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United States Patent (19) | 1 || 3,904,654 S Consis (45) Sept United States Patent (19) | 1 || 3,904,654 s consis (45) Sept. 9, 1975 54 UREA-PHOSPHORUS COMPOUNDS -ROH 75 Inventor: Gail H. Birum, Kirkwood, Mo. CHNHCNHCH + (RO),PR' + R''CHO 73) Assignee: Monsanto Company, St. Louis, Mo. O 22 Filed: Aug. 6, 1973 R'-P--CHR' HO O! R' Y > Ho-CHNENHCH 21 Appl. No.: 385,933 CHN NCH R’ CH 52 U.S. Cl........ 260/347.2; 260/347.8; 260/465 E; 260/502.5; 260/551 P; 260/936; 71/86; 71/87 t (51) int. Cl....................... C07d 105/02; CO7d 5/14 58) Field of Search ..... 260/502.5, 551, 936, 347.2, where -- 260/347.8 R is aryl or chloroalkyl of 2 to 10 carbon atoms, R" is aryl, aryloxy or chloroalkyloxy of 2 to 10 56 References Cited carbon atoms, UNITED STATES PATENTS R' is hydrogen, alkyl, alkenyl, furanyl or aryl of 1 3,673,248 6/1972 Peterson............................. 260/553 to 15 carbon atoms and substituted aryl forms where the substituent is fluorine, chlorine, Primary Examiner-Harry I. Moatz bromine, cyano, hydroxyl, alkyloxy, alkylthio or mixtures of such substituents, and 57) ABSTRACT Y is O or S. The present invention relates to new compounds con The organophosphorus compounds have biological taining urea and organophosphorus moieties in cyclic activity and are also useful as fire retardants. structures, to a new process for production of such compounds, and to new organophosphorus acids pro duced by hydrolysis of the cyclic structures. 3 Claims, No Drawings 3,904,654 1 2 UREA-PHOSPHORUS COMPOUNDS O The present invention relates to new compounds church, -- OHC ( ) -OH (CHO)P containing urea and organophosphorus moieties in cyc N OCH lic structures. A new process for production of such 5 compounds is also a part of the present invention. OCH, Also included as part of the invention are new or t ganophosphorus acids that are obtained by ring opening hydrolysis reactions of the cyclic structures of of ( ) -OH this invention. CHN NCH The general method for the production of the novel 1() + 2CHOH cyclic structures is in accordance with the following equation: O 15 The present invention also includes the free acids of Y the corresponding cyclic esters discussed above. These CHNHCNHCH + (RO)PR' + R'CHO - acids are produced by ring-opening hydrolysis reac O tions. Thus, when a cyclic ester having the phosphinate structure is hydrolyzed, an open-chain phosphinic acid is produced according to the following equation: R--CHN NCH Hr + 2ROH C O I O R' Y Y 25 . RP-...-CHR' II -- -- HO - HOP-CHNCNHCH CHN NCH where R" CH R is aryl or chloroalkyl of 2 to 10 carbon atoms, R" is aryl, aryloxy or chloroalkyloxy of 2 to 10 carbon tons, 3() R' is hydrogen, alkyl, alkenyl, furanyl or aryl of 1 to where 15 carbon atoms and substituted aryl forms where R" is aryl of 6 to 10 carbon atoms, the substituent is fluorine, chlorine, bromine, cy R" is alkyl, alkenyl, furanyl or aryl of 1 to 15 carbon ano, hydroxyl, alkoxy, alkylthio or mixtures of such atoms and substituted aryl forms where the substit substituents, and 3 5 uent is fluorine, chlorine, bromine, cyano, hy Y is O or S. droxyl, alkyloxy, alkylthio or mixtures of such sub A specific compound is 3-( 2,4-dichlorophenyl )-1,4- stituents, and dimethyl-2-phenyl-1,4,2-diazaphospholidin-5-one-2- Y is O or S. ". oxide which is prepared from 1,3-dimethylurea, di The use of basic materials in the hydrolysis mixture, phenyl phenylphosphonite, and 2,4- for example dilute acqueous sodium hydroxide, may aid dichlorobenzaldehyde according to the following equa in the hydrolysis reaction. In such cases the initial hy tion: - drolysis products are salts, and these can be converted to the free phosphinic acids by acidification of the hy drolysis reaction mixture. 45 When cyclic esters of this invention having phospho O nate structures are hydrolyzed, the products are the CHNHCNHCH + (CHO). PCH + 2.4-ClCHCHO -) corresponding open-chain phosphonic acids: C) CHP--CHCHCl-24 O O R'' Y ch NCH, + 2CHOH ROP--CHR'' V / + HO -) (HOP-CHNCNHCH -- ROH C CHN NCH CH () y/ Whereas the cyclic product of the above cquation where contains the organophosphorus moiety in a phosphi R is aryl or chloroalkyl of 2 to 10 carbon atoms nate structure, that is, the phosphorus is bonded to two R'' is alkyl, alkenyl, furanyl or aryl of 1 to 15 carbon carbon atoms, when the trivalent phosphorus ester re atoms and substituted aryl forms where the sub actant is a phosphite ester, the cyclic product has the stitutent is fluorine, chlorine, bromine, cyano, hy phosphorus in a phosphonate structure, that is, bonded droxyl, alkyloxy, alkylthio or mixtures of such sub to only one carbon atom. This is exemplified by the for stituents, and , mation of i,4-dimethyl-3-(4-hydroxy-3- Y is O or S. : - ' methoxyphenyl)-2-phenoxy-1,4,2-diazophospholidin 65 A specific example of the phosphinic acids of this in 5-one-2-oxide from the reaction of 1,3-dimethylurea vention is . Cy-(1,3-dimethylureido)-2,4- and vanillin with triphenyl phosphite. - - - - - dichlorobenzyll phenylphosphinic acid, 3,904,654 4. of I and II and appreciable differences in their nmr spectra. For I: “P nmr -28.9 ppm (in CDCl), -38.6 O CH Il ppm (in CFCO,H); H nmr (CDCla) 87.3 (m, 8, aryl), ChP-CHNCONHCH 5.2 (d. 1, J = 22Hz, PCH), 3.1 (s, 3, CHNCH), 2.9 (d, 3, J = 8Hz, PNCH); ms 370(6) (molecular ion), HO CHCl-2.4 368(10). (molecular ion), 335 (10), 333 (25), 311 (6), A specific example of a phosphonic acid is o-(1,3- 278(23), 276(100), 186(38), 124(43), 77 (29). For II: dimethylureido)-4-hydroxy-3-methoxybenzylphos 'P nmr -25.0 ppm (in CDCla), -32.9 ppm (in phonic acid, CFCOH); H nmr (CDCl3) 87.6 (m, 8, aryl), 5.2 (d, () 1, J = 9Hz, PCH), 2.9 (s, 3, CHNCH), 2.85 (d, 3, J = 8Hz, PNCH) (decoupling from P converted the dou O CH blets at 5.2 and 2.85 ppm to singlets); ms 370(1), I 368(1), 335 (12), 333(66), 311 (2), 278(13), (HO)PCHNCONHCH 276(100), 186(29), 124(32), 77(13). Kyot 5 Anal.(II) Calcd for CHNCOP: C, 52.05; H, NOCH, 4.10; C1, 19.21; N, 7.59; P, 8.39. Found: C, 52.33; H, 4.14; Cl, 18.82; N, 7.50; P, 8.31. Formation of the cyclic products of this invention is EXAMPLE 2 usually initiated when a mixture of the three reactants, preferably in an inert solvent such as toluene or chloro 1,4-Dimethyl-2-(4-methylphenoxy)-3-phenyl-1,4,2- benzene, is warmed to about 70°C. The reaction is usu diazaphospholidin-5-one-2-oxide. ally complete after an hour at 80°-120°C., but warming at higher or lower temperatures is sometimes advanta O geous. Gradual addition of the aldehyde reactant to a stirred mixture of the phosphorous ester and 1,3- 4-CHCHOP--CHCH dimethylurea reactants in a solvent at reaction temper NCH ature, usually from about 70 to 120°C., may facilitate control of heat of reaction. The cyclic products may be isolated from the reac tion mixtures and purified by standard techniques be 30 fore being subjected to hydrolysis to the corresponding Benzaldehyde, 0.5 mole, is added dropwise to a solu acids. However, it is frequently more convenient, par tion of 0.5 mole of 1,3-dimethylurea and 0.5 mole of ticularly with the cyclic phosphonates, to treat the tris(p-tolyl) phosphite in 100g of benzene as the solu crude, unisolated product in the reaction mixture with tion was warmed from 60-90. Warming is continued the required amount of water and then stir and warm 35 at 90 for 3 hr, giving a reaction mixture having P nmr the mixture until the desired hydrolysis is complete. peaks at -24.2 and -21.9 ppm (~6:1 areas). The sol The low solubility of the free acids in the reaction mix vent and most of the by-product p-cresol are removed tures usually makes the acids easier to isolate than the by stripping to 120/0.5mm, and the remaining yellow, parent cyclic structures. viscous oil is dissolved in acetone. A solid that sepa Specific examples showing the preparation and isola 40 rates is recrystallized from acetone to give a white tion of representative compounds of the present inven solid: mp 126.5-128; “P nmr -24.2 ppm; "H nmr tion are set forth herewith, but are not limitative of the 86.9–7.5 (m, 9, aryl), 4.6 (d. 1, J = 19Hz, PCH), 2.9 scope of the invention. (d. 3, J = 8Hz, PNCH), 2.7 (s, 3, NCH), 2.3 (s, 3, CH); ms 330(50) (molecular ion). 273(1), 244(4), EXAMPLE 1 45 239(6), 223(27), 182(4), 166(100), 118(49), 107(5), 3-( 2,4-Dichlorophenyl )-1,4-dimethyl-2-phenyl-1,4,2- 91 (17), 77(14), 60(42). diazaphospholidin-5-one-2-oxide Anal. Calcd for CHNOP: C, 61. 18; H, 5.80; N, 8.48; P, 9.38. Found: C, 61.81; H, 5.67; N, 8.33; P, 933. O 50 EXAMPLE 3 CHP--CHCHCl-2.4 1,4-Dimethyl-2,3-diphenyl-1,4,2-diazaphospholidin CHN NCH V / 5-one-2-oxide C 55 O O A solution of O.3 mole each of diphenyl phenylphos CHP--CHCH phonite, 2,4-dichlorobenzaldehyde, and 1,3- CHNV NCH dimethylurea in 150g of toluene is stirred under Ng and 60 c/ warmed at 100°-1 10° for 2 hr.
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