US2818406A - Phosphonic diamides - Google Patents

Description

"saturated or' unsaturated.

United States Pate'fit'f) PHOSPHONIC I DIAMIDES James N. Short, Berger, Tex., assignor to Phillips Petroleum Company, a corporation of Delaware No'nmwin Application April 26, 1954 Serial No. 425,770

21" claims; cl."26o sti This invention relates to phosphonic diamides. In one aspect this invention relates to alkapolyenephosphonic diamides as new compounds. In another aspect this 1nvention relates 'to' alkenynephosphonic diamides. In another aspect this invention relates to alkapolyynephosphonic diamides. In another aspect this invention relates "to reacting a haloalkeneph'osphonicdihalide containing at ..least one ethyleniclinkage with an amine containing at ,least one hydrogen atom attached to-the 'nitrogen atom.

l-n still another aspectthis invention relates to polymers of the said phosphonic diamides. Instillanother aspect this invention relates to new chemical compounds-represented by the structural-formulas-given and defined below.

Further according to'the invention there are provided as new compounds phosphonic diamides represented by I the structural formula .wherein A is a membcr selected -from- 'a group consisting of unsubstituted and halogen-substituted alkapolyene,

alkenyne and alkapolyyne hydrocarbon radicals, and a five to six membered ring' containirigat least one of said unsubstituted or halogen-substituted hydrocarbon radicals; R' is amembercontaining from-zero to-ten-carbon atoms selected from the group consisting of hydrogen, hydro- "eatersend heterocycli'c radicals, said hydrocarbon radi-' cals being selected from the group consisting of aromatic,

i satu' ratejd and unsaturated acyclic, and" saturated and unsa urated alic'yfclic' radicals, and cornbinationsbflthe radicals 'a's' defined by R; andwheregin addition, two

R radicals together with the nitrogen aftach'ednhere'to can form a heterocyclic ring containing from five to seven atoms, at least three of which are carbon, the remainder being selected from the group consisting of carbon, nitrogen, si'ilfu'r'a'n'd oxygen. The heterocyclicrad ical can be Throii'lioiit the specification and in the clai'msz t'lie fter'fi'i alke'ne means a hydrocarbon radical containing at least one e'tliylenic linkage; the term alkapolyene means a "hydroc'a'rbo'n' radical containing at least two ethylenic 6 Nov"):

2,818,406 latented Dec. 31, 1957 "ice "R--GEO'CEC-P N RI/I VI )2 where R """is' as 'defined" above. R, R and R" are selected from the group consisting of hydrogen; halogen; and unsubstituted and: halogen-substituted hydrocarbon radicals,

"said radicals being selected from the group consisting of "aromatic, saturated a'ndunsaturated acyclic, and saturated and unsaturated' alicyclic radicals, and combinations of these radicals, and wherein R, R and R can'be the same "or' 'different." In addition, in the case of Formula'sl, III, lV' andV'and R and R together with the-four-carbon The sum of all-the 'It is to{ be noted thatthe phosphoniddiam'ides of 'the invention are characterized" by either an alkapol'yiene grouping, an -alkenyne grouping, an alkapolyyne group- Included in the group of compounds repre'sented by' the above formulas are: N,N,N',N-tetraallyl-1,3 butadienel pllosph'oni'c diamide, N,N,N',N-tetraallyl-l,3'butadiene- -2 =phosphonic diamide, N,N,N',N-tetracyclohexenyl-2,3- dimthyl-LB-butadiene l phosphonic diamide, 'N,N',N",N'- tetra -'p*--'2v-"butenylphenyl -4 phenyl 1,3 butadie'n'el-phosphonic diamide, N,N,N,N-tetracinnamyl-1,3-cyclohexadiene-l-phosphonic diamide, N,N,N,N'-tetraa1lyl- 3-buten-1-yne-1-phosphonic diamide, N,N,N',N'-tetraallyl-l-butene-3-yne-l-phosphonic diamide, N,N'-dially1- -1,3-cyclopentadiene-l--phosphonic diamide, N,N'--dii- 2- quinolyl lj-hexadiene-l--phosphonic diamide, 1,3-hexadiene-Z-phosphonic dipiperazide, 1,3,7-tetradecatriene-lphosphonic 'dirnorpholide, N-,N,N',Nrtetraphenylt-(p- 'tert-butylphenyl)- 1',3 butadie'ne-l phosphonic diamide, N,N,N,N'-tetramethyl 1 ,3-butadiene-lrphosphonic 'diamide, N,N,N,N tetramethyl-1,3-butadiene-2-phosphonic diamide, 1,3-butadiene-l-phosphonic'diamide, 1,3-hexa'dione-lephosphonic diamide, N,N-,N,N'-tetramethyl-3-bu- 2-chloro-1 3-butadiene-1'-phosphonic diamide,. N,N uallylbenzyl-3-he en l-yne-2-phosphonic diamide, N,N bis(4*-phenylbuty1)-3,5 hexadien -l-yne -'l -phosphonic diamide, N,N,N ,N'-tetracyclohexyl-1,3-pentadiyne1 l phosphonic diamide, N,N'-bis( 2-napht-hyl)-2bromo 1:,3-butadiene l-phosphonic diamide andN,N,N,N"-tetra-(.decyl')- 7-octen-l,3-diyne-l-phosphonic diamide.

Further, according to the invention, there arepro'vided newcompositionsof; mattercompr-ising polymers ofi the pholine.

novel phosphonic diamides represented by the above structural formulas.

Still further according to the invention, there is provided a method of preparing the phosphonic diamides represented by the above structural formulas.

A preferred method of preparing these new unsaturated hydrocarbon phosphonic diamides is by reacting under anhydrous conditions a haloalkene-phosphonic dihalide containing at least one olefinic double bond with an amine containing at least one hydrogen attached to the nitrogen atom or with ammonia in an amount in excess of the stoichiometric quantity needed. When employing strongly basic amines the reaction is believed to proceed according to the following equation:

N(R')2 where R, R, R", and R are groups as defined above, and X is either C1 or Br.

It is desirable to use at least 4 mols of amine to one mol of haloalkenephosphonic dihalide to bring about complete amidation, plus an additional mol of amine for each chlorine which is attached to carbon and which is to be removed by dehydrohalogenation. When a relatively weak amine is employed the dehydrohalogenation may not occur simultaneously with the amide formation. In such instances, if it is desired to dehydrohalogenate it will be necessary to treat the amide with a relatively strong base in a subsequent step.

One method of operation is to add the haloalkenephosphonic dihalide, with constant stirring. to an excess of the amine, either undiluted or diluted with a suitable solvent. The reaction is usually eifected at a temperature in the range between and 70 C., preferably between 40 and 50 C. After the reaction is substantially complete, the excess amine is removed by suitable means, as, for example by gentle warming. Ether is then added to facilitate separation of the amine hydrohalide, which is then removed from the reaction mixture by filtration. After the ether has been removed by evaporation at room temperature, the unsaturated hydrocarbon phosphonic diamide is separated from the residual mixture by conventional means, such as, for example, by fractional distillation under reduced pressure. In some instances, a portion of the product polymerizes during purification and a polymer remains in the reactor. Amines which are applicable are primary and secondary amines of the formula where R' is the same as heretofore defined. Although in general primary and secondary amines are applicable I prefer to use the primary or secondary aromatic amines, such as aniline, N-methylaniline, 2-aminoquinoline, 2- naphthylamine, diphenylamine, o-tolylamine; and secondary aliphatic, carbocyclic, or heterocyclic amines, such as diallylamine, dicyclohexenylamine, di-Z-butenylamine, dimethylamine, dicyclohexylamine, piperidine, and mor- Additional examples of amines are allylamine, alpha-allylbenzylamine, bis-( p 2 butenylphenyl) amine, dicinnamylamine, and 4-phenylbutylamine. In some instances ammonia can be used to produce the amide.

In my copending application, Serial No. 425,769, filed April 26, 1954, there are set forth, described and claimed certain haloalkenephosphonic dihalides and a method of preparation therefor. The haloalkenephosphonic dihalides of said application, which have a hydrogen atom attached to the same carbon atom to which the phosphorus atom is attached, are among those suitable as starting materials for the preparation of phosphonic diamides of this invention. As stated therein, the said dihalides are preferably prepared by reacting the corresponding haloalkenephosphorus tetrahalide with a carboxylic acid. Thus, 2-chloro- 3-butenephosphorus tetrachloride, which is the preferred starting material, is reacted with acetic acid in accordance with the following equation:

As stated in the above referred to application when 1,3- butadiene is reacted with phosphorus pentachloride to form a chlorobutenephosphorus tetrachloride three possible isomers can be obtained, i. e.,

+ CHaCOCl H01 At present it is believed that isomer No. 1, above, predominates. When a mixture of the said isomers is reacted with a carboxylic acid according to the above given equation a mixture of the corresponding chlorobutenephosphonic dichlorides is obtained. Thus, when a mixture of the said chlorobutenephosphonic dichlorides is used as a starting material in the reaction with an unsaturated amine such as diallylamine the corresponding alkadienephosphonic diamides are obtained, i. e.,

urated amine such as diallylamine the corresponding chloroalkadienephosphonic diamide is obtained, i. e.

N,N,N',N tetraallyl 2 chloro 1,3 butadiene 1- phosphonic diamide.

Where preferable, dehydrohalogenation involving a halogen atom attached to a carbon atom can be accomplished by a separate step additional to the amidation step, such as, for example, by treatment of a haloalkenephosphonic diamide with alcoholic potassium hydroxide, powdered potassium hydroxide, powdered sodium hydroxide, 2,6-dimethylpyridine or dimethylamine.

The products of this invention are valuable as plasticizers for a wide range of polymeric materials, including .aisn

. synthetic resins and syntheticrubber. They are also useful as textile-treating agents, and as monomers in the formation of polymers and copolymers. The polymers range from viscous liquids to brittle resins and rubbery solids.

Example I The isomeric N,N,N ,N' tetraallyl 1,3 butadienephosphonic diamides were prepared by the following method:

To a solution of 107 g. (1.1 mol) of anhydrous diallylamine in 100 ml. of anhydrous ether, cooled to about -46 C., was added dropwise, with constant stirring, 41.5

v g. (0.2 mol) of the chlorobutenephosphonic dichloride,

the preparation of which is described below (Example 11). When all of the phosphonic dichloride had been added, the flask was warmed gently to room temperature, and the reaction was allowed to proceed with intermittent cooling to keep the temperature below 40 C., until, after about one hour, cessation of heat evolution indicated that the reaction had proceeded substantially to completion.

The precipitate of amine hydrochloride was removed by filtration, washed with ether, and dried. The ether was removed from the filtrate by distillation, and 100 ml. of npentane was added to precipitate the remaining amine hydrochloride, which was removed by filtration. The

Example II The isomeric chlorobutenephosphonic dichlorides were prepared by the following procedure:

To a suspension of 454 g. of phosphorus pentachloride in 1200 cc. of dried benzene was added, with constant stirring, 250 g. of butadiene. After standing at 15-20 C. overnight, 100 cc. (about 60 g.) of butadiene were added to replaceany butadiene that might have evaporated, and the suspension was stirred for 8 hours. The next day, an additional 100 cc. of butadiene was added, and the suspension was stirred for two hours. After cooling the flask in an ice bath, 2.2 mols of glacial acetic acid was added, while stripping off HCl, acetyl chloride, and some of the benzene in vacuo. The remainder of the solvent was then removed in vacuo from the resulting solution, and the residue distilled to yield 130 g. (33 percent) of chlorobutenephosphonic dichloride which boiled at 106 C. at 1.0 mm. Hg. It had the following characteristics: refractive index of 1.5185 at 25 under white light; density of 1.436 at room temperature, and molecular refractivity, calculated, 42.05; found, 43.85.

A sample prepared by the procedure similar to the one described above had a chlorine content of 50.4 percent, as compared with a calculated value of 51.2 percent.

Example III A 500 ml. flask equipped with dropping funnel, stirring unit, and reflux condenser was placed in a Dry Ice-acetone I reduced pressure.

amine hydrochloride was dried for 3 hours at.105 C..and

---then weighed. 72.9 grwere obtain'ed, a 91 percent theoret-ical yield. "The'filtrate was strippedito 50. C., under 62.2 g. r of a red, very viscous, jellylike oil remained. 1 When it was attempted to distill 61.1 g. of this crude product at reducedpressure, 14.89, g. of diallylamine and 2.5 g. of a liquid boiling at 25, C., at

0.45 mm: Hg-were obtained asoverhead while polymerization occurred in the flask to yield-43.3 g. of a dark plastic solid.

' Example IV Acsecond run was made forithe purpose of "preparing .additional isomeric;chlorobutenephosphonic dichlorides. 453 g. (2.17mol) .of-PCl 'was dissolvedin 1500 cc. of

vigorously refluxingwbenzene containediin a- 3-liter,' 3-

-necked flaskwhich was equipped with a reflux condenser and dropping funnel. The flask was packed in ice, and cooled to below 40 C. 136. g. (2.52 mol) of butadiene dissolved in'300 cc. of benzene was then added over a 25 minute period. The material, packed Jinice, "was then stirred for 7 hours and allowed tostand overnight. To the pasty reaction mass was added dropwise, with constant stirring, 131 g. (2.18 mol) of acetic acid. The thick mixture turned clear, pale yellow. It was stripped with stirring to 25 C. at 20 mm. 'A dark tan oil, weighing 289.7 g.

(64.4 percent theoreticalyresulted. 'From 286.9 g. of this crudematerialwas obtained 184.5 g. (41.5 percent'theo- .retical) of a fraction' boiling at 97-112 C. at 0.4 to 2.0

mm. Hg. It had arefractive index of 11 1.5186.

Example V The isomeric N,N,N,N'-tetrarnethyl-1,3-butadienephosphonic diamides were prepared by the following method:

.warm to roomtemperature, and the excess dimethylamine was driven ofi by gentle heating. After adding 50 ccwof ether, the amine hydrochloride was removed by filtration, and washed with 100 cc. of ether. 46 g. of dimethylamine hydrochloride was obtained. The ether was removed from the filtrate, and the residue was distilled in vacuo to yield 21.5 g. of isomeric N,N,N',N-tetramethyl-1,3-butadienephosphonic diamides, boiling at 102-120 C. at 1.25- 2.5 mm. The residue remaining in the distillation flask was a clear, amber resin.

A sample prepared by a method similar to the one described above gave the following analysis:

Calculated for CaHmPONzZ C, 51.1; H, 9.11; P, 16.5.

Found: C, 50.1; H, 9.6; P, 15.9.

Example VI A second run was made for the purpose of preparing additional isomeric N,N,N,N-tetramethyl-1,3-butadienephosphonic diamides. 100 g. (2.22 mol) of anhydrous dimethylamine was placed in a 500 cc. B-necked flask, equipped with stirring unit, dropping funnel, and thermometer. It was cooled to -70 C. by means of a Dry Iceacetone bath, and then into it was dropped slowly 42.5 g. (0.205 mol) of chlorobutenephosphonic dichloride which was prepared according to the procedure described above in Example IV. During this addition the temperature was maintained at 70 to 40 C. The amine hydrochloride separated readily. 50 cc. of ether was added. After two hours, the mixture was warmed gently. The precipitate of dimethylamine hydrochloride was filtered and washed well. 44.6 g. (88.8 percent theoretical) was obtained. The filtrate, which was a clear yellow oil, was stripped of ether, and then distilled under reduced pressure. 20.7 g. (53.7 percent theoretical) of a fraction boiling at 116ll8 C. at 0.9 to 1.2 mm. Hg was obtained. lts refractive index was n l.5023.

In the above examples anhydrous conditions were employed. While anhydrous conditions are preferred less than anhydrous conditions can be employed. Water reacts with the phosphonic dihalide causing it to hydrolyze, resulting in a lower yield. Otherwise, its presence is not harmful.

Although there is no reason to suspect that the structural formulas given as representing the compounds of the invention are incorrect, since said formulas were developed according to standard methods well known to those skilled in the art, the invention is not to be unduly limited by said formulas.

Obviously, one reading the above specification will realize that the various phosphonic diamides represented by the formulas given herein are not necessarily equivalents in the usual sense of that term but rather are alternatives each possessing different properties and, therefore, diiferent uses.

Reasonable variation and modification are possible within the scope of the foregoing disclosure and the appended claims to the invention, the essence of which is that: new compounds represented by the structural formula N(R)z defined hereinabove have been provided, said new compounds being phosphonic diamides characterized by either an alkapolyene grouping, an alkenyne grouping, an alkapolyene grouuin or a five or six membered ring f rmed from one of said groupings, Formulas I, II, III, IV, V, and VI given herein being representative of said new com pounds; new compositions of matter comprising polymers of said phosphonic diamides have been provided; and a method of preparing said phosphonic diamides which comprises reacting a halophosphonic dichloride with an amine.

I claim:

1. A phosphonic diamide represented by the structural formula wherein: A is a member selected from the group consisting of unsubstituted and halogen-substituted alkapolyene, alkenyne and alkapolyyne hydrocarbon radicals, and a five to six membered ring, said ring having a skeleton consisting of carbon atoms and having therein the carbon skeleton of one of said hydrocarbon radicals; R is a member containing from zero to ten carbon atoms selected from the group consisting of hydrogen, hydrocarbon, and heterocyclic radicals, said hydrocarbon radicals being selected from the group consisting of aromatic, saturated and unsaturated acyclic, and saturated and unsaturated alicyclic radicals, and combinations of the radicals as defined by R; and where, in addition, two R' radicals together with the nitrogen atom attached thereto can form a heterocyclic ring containing from five to seven atoms, at least three of which are carbon, the remainder being selected from the group consisting of carbon, nitrogen, sulfur and oxygen.

2. N,N,N,N tetramethyl 1,3 butadiene 1 phosphonic diamide.

3. N,N,N',N tetramethyl 1,3 butadiene 2 phosphonic diamide.

4. N,N,N',N' tetraallyl 1,3 butadiene 1 phosphonic diamide.

5. N,N,N,N tetraallyl 1,3 butadiene 2 phosphonic diamide.

6. A mixture of isomeric alkadienephosphonic diamides comprising N,N,N',N' tetramethyl 1,3 butadiene 1- butadiene-Z-phosphonic diamide.

7. A mixture of isomeric alkadienephosphonic diamides comprising N,N,N',N tetraallyl 1,3 butadiene 1- phosphonic diamide, and N,N,N',N' tetraallyl 1,3- butadiene-Z-phosphonic diamide.

8. Polymeric N,N,N',N' tetramethyl 1,3-butadienel-phosphonic diamide.

9. Polymeric N,N,N',N tetramethyl 1,3 butadiene- Z-phosphonic diamide.

10. Polymeric N,N,N',N' tetraallyl 1,3 butadienel-phosphonic diamide.

11. Polymeric N,N,N',N tetraallyl 1,3 butadiene- 2-phosphonic diamide.

12. A polymeric composition of matter comprising polymers of the isomeric mixture defined in claim 6.

13. A polymeric composition of matter comprising polymers of the isomeric mixture defined in claim 7.

14. The method of preparing a phosphonic diamide having a structural formula as defined in claim 1 which comprises reacting a haloalkenephosphonic dihalide with a compound selected from the group consisting of ammonia and an amine containing at least one hydrogen atom attached to the nitrogen atom.

15. The method of preparing a phosphonic diamide having a structural formula as defined in claim 1 which comprises reacting a haloalkenephosphonic dihalide with a compound selected from the group consisting of ammonia and an amine containing at least one hydrogen atom attached to the nitrogen atom to form a haloalkadienephosphonic diamide reaction product and reacting said product with a strong base.

16. The method of preparing a phosphonic diamide having a structural formula as defined in claim 1 which comprises: adding a haloalkenephosphonic dichloride to at least a stoichiometric quantity of a compound selected from the group consisting of ammonia and an amine containing at least one hydrogen atom attached to the nitrogen atom, dissolved in a suitable inert solvent to form a reaction mixture, maintaining said reaction mixture at a temperature within the range of 0 to C. during said addition, warming said reaction mixture, maintaining said reaction mixture within the range of 0 to C. until said reaction is substantially complete as indicated by cessation of heat evolution, filtering said reaction mixture to obtain a precipitate and a filtrate and recovering said phosphonic diamide from said filtrate.

17. The method of claim 16 wherein said amine is diallylamine, said halophosphonic dichloride is chlorobutenephosphonic dichloride and said alkapolyenephosphonic diamide is N,N,N,l tetraallyl 1,3 butadienephosphonic diamide.

18. The method of claim 16 wherein said amine is dimethylamine, said halophosphonic dichloride is chlorobutenephosphonic dichloride and said alkapolyenephosphonic diamide is N,N,N',N-tetramethyl-1,3-butadienephosphonic diamide.

19. The product of the reaction between diallylamine and a chlorobutenephosphonic dichloride which has a boiling point ranging from 157 to 170 C. at 1 mm. of Hg.

20. The product of the reaction between dimethylamine and a chlorobutenephosphonic dichloride which has a boiling point ranging from 102 to C., at 1.25 to 2.5 mm. Hg.

21. The product of the reaction between dimethylamine and a chlorobutenephosphonic dichloride which has a boiling point ranging from 116 to 118 C., at 0.9 to 1.2 mm. Hg.

References Cited in the file of this patent UNITED STATES PATENTS 2,486,657 Kosolapoif Nov. 1, 1949 2,666,750 Dickey et a1 Jan. 19, 1954 Patent No, 2,818,406

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION December 31, 1957 James No Short It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 33, for "and second occurrence read m when m Signed and sealed this 27th day of January 1959o (SEAL) Attest:

KARL Ho AXLINE Attesting Officer ROBERT C. WATSON Commissioner of Patents

Claims (1)

1. A PHOSPHONIC DIAMIDE REPRESENTED BY THE STRUCTURAL FORMULA