 90 yzes 1.28% boron and 1.69% nitrogen. The B/N atom The procedure of the previous example is repeated ex O ratio is 1.4. cept that only 12.15 parts of boric acid (0.1967 mol) is EXAMPLE 96 used to give a product analyzing 0.20% boron and 1.69% To a suitable reaction vessel containing a slurry of 12.2 nitrogen. The B/N atom ratio is 0.153. parts of triethylenetetramine (0.0834 mol) in process oil, EXAMPLE 91. there is charged 6.0 parts of butyraldehyde (0.0834 mol). To a suitable reaction vessel containing 23.0 parts of 5 Then 145 parts of polybutenylsuccinic anhydride (0.1 tetraethylenepentamine (0.1215 mol) and 75 ml. tolu mol) having a polybutenyl group with an average molec ene, there is added 6.4 parts of benzaldehyde (0.0607 ular weight of 980 in process oil is added rapidly and mol) followed by the addition of 247 parts of polybute the resulting mixture is heated to and maintained at 150 nylsuccinic anhydride (0.1458 mol) in which the poly C. and a system pressure of 40-50 mm. of mercury for butenyl group has an average molecular Weight of 190 20 about one hour while removing the water of reaction. The in 90 ml. of toluene. Thereupon an additional 6.4 parts reaction mixture is then cooled to about 80° C. and 25.9 of benzaldehyde is charged and the reaction mixture is parts of boric acid (0.417 mol) and 3 ml. of water are heated at reflux while removing water of reaction. After added. The reaction mixture is then heated at about 90 heating the reaction mixture for about two and one-half C. for about two hours and then at about 150° C. and hours at reflux the toluene is removed to leave 280 parts 25 a System pressure of 50 mm. of mercury for about one of product, which is diluted with 140 parts of process oil. hour during which water of reaction is removed. Filter To 405 parts of the above-prepared product there are aid is then added and the reaction mixture filtered to pro added 39.3 parts of boric acid (0.636 mol) and 4 ml. of vide the desired reaction product which contains 1.52% water. The resulting mixture is heated at 90° C. for about 30 boron and 1.66% nitrogen. The B/N atom ratio is 1.14. 35 minutes and then heated to 150° C. with a system pressure of 35 mm. of mercury to remove water of re EXAMPLE 97 action. The resulting product is then filtered to provide Following the general procedure of the previous exam the desired reaction product which analyzes 1.42% boron ple, 6.0 parts of butyraldehyde, 12.2 parts of triethylene and 1.78% nitrogen. The B/N atom ratio is 1.03. tetramine and 167 parts of polybutenylsuccinic anhydride 35 in which the polybutenyl group has an average molecular EXAMPLE 92 weight of 1350 are reacted to form an intermediate prod The previous example is repeated except that the amount luct which is in turn reacted with 25.8 parts of boric acid of boric acid charged is varied so that the resulting prod to provide the desired reaction product which analyzes uct analyzes 0.71% boron and 1.59% nitrogen and has a 40 1.29% boron and 1.50% nitrogen.The B/N atom ratio is B/N atom ratio of 0.58. 1.11. EXAMPLE 93 EXAMPLE 98 To a suitable reaction vessel there is charged 240 parts To a suitable reaction vessel there are charged in the (0.159 mol) of 11-(polybutenylsuccinimido)-3,6,9-triaza following order 27.9 parts of tetraethylenepentamine undecylamine in which the polybutenyl group has an aver (0.1477 mol), 7.8 parts of benzaldehyde (0.0788 mol), 45 age molecular weight of 980, process oil and 11.5 parts 300 parts of polybutenylsuccinic anhydride (0.177 mol) of butyraldehyde (0.159 mol) and the resulting mixture in which the polybutenyi group has an average molecul is heated at 150° C. and 35 mm. of mercury for about lar weight of 1350, 7.8 parts of benzaldehyde and 174 two hours while removing water of reaction. The reaction parts process oil. The resulting mixture is heated at 150 mass is then cooled to about 75° C. and 39.3 parts of C. and a total pressure of 30 mm. of Hg for about two 50 boric acid (0.636 mol) is added. The resulting mixture is hours and then cooled to 85 C. After cooling, 28.0 parts then heated at 90° C. for about one hour and then 150° of boric acid (0.436 mol) and 4.5 ml. of water are charged C. and 30 mm. of Hg for one hour during which water and the resulting mixture heated to 90° C. for about one of reaction is removed. Filter aid is then added and the hour and then at 150° C. and 30 mm. of Hg for one reaction mass filtered to provide the desired product, hour. The reaction mass is then filtered to give an oil So 55 which analyzes 3.21% nitrogen and 2.15% boron. The lution of the desired product which analyzes 0.82% boron B/N atom ratio is 0.87. and 1.78% nitrogen. The B/N atom ratio is 0.597. EXAMPLE 99 EXAMPLE 94 An intermediate reaction product is prepared by heat In the manner of Example 93, a product is prepared 60 ing together at reflux a toluene solution of 262 parts of containing 1.36% boron and 1.80% nitrogen. The B/N polybutenylsuccinic anhydride (0.1912 mol) in which the atom ratio is 0.98. polybutenyl group has an average molecular weight of EXAMPLE 95 980, 32.9 parts of tetraethylenepentamine (0.1738 mol), and 12.5 parts of butyraldehyde (0.1738 mol). From the To a suitable reaction vessel there is charged 159.8 65 foregoing there is obtained 301 parts of an intermediate parts of triethylenetetramine (1.092 mol) and 500 parts reaction product in toluene. 225 parts of the intermediate process oil, followed by the addition of 115.9 parts of reaction product is diluted with oil, after which 200 ml. benzaldehyde (1.092 mol) which causes the temperature of toluene and 50.6 parts of boric acid (0.390 mol) are of the reaction mass to rise about 20° C. Next there is charged. The resulting mixture is then heated at about charged 1900 parts of polybutenylsuccinic anhydride 70 95-120° C. for about one hour while removing water of (1.310 mol) in which the polybutenyl group has an aver reaction by azeotropic distillation. Thereafter the reac age molecular weight of 980 and 566 parts of process oil. tion mixture is filtered and the toluene removed by dis The reaction mixture is then heated for one and one-half tillation to leave an oil solution of the desired reaction hours at 150° C. and a system pressure of 35 mm. of product, which analyzes 1.73% nitrogen and 1.83% mercury while removing water of reaction. Thereafter 75 boron. The B/N atom ratio is 1.37. 3,658,836 43 44 EXAMPLE 100 eral hours while removing water of reaction. The toluene A large quantity of boron-free reaction product is pre is then removed by vacuum distillation to provide 374 pared in the manner of the previous example except that parts of intermediate product which is then diluted with a 20% molar excess of polybutenylsuccinic anhydride 187 parts of process oil. (i): (ii) ratio of 1.2:1 is used. 402 parts of Such a reac A small sample of the above prepared product is re tion product is then placed in a suitable reaction vessel moved for analysis to leave 503 parts of diluted product and the toluene is removed by distillation to provide 284 which is then heated with 30.2 parts of boric acid (0.489 parts of solvent-free material to which is added 28.1 parts mol) and 5 ml. of water at 90° C. for about 30 minutes. of boric acid, 3 ml. of water and 142 parts of process oil. The temperature of the reaction mass is carefully raised The reaction mass is then heated at 90° C. for about 30 O to 150° C. while at the same time reducing the system minutes and then the temperature is raised to 150 C. and pressure to 35 mm. of mercury. Heating is then continued the system pressure reduced to 35 mm. of mercury. Heat at the latter conditions until essentially all water of reac ing is continued at the latter conditions for approximately tion has been removed. The reaction product is then fil one hour. The resulting reaction product is then filtered and tered and found to contain 0.76% boron and 1.5% nitro found to analyze 0.96% boron and 1.82% nitrogen. The 5 gen. The B/N atom ratio is 0.65. B/N atom ratio is 0.60. EXAMPLE 104 EXAMPLE 101. Into a suitable reaction vessel, fitted as previously described, and containing 118.2 parts of tetraethylene In a manner similar to the above example, 361.5 parts pentamine (0.624 mol) in process oil, there is slowly of solvent and boron-free intermediate is reacted with 20 charged 45.0 parts of butyraldehyde (0.624 mol). Poly 23.8 parts of boric acid in oil to provide a product which butenylsuccinic anhydride, 1250 parts (0.749 mol: the analyzes 0.60% boron and 2.02% nitrogen. The B/N atom average molecular weight of the alkenyl group is 1350) ratio is 0.385. in process oil is then slowly added. After completing the EXAMPLE 102 anhydride addition, the resulting mixture is heated at Initially a large quantity of intermediate boron-free re 25 about 150 C. and 35 mm. Hg for about two hours while action product is prepared from polybutenylsuccinic an continuously removing water formed in the reaction to hydride in which the molecular weight of the polybutenyl provide an intermediate reaction product. group averaged 1350, tetraethylenepentamine and butyr The reaction mass is then cooled to about 85 C. and aldehyde, the mol ratio of these reactants being 1.2:1:1, 205 parts of boric acid (3.25 mois) and 20 ml. of water respectively. The intermediate product is prepared by 30 are added and the resulting mixture is heated at 90° C. adding the butyraldehyde to a toluene solution of tetra for about forty-five minutes. The reaction mass tempera ethylenepentamine, followed by the addition of a toluene ture is then raised to about 150° C. and the pressure solution of the polybutenylsuccinic anhydride. The reac is reduced to about 35 mm. of Hg in order to remove tion mass is then warmed to 90° C. followed by the addi water. The 150° C. temperature and reduced pressure are tion of the other half of the butyraldehyde to be used and 35 maintained for about one and one-quarter hours and the the resulting mixture is heated at reflux for about two reaction mixture is then filtered to leave the desired prod hours, after which the system is placed under vacuum uct, which analyzes 1.23% boron and 1.55% total nitro and the toluene removed. gen. The B/N atom ratio is 1.02. (a) 359 parts of an oil solution of the above-prepared boron-free reaction product containing 0.200 gram atoms 40 EXAMPLE 105 of basic nitrogen is reacted with 9.24 parts of boric acid In the manner of Example 104, and utilizing the same (0.149 moi) by heating the reaction mixture at 90° C. reactants, 150 parts of an intermediate reaction product for about 30 minutes, followed by heating at 150° C. is prepared which contains 0.125 gram atoms of basic and a system pressure of 35 mm. of mercury until essen nitrogen. After cooling the intermediate to about 85 C., tially all water of reaction is removed, followed by the 45 38.8 parts of boric acid (0.626 mol) and 3 ml. of water usual filtration step. The product analyzes 0.36% boron are charged. The resulting mixture is then heated at 90 and 1.49% nitrogen. The B/N atom ratio is 0.313. C. for one hour after which the temperature is increased (b) 352 parts of an oil solution of the above-prepared to 150° C. over a period of about twenty-five minutes. boron-free reaction product containing 0.293 gram atoms The reaction mass is then held at 150° C. for about one of basic nitronen is reaction with 18.2 parts of boric acid 50 hour during which time the system total pressure is (0.293 mol) in the same manner as in (a) to provide lowered to 20 mm. of Hg (water is removed during the a reaction product which analyzes 0.78% boron and heating period when the temperature is above 100 C.). 1.54% nitrogen. The B/N atom ratio is 0.65. - Heating is then discontinued, 77 parts of process oil is (c) 315 parts of an oil solution of the above-prepared added (resulting in a 50% solution of reaction product boron-free reaction product containing 0.263 gram atoms 55 in oil) and the mixture filtered to leave an oil solution of of basic nitrogen is reacted with 24.4 parts of boric acid the desired product which analyzes 2.47% boron and (0.3938 mol) in the same manner as in (a) above to 1.03% total nitrogen. The B/N atom ratio is 3.14. provide a reaction product which analyzes 1.17% boron and 1.54% nitrogen. The B/N atom ratio is 0.98. EXAMPLE 106 (d) 497 parts of an oil solution of the above-prepared 60 Into a suitable reaction vessel, fitted as previously de boron-free reaction product is reacted with 46.8 parts of scribed, and containing 11.9 parts of tetraethylenepenta boric acid (0.759 mol) in the same manner as in (a) mine (0.063 mol) in mineral oil, there is charged 4.5 parts above to provide a product which analyzes 1.42%, boron of butyraldehyde (0.063 mol). The temperature of the and 1.63% nitrogen. The B/N atom ratio is 1.12. reaction mass is then increased to 150° C. During the 65 heat-up period 135 parts of polybutenylsuccinic anhydride EXAMPLE 103 is charged (0.076 mol: the average molecular weight Into a suitable reaction vessel containing 30.9 parts of of the polybutenyl group is 1315). After completing addi tetraethylenepentamine (0.1633 mol) in toluene there is tion of the anhydride, the pressure within the reaction slowly added 11.8 parts of butyraldehyde (0.1633 mol). vessel is reduced to 25 mm. of Hg and heating at 150° C. The reaction mixture is kept at about 15° C. during the 70 is continued for about and one-half hour. The reaction addition of the butyraldehyde. Thereafter with rapid mass is then cooled to 125 C. and 19.5 parts of boric agitation a solution of 338 parts of polybutenylsuccinic acid (0.32 mol) is charged. The reaction mass is then anhydride (0.196 mol: the polybutenyl group has an aver heated at 150° C. and a pressure of 25 mm. of Hg for age molecular weight of 1350) in toluene is added rapidly an additional two hours during which time water of re and the resulting mixture heated at reflux (122° C.) sev 5 action is removed by distillation. Filter aid is then added 3,658,836 45 46 and the reaction mass filtered to provide the desired re merely increasing the chain length or molecular weight action product which analyzes 1.52% boron and 1.97% of the polyalkenyl group from 980 to 1350 gives a signifi nitrogen. The B/N atom ratio is 1.00. cant increase in detergency effectiveness of the product of Example 100 with the product of Example 102(b) and EXAMPLE 107 the product of Example 96 with the product of Exam ple 97. Into a suitable reaction vessel, fitted as previously de The results of the LDT also show that wide variations scribed, and containing 193.6 parts of pentaethylene in boron content or B/N atom ratio have essentially no hexamine (0.833 mol), there is slowly charged 60.1 parts effect on detergency effectiveness (as measured by the of butyraldehyde (0.833 mol) followed by 500 parts of 10 LDT). Thus, note that almost doubling the B/N atom process oil. The reaction mass is kept at 20-30 C. dur ratio has little effect on detergency effectiveness; com ing addition of butyraldehyde. 1888 parts of polybutenyl pare the LDT results of the products of Example 100 with succinic anhydride (1.0 mol), in which the polybutenyl Example .10; and compare the LDT results of the prod group has an average molecular weight of 1315, is then ucts of Examples 102(a) (B/N=0.313), (b) (B/N added and the resulting mixture heated at 150° C. and 5 =0.65), (c) (B/N=0.98) and (d) (B/N=1.12). Also a pressure of 25 mm. of Hg for one and one-half hours note the LDT result of the product of Example 105 during which water of reaction is removed. The reaction (B/N=314). Such results are readily understandable mass is then cooled to 85-90° C. and 257.8 parts of boric when it is realized that the LDT is only designed to acid (4.165 mol) and 23 ml. of water are charged. The measure detergency and, therefore, so long as the amount resulting mixture is then heated at 90° C. for thirty 20 of boron used is not so great as to cause an oil solubility minutes, 95 C. for thirty minutes, 100° C. for thirty problem boron content has little or no effect on low minutes and 150° C. and 25 mm. of Hg pressure for one temperature detergency as measured by the LDT. The hour during which water is removed. An additional 645.7 role of boron, in the products of this invention, is, as will parts of process oil is added and the resulting mixture be hereinafter shown, to provide improved high tempera filtered to provide an oil solution of the desired reaction 25 ture detergency and anti-rust protection. product which analyzes 1.95% nitrogen and 1.17% The LDT results also show that improvements in de boron. The B/N atom ratio is 0.78. tergency effectiveness are realized by using a molar ex The effectiveness of the aforedescribed reaction prod cess of polyalkenylsuccinic anhydride (compared to ucts of this invention to impart low temperature detergent polyethyleneamine) in preparing the instant products. properties is illustrated by the results obtained with such 30 Thus, for example, compare the LDT results of Example products in a bench scale detergency test, referred to 98 (no excess) with Example 99 (10% excess). herein as the "Lacquer Deposition Test.” The Lacquer Other observations which can be made are that when Deposition Test involves passing burned gasoline fumes using the higher molecular weight polyalkenylsuccinic through a sample of an oil formulation containing a anhydrides, highly effective detergents can be obtained product of this invention, in a suitable container, under 35 even with products containing relatively low amounts of controlled conditions of flow rates and temperature boron (compare the LDT results of Examples 89 and 90) (285 C.) after which the sample is aged in an oven held and that as the molecular weight of the polyalkenyl group at 110° C. The amount of deposit is then determined by is decreased higher amounts of boron cause a decrease washing away the oil with hexane. A control formula in detergency (compare the LDT results of Examples 96 tion is run simultaneously. The difference in the amount of 40 and 97). Also a comparison of the procedure used to deposits present when no test product is present less the prepare the product of Example 89 and its LDT results amount of deposits present when a test product is present with the procedure used to prepare the product of Ex is reported as the percent reduction in deposits. ample 93 and its LDT results shows that the order in Following the procedure for the Lacquer Deposition which the reactants are utilized is not critical to the Test (LTD) given above selected examples of the above production of reaction products which have good deter described reaction products were tested for their de 45 gent properties. This is also shown by comparing the tergency effectiveness. The results observed are reported in LDT results of the products of Examples 103 and 104 Table IX, below. with the LDT results of the products of Examples 102(b) and (d). 50 Further evidence of the usefulness of the new products TABLE IX of this invention in lubricating oils is shown by the re Concen Lacquer Concent Lacquer Sults obtained in full-scale engine tests of lubricating oil Product tration, depo Product tration, depo formulations containing such products. The tests utilized tested percent sition, tested percent sition, (Exam py percent by percent include those known as the Engine Test Sequences for Weight Weight pie No.) reduction reduction 55 Evaluating Oils for API Service MS (1963) (Sequences

73-- 9. 99 I, II, III and V), and the Caterpillar CRC-L-1, Supple 95 65 ment 1, engine test. 81 65 97 54 Sequences I, II and III measure the ability of a lubri 97 88 9. 98 cant to properly lubricate and protect an engine operat 95 97 ing under conditions likely to cause scuffing, wear, rust 93 96 60 91 86 ing, deposit formation and high-temperature oil deteriora 75 92 tion. The engine used for these sequences is a 1960 Olds 28 9. 9 87 mobile V-8 and accordingly these test sequences are often 85 98 referred to as the Oldsmobile test. Specifically, Sequence I is designed to measure low-temperature, medium-speed 65 Scuffing; Sequence II is designed to measure low-tempera ture rusting and deposits; and Sequence III is designed to measure high-temperature oxidation. On completion of From the above results several conclusions can be made the test (all sequences) the engine is disassembled and with regard to the reaction products of this invention. 70 inspected for scuffing, wear, rusting, corrosion and sludge Thus, it is evident that while all the products contem and varnish deposition. Ratings are reported for the effect plated herein are useful as detergents, it is also evident of the test additive on these problems at various locations that some products are considerably more effective than in the engine. All values reported (Table X) in this test others. For example, the results of the LDT show that at are based on a 0-10 scale, with a rating of 10 being the essentially the same boron to nitrogen atom ratio (B/N) 75 best rating obtainable. 3,658,836 ...... 47 Sequence V is designed to measure the ability of a ABLE XI lubricant to prevent or reduce engine deposits produced Caterpillar Engine Test Results (L-1 Supplement 1) by low- and medium-temperature operating conditions. Test Additive Percent In this sequence, which places emphasis on the antisludg additive concentra- ring ing, anticlogging and insolubles suspension characteristics (Exam, tion, percent Lacquer groove Land Total of a lubricant, a 1957 Lincoln-Mercury ECU engine is ple No.) by weight Hours demerits filling lacquer rating 120 O 2 Nil 99.6 used and accordingly the test is often merely referred to 92------2 240 0.3 5 Nil 98.0 as the Lincoln engine test. The engine conditions of the . . . . . 480 12.7 25 2.5 81.6 102------2 35 7.3 ... 6 90.2 Lincoln engine test are typical of the conditions encoun 120 0 0 Nil 99.9 tered in present-day "stop-and-go' driving. On comple lo 102(b)---- 2 240 0.6 O Nil 99.0 480 9.02 . 2 2. - 8.4 tion of the test the engine is disassembled and ratings are - 2 { 240 O 7 O 99.2 given for the extent of sludge formation, varnish, etc. at 104------480 7.3 13 1.0 76,2 various locations in the engine. With respect to the data - 3 480 0.0 7 Nil 98. reported in Table XI, piston varnish and camshaft thrust piston varnish are rated on a scale of 0-10 with 10 being 5 the highest rating attainable (i.e., no varnish). The rat By analyzing the data set forth in the above tables, it ings for total varnish and total adjusted sludge are on a is evident that with the type of products within the scope scale of 0-50 with 50 being the highest rating attainable of the present invention the presence of boron has no (i.e., no varnish or no sludge). Ring plugging or clogging pronounced effect on the efficacy of such products as low is rated on a scale of 0-100%, 0 being the highest rating 20 temperature detergents compare the Lincoln engine test attainable (i.e., no clogging). . . . data for the product of Example 102 which is boron free, Details of the Sequence I, II, III and V test procedures with the data for the product of Example 102(b)). On are fully set forth in ASTM Special Technical Publica the other hand, it is also evident that the instant reaction tion No. 315A. . . . -- products have good anti-rust properties (as measured in The other full-scale test utilized to demonstrate the use 25 the Oldsmobile engine tests) and also that under condi fulness of the products of this invention, the Caterpillar tions of high temperature and high speed operation, e.g., CRC-L-1 engine test, modified to the extent of using a diesel engine conditions of which the L-1 is a direct fuel having a 1% sulfur content (Supplement I), is a test measurement thereof, that the instant reaction products designed to measure the efficacy of a lubricant under are good detergents and that the presence of boron sig engine conditions of high temperature and high speed 30 nificantly contributes to such high temperature detergency operation. Ratings are reported for lacquer demerits compare the data in Table XII for the product of Ex (piston cleanliness) on a scale of 0-100, 0, being a per ample 102 which is boron free with the data for the prod fectly clean piston; percent ring groove filling on a scale uct of Example 102(b). . From the above, it is clear that the addition to lubri of 0-100% (25% or lower is passing); land lacquer on 35 cating oils of the various salts and reaction products of a scale of 0-100; and a total rating, on a scale of 0-100, the present invention brings with it a clear improvement of where 100 is the highest rating attainable. Details of the various properties of said oils. Nevertheless the greater L-1 test procedure can be found in Caterpillar Diesel part of the commercial lubricating oils sold today are Lubricant Test Manual (1956). . - subject to a large number of uses, and it is, therefore, For the data reported in the tables below the test lubri 40 generally necessary to employ more than one type of cant consisted of a conventionally (solvent) refined Mid additive in a finished lubricant composition. Thus, al Continent mineral oil, SAE 30, containing 0.95% zinc though the products of the present invention are effective dialkyl dithiophosphate and a product of this invention detergents, possessing good anti-rust properties, it is fre at the concentration indicated. - quently desirable or necessary to use such products in 45 combination with other types of additives, such as metal containing detergents and/or dispersants, corrosion in hibitors, anti-rust agents, oxidation inhibitors, extreme pressure agents, viscosity index improvers, pour-point de pressors, anti-foaming agents, and the like. TABLE X 50 A particularly useful combination of additives intended Oldsmobile Engine Test Results ...... to be applied in motor lubricants is the combination of Additive a salt of the present invention and a metal-containing Test addi- concentra derivative of phosphorus such as a metal phosphoro ampletive (Ex... No.) . tion,cent per- by Average Average- Lifter, Engine,. . . . dithioate, e.g., zinc dihexyl phosphorodithioate, the Zinc weight warnish sludge averag average 55. salt, of mixed alkyl phosphorodithioates where the alkyl 9.8 5.9 groups are obtained, for example, from equal mixtures 9.8 7.0 9.7 7. of isobutyl and n-amyl or isopropyl and 2-ethylhexyl 2 9.8 9.3 9.7 4.6 alcohols and the metal salts of phosphorus sulfide-olefin 2. 9.9 - 8.7 polymer reaction products. 60. Lubricating oils which can be used as the base oils to . which the new compounds of this invention are added are not limited as far as detergent effects are concerned, and, accordingly, can be lubricating oils which are of a naph thenic base, paraffinic base, and other hydrocarbon bases, ABLE X 65 as well as lubricating oils derived from coal products and Lincoln Engine Test Results '. synthetic oils, such as alkylene polymers, alkylene oxide Detergent - i. polymers, dicarboxylic acid esters, alkylated benzenes, Test . . . coCell- Camshaft. Ring detergent tration, Average thrust Total plugg silicate esters, silicon polymers, and the like, are suitable. (Example percent by piston piston war- Total ling, No.), weight warnish warnish nish sludge percent : The new compounds and reaction products can be used 70 in such lubricating oils in amounts of from about 0.05% 7. 7.0 31.4 32.4 30 to about 25% by weight. Additive concentrates of 60 8.5, 9.0 39.7, 45.9 7.5 7.6 33, 7, 35.8 22 95% are also contemplated. It has been found, however, 6.4 7.0 29.3 - 3.. 6 28 that in finished formulations, for most applications, 7.5 7.5 32.1 35.0 34 6.7 7.4 33.1 37.8 3 amounts of from about 0.25% to about 10% by weight 75 are sufficient. In addition, the new products of this in 3,658,836 49 50 vention can be used in fuel oils and in various light prod 4. The 1-11-(polybutenylsuccinimido)-3,6,9-triazaun lucts, such as gasoline, wherein they also function as decyl-2-propylimidazolidine monoammonium salt of detergents or dispersants. spiro (3,5-dihydroxyboroxin) - 1,1 - (3',5'-dihydroxy While this invention has been described with reference boroxin) where the polybutenyl group has an average to various specific examples and embodiments, it is un molecular weight of about 1350. derstood that the invention is not limited thereto and that 5. A monoammonium salt of spiro (3,5-dihydroxy it can be variously practiced within the scope of the fol boroxin)-1,1'-(3',5'-dihydroxyboroxin) represented by lowing claims. the structure The embodiments of the invention in which an ex clusive property or privilege is claimed are defined as 0 1.O n follows: O - B B - OH 1. A monoammonium salt of spiro (3,5-dihydroxy b. b G boroxin)-1,1'-(3',5'-dihydroxyboroxin) represented by n1B36) H-Qa the structure g Si 5 Ho - B-B - Ott Ho - B1B-0 - OH where Q is a bis-imidazolidine represented by the struc b. b e ture N1BG He 20 R. r; Q O Ho - B-B - Oil R. R CH-C-R. R-CH-C N-CH2 - C - (NH-CH2-C) - NNH CHa-C^ CR4 where Q is an imidazolidine represented by the structure 25 R R. M O 2

R. where R is a polyalkenyl having a molecular weight of O from about 700 to about 2500; R1 is selected from the Rl R. CHa-C-R. R-CH-C- group consisting of hydrogen and alkyl of 1 to 3 carbon N-CH2-C-(NH-CH2-C)-N NH 30 atoms; R is selected from the group consisting of hydro CHe-C/ -Ca gen and alkyl of 1 to 20 carbon atoms; T is selected from R. R. R2 Ra the group consisting of alkylene of 1 to 20 and alkenylene of 2 to 20 carbon atoms; and x is a whole number from 0 to 3. where R is a polyalkenyl having a molecular weight of 6. A compound of claim 5 where R is polybutenyl from about 700 to about 2500; R is selected from the having an average molecular Weight of from about 900 group consisting of hydrogen and alkyl of 1 to 3 carbon to about 1500; R1 and R4 are hydrogen; x is 3 and T is atoms; R2 and R3 are each selected from the group con trimethylene. sisting of hydrogen, alkyl, alkenyl and haloalkyl of 1 References Cited to 20 carbon atoms; and x is a whole number from 0 to 3. 40 2. A compound of claim 1 where R is polybutenyl UNITED STATES PATENTS having an average molecular weight of from about 900 3,087,936 4/1963 Le Suer ------260-326.3 to about 1500, x is 2, R1 and R2 are hydrogen and R. is propyl. HENRY R. JILES, Primary Examiner 3. The 1-8-(polybutenylsuccinimido) - 3,6 - diazo 45 octyl)-2-propylimidazolidine monoammonium salt of U.S. C. X.R. spiro (3,5-dihydroxyboroxin) - 1,1 - (3',5'-dihydroxy 252-49.6; 260-240; 44-63, 71; 260-293.51, 293.72; boroxin) where the polybutenyl group has an average 424-148, 185; 117-137; 260-243, 268, 247, 290, 309, molecular weight of about 1350. 309.6, 306.7, 326.61, 567.6