United States Patent 19 11) 4,081,445 Hermans 45) Mar. 28, 1978 54 CERTAIN BISPIPERAZIDO PHOSPHORUS 58) Field of Search ................... 260/268 K, 959, 958, COMPOUNDS 260/268 MK 75) Inventor: Johny C. Hermans, Wespelaar, (56) References Cited Belgium U.S. PATENT DOCUMENTS 73. Assignee: s.a. Texaco Belgium in.v., Brussels, 3,298,937 1/1967 Strauss et al. ........................ 260/959 Belgium 3,531,550 9/1970 Herber et al. ........................ 260/959 Primary Examiner-R. Gallagher 21 Appl. No.: 628,288 Attorney, Agent, or Firm-Thomas H. Whaley; Carl G. 22 Filed: Nov. 3, 1975 Ries; Carl G. Seutter (30) Foreign Application Priority Data 57 ABSTRACT Compounds useful as lube oil additives are prepared by May 21, 1975 United Kingdom ............... 21796/75 reaction of phosphorus halides and piperazine deriva 51 int. C.?................... C07D 295/16; CO7D 295/22 tives. 52 U.S. Cl. ............................... 260/268 K; 252/46.7; 252/49.9; 252/389 A; 544/121 5 Claims, No Drawings 4,081,445 1. 2 X represents an oxygen or sulphur atom or is absent, CERTAN BESPPERAZIDO PHOSPHORUS Y represents an (i) aliphatic, cycloalliphatic, or COMPOUNDS aromatic hydrocarbon group or a heterocyclic group; (ii) a group of the formula -NR in which FIELD OF THE INVENTION each group R represents a hydrogen atom, an ali This invention concerns bis-piperazido phosphorus phatic, cycloaliphatic, or aromatic hydrocarbon and trispiperazido phosphorus compounds, and meth group or a heterocyclic group, or the two groups ods for the preparation of these compounds. R, together with the nitrogen atom to which they Various of the compounds obtained according to the are attached, represent a N-containing heterocyclic invention are of interest as components of petroleum 10 ring; (iii) a group of the formula -OR in which R compositions, as additives for plastics materials, as com has the meaning given above; or (iv) a group of the ponents of flameresistant or flame-retardant polymers, formula: as pharmaceuticals or as intermediates in the production of pharmaceuticals. 15 III BACKGROUND OF THE INVENTION a-N N-R It is known that halides of phosphorus are able to react with primary and secondary amines, thereby pro (R), ducing amides of the various acids or phosphorus. For instance, as long ago as 1898, Michaelis and Kaehner in 20 R represents a substituent on the piperazine ring; Ber, 31 (1898), pp 1040-1047 described the reaction of R’ represents a hydrogen atom or a substituted or piperidine and tetrahydroquinoline with phenyl phos unsubstituted aliphatic, cycloaliphatic or heterocy phorus dichloride to form the corresponding bispiperi clic radical or heterocyclic group, an acyl group, a dide and bis-tetrahydroquinolide. These compounds sulphonyl group a substituted phosphonyl group or could be converted into the corresponding amides of 25 phosphonic and phosphonothionic acid. a substituted carbamoyl group; and Subsequent work has described the reaction of phos in represents 0 or an integer, and salt of such com phorus halides or oxyhalides with a variety of amines, pounds in which at least one of the groups Rrepre and hydrazine. Attention is to be directed in this con sents a hydrogen atom; nection, for instance, to U.S. Pat. No. 2906770; 3107231; 30 but with the proviso that Y does not represent di 3260702 and 3649594. Little attention, however, has methylamino when X represents oxygen and R' been paid to the use of piperazine or substituted pipera and Rboth represent hydrogen. zines as amine reactants. DESCRIPTION OF THE INVENTION A paper by Bello etal in Macromolecules, 3 (1970) pp 35 In the present invention the symbol X can represent 98-100 describes the reaction of dimethylphosphora an oxygen or sulphur atom, or it can be absent. The midic dichloride (CH3)-N-POCl, with an excess of compounds according to the invention are therefore piperazine to give phosphoric dimethylamidobispipera amides of phosphoric acid (when X represents oxygen), zide. thiophosphoric acid (when X represents sulphur), and phosphorous acid (when X is absent). Y N The symbol Y can represent a group of the formula: (CH)-N-PON NH N-1 2. I This compound was subsequently reacted with oxalyl 45 dichloride or piperazine - 1,4-dicarbonyl chloride to -la.N. N-R give polymers. Polymers with alternating piperazine and (CH),N-PO: groups were obtained by using an (R') excess of the phosphorus halide. The object of the present invention is the preparation 50 in which case, the compounds of the invention are tris of novel phosphorus compounds containing piperazine piperazides. When Y has one of its other meanings, the rings. Other objects of the invention are to produce compounds are bispiperazides. novel phosphorus compounds useful as components of Y can for example represent a substituted or unsubsti petroleum compositions. Further objects will be appar-5s tuted hydrocarbon group, which can be of aliphatic, ent to those skilled in the art. cycloaliphatic or aromatic nature. Examples of suitable aliphatic groups are alkyl, such as methyl, ethyl, propyl, STATEMENT OF THE INVENTION butyl, octyl, dodecyl, or octadecyl; alkenyl, such as The present invention provides compounds of the allyl; or alkynyl, such as propargyl. formula: 60 Examples of suitable cycloaliphatic groups are cyclo alkyl, such as cyclohexyl, tetrahydronaphthyl or (R'), decahydronaphthyl; and cycloalkenyl, such as cyclo X hexenyl. / N 2 Examples of suitable aromatic hydrocarbon groups YeP N NaR 2 65 are aryl groups, such as phenyl, naphthyl, biphenyl, or N-1 phenanthryl; aralkyl, such as benzyl, or phenylethyl; and alkaryl, such as tolyl, dimethylphenyl, trimethyl and salts of such compounds, wherein phenyl, cumyl, or p-octylphenyl. 4,081,445 3 4. Y can alternatively represent a heterocyclic group, Rcan also represent a substituted phoshorus-contain linked to the phosphorus atom through a carbon atom, ing group, e.g. a group of the formula as in the tetrahydrofurfuryl or 2-pyridyl radicals. Y can also represent a group of the formula-NR2, in -PX R. which each R represents a hydrogen atom, or an ali- 5 phatic, cycloaliphatic, or aromatic hydrocarbon group in which X has the meaning given above, and or a heterocyclic group. Examples of these hydrocar R represents an aliphatic, cycloaliphatic or aromatic bon groups or heterocyclic groups are given above. group, or a group of the formula -OR, -SR or Specific examples of suitable amino radicals are dimeth NR, in which R has the meaning given above. An ylamino, diethylamino, dipropylamino, dibutyl amino, 10 example of such a group is dimethylaminophospho monomethyl amino, monoethylamino, monododecyl nyl. R can also represent a substituted carbamoyl amino, mono-(Co) alkylamino, monooctadecylamino, group -CO-NHR wherein R has the meaning given anilino, p-dodecylanilino, and N-butylanilino. above. An example of such a group is phenylcar Alternatively, both symbols R, and the nitrogen atom bamoyl. 5 The invention also provides lubricating compositions to which they are attached, can together represent a -- comprising a major amount of a lubricating oil, and a heterocyclic radical linked to the phosophorus atom minor amount (e.g. 0.1 to 10% by weight, preferably 0.5 through the nitrogen atom. Examples of such groups to 2.5% by weight) of a piperazidophosphorus com are morpholino, piperidino, tetrahydroquinolino, pyr pound as defined above. The invention further provides rolidino etc. The compounds in which Y represents a a concentrate suitable for incorporating in a lubricating further piperazino group are, of course, a special in oil comprising a piperazidophosphorus compound as stance of this. defined above and an inert diluent. The proportions of Y can also represent a group of the formula -OR in the diluent are not critical and the weight ratio of which R has the meaning given above. Examples of piperazidophosphorus compound to diluent may, for such groups are alkoxy, such as methoxy, ethoxy, 5 instance, range from 9:1 to 1:9 depending on miscibility. propoxy, butoxy, dodecyloxy and octadecyloxy; and Preferred lubricating compositions and concentrates aryloxy such as phenoxy, tolyloxy, or benzyloxy. comprise p-(p'-dodecylanilino) phenyl bispiperazido Any of the above radicals can if desired, be substi thiophosphate, and p-(p'-ethylanilino) phenyl bis-(N'-(3- tuted. The only limitation upon the nature of the substit carbethoxyethylpiperazido) thiophosphate. uents is that they should be inert under the conditions of 30 This invention also provides methods for the synthe the reaction employed in synthesizing the compound. sis of the compounds described above. According to a In the group of the formula: preferred method, a compound of the formula: I -N N-R 35 x= (Hal), N/ y (Y), wherein y is an interger 0-1 (When y is 0, the com pound has the formula iv.; when y is 1, the compound R represents a substituent on the piperazine ring. Here 40 has the formula v. again, the only limitation upon the nature of the substit uent is that it should be inert under the conditions of the XP(Hal) or IV reaction used to synthesize the compound. The substitu X tent can, for example, be one of the groups set out above for Y, provided that such a group is inert. When pres- 45 y--(Hal), ent, it can for example be an alkyl group, such as a methyl group. Alternatively, the substituent can have a in which X and Y have the meanings given above and meaning not set out above, insofar as it might not be an Hal represents chlorine and bromine) is reacted with an appropriate group for attachment to phosphorus; for excess of a piperazine derivative of the formula: example, an oxo group. Specific examples of substituted 50 piperazine groups are 2,5-dimethylpiperazino and 2,5- (R), dioxopiperazino groups, n is 0 or an integer, and is pref erably 0, 1 or 2: -- R2 can represent a hydrogn atom or a substituted or HeN N-R unsubstituted aliphatic, cycloaliphatic or aromatic 55 hydrocarbon group or a heterocyclic group.