3,264,324. United States Patent Office Patented August 2, 1966 2 3,264,324 di-2-chlorophenyl benzenephosphonite, PHOSEPHONTES di-phenyl 2-methylbenzenephosphonite, Henry Gould, West Orange, N.J., and Lester Friedman, diphenyl-2,4-dimethylbenzenephosphonite, Whitestone, N.Y., assignors, by mesne assignments, to diphenyl-3-methylbenzenephosphonite, Union Carbide Corporation, a corporation of New 5 diphenyl-4-methylbenzenephosphonite, York di-o-cresyl-3-methylbenzenephosphonite, No Drawing. Filed Sept. 15, 1960, Ser. No. 56,118 p-chlorophenyl 2-chlorobenzenephosphonite. 5 Claims. (C. 260-347.8) The preferred starting phosphonite is diphenyl benzene This invention relates to the preparation of phospho phosphonite. nites. O As the alcohol there can be used alkanols, e.g. methyl It is an object of the present invention to develop an alcohol, n-octanol, n-decyl alcohol, isodecyl alcohol (a improved process for preparing phosphonites. mixture of isomeric decyl alcohols prepared by the oxo Another object is to prepare such phosphonites having process), lauryl alcohol, cetyl alcohol, octadecyl alcohol improved physical properties and particularly having im (stearyl alcohol), cyclohexanol, 1,2-alkanediols and 1,3- proved purity. 5 alkanediols, e.g. ethylene glycol, propylene glycol, tri A further object is to prepare novel phosphonites. methylene glycol 1,2-butylene glycol, 2,3-butyleneglycol, Still further objects and the entire scope of applicability pinacol, 1,2-pentanediol, 2-methyl-2,4-pentanediol (hex of the present invention will become apparent from the ylene glycol), 1,3-butylene glycol, neopenty glycol (2,2- detailed description given hereinafter; it should be under dimethyl-1,3-propanediol), neohexylene glycol (2-methyl stood, however, that the detailed description and specific 20 2-ethyl-1,3-propanediol), 2-ethyl-1,3-hexanediol, 2,4-pen examples, while indicating preferred embodiments of the tanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2 invention, are given by way of illustration only, since ethyl-2-n-butyl-1,3-propanediol, heterocyclic alcohols such various changes and modifications within the spirit and as tetrahydrofurfuryl alcohol, pentaerythritol, glycol mono scope of the invention will become apparent to those ethers such as methoxyethanol, methoxyethoxyethoxy skilled in the art from this detailed description. 25 ethanol (methoxytriglycol) butoxyethanol, ethoxyethanol, It has now been found that these objects can be at methoxyethoxyethanol, phenoxyethanol, methoxy Carbo tained by transesterifying a phosphonite having the for wax. 350 (methyl ether of polyethylene glycol having a mula molecular weight of 338, methoxy Carbowax 550 (methyl OR 30 ether of polyethylene glycol having a molecular weight / RP of 538), butyl Carbitol (butoxyethoxyethanol). N For the catalyst there can be employed phosphites OR Such as diphenyl phosphite, didecyl phosphite, phenyl where R, R2 and R are aryl or haloary with a mono decyl phosphite, di-isodecyl phosphite, di-o-cresyl phos or polyhydric alcohol in the presence of a phosphite hav 35 phite, di-p-cresyl phosphite, di-m-cresyl phosphite, di-2,4- ing the formula dimethylphenyl phosphite, distearyl phosphite, dilauryl phosphite, dibutyl phosphite, di-2-chlorophenyl phos RO phite. The phosphonite, e.g. diphenyl benzene phosphonite 40 can be reacted with one or two mols of the monohydric where R and R5 and hydrocarbon or halohydrocarbon alcohol to replace either one or two of the phenoxy as a catalyst. The catalyst is preferably used in an groups with the alcohol groups. Typical examples of amount of 0.1 to 1% of the starting phosphonite by compounds which can be made according to the invention weight although Smaller or larger amounts of catalyst can be used. 45 didecyl benzenephosphonite, Preferably the mono or polyhydric alcohol has a boil di-isodecyl benzenephosphonite, ing point above that of the phenol liberated in the trans phenyl decyl benzenephosphonite, esterification. The transesterification also is preferably dilauryl benzenephosphonite, carried out at reduced pressure, e.g. 0.1-100 mm. and distearyl benzene:phosphonite, preferably 10-20 mm. while distilling to remove the 50 dimethyl benzenephosphonite, phenol formed, although atmosphere or Superatmospheric diphenoxyethyl benzenephosphonite, pressure can be employed. dietetrahydrofurfuryl benzenephosphonite, The starting phosphonites can be formed in conven phenyl tetrahydrofurfury benzenephosphonite, tional fashion as illustrated by the following equations: isodecyl tetrahydrofurfuryl benzenephosphonite, 55 dimethoxyethyl benzenephosphonite, ( ) - Cl3 --> (D-Pol, -- C dimethoxyethoxyethoxyethyl benzenephosphonite, dibutoxyethyl benzenephosphonite, 2 -- diethoxyethylbenzenephosphonite, 0.1% MgCl2 dimethoxyethoxyethyl benzenephosphonite, 60 dimethoxy Carbowax. 350 benzenephosphonite, O-( ) dimethoxy Carbowax 550 benzenephosphonite, ( >-PCP -- 2EC dibutoxyethoxyethyl benzenephosphonite, O diisodecyl 2-methylbenzenephosphonite, N ( ) distearyl 3-methylbenzenephosphonite, As starting phosphonites there can be used 65 dilauryl 4-methylbenzenephosphonite, diphenylbenzenephosphonite, diisodecyl 3-chlorobenzenephosphonite, di-o-cresyl benzenephosphonite, phenyl laury benzenephosphonite, di-p-cresy benzenephosphonite, phenyl stearyl benzenephosphonite. di-m-cresyl benzenephosphonite, 70 These compounds wherein the alkyl group has 10 to 18 phenyl p-cresyl benzenephosphonite, carbon atoms of where there is one or more ether groups di-2,4-dimethylphenyl benzenephosphonite, present are new compounds. 3,264,324 3 4 Two mols of the starting aromatic phosphonite can be Example 1 reacted with one mol of pentaerythritol in the presence Diphenylbenzenephosphonite -- 294 grams (1.0 mol). of the phosphite catalyst and form new compounds hav Isodecyl alcohol ------160 grams (1.01 mols). ing the formula: Diphenylphosphite ------. 0.8 gram (0.28% of the dip he nyl benzene o ce CB.o. phosphonite). RP / N P-R This mixture was heated at 110-120° C. for 30 minutes. O C2 CH2O The phenol formed was then distilled at 10-15 mm. until one mol had been collected. The phenyl isodecyl ben where R is an aryl or haloaryl group. Examples of Such O Zenephosphonite was left in the reaction pot and after compounds are filtration was obtained as a colorless liquid in near quan 3,9-diphenyl-2,4,8,10-tetraoxa-3,9-diphosphaspiro-5,5) titative yield. undecane, Example 2 3,9-di-2'-methylphenyl-2,4,8,10-tetraoxa-3,9- Example 1 was repeated replacing the 160 grams of diphosphaspiro-5,5) undecane, isodecyl alcohol by 319 grams of isodecyl alcohol (2.01 3,9-di-4'-methylphenyl-2,4-8, 10-tetraoxa-3,9- mols). The distillation was continued at 10-15 mm. diphosphaspiro-I5,5) undecane, until two mols of phenol had been removed. Then the 3,9-di-3'-methylphenyl-2,4,8,10-tetraoxa-3,9- diisodecyl benzenephosphonite was recovered from the diphosphaspiro-5,51 undecane, 20 3,9-di-4'-chlorophenyl-2,4,8,10-tetraoxa-3,9- pot as a colorless liquid in substantially quantitative yield. diphosphaspiro-5,5l undecane. Example 3 Example 2 was repeated but the disphenyl phosphite By reacting one mole of the aromatic phosphonite with was replaced by 0.8 gram of diisodecyl phosphite and one mol of a 1,2-glycol or 1,3-glycol there are prepared 25 the diisodecyl benzenephosphonite were recovered from compounds having the formula: the pot in Substantially quantitative yield. R Example 4 Example 2 was repeated but the isodecyl alcohol was 30 replaced by two mols of octadecyl alcohol. The di-octa decyl benzenephosphonite formed was recovered from the pot in excellent yields. 6 Example 5 where R1, R2, R3, RA, R5 and R6 are hydrogen or lower 35 Diphenyl benzenephosphonite ------mols-- 1 alkyl, n is 0 or 1 and R is aryl or haloaryl. Preferably Tetrahydrofurfuryl alcohol ------do---- 1 n is 1 and R is phenyl. Diphenyl phosphite ------grams-- 1 Example of such compounds are ethylene benzene phos The procedure of Example 1 was repeated and phenyl phonite tetrahydrofurfuryl benzenephosphonite was recovered as I2-phenyl-1,3,2-dioxaphospholanel, 40 the final product. 2-phenyl-4-methyl-1,3,2-dioxaphospholane, Example 6 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, 2-phenyl-4,5-dimethyl-1,3,2-dioxaphospholane, Diphenyl benzenephosphonite ------mols-- 1 2-phenyl-4-ethyl-1,3,2-dioxaphospholane, Tetrahydrofurfuryl alcohol ------do---- 2 2-phenyl-4-propyl-1,3,2-dioxaphospholane, Diphenyl phosphite ------grams-- 1 2-o-tolyl-1,3,2-dioxaphospholane, The procedure of Example 2 was followed and ditetra 2-p-tolyl-4-methyl-1,3,2-dioxaphospholane, hydrofurfuryl benzenephosphonite was recovered as the 2-p-chlorophenyl-1,3,2-dioxaphospholane, final product. 2-phenyl-1,3,2-dioxaphosphorinane, Example 7 hexylene benzenephosphonite (2-phenyl-4,4,6-trimethyl 50 1,3,2-dioxaphosphorinane), Phenyl isodecyl benzenephosphonite ------mols-- 1 1,3-butylene benzenephosphonite (2-phenyl-4-methyl Tetrahydrofurfuryl alcohol ------do---- 1 1,3,2-dioxaphosphorinane), Di-isodecyl phosphite ------grams. - 1 neopentylene benzenephosphonite (2-phenyl-5,5- The procedure of Example 1 was followed and isodecyl dimethyl-1,3,2-dioxaphosphorinane), 55 tetrahydrofurfuryl benzenephosphonite was recovered as neohexylene benzenephosphonite (2-phenyl-5-methyl-5- the final product. ethyl-1,3,2-dioxaphosphorinane), Example 8 2-phenyl-4-propyl-5-ethyl-1,3,2-dioxaphosphorinane, Diphenyl benzenephosphonite ------mols-- 1 2-phenyl-4,6-dimethyl-1,3,2-dioxaphosphorinane, Stearyl alcohol ------do---- 1 2-phenyl-4-methyl-6-propyl-1,3,2-dioxaphosphorinane, 60 Tetrahydrofurfuryl alcohol ------do---- 1 2-phenyl-5,5-diethyl-1,3,2-dioxaphosphorinane, . Diphenyl phosphite ------grams-- 1 2-phenyl-5-ethyl-5-butyl-1,3,2-dioxaphosphorinane, neopentylene 2-methylbenzenephosphonite, This mixture was heated to 110-120° C. for 30 minutes neopentylene 3-methylbenzenephosphonite, and then two mols of phenol formed by the transesteri hexylene 4-methylbenzenephosphonite, fication was removed by distillation at 10-15 mm. The neopentylene 2-chlorobenzenephosphonite and Stearyl tetrahydrofurfuryl benzenephosphonite was recov neopentylene 2,4-dimethylbenzenephosphonite. ered from the pot in excellent yields. Example 9 The new compounds of the present invention are use Diphenyl benzenephosphonite ------mols-- 1 ful as flame retardant agents, as antioxidants for poly 70 olefins, e.g. polyethylene and polypropylene, as stabilizers Butyl Carbitol (butoxyethoxyethanol) ------do---- 2 for polyurethanes, as stabilizers and curing agents for Diphenyl phosphite ------grains-- 1 epoxy resins and to increase the effectiveness of phenolic The procedure of Example 8 was followed and dibutyl antioxidants, e.g. in stabilizing polypropylene. Carbitol benzenephosphonite was recovered as the final Unless otherwise indicated all parts are by weight. 75 product. 3,264,324. 5 6. Example 10 Example 19 Diphenyl benzenephosphonite ------mols-- 1 Diphenyl benzenephosphonite ------mols-- 1 Methoxy CarboWax 350------do---- 2 Pinacol ------do---- 1 Dilauryl phosphite ------grams-- 1 Diphenyl phosphite ------grams-- 1 5 The process of Example 8 was repeated and dimethoxy The process of Example 16 was repeated and 2-phenyl Carbowax 350 benzenephosphonite was recovered as the 4,4,5,5-tetramethyl-1,3,2-dioxaphospholane was recovered final product. as the final product. Example 11 Example 20 Diphenyl benzenephosphonite ------nols-- 1 0 Di-o-cresyl 2-methylbenzenephosphonite ---...-mols-- 1 Methoxyethanol ------do---- 1 1,2-pentanediol ------do---- 1 Diphenyl phosphite ------grams-- 1 Diisodecyl phosphite ------grams-- 1 The procedure of Example 1 was repeated and phenyl The process of Example 16 was repeated and 2-o- methoxyethyl benzenephosphonite was recovered as the 5 methylphenyl-4-propyl-1,3,2-dioxaphospholane was re final product. covered as the final product. Example 12 Example 21 Diphenyl benzenephosphonite ------mols-- 1 Diphenyl benzenephosphonite ------mols.l.. 1 Methoxyethoxyethoxyethanol ------do---- 2 Neopentyl glycol ------do---- 1 Diphenyl phosphite ------grams-- 1 20 Diphenyl phosphite ------grams-- 1 The procedure of Example 8 was repeated and dimeth This mixture was heated to 110-120° C. for 30 minutes oxyethoxyethoxyethyl benzenephosphonite was recovered and then distillation was begun at 10-15 mm. pressure. as the final product. This distillation was continued until two mols of phenol Example 13 25 were collected. The neopentylene benzenephosphonite Phenyl isodecyl benzenephosphonite ------mols. - 1 (2-phenyl-5,5-dimethyl-1,3,2-dioxaphosphorinane) was Methoxyethoxyethanol ------do---- 1 left in the reaction pot and after filtration was recovered Diphenyl phosphite ------do---- 1 as a low melting solid in 95% yield. The process of Example 1 was repeated and isodecyl 30 Example 22 methoxyethoxyethyl benzenephosphonite was recovered The process of Example 21 was repeated replacing the as the final product. diphenyl phosphite by 1 gram of diisodecyl phosphite. Example 14 The neopentylene benzenephosphonite was recovered in Diphenyl benzenephosphonite ------mois-- 2 equally good yield. Pentaerythritol ------do---- 1 Example 23 Diphenyl phosphite ------grams-- 1.6 Didecyl benzenephosphonite ------mol-- 1 This mixture was heated to 110-120 C. for 30 minutes Trimethylene glycol ------do-...- 1 and then four mols of phenol formed by the transesteri Distearyl phosphite ------gram-- 1 fication was removed by distillation at 10-15 mm. The 40 The process of Example 21 was repeated and 2-phenyl 3,9-diphenyl - 2,4,8,10-tetraoxa-3,9-diphosphaspiro 5,5) 1,3,2-dioxaphosphorinane and was recovered as the final undecane was recovered from the pot in excellent yields. product. Example 15 Example 24 Example 14 was repeated replacing the diphenyl benz Diphenyl benzenephosphonite ------mol-- 1 enephosphite by two mols of di-o-cresyl-2-methylbenzene Hexylene glycol (2-methyl-2,4-pentanediol) ---do--- 1 phosphonite and 3,9-di-2'-methylphenyl-2,4,8,10-tetraoxa Diphenyl phosphite ------gram-- 1 3,9-diphosphaspiro-5,5-undecane was recovered from The process of Example 21 was repeated and hexylene the pot in excellent yields. benzenephosphonite (2 - phenyl-4,4,6-trimethyl-1,3,2-di Example 16 50 oxaphosphorinane) was recovered as the final product. Diphenyl benzenephosphonite ------mols-- 1 Example 25 Ethylene glycol ------do---- 1 Diphenyl benzenephosphonite ------moll. 1 Diphenyl phosphite ------grams-- 1 1,3-butylene glycol ------do---- 1 This mixture was heated to 110-120° C. and then dis 55 Diphenyl phosphite ------gram. - 1 tillation was begun at 10-15 mm. pressure. The distilla The process of Example 21 was repeated and 1,3-butyl tion was continued until two mols of phenol were col ene benzenephosphonite (2-phenyl-4-methyl-1,3,2-dioxa lected. The ethylene benzenephosphonite (2-phenyl-1,3, phosphorinane) recovered as the final product. 2-dioxaphospholanel was left in the reaction pot and after filtration was obtained in excellent yield. 60 Example 26 Diphenyl benzenephosphonite ------mol.-- 1 Example 17 Neohexylene glycol ------do---- 1 The process of Example 16 was repeated replacing the Diphenyl phosphite ------gram-- 1 diphenyl benzenephosphonite by one mol of didecyl The process of Example 21 was repeated and neohex benzenephosphonite and replacing the diphenyl phosphite 65 ylene benzenephosphonite (2-phenyl-5-methyl-5-ethyl by 1 gram of didecyl phosphite. The ethylene benzene 1,3,2-dioxaphosphorinane) was recovered as the final phosphonite was recovered in equally good yield. product. Example 18 Example 27 Di-p-cresyl 2-methylbenzenephosphonite ------moll- 1 Diphenyl benzenephosphonite ------mols-- 1 70 Propylene glycol ------do---- 1 Neopentyl glycol ------do---- 1 Diphenyl phosphite ------grams-- 1 Di-o-cresyl phosphite ------gram. - 1 The procedure of Example 16 was repeated and propy The process of Example 21 was repeated and neopen lene benzenephosphonite (2-phenyl-4-methyl-1,3,2-dioxa tylene-2-methylbenzenephosphonite recovered as the final phospholane) was recovered as the final product. 75 product.

3,264,324 7 - 8 What is claimed is: - . . . . 1. A compound having the formula 10. A compound of the formula OR 1. RP N OR3 where R is selected from the group consisting of phenyl, halophenyl and alkylphenyl, R2 is tetrahydrofurfuryl and R3 is selected from the group consisting of phenyl, halo phenyl, alkylphenyl, alkyl and tetrahydrofurfuryl. where R1, R2, R3, R4, R5 and Rs are each a member of 2. Ditetrahydrofurfuryl phenylphosphonite. O the group consisting of hydrogen and lower alkyl and R. 3. Tetrahydrofurfuryl phenyl phenylphosphonite. is a member of the group consisting of phenyl and tolyl. 4. Tetrahydrofurfuryl alkyl phenylphosphonites where 11. 2-phenyl-1,3,2-dioxaphosphorinane having up to in the alkyl group has 10-18 carbon atoms. three lower alkyl groups attached to carbon atoms of the 5. A compound having the formula 5 dioxaphosphorinane ring. OR2 12. A compound according to claim 11 which is neo / pentylene benzenephosphonite. RP N 13. A compound according to claim 11 which is 1,3- OR3 butylene benzenephosphonite. where R is selected from the group consisting of phenyl, 20 14. A compound according to claim 11 which is 2 halophenyl and alkylphenyl, R is selected from the group phenyl-4,4,6-trimethyl-1,3,2-dioxaphosphorinane. consisting of aryloxyethyl, and alkoxy (C2H4O)x ethyl - 15. A compound according to claim 11 which is neo where X is an integer of at least one and R3 is selected hexylene benzenephosphonite. from the group consisting of R1, R2 and alkyl. 6. 25 References Cited by the Examiner UNITED STATES PATENTS ochschico CHCH2)xOR1 2,234,379 3/1941 Martin ------260-461.308 { X-PN 2,326,140 8/1943 Gzemski------260-461.315 OCH2CH2(OCH2CH2)xOR2 2,769,743 11/1956 Mattson et al. ---- 260-461.308 where R1 and R2 are lower alkyl and X is an integer of 30 2,841,608 7/1958 Hechenbleikner et al. at least one. 260-461.315 7. 2,847,443 8/1958 Hechenbleikner et al. OCH CEIa-O 260-461.315 N RP 2,860,155 11/1958 Walsh ------260-461.308 N - P-R 2,867,646 1/1959 Whetstone ------260-461.308 OCH CEI-O 2,903,475 9/1959 Horowitz ------260-461.308 where R is selected from the group consisting of phenyl, 2,907,787 10/1959 Hoffmann et al. ------260-982 alkylphenyl and halophenyl. 2,970,166 1/1961 Rosin ------260-461.315 8. 3,9-diphenyl - 2,4,8,10-tetraoxa-3,9-diphosphaspiro 3,009,939 1 1/1961 Friedman ------260-461.315 5,5undecane. 40 3,031,489 8/1962 Birum ------260-461.304 9. OTHER REFERENCES Ri Hoffmann et al.: J. Am. Chem. Soc., vol. 78, Nov. 20, R-(-o 1956, pp. 5817-5822. R-C-R. P-R, 45 Landauer et al.: J. Chem. Soc., 1953, pp. 2224,2234. R-8-0, CHARLES B. PARKER, Primary Examiner. R. H. J. LIDOFF, LEWIS GOTTS, JOSEPH P. BRUST, where R1, R2, R3, R4, R5 and Rs are selected from the group consisting of hydrogen and lower alkyl and R is 50 Examiners. selected from the group consisting of phenyl, alkylphenyl H. JILES, J. R. GENTRY, F. M. SIKORA, R. L. RAY and halophenyl. MOND, Assistant Examiners.