3,382,301 United States Patent Office Patented May 7, 1968 1. 2 3,382,301 where R is alkyl, alkenyl, aralkyl or R, R is alkyl, DHYDROXY PHOSEPHONATES alkenyl, aralkyl, aryl, haloaryl or R and R is Ingenuin Hechenbleikner, Kenwood, and Kenneth R. Moit, Cincinnati, Ohio, assignors to Carlisle Chemical Works, R6 R3 R4 Rs Inc., Reading, Ohio, a corporation of Ohio 5 -(CHCHo). (CH)-6-d No Drawing. Continuation-in-part of application Ser. No. 245,976, Dec. 20, 1962. This application Sept. 3, 1964, () ) Ser. No. 394,320 N c^ 5 Claims. (C. 260-953) R? Y, 0 where R1 is hydrogen alkyl, aryl, haloaryl or nitroaryl, R2 is hydrogen, alkyl aryl, haloaryl or nitroaryl; or ABSTRACT OF THE DISCLOSUIRE Dihydroxy phosphonates of the formula

RO O Rs R4 Rs is an alicyclic, i.e., a cycloalkyl group, R3 is hydrogen, N b. alkyl or aryl, R4 is hydrogen or alkyl, R is hydrogen or P-(CH-CHO) (CH)-- alkyl, R6 is hydrogen, or lower alkyl, e.g., methyl or RO OB OH ethyl, v is 0 or an integer, e.g., from 1 to 100, n is an 20 integer between 1 and 10, m is 1 or 2; where R1 and R2 are selected from the group consisting of 90-ce CH-O R alkyl, alkenyl, monocyclic carbocyclic aryl, naphthyl, R10 benzyl, alkylbenzyl and halophenyl; / Yr, R8 is selected from the group consisting of hydrogen and lower alkyl; R and R5 are selected from the group consisting of where Rio is alkyl, alkenyl or aralkyl and R1 and R2 are hydrogen and alkyl; as defined above Ra is selected from the group consisting of hydrogen, alkyl and monocyclic carbocyclic aryl; O R O y is an integer of at least Zero; R10- 1–0CH)-o-C-O-CH).o 1-R, m is an integer between 1 and 2 inclusive; and R11- l, () R n is an integer between 1 and 10 inclusive, are prepared by hydrolyzing corresponding 1,3-dioxolanes and 1,3-di III OXalcS. where R11 is alkyl, alkenyl aryl, haloaryl or aralkyl and -a assrs. Scramma R1,R2, and Rio are as defined above This application is a continuation-in-part of application is . . . . . 245,976, filed Dec. 20, 1962, now Patent 3,206,474, which in turn is a continuation-in-part of application 214,508, 40 R--OCHCHo)-ochschooooh,dhoolcho.--RsR11-O R2 R11 filed Aug. 3, 1962, now Patent 3,096,345 issued July IV 2, 1963. The present invention relates to novel phosphonates. where R1, R2, R6, R10, R11 are as defined above and x is It is an object of the present invention to prepare phos an integer of at least 1, e.g., from 1 to 100. phonates of polyhydric alcohols having at least three There are also included phosphonates of diacetals and hydroxyl groups. ketals or hexitols such as sorbitol and mannitol. Typical Another object is to prepare novel heterocyclic acetal of such materials are compounds having the formula and ketal phosphonates. A further object is to prepare novel phosphonates by R the hydrolysis of acetal and ketal phosphonates. A still further object is to prepare novel open chain acetal and ketal phosphonates. Still further objects and the entire scope of applicability of the present invention will become apparent from the C--O O. detailed description given hereinafter; it should be under stood, however, that the detailed description and specific CH-O examples, while indicating preferred embodiments of the v invention are given by way of illustration only, since various changes and modifications within the spirit and where R1,R2 and Rio are as defined above. scope of the invention will become apparent to those 60 In Formula V no attempt has been made to show the skilled in the art from this detailed description. position of the hydrogen atoms on the asymmetric car It has now been found that these objects can be attained bon atoms. The position of the acetal and ketal groups by preparing novel acetals and ketals having one of the also can be varied so long as there are two such groups formulae in the molecule. The compounds of the present invention are useful as water dispersible wetting and suspending agents. They can also be employed as fire retardants for cellulose, R7-P-ORg cellulose esters, e.g. cellulose acetate, polyolefin resins, e.g. polyethylene and polypropylene. A particular important use for the acetals and ketals of the present invention is to hydrolyze them to give hy 3,382,301 3 4 droxyl containing phosphonates. Such hydroxyl contain or superatmospheric pressure. The halide remaining after ing phosphonates have the following formulae the reaction can normally be removed by distillation. Among the halides which are employed in the Arbuzov reaction are R-0 R13 5 methyl bromide, methallyl iodide, methyl iodide, crotyl bromide, ethyl bromide, vinyl bromide, wherein R is as defined above, R12 is alkyl, alkenyl, ethyl iodide, oleyl bromide, aralkyl, aryl, haloaryl or R13 and R13 as n-propyl iodide, oleyl iodide, Rs R3 R R5 O isopropyl iodide, benzyl chloride, amyl bromide, benzyl bromide, -(CH&Ho) (CH)-b-cé. amyl chloride, benzyl iodide, ÖH. Ó It amyl iodide, o-dodecylbenzyl chloride, where R3, R4, R5, R6, V, in and m are as defined above; butyl bromide, p-dodecylbenzyl chloride, 5 hexyl iodide, m-dodecylbenzyl chloride, O OCH CH2OH. octyl bromide, p-dodecylbenzyl bromide, R octyl iodide, epichlorhydrin, YoCH/ YoHoH decyl bromide, epibromohydrin, WI decyl iodide, epiiodohydrin, dodecyl iodide, ethylene chlorhydrin, wherein Rio is as defined above; octadecyl bromide, ethylene bromohydrin, HCO octadecyl iodide, ethylene iodohydrin, HO bH allyl bromide, propylene chlorhydrin, CHOH allyl iodide, propylene bromohydrin. Hob O allyl chloride, The compounds of Formulae VI through VIII are pre pared by hydrolysis of the compounds of Formulae I, II, and V. The hydrolysis is carried out with the aid of water, WII 30 preferably with heating, e.g. up to 100° C. The reaction where Rio is as defined above. mixture is usually slightly acidic due to the starting phos The hydrolyzed phosphonates, i.e. the compounds of phonate. After hydrolysis is completed, an alkaline mate Formulae VI, VII, and VIII, have the uses set forth rial, e.g. sodium hydroxide, sodium carbonate, sodium bi Supra and in addition are useful for preparing polyure carbonate or potassium hydroxide is added to neutralize thanes by reaction with organic isocyanates, e.g. toluene 35 the product. diisocyanate and PAP (polyphenylene isocyanate aver Illustrative examples of starting phosphites (which can aging about 3 units in the poymer). The polyurethanes be prepared in the manner set forth in the parent applica can be prepared as foams or as elastomers. The presence of the phosponate group renders the polyurethane flame tion) to prepare the phosphonates of Formula I are resistant. The phosphonate need be used only as a portion 40 phenyl bis (4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) of the polyols employed. Thus, the use of 20% of a methyl) phosphite diphenyl-4-(2-methyl-2-ethyl-1,3- polyhydroxyl containing phosphonate according to the dioxacyclopentyl) methyl phosphite; present and 80% of another polyol, e.g. glycerine pro methyl bis (4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl)- pylene oxide adduct molecular weight 3000 or polypro methyl) phosphite; pylene glycol 2025 will give a polyurethane with im dimethyl 4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl)methyl proved flame resistance. phosphite; The novel compounds of Formulae I through V of the ethyl bis(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl)- present invention are prepared by Arbuzov rearrange methyl) phosphite, ment of the corresponding phosphite prepared according tris(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) methyl) to the parent application. The entire disclosure of the parent application is hereby incorporated by reference. phosphite; Thus, there is employed an alkyl halide, alkenyl halide, decyl bis(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) aralkyl halide, halohydrin or epihalohydrin with a phos methyl) phosphite; phite of the parent application that is isomeric with a octadecyl bis(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) phosphonate of Formulae I through V above. The iodides methyl) phosphite; and bromides are preferred although there can also be dioctadecyl 4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) employed the chlorides. The halides can be employed in methyl phosphite; catalytic amounts, e.g. 0.5-5 mol precent based on the oleyl-bis (4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) phosphite to be rearranged. If the hydrocarbon group of methyl) phosphite; the halide is the same as one of the esterifying groups of 60 benzyl-bis (4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) the phosphite, then no impurities are introduced into the methyl) phosphite; phosphonate product. By employing a large amount of p-dodecylbenzyl-bis (4-(2-methyl-2-ethyl-1,3-dioxacyclo the halide, e.g. 80 mol percent, or perferably 100 mol pentyl) methyl) phosphite; percent or more, based on the phosphite employed in cyclohexyl-bis-(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) the Arbuzov reaction, then the product is one in which 65 methyl) phosphite; one of the esterifying groups on the phosphorus atom is tris (5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl)methyl) removed and the phosphorous atom is directly attached phosphite; to the hydrocarbon, hydroxyhydrocarbon or epoxyhydro ethyl-bis (5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl) carbon group of the halide employed. When one of the methyl) phosphite; esterifying groups of the phosphite is aryl or haloaryl, 70 dimethyl-5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl) sufficient alkyl halide or the like must be used to re methyl phosphite; place the aryl or haloaryl group since aryl halides do lauryl-bis-(5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl) not normally take part in the Arbuzov reaction. The methyl) phosphite; Arbuzov reaction is usally carried out at elevated temper allyl-bis (5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl) atures, e.g. 120-200 C. at atmospheric, subatmospheric methyl) phosphite;

3,382,301 10 bis (4-(2-bromophenyl-1,3-dioxacyclopentyl) methyl) bis (4-(2,2-diphenyl-1,3-dioxacyclopentyl) butyl) (4-(2-bromophenyl-1,3-dioxacyclopentyl) methyl) heptane phosphonate; 4-(2-bromophenyl-1,3-dioxacyclopentyl) methane bis (4-(2,2,5-trimethyl-1,3-dioxacyclopentyl) methyl) phosphonate; 4-(2,2,5-trimethyl-1,3-dioxacyclopentyl) methane bis (4-(2-methyl-2-propyl-1,3-dioxacyclopentyl) methyl) 5 phosphonate; 4-(2-methyl-2-propyl-1,3-dioxacyclopentyl) methane bis (4-(2,2,5-trimethyl-1,3-dioxacyclopentyl) methyl) phosphonate; propane phosphonate; bis (4-(2-methyl-2-propyl-1,3-dioxacyclopentyl) methyl) bis (4-(2,2-dimethyl-5-ethyl-1,3-dioxacyclopentyl) decane phosphonate; methyl) butane phosphonate; bis (4-(2,2-diethyl-1,3-dioxycyclopentyl) methyl) O bis (4-(2,4,5-trimethyl-2-ethyl-1,3-dioxacyclopentyl) 4-(2,2-diethyl-1,3-dioxacyclopentyl) methane methyl) methane phosphonate; phosphonate; bis (5-(2,5-dimethyl-1,3-dioxacyclohexyl) methyl) amyl (4-(2,2-diethyl-1,3-dioxacyclopentyl) methyl) decane phosphonate; pentane phosphonate; bis (5-(2-methyl-2,5-diethyl-1,3-dioxacyclohexyl) bis (4-(2-methyl-2-butyl-1,3-dioxacyclopentyl) methyl) 5 methyl) butane phosphonate; methane phosphonate; amyl-(5(2-methyl-2,5-diethyl-1,3-dioxacyclohexyl) bis (4-(2-ethyl-2-propyl-1,3-dioxacyclopentyl) methyl) methyl) pentane phosphonate; (4-(2-ethyl-2-propyl-1,3-dioxacyclopentyl) methyl) bis (5-(2,2-dimethyl-5-propyl-1,3-dioxacyclohexyl) 4-(2-ethyl-2-propyl-1,3-dioxacyclopentyl) methane methyl) ethane phosphonate; phosphonate; 20 bis (5-(2,2-dimethyl-5-heptadecyl-1,3-dioxacyclohexyl) bis (4-(2-ethyl-2-propyl-1,3-dioxacyclopentyl) methyl) methyl) propene phosphonate; methane phosphonate; bis (5-(5-methyl-1,3-dioxacyclohexyl) methyl) 5-5-meth bis (4-(2,2-dipropyl-1,3-dioxacyclopentyl) methyl) yl-1,3-dioxacyclohexyl) methane phosphonate; ethane phosphonate; bis (5-(5-methyl-1,3-dioxacyclohexyl) methyl) bis (4-2,2-diheptadecyl-1,3-dioxacyclopentyl)methyl) 25 hexadecane phosphonate; 4-(2,2-diheptadecyl-1,3-dioxacyclopentyl) methane bis (5-(5-ethyl-1,3-dioxacyclohexyl) methyl) 5-(5-ethyl phosphonate; 1,3-dioxacyclohexyl) methane phosphonate; bis (4-(2,2-diheptadecyl-1,3-dioxacyclopentyl) methyl) bis(5-(5-ethyl-1,3-dioxacyclohexyl) methyl) dodecane butane phosphonate; phosphonate; bis (3-(1,4-dioxaspiro (5.5) decyl) methyl) 3-(1,4-di bis (5-(2,5-dimethyl-1,3-dioxacyclohexyl) methyl) oxaspiro (5,5) decyl) methane phosphonate; 5-(2,5-dimethyl-1,3-dioxacyclohexyl) methane bis (3-(1,4-dioxaspiro (5,5) decyl) methyl) butane phosphonate; phosphonate; bis ((5-(2,5-dimethyl-1,3-dioxacyclohexyl) methyl) bis (3-(1,4-dioxaspiro (5,5) nonyl) methyl) methane ethane phosphonate; phosphonate; bis (5-(2-methyl-5-ethyl-1,3-dioxacyclohexyl) methyl) bis (4-(2,2-diphenyl-1,3-dioxacyclopentyl) methyl) 5-(2-methyl-5-ethyl-1,3-dioxacyclohexyl) methane 4-(2,2-diphenyl-1,3-dioxacyclopentyl) methane phosphonate; phosphonate; bis (5-(2-methyl-5-ethyl-1,3-dioxacyclohexyl) methyl) bis (4-(2,2-diphenyl-1,3-dioxacyclopentyl) methyl) ethane phosphonate; octane phosphonate; 40 bis (5-(2-isobutyl-5-ethyl-1,3-dioxacyclohexyl) methyl) bis (4-(2-methyl-2-phenyl-1,3-dioxacyclopentyl)methyl) methane phosphonate; 4-(2-methyl-2-phenyl-1,3-dioxacyclopentyl) bis (5-(2-phenyl-5-ethyl-1,3-dioxacyclohexyl) methyl) methane phosphonate; propanephosphonate; bis (4-(2-methyl-2-phenyl-1,3-dioxacyclophenyl) methyl 5-(2,2-dimethyl-5-ethyl-1,3-dioxacyclohexyl) methyl) methane phosphonate; methyl methane phosphonate; bis (4-(2,2-dimethyl-1,3-dioxacyclopentyl) propoxy 4 5 bis (5-(2,2,5-trimethyl-1,3-dioxacyclohexyl) methyl) methyl)ethane phosphonate 5-(2,2,5-trimethyl-1,3-dioxacyclohexyl) methane O CH3 phosphonate; C.H.P (obHCH-O-CH-CHCH) bis (5-(2,2,5-trimethyl-1,3-dioxacyclohexyl) methyl) / N 50 propane phosphonate; O O bis (5-(2-methyl-2-phenyl-5-ethyl-1,3-dioxacyclohexyl) methyl) methane phosphonate; bis (5-(2,5-dimethyl-2-phenyl-1,3-dioxacyclohexyl) methyl) ethane phosphonate; bis (4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) poly bis (5-(2,2-diethyl-5-methyl-1,3-dioxacyclohexyl) ethoxymethyl) methane phosphonate (when the poly methyl) 5-(2,2-diethyl-5-methyl-1,3-dioxacyclohexyl) ethoxy radical contains 30 ethoxy groups); methane phosphonate; bis (4(2,2-dimethyl-1,3-dioxacyclopentyl) butyl) bis (5-(2,2-diethyl-5-methyl-1,3-dioxacyclohexyl) 4-(2,2-dimethyl-1,3-dioxacyclopentyl) butane phos methyl) octadecane phosphonate; phonate; 60 bis (3-(3-methyl-1,5-dioxaspiro (6,6) undecyl) methyl bis (4-(2,2-dimethyl-1,3-dioxacyclopentyl) butyl) 3-(methyl-1,5-dioxaspiro (6,6) undecyl) methane decane phosphonate; phosphonate; ethyl-4 (1,3-dioxacyclopentyl) butyl ethane phosphonate; bis (3-(3-methyl-1,5-dioxaspiro (6,6) undecyl) methyl) bis (4-(2-methyl-1,3-dioxacyclopentyl) butyl) methane pentane phosphonate; phosphonate; bis (3-(3-ethyl-1,5-dioxaspiro (6,6) undecyl) methyl) bis (4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) butyl) 3-(3-ethyl-1,5-dioxaspiro (6,6) undecyl methane hexane phosphonate; phosphonate; bis (4-(1,3-dioxacyclopentyl) butyl) 4-(1,3-dioxacyclo bis (3-(3-ethyl-1,5-dioxaspiro (6,6) undecyl) methyl) pentyl) butane phosphonate; butane phosphonate; bis (4 (1,3-dioxacyclopentyl) butyl) methane 70 bis (5-(2-cyclohexyl-5-methyl-1,3-dioxacyclohexyl) phosphonate; methyl) ethane phosphonate; bis (4-(2-methyl-1,3-dioxacyclopentyl ethane bis (5-(2,2-diamyl-5-ethyl-1,3-dioxacyclohexyl) methyl) phosphonate; methane phosphonate; bis (4-(2,2-dimethyl-1,3-dioxacyclopentyl) butyl) bis (5-(2,2-dimethyl-5-phenyl-1,3-dioxacyclohexyl) phenyl-methane phosphonate; nethyl) methane phosphonate.

3,382,301 3 14 2-(ethane)-9-m-nitrophenyl-1,3,8,10-tetraoxa-2-phos 1,1-bis (dihexoxyphosphaoxybutoxy) (cyclohexyl) meth phono-spiro (5,5) undecane; ale; 2-(decane)-9-methyl-9-propyl-1,3,8,10-tetraoxa-2-phos bis (dioctoxyphosphaoxybutoxy) (phenyl) methane; phono-spiro (5,5) undecane; bis (dimethoxyphosphaoxypentoxy) (p - methylphenyl) 2-(pentane)-9,9-diethyl-1,3,8,10-tetraoxa-2-phosphono methane; spiro (5,5) undecane; bis (dioctadecoxyphosphaoxybutoxy) (o-chlorophenyl) 2-(hexane)-9-methyl-9-butyl-1,3,8,10-tetraoxa-2-phos methane; phono-spiro (5,5) undecane; bis (dimethoxyphosphaoxybutoxy) (m. - nitrophenyl) 2-(methane)-9-ethyl-9-propyl-1,3,8,10-tetraoxa-2-phos methane; phono-spiro (5,5) undecane; 10 2,2-bis (didecoxyphosphaoxybutoxy ) pentane; 2-(ethane)-9-methyl-9-butyl-1,3,8,10-tetraoxa-2-phos 2,2-bis dimethoxy phosphapentoxy) pentane; phono-spiro (5,5) undecane; 3,3-bis (dimethoxyphosphaoxybutoxy) pentane; 2-(methane)-9,9-dipropyl-1,3,8,10-tetraoxa-2-phosphono 3,3-bis (dipentoxyphosphaoxydecoxy) pentane; spiro (5,5) undecane; 2,2-bis (dimethoxyphosphaoxypentoxy) hexane; 2-(decane)-9,9-diamyl-1,3,8,10-tetraoxa-2-phosphono 15 3,3-bis (diethoxyphosphaoxybutoxy) hexane; spiro (5,5) undecane; 2,2-bis (dimethoxyphosphaoxybutoxy) 3,3-dimethylbu 2-(ethane)-9,9-diheptadecyl-1,3,8,10-tetraoxa-2-phos tane; phono-spiro (5,5) undecane; 4,4-bis (dipropoxyphosphaoxyhexoxy) heptane; 2-(butane)-1,3,8,10-tetraoxa-2-phosphono-dispiro 6,6-bis (dihexadecoxyphosphaoxybutoxy) undecane; (5,5,9,9) hexadecane 20 18, 18-bis (dimethoxyphosphaoxybutoxy) pentatricon OCH CH2O CIHCH tane; N 1,1-bis (dibutoxyphosphaoxybutoxy) cyclohexane; (CH-PC )e( SoC CH, 1,1-bis (dimethoxyphosphaoxybutoxy) cyclopentane; O cf. CH,0^ CH2CH2 bis (dioctoxyphosphaoxybutoxy) (diphenyl) methane; 2-(octadecane)-1,3,8,10-tetraoxa-2-phosphono-dispiro 1,1-bis (dimethoxyphosphaoxyoctoxy)-1-phenylethane; (5,5,9,9) pentadecane; 1,1-bis (dimethoxyphosphaoxybutoxy) -1-phenyl prop 2-(octane)-9,9-diphenyl-1,3,8,10-tetraoxa-2-phosphono ane; spiro (5,5) undecane; bis (dimethoxyphosphaoxyethoxyethoxy) methane; 2-(methane)-9-methyl-9-phenyl-1,3,8,10-tetraoxa-2-phos 1,1-bis (dipropoxyphosphaoxyethoxyethoxy) ethane; phono-spiro (5,5) undecane; 30 1,1-bis (didecoxyphosphaoxyethoxyethoxy)butane; 2-(propane)-9,9-dimethyl-1,3,8,10-tetraoxa-2-phosphono 2,2-bis (diethoxyphosphaoxyethoxyethoxy) propane; spiro (5,5) undecane; 2,2-bis (dimethoxyphosphaoxyethoxyethoxy) butane; 2-(ethane)-9-butyl-1,3,8,10-tetraoxa-2-phosphono-spiro 1,1-bis (dimethoxyphospha-2'-oxypropoxypropoxy) eth (5,5) undecane; arle; 2-(methane)-9-cyclohexyl-1,3,8,10-tetraoxa-2-phosphono 2,2-bis (dibutoxyphospha-2'-oxypropoxypropoxy) prop spiro (5,5) undecane. ane; Illustrative examples of starting phosphites (which can 2,2-bis (dipentoxyphospha-2'-oxypropoxypropoxy) bu be prepared in the manner set forth in the parent applica tane; tion) useful for preparing the phosphonates of Formulae 2,2 - bis (dimethoxyphosphaoxypolyethoxy) propane III and IV are 40 (where the polyethoxy group has a molecular weight of 2000); 2,2-bis (diphenoxyphosphaoxybutoxy) propane; 2,2-bis (dioctoxyphosphaoxypolypropoxy)butane (where 2,2-bis (dimethoxyphosphabutoxy) propane; the polypropoxy group has a molecular weight of 1000); 2,2-bis (didecoxyphosphaoxybutoxy) propane; 1,1-bis (diethoxyphosphaoxybutoxybutoxy) cyclohexane; 2,2-bis (phenoxydecoxyphosphaoxybutoxy) propane; bis (dimethoxyphosphaoxyethoxyethoxyethoxy) (phenyl) 2,2-bis (dioctadecoxyphosphaoxybutoxy) propane; methane. 2,2-bis (di-olleyloxyphosphaoxybutoxy) propane; 2,2-bis (di-cyclohexoxyphosphaoxybutoxy) propane; Illustrative of phosphonates of the present invention 2,2-bis (di-allyloxyphosphaoxybutoxybutoxy) propane; within Formulae III and IV are 2,2-bis (di-benzyloxyphosphaoxybutoxy) propane; 2,2-bis(methoxy) (methanephosphonobutoxy) propane 2,2-bis (di-butoxyphosphaoxybutoxy)butane; 2,2-bis (di-ethoxyphosphaoxypentoxy) butane; GH 9 2,2-bis (dimethoxyphosphaoxydecoxy) butane; CH-p-o CHO go CHO p-CH, 2,2-bis (dioctoxyphosphaoxydecosanoxy)butane; CHO CH3 O CH 2,2-bis (diethoxyphosphaoxyhexoxy) butane; 2,2-bis((methoxy)2'-hydroxyethanephosphonobutoxy) bis (di-octadecoxyphosphaoxybutoxy) methane; propane; bis (di-dodecycloxyphosphaoxypentoxy) methane; 2,2-bis((methoxy)2'-hydroxypropanephosphonobutoxy) bis (dimethoxyphosphaoxydecoxy) methane; propane; 1,1-bis (diethoxyphosphaoxybutoxy) ethane; 2,2-bis((methoxy) epoxypropanephosphonobutoxy) 1,1-bis (dipropoxyphosphaoxydecoxy) ethane; 60 propane; 1,1-bis (dioleyloxyphosphaoxybutoxy) propane; 2,2-bis((decoxy) decanephosphonobutoxy) propane; 1,1-bis (dipentoxyphosphaoxydecoxy) propane; 2,2-bis((phenoxy) decane-phosphonobutoxy) propane; 1,1-bis (dioleyloxyphosphaoxypentoxy) propane; 2,2-bis((octadecoxy) octadecanephosphonobutoxy) 1,1-bis (didecoxyphosphaoxybutoxy) butane; propane; 1,1 - bis (dicyclohexoxyphosphaoxybutoxy) - 2-methyl 2,2-bis((oleyloxy) A9-octadecenephosphonobutoxy) propane; propane; 1,1-bis (dimethoxyphosphaoxybutoxy) dodecane; 2,2-bis((cyclohexoxy)cyclohexanephosphonobutoxy) 1,1-bis (diisopropoxyphosphaoxydecoxy) dodecane; propane; 1,1-bis (dimethoxyphosphaoxybutoxy) octadecane; 2,2-bis((allyloxy) propenephosphonobutoxy) propane; 1,1-bis (diethoxyphosphaoxydecoxy) octadecane; 2,2-bis((benzyloxy)phenylmethanephosphonobutoxy) bis (dibutoxyphosphaoxybutoxy) (phenyl) methane; propane; 1,1-bis (di-dodecoxyphosphaoxybutoxy) propene-2; 2,2-bis((butoxy)butanephosphonobutoxy)butane; 1,1-bis (diethoxyphosphaoxydecoxy) propene-2; 2,2-bis((ethoxy)ethanephosphonopentoxy)butane; 1,1-bis (dipropoxyphosphaoxybutoxy) butene-2; 2,2-bis((methoxy) methane phosphonodecoxy)butane; 1,1-bis (dimethoxyphosphaoxybutoxy) octadecene-9; 5 2,2-bis((octoxy) octanephosphonoeicosanoxy)butane; 3,382,301 15 16 2,2-bis((ethoxy)ethanephosphonohexoxy)butane; 2,2-bis((octoxy) octanephosphonopolypropoxy)butane bis((octadecoxy) octadecanephosphonobutoxy) methane; (where the polypropoxy group has a molecular weight bis((dodecyloxy) dodecanephosphonopentoxy) methane; of 1000); bis(methoxy) methanephosphonodecoxy) methane; 1,1-bis((ethoxy)ethanephosphonobutoxybutoxy) cyclo 1,1-bis((ethoxy)ethanephosphonobutoxy)ethane; 5 hexane; 1,1-bis((propoxy) propanephosphonodecoxy)ethane; bis((methoxy) methanephosphonoethoxyethoxy-ethoxy) 1,1-bis((oleyloxy) A9-octadecenephosphonobutoxy) phenyl)methane. proparie; Illustrative examples of starting phosphites (which 1,1-bis((pentoxy) pentanephosphonodecoxy) propane; can be prepared in the manner set forth in the parent 1,1-bis(Coleyloxy) A9-octadecenephosphonopentoxy) O application) useful for preparing the phosphonates of 1,1-bis((decoxy)propane; decanephosphonobutoxy)butane; the Formula V are 1,1-bis((cyclohexoxy) cyclohexanephosphono-butoxy-2- 5,6 monophenylphosphite ester of 1,3,2,4-diisopropylidene methylpropane; sorbitol; 1,1-bis((methoxy) methanephosphonobutoxy) dodecane; 15 5,6-mono methyl phosphite ester of 1,3,2,4-diisopropyl idene sorbital; 1,1-bis((isopropoxy)isopropanephosphonodecoxy) 5,6-mono benzyl phosphite ester of 1,3,2,4-diisopropyl 1,1-bis((methoxy)dodecane; methanephosphonobutoxy) octadecane; idene sorbitol; 1,1-bis((ethoxy)ethanephosphonodecoxy) octadecane; 5,6-monodecyl phosphite ester of 1,3,2,4-diisopropylidene bis((butoxy)butanephosphonobutoxy) (phenyl)methane; 20 sorbitol; 1,1-bis((dodecoxy) dodecanephosphonobutoxy)propane-2; 5,6-mono octadecyl phosphosphite ester of 1,3,2,4-diiso 1,1-bis((ethoxy)ethanephosphonodecoxy) propene-2; propylidene sorbitol; 1,1-bis((propoxy) propanephosphonobutoxy)butene-2; 5,6-mono oleyl phosphite ester of 1,3,2,4-diisopropylidene sorbitol; 1,1-bis((methoxy) methanephosphonobutoxy) octadecene 5,6-mono cyclohexyl phosphite ester of 1,3,2,4-diiso 9; propylidene sorbitol; 1,1-bis(hexoxy) hexanephosphonobutoxy) (cyclohexyl) 5,6-monobutyl phosphite ester of 1,3,2,4-diethylidene bis((octoxy)methane; octanephosphonobutoxy) (phenyl)methane; sorbitol; bis((methoxy) methanephosphonopentoxy) (p-methyl 5,6-mono ethyl phosphite ester of 1,3,2,4-dibenzylidene phenyl)methane; 30 sorbitol; bis((octadecoxy) octadecanephosphonobutoxy) (o-chloro 3,4-mono-allyl phosphite ester of 1,2,5,6-diisopropylidene phenyl)methane; mannitol; bis((methoxy) methanephosphonobutoxy) (m-nitro 3,4-mono hexadecylphosphite ester of 1,2,5,6-diisopropyl phenyl)methane; idene mannitol; 2,2-bis((decoxy) decanephosphonobutoxy) pentane; 5,6-mono decyl phosphite ester of 1,3,2,4-dicyclohexyl 2,2-bis((methoxy) methanephosphonopentoxy) pentane; idene sorbitol; 3,3-bis((methoxy) methanephosphonobutoxy) pentane; 5,6-mono methyl phosphite ester of 1,3,2,4-di-methylene 3,3-bis((pentoxy) pentanephosphonodecoxy) pentane; sorbitol; 2,2-bis((methoxy) methanephosphonopentoxy) hexane; 5,6-mono methyl phosphite ester of 1,3,2,4-diisobutyl 3,3-bis((ethoxy)ethanephosphonobutoxy) hexane; 40 idene sorbitol; 2,2-bis((methoxy) methanephosphonobutoxy)3,3- 3,4-mono amyl phosphite ester of 1,2,5,6-di benzylidene dimethylbutane; mannitol; 4,4-bis((propoxy) propanephosphonoxhexoxy) heptane; 3,4-mono decyl phosphite ester of 1,2,5,6-diethylidene mannitol; 6,6-bis((hexadecoxy) hexadecanephosphonobutoxy) 5,6-mono cyclohexyl phosphite ester of 1,3,2,4-din-butyl 18,undecane; 18-bis((methoxy) methanephosphonobutoxy) idene sorbitol. pentatricontane; Illustrative of phosphonates of the present invention 1,1-bis((butoxy)butanephosphonobutoxy) within Formula V are cyclohexane; 1,1-bis((methoxy) methanephosphonobutoxy) 50 5,6-methanephosphonate ester of 1,3,2,4-diisopropylidene cyclopentane; sorbitol bis((octoxy) octanephosphonobutoxy) (diphenyl) methane; 1,1-bis((methoxy) methanephosphonooctoxy)-1- Cl V / CH phenylethane; 5 5 O CH 1,1-bis((methoxy) methanephosphonobutoxy)-1- phenylpropane; H bis((methoxy) methanephosphonoethoxyethoxy) -N- C- C methane; 1,1-bis((propoxy) propanephosphonoethoxyethoxy) 60 1,1-bis((decoxy)ethane; decanephosphonoethoxyethoxy)butane; 2,2-bis((ethoxy)ethanephosphonoethoxyethoxy) propane; 5,5-2'-hydroxyethanephosphonate ester of 1,3,2,4-diiso 2,2-bis((methoxymethanephosphonoethoxyethoxy) propylidene sorbitol; butane; 65 4,5-2'-hydroxypropanephosphonate ester of 1,3,2,4-diiso 1,1-bis((methoxy) methanephosphonoisopropoxyiso propylidene sorbitol; propoxy)ethane; 5,6-epoxypropane-phosphonate ester of 1,3,2,4-diisopro 2,2-bis((butoxy)butanephosphonoisopropoxyisopropoxy) pylidene sorbital; propane; 70 5,6-phenylmethanephosphonate ester of 1,3,2,4-diisopro 2,2-bis((pentoxy) pentanephosphonoisopropoxyiso pylidene sorbitol; propoxy)butane; 5,6-decanephosphonate ester of 1,3,2,4-diisopropylidene 2,2-bis((methoxy) methanephosphonopolyethoxy) sorbitol; propane (where the polyethoxy group has a molecular 5,6-octadecanephosphonate ester of 1,3,2,4-diisopropyl weight of 2,000; 75 idene sorbitol; 3,382,301 17 18 5,6-A9-octadecenephosphonate ester of 1,3,2,4-diisopro bis(2,3-dihydroxypropyl) pentanephosphonate; pylidene sorbitol; bis(2,3-dihydroxypropyl) dodecanephosphonate; 5,6-cyclohexanephosphonate ester of 1,3,2,4-diisopropyl bis(2,3-dihydroxypropyl) octanephosphonate; idene sorbital; amyl 2,3-dihydroxypropyl pentanephosphonate; 5,6-butanephosphonate ester of 1,3,2,4-diethylidene bis(2,3-dihydroxypropyl) butanephosphonate; sorbitol; bis(2,3-dihydroxypropoxy 1-methylethyl) ethylphospho 5,6-ethanephosphonate ester of 1,3,2,4-dibenzylidene nate sorbitol; 3,4-propenephosphonate ester of 1,2,5,6-diisopropylidene mannitol; 3,4-hexadecanephosphonate ester of 1,2,5,6-diisopropyl O bis(2,3-dihydroxypropoxy polyethoxy methylphosphonate idene mannitol; having 30 ethoxy groups 5,6-decanephosphonate ester of 1,3,2,4-dicyclohexylidene sorbitol; O 5,6-methanephosphonate ester of 1,3,2,4-di-methylene (CHP-co (CH2CH2O)30 CHCHOHCH3OH) sorbitol; bis(5,6-dihydroxyhexyl) 5,6-dihydroxyhexylphosphonate 5,6-methanephosphonate ester of 1,3,2,4-di-isobutylidene sorbitol; O 3,4-pentanephosphonate ester of 1,2,5,6-di-benzylidene HOCH2CHOH citish (OCHCHOHCH2OH)2) mannitol; 20 bis(5,6-dihydroxyhexyl decanephosphonate; 3,4-decane phosphonate ester of 1,2,5,6-diethylidene ethyl 5,6-dihydroxyhexyl ethanephosphonate; mannitol; bis(5,6-dihydroxyhexyl) methanephosphonate; 1,5,6-cyclohexyanephosphonate ester of 1,3,2,4-din bis(5,6-dihydroxyhexyl) hexanephosphonate; butylidene sorbitol. bis(5,6-dihydroxyhexyl) phenylmethanephosphonate; Illustrative of phosphonates of the present invention 25 bis(5,6-dihydroxyhexyl) heptanephosphonate; within Formula V are bis(2,3-dihydroxybutyl) 2,3-dihydroxybutanephospho nate; phenyl 2,3-dihydroxypropylmethylphosphonate bis(2,3-dihydroxybutyl) propanephosphonate; bis(2,3-dihydroxyamyl) butanephosphonate; CH, ho CECHCH2OH 30 bis(2-methyl-2,3-dihydroxybutyl) methanephosphonate; bis(2,2-di(hydroxymethyl) propyl) decylphosphonate CH3 bis (2,3-dihydroxypropyl) methane phosphonate; bis (2,3-dihydroxypropyl) 2-hydroxyethanephosphonate; (C.H. PoCH.) CH2OH. bis (2,3-dihydroxypropyl) 2-hydroxypropanephosphonate; 35 CHOH methyl 2,3-dihydroxypropyl methanephosphonate; bis 2,3-dihydroxypropyl) ethanephosphonate; bis(2,2-di(hydroxymethyl) butyl) butanephosphonate; bis (2,3-dihydroxypropyl) 2,3-dihydroxypropanephos amyl 2,2-di(hydroxymethyl) butyl pentylphosphonate phonate; 40 7 bis (2,3-dihydroxypropyl) decanephosphonate; CEP CH2OH. bis (2,3-dihydroxypropyl) octadecanephosphonate; / octadecyl 2,3-dihydroxypropyl octadecanephosphonate; O-CH2- CCHCH, bis (2,3-dihydroxypropyl) A9-octadecanephosphonate; CH2OH. bis (2,3-dihydroxypropyl) phenylmethanephosphonate; bis(2,2-di(hydroxymethyl) amyl) ethanephosphonate; bis (2,3-dihydroxypropyl) p-dodecylphenylmethanephos 45 bis(2,2-di(hydroxymethyl)monadecyl) propenephospho phonate; nate; bis (2,3-dihydroxypropyl) cyclohexanephosphonate; bis(2,2-di(hydroxymethyl) propyl) 2,2-di(hydroxymeth bis (3-methyl-2-4-dihydroxybutyl) 3-methyl 2,4-dihy yl) propanephosphonate; droxybutylphosphonate 50 bis(2,2-di(hydroxymethyl) propyl) hexadecanephospho nate; pH, bis(2,2-di(hydroxymethyl) butyl) 2,2-di(hydroxymethyl) HO CHCH HCH-P (-ooHipHCHCH.0 H)2 butanephosphonate; OE OH bis(2,2-di(hydroxymethyl) butyl) dodecanephosphonate; bis (3-methyl-2,4-dihydroxybutyl) ethanephosphonate; 55 bis(2,2-di(hydroxymethyl) butyl) ethanephosphonate; methyl 3-methyl-2,4-dihydroxybutyl methylphosphonate bis(2,2-di(hydroxymethyl) butyl) propanephosphonate; O O CH3 methyl 2,2-di(hydroxymethyl) butyl methanephospho M nate; CHP CH bis(2,2-di(hydroxymethyl) propyl) ethanephosphonate; O CH, HCHCH.On 60 bis(2,2-di(hydroxymethyl) propyl) octadecanephospho OH nate; bis (3-methyl-2,4-dihydroxybutyl) dodecanephosphonate; bis(2,2-di(hydroxymethyl) propyl) pentanephosphonate; bis (3-methyl-2,4-dihydroxybutyl) propenephosphonate; bis(2,2-di(hydroxymethyl) butyl) butanephosphonate; bis (3-methyl-2,4-dihydroxybutyl) cyclopentanephos bis(2,2-di(hydroxymethyl) propyl) methanephosphonate; phonate; bis(2-hydroxymethyl-2-phenyl-3-hydroxy propyl) meth butyl 3-methyl-2,4-dihydroxybutylbutanephosphonate; anephosphonate. bis(3-methyl-2,4-dihydroxybutyl) butanephosphonate; Illustrative of phosphonates of the present invention bis(3-methyl-2,4-dihydroxybutyl) propanephosphonate; within Formula VII are bis(2,3-dihydroxypropyl) isobutanephosphonate; 70 5,5-dihydroxymethyl-1,3-dioxa-2-methylphosphonocyclo O hexane (Ch. Hohlfo CHCHOHCHOH)2 CH3 CH3P OCHA C CH-OH N / N oleyl. 2,3-dihydroxypropane A9-octadecenephosphonate; OCH CIOE 3,382,301 19 20 5,5-di(hydroxymethyl)-1,3-dioxa-2-(2-hydroxyethane) acid were refluxed in the manner described in Example phosphonocyclohexane; 1. From the reaction mixture was isolated 2-methyl-2- 5,5-di(hydroxymethyl)-1,3-dioxa-2-(2-hydroxypropane) ethyl-5-methylol-1,3-dioxacyclopentane, a colorless liquid phosphonocyclohexane; boiling at 63-67 C./0.3 mm., yield 485 grams (82.8% 5,5-di(hydroxymethyl)-1,3-dioxa-2-octadecanephospho of theory), hydroxy value 382.7 (theory 383) having nocyclohexane; the formula 5,5-di(hydroxymethyl)-1,3-dioxa-2-propenephosphono H cyclohexane Hoolig-H, CHOI O O (pCHA / 10 -c N The product is also called 2-methyl-2-ethyl-4-methylol nounkOCH CH2OH 1,3-dioxacyclopentane. 5,5-di(hydroxymethyl)-1,3-dioxa-2-A9 octadecenephos phonocyclohexane; Example 3 5,5-di(hydroxymethyl)-1,3-dioxa-2-phenylmethanephos 15 2.1 moles of cyclohexanone, 2.0 moles of glycerine, phonocyclohexane; 100 grams of toluene and 2 grams of 50% aqueous sul 5,5-di(hydroxymethyl)-1,3-dioxa-2-p-dodecylphenylene furic acid were refluxed for 3 hours into a Dean and ethanephosphonocyclohexane; Stark trap during which time the theoretical amount of 5,5-di (hydroxymethyl)-1,3-dioxa-2-decanephos water was collected. The reaction mixture was neutralized phonocyclohexane; 20 with 2 grams of sodium carbonate, filtered and the solvent 5,5-di (hydroxymethyl)-1,3-dioxa-2-cyclohexane removed in vacuo. The product which was recovered by phosphonocyclohexane; distillation was 2,2-pentamethylene-5-hydroxymethyl-1,3- 5,5-di (hydroxymethyl)-1,3-dioxa-2-butanephos dioxacyclopentane, a colorless liquid, B.P. 98-103' phonocyclohexane; C./0.6 mm., n.201.4780, showing strong infrared absorp 5,5-di (hydroxymethyl-1,3-dioxa-2-pentanephos tion at 2.78(OH) and 9.05 (ether) microns; yield 305 phonocyclohexane; grams (88.5% of theory). 5,5-di (hydroxymethyl)-1,3-dioxa-2-ethanepos phonocyclohexane; Example 4 5,5-di (hydroxymethyl)-1,3-dioxa-2-(1'-methyl) 6.0 moles of methyl ethyl ketone, 3.0 moles of 1,2,6- ethanephosphonocyclohexane; 30 hexanetriol, 400 grams of hexane and 10 grams of p 5,5-di(hydroxymethyl) 1,3-dioxa-2-dodecanephos toluenesulfonic acid were refluxed for 8 hours while col phonocyclohexane; lecting the water formed by the reaction in a Dean and 5,5-di(hydroxymethyl)-1,3-dioxa-2-octanephos Stark trap. From the reaction mixture was isolated 490 phonocyclohexane; grams (86.7% yield) of 2-methyl-2-ethyl-5-(4-hydroxy 5,5-di (hydroxymethyl)-1,3-dioxa-2-hexadecanephos 3 5 butyl) 1,3-dioxacyclopentane, a colorless liquid B.P. 106 phonocyclohexane; 110° C./0.6 mm., hydroxyl value 294.5 (theory 298). 5,5-di(hydroxymethyl)-1,3-dioxa-2-hexanephos Example 5 phonocyclohexane; 5,5-di (hydroxymethyl)-1,3-dioxa-2-propanephos 40 1.0 mole of trimethyl phosphite and 2.0 moles of 2 phonocyclohexane. methyl-2-ethyl-5(4-hydroxybutyl) - 1,3 - dioxacyclopen tane. The ketal of Example 4 were heated with 1 gram Illustrative of phosphonates of the present invention of sodium methoxide for 1 hour at 80 to 140° C. (pot within Formula VIII are temperature) while allowing methanol to distill from the 5,6-methanephosphonate ester of sorbitol; reaction mixture through a packed column. After vacuum 5,6-(2'-hydroxy) ethane phosphonate ester of sorbitol; stripping, the product was filtered to give 430 grams 5,6-(2'-hydroxy) propanephosphonate ester of sorbitol; (98.5% of theory) of methyl bis(4-(2-methyl-2-ethyl 5,6-phenylmethanephosphonate ester of sorbitol; 1,3-dioxacyclopentyl) butyl) phosphite a colorless liquid 5,6-decanephosphonate ester of sorbitol; having the formula 5,6-octadecanephosphonate ester of sorbitol; CEOPOCH CECH2CH2CH-CH 5,6-A9-octadecenephosphonate ester of sorbitol; 50 5,6-butanephosphonate ester of sorbitol; N / 5,6-ethanephosphonate ester of sorbitol; / ca 3,4-propenephosphonate ester of mannitol; CE3 C2H2 3,4-hexadecanephosphonate ester of mannitol; 5 5 3,4-pentanephosphonate ester of mannitol; Example 6 3,4-decanephosphonate ester of mannitol. The procedure of Example 5 was repeated but utiliz ing 2.0 moles of 2,2-pentamethylene-5-hydroxymethyl Unless otherwise indicated, all parts and percentages 1,3-dioxacyclopentane (the ketal of Example 3) in place are by weight. of the ketal of Example 4. The product was methyl bis Example 1 60 (3(1,4-dioxaspiro-(5,5)-decyl)methyl) phosphite, a color 8 moles of acetone, 2 moles of trimethylolethane, 400 less viscous liquid obtained in a yield of 96.3% and hav grams of pentane and 6 grams of p-toluenesulfonic acid ing the formula were mixed and heated at reflux and the water of reac tion was collected in a Dean and Stark trap. Heating was CH-O-P o–CH-I-H, continued until the theoretical amount of water had been o, o removed. The product was 2,2,5-trimethyl-5-methylol / ca 1,3-dioxacyclohexane, a colorless viscous liquid, yield GH, GH, 283 grams (88.2% of theory) B.P. 84-88 C./0.8 mm., CH, CH2 showing significant infrared absorptions at 2.78(OH) and 70 N / 9.22 (cyclic ether) microns. CH 2 Example 2 Example 7 8 moles of methyl ethyl ketone, 4 moles of glycerine, The procedure of Example 5 was repeated but utilizing 400 grams of hexane and 10 grams of p-toluene sulfonic 75 2.0 moles of 2,2,5-trimethyl-5-methylol-1,3-dioxacyclo 3,382,301 21 22 hexane (the ketal of Example 1) in place of the ketal Example 13 of Example 4. The product was methyl bis(5-(2,5-dimeth yl-3-ethyl-1,3-dioxacyclohexyl)methyl)phosphite. The procedure of Example 9 was repeated replacing the ketal phosphite of Example 5 by 2-methoxy-9-methyl Example 8 5 9 - ethyl - 1,3,8,10 - tetraoxa - 2 - phosphaspiro (5,5) The procedure of Example 5 was repeated but utilizing undecane and using 1 gram of methyl iodide as the cata 2.0 moles of 2-methyl-2-ethyl-5-methylol-1,3-dioxacyclo lyst. The product was 2-(methane)-9-methyl-9-ethyl-1,3, pentane (the ketal of Example 2) in place of the ketal 8,10-tetraoxa-2-phosphonospiro (5,5) undecane. of Example 4 and using 1 mole of trioctadecyl phosphite Example 14 in place of the trimethyl phosphite. The product was O octadecyl bis(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) The procedure of Example 9 was repeated replacing methyl)phosphite. the ketal phosphite of Example 5 by 200 grams of 2,2-bis Example 9 (dimethoxyphosphabutoxy) propane and using 1 gram of 200 grams of the methyl bis(4-(2-methyl-2-ethyl-1,3- methyl iodide as the catalyst. The product was 2,2-bis dioxacyclopentyl) butyl phosphite (the ketal phosphite (methoxy) methanephosphonobutoxy) propane. prepared in Example 5) was heated for 7 hours at 140 Example 15 150 C. with one gram of ethyl iodide as a catalyst. The conversion to phosphonate was followed by periodic sam The procedure of Example 9 was repeated replacing pling and titration with 0.1 N iodine in benzene during the ketal phosphite of Example 5 by 200 grams of the the heating period. All of the phosphite was converted 5,6-monodecyl phosphite ester of 1,3,2,4-diisopropylidene after the 7 hours of heating. After vacuum stripping, there sorbitol and using 1 gram of decyl iodide as the catalyst. was obtained as the product in a yield of 99.4% bis(4- The product was 5,6-decylphosphonate ester of 1,3,2,4- (2 - methyl - 2 - ethyl - 1,3 - dioxacyclopentyl) butyl) diisopropylidene sorbitol. methylphosphonate as a colorless liquid having the struc 2 5 ture: Example 16 O 100 grams of bis(4-(2-methyl-2-ethyl-1,3-dioxacyclo CHF och. CHCHigh CH2 pentyl) butyl)methanephosphonate (the ketal phospho 30 nate of Example 9) was heated for 30 minutes at 80° C. o, / with an equal weight of water. The pH of the mixture was between 2 and 4 due to a small residual acidity of CH3*...) CH5.2 the ketal phosphonate. By the end of the heating period, There was a slight impurity of bis(4-(2-methyl-2-ethyl the reaction mixture was homogeneous due to hydrolysis 1,3-dioxacyclopentyl)butyl)ethane-phosphonate. In an of the ketal groups. There was no change in acidity indi other run by using methyl iodide rather than ethyl iodide cating no hydrolysis of the phosphonate to phosphonic as the catalyst the impurity was completely eliminated. acid. The reaction mixture was cooled, neutralized to a pH of 7 with sodium hydroxide and the water was re Example 10 moved in vacuo. The filtered product was bis(5,6-dihy 40 droxyhexyl)methylphosphonate, a colorless viscous liq The procedure of Example 9 was repeated replacing the quid obtained in quantitative yield, and having a hydroxyl ketal phosphite of Example 5 with 200 grams of methyl value of 694 (Theory 683) and having the formula bis(3 (14 - dioxaspiro (5,5) decyl)methyl)phosphite (the ketal phosphite of Example 6) and using 1 gram of ethyl O iodide as a catalyst. The product was bis(3(1,4-dioxa spiro (5,5) decyl)methyl)methane phosphonate, a viscous CH, (OCHCHCHCH-HCH-OH). slightly yellow liquid having the formula OH O Example 17 CHF O CHCH- CE The procedure of Example 16 was repeated replacing the ketal phosphonate of Example 9 by 100 grams of bis () ) (3(1,4-dioxaspiro (5,5) decyl)methyl methanephosphonate Y/ (the ketal phosphonate of Example 10). The product was bis (2,3-dihydroxypropyl)methanephosphonate, a colorless 5 5 syrup obtained in a yield of 98.7% and having the formula O CHP (O CHCHCHOH) Example 11 H 60 The procedure of Example 10 was repeated replacing Example 18 the ketal phosphite of Example 6 with 200 grams of methyl bis(5(2,5-dimethyl-2-ethyl-,1,3-dioxacyclohexyl) The procedure of Example 16 was repeated replacing methyl)phosphite and using 1 gram of methyl iodide as the ketal phosphonate of Example 9 by 100 grams of 2 the catalyst. The product was bis(5(2,5-dimethyl-2-ethyl (methane)-9-methyl-9-ethyl-1,3,8,10-tetraoxa - 2 - phos phono spiro (5,5) undecane. The product was 5,5-di-hy 1,3-dioxacyclohexyl)methyl)methanephosphonate. droxymethyl - 1,3 - dioxa - 2 - methanephosphonocyclo Example 12 hexane Example 19 The procedure of Example 9 was repeated replacing the The procedure of Example 16 was repeated replacing ketal phosphite of Example 5 with 200 grams of octa the ketal phosphonate of Example 9 by 100 grams of 5,6- decyl bis(4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl)meth decanephosphonate ester of 1,3,2,4-diisopropylidene sor yl) phosphite and using 1 gram of octadecyl bromide as bitol. The product was the 5,6-decanephosphonate ester the catalyst. The product was bis(4-(2-methyl-2-ethyl of sorbitol. 1,3-dioxacyclopentyl)methyl) octadecanephosphonate. 75 In addition to the compounds set forth supra the pres 3,382,301 23 24 The novel compounds of Formula A can be prepared by ent invention in one aspect is directed to the preparation Several procedures. Thus they can be prepared in pure of compounds (acetals and ketals) having the formula form by reacting (1) a trihydrocarbon phosphite, e.g. a RO O R3 Rs R Rs trialkyl phosphite, or a trihalophenyl phosphite with (2) YkCHéHo), (CHSc-os, at least an equimolar amount of a 4-haloalkyl dioxolane Rio? () () 5 or a 4-haloalkoxyalkyl dioxolane or a 4-haloalkyl dioxane or 4-haloalkoxyalkyl dioxane. Y^ As the starting phosphite there can be used trimethyl R? y; phosphite, triethyl phosphite, tri n-propylphosphite, tri O isopropyl phosphite, tri n-butyl phosphite tri sec. butyl or the formula phosphite, tri t-butyl phosphite, tri n-amyl phosphite, tri hexyl phosphite, tris decyl phosphite, tris n-octyl phos RO O R3 R1s phite, tris 2-ethylhexyl phosphite, tris isooctyl phosphite, Y-(CH&HO). CH-)-CH-0 Rs tris isodecyl phosphites, tris dodecyl phosphite, tris octa &H-0-6, decyl phosphite, dimethyl ethyl phosphite, methyl diethyl phosphite, phenyl didecyl phosphite, diphenyl decyl phos R phite, triphenyl phosphite, trip-cresyl phosphite, trim A. cresyl phosphite, trio-cresyl phosphite, tri xylenyl phos In Formula A and A' above R1 and R2 are alkyl, alkenyl phite, tria-naphthyl phosphite, trig-naphthyl phosphite, monocyclic carbocyclic aryl e.g. phenyl and alkyl phenyl, tris cyclohexyl phosphite, tri oleyl phosphite, trially benzyl, alkylbenzyl, naphthyl or halophenyl, R3 is hydro 20 phosphite, tri o-chlorophenyl phosphite, tri p-chloro gen or lower alkyl, R4 and R5 are hydrogen or alkyl, R6 phenyl phosphite, dibutyl phenyl phosphite, trim-chloro and R individually are hydrogen, alkyl, alkenyl, mono phenyl phosphite, trip-bromophenyl phosphite, butyl di cyclic carbocyclic aryl, e.g. phenyl and alkyl phenyl, phenyl phosphite, methyl diphenyl phosphite, dioctyl naphthyl, halophenyl or nitrophenyl and phenyl phosphite, dimethyl phenyl phosphite, tris benzyl R6 N phosphite, tricetyl phosphite, tris methylbenzyl phosphite. C The 4-haloalkyl dioxolane (or dioxane) type com / pound can be prepared in known fashion by reacting R epichlorhydrin 1,2-epoxy-12-chlorododecane, 1,2-epoxy together can be a cycloalkyl ring of 5 to 6 carbon atoms, 30 4-chlorobutane, 1,2-epoxy-6-chlorohexane, 1,2-epoxypro Ra is hydrogen alkyl, phenyl or alkyl phenyl, Ris is alkyl, poxyethyl chloride, 3-chloro-1,2-propylene glycol, 1,2-di v is zero or an integer, m is an integer between 1 and 2 hydroxy-12-chlorododecane, 1,3 - dihydroxy-4-chlorobu inclusive and n is an integer between 1 and 10 inclusive. tane, 1,3-dihydroxy-5-chloropentane, or 1,3-dihydroxy The compounds of the present invention in general are 12-chlorododecane with an aldehyde or ketone such as high boiling liquids. formaldehyde, isobutyraldehyde, acetaldehyde, propion Compounds of Formula A and A' have many uses. aldehyde, butyraldehyde, valeraldehyde, lauraldehyde, Thus they can be used as water dispersible wetting and stearaldehyde, isovaleraldehyde, heptaldehyde, benzalde suspending agents. They can also be employed as fire re hyde, acrolein, crotonaldehyde, oleic aldehyde, o-tolu tardants for cellulose, cellulose esters, e.g. cellulose ace aldehyde, p-tolualdehyde, ox-naphthaldehyde, 6-naphth tate and cellulose acetate butyrate, polyolefin resins, e.g. 40 aldehyde, p-chlorobenzaldehyde, o-chlorobenzaldehyde, polyethylene, polypropylene, ethylene-propylene copoly o-nitrobenzaldehyde, p-nitrobenzaldehyde, 2,4-dichloro mers and copolymers of ethylene or propylene with mono benzaldehyde, m-chlorobenzaldehyde, o-bromobenzalde olefins having more than 3 carbon atoms. hyde, hexahydrobenzaldehyde, acetone methyl ethyl ke A particularly important use for the acetals and ketals tone, methyl n-propyl ketone, diethyl ketone, hexanone-2, of Formula A and A is to hydrolyze them to give hy hexanone-3, methyl t-butyl ketone, di n-propyl ketone, droxyl containing phosphonates having the following for diisopropyl ketone, disobutyl ketone, di no-amyl ketone, mula stearanone, cyclohexanone, cyclopentanone, benzaphe RO O R3 R8 R4 Rs NE N / none, acetophenone, propiophenone, and methyl cyclo P(CHCHo). (CII)--(p- hexanone. RO OH &H Illustrative of such starting dioxolanes and dioxanes B for preparing the compounds of Formula A are 2-methyl-2-ethyl-4-chloromethyl dioxolane, or the formula 2,5-dimethyl-2-ethyl-5-chloromethyl m-dioxane, RO. O. R3 CHOH N / 5 5 2,2,5-trimethyl-5-chloromethyl m-dioxane, P-(CH2CHO). CH-C N 2,2-dimethyl-4-chloromethyl dioxolane, RO R15CH2OH. 4-chloromethyl dioxolane, B 2-methyl-4-chloromethyl dioxolane, In Formula B the terms R1, R2, R3, R4, R5, Ra, R15, v, 2-ethyl-4-chloromethyl dioxolane, m and n are the same as defined in Formula A and A. 60 2-propyl-4-chloromethyl dioxolane, The hydroxyl containing phosphonates of Formula B and 2-isopropyl-4-chloromethyl dioxolane, B' have the uses set forth for the compounds of Formula 2-undecyl-4-chloromethyl dioxolane, A and in addition are useful for preparing polyurethanes 2-heptadecyl-4-chloromethyl dioxolane, by reaction with organic icocyanates, e.g. toluene di 2-heptadecenyl-4-chloromethyl dioxolane, isocyanate and PAPI (polyphenylene isocyanate averag 2-vinyl-4-chloromethyl dioxolane, ing about 3 units in the polymer). The polyurethanes can 2-phenyl-4-chloromethyl dioxolane, be prepared as foams or as elastomers. The presence of 2-p-methylphenyl-4-chloromethyl dioxolane, the phosphonate group renders the polyurethane flame 2-o-chlorophenyl-4-chloromethyl dioxolane, resistant. The phosphonate of Formula B and B' need 2-m-nitrophenyl-4-chloromethyl dioxolane, be used only as a portion of the polyols employed. Thus 70 2-a-naphthyl-4-chloromethyl dioxolane, the use of 20% of a polyhydroxyl containing phosphonate 2-m-bromophenyl-4-chloromethyl dioxolane, of Formula B and 80% of another polyol, e.g. glycerine 2-methyl-2-propyl-4-chloromethyl dioxolane, propylene oxide adduct molecular weight 3000 or poly 2,2-diethyl-4-chloromethyl dioxolane, propylene glycol 2025 will give a polyurethane with im 2-methyl-2-butyl-4-chloromethyl dioxolane, proved flame resistance. 2-ethyl-2-propyl-4-chloromethyl dioxolane, 3,382,301 25 26 2-methyl-2-t-butyl-4-chloromethyl dioxolane, atmospheric or superatmospheric pressure. The halide re 2,2-dipropyl-4-chloromethyl dioxolane, maining after the reaction is removed by distillation. 2,2-diamyl-4-chloromethyl dioxolane, The halides which can be employed in the Arbuzov 2,2-diheptadecyl-4-chloromethyl dioxolane, reaction include as stated previously methyl iodide, methyl 2-pentamethylene-4-chloromethyl dioxolane, 5 bromide, ethyl bromide, ethyl iodide, n-propyl iodide, iso 2-tetramethylene-4-chloromethyl dioxolane, propyl iodide, amyl bromide, amyl chloride, amyl iodide, 2,2-diphenyl-4-chloromethyl dioxolane, butyl bromide, butyl iodide, hexyl iodide, octyl bromide, 2-methyl-2-phenyl-4-chloromethyl dioxolane, octyl iodide, decyl bromide, decyl iodide, dodecyl iodide, 2,2-dimethyl-4-chloroethoxymethyl dioxolane, octadecyl bronide, octadecyl iodide, allyl bromide, allyl 2,2-dimethyl-4-chloroisopropoxymethyl dioxolane, 0 iodide, allyl chloride, methallyl iodide, crotyl bromide, 2-methyl-2-ethyl-4-chloropolyethoxymethyl dioxolane vinyl bromide, cleyl bromide, oleyl iodide, benzyl chlo ride, benzyl bromide, benzyl iodide, o-dodecylbenzyl chlo wherein the polyethoxy contains 30 ethoxy groups, 2 ride, p-dodecylbenzyl bromide, epichlorhydrin, epibromo methyl - 2-ethyl-4-chloropolyisopropoxymethyl dioxolane hydrin, epiiodohydrin, ethylene chlorohydrin, ethylene wherein the polyisopropoxy contains 25 isopropoxy 5 bronnohydrin, ethylene iodohydrin, propylene chlorohy groups, drin and propylene bromohydrin. 2-methyl-4-chloro(ethyl)ethoxymethyl dioxolane, illustrative of the phosphites which can be employed 2,2-dimethyl-4-chlorobutyl dioxolane, for the Arbuzov rearrangement to make compounds of 2,2-dimethyl-4-chlorodecyl dioxolane, Formula A are 2,2-dimethyl-4-chlorohexyl dioxolane, 20 bis phenyl-4-(2-methyl-2-ethyl-1,3-dioxacyclo-pentyl) 2-methyl-2-ethyl-4-chlorobutyl dioxolane, methyl phosphite, 4-chlorobutyl dioxolane, dimethyl-4-(2-methyl-2-ethyl-1,3-dioxacyclo-pentyl) 2-propyl-4-chlorobutyl dioxolane, methyl phosphite, 2,2,5-trimethyl-4-chloromethyl dioxolane, bis octadecyl-4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) 2,2-dimethyl-5-ethyl-4-chloromethyl dioxolane, 25 methyl phosphite, 2,4,5-trimethyl-2-ethyl-4-chloromethyl dioxolane, bis p-butylphenyl-4-(2-methyl-2-ethyl-1,3-dioxacyclo 2,5-dimethyl-5-chloromethyl m-dioxane, pentyl) methyl phosphite, 2-methyl-2,5-diethyl-5-chloromethyl m-dioxane, bis o-chlorophenyl-4-(2-methyl-2-ethyl-1,3-dioxacyclo 2,2-dimethyl-5-propyl-5-chloromethyl m-dioxane, pentyl) methyl phosphite, 2,2-dimethyl-5-heptadecyl-5-chloromethyl m-dioxane, 30 bis phenyl-5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl) 5-methyl-5-chloromethyl m-dioxane, methyl phosphite, 5-ethyl-5-chloromethyl m-dioxane, dimethyl-5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl) 2-methyl-5-ethyl-5-chloromethyl m-dioxane, methyl phosphite, 2-butyl-5-methyl-5-chloromethyl m-dioxane, bis lauryl-5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl) 2-isobutyl-5-ethyl-5-chloromethyl m-dioxane, methyl phosphite, 2-phenyl-5-methyl-5-chloromethyl m-dioxane, bis o-decylphenyl-5-(2,5-dimethyl-2-ethyl-1,3-dioxacyclo 2phenyl-5-methyl-5-chloromethyl m-dioxane, hexyl) methyl phosphite, 2-phenyl-5-ethyl-5-chloromethyl m-dioxane, bis m-chlorophenyl-5-(2,5-dimethyl-2-ethyl-1,3-dioxa 2-p-methylphenyl-5-methyl-5-chloromethyl m-dioxane, 40 cyclohexyl) methyl phosphite, 2-o-chlorophenyl-5-ethyl-5-chloromethyl m-dioxane, dibutyl-5-(2,2,5-trimethyl-1,3-dioxacyclohexyl) methyl 2-m-nitrophenyl-5-methyl-5-chloromethyl m-dioxane, phosphite, 2,2-dimethyl-5-ethyl-5-chloromethyl m-dioxane, diphenyl-5-(2,2,5-trimethyl-1,3-dioxacyclohexyl) methyl 2,2,5-trimethyl-5-chloromethyl m-dioxane, phosphite, 2-methyl-2-phenyl-5-ethyl-5-chloromethyl m-dioxane, dimethyl-4-(2-heptadecyl-1,3-dioxacyclopentyl) methyl 2,5-dimethyl-2-phenyl-5-chloromethyl m-dioxane, 45 phosphite, 2,2-diethyl-5-methyl-5-chloromethyl m-dioxane, bis octadecyl-4-(1,3-dioxacyclopentyl) methyl phosphite, 2-pentamethylene-5-methyl-5-chloromethyl m-dioxane, diphenyl-4-(2-methyl-1,3-dioxacyclophenyl) methyl 2-pentamethylene-5-ethyl-5-chloromethyl m-dioxane, phosphite, 2-cyclohexyl-5-methyl-5-chloromethyl m-dioxane, 50 bis cleyl-4-(2-ethyl-1,3-dioxacyclopenty) methyl 2,2-diamyl-5-ethyl-5-chloromethyl m-dioxane, and phosphite, 2,2-dimethyl-5-phenyl-5-chloromethyl m-dioxane. diphenyl-4-(2-propyl-1,3-dioxacyclopentyl) methyl phosphite, The compounds of Formula A can also be formed by dimethyl-4-(2-heptadecyl-1,3-dioxacyclopentyl) methyl the Arbuzov rearrangements of the corresponding phos 55 phosphite, phite of parent Patent 3,096,345. If both R1 and R2 are diphenyl 4-(2-vinyl-1,3-dioxacyclopentyl) methyl aryl, halaryl or tert. alkyl, relatively pure products of phosphite, Formula A are produced. There is employed an alkyl bis octadecyl-4-(2-O-chlorophenyl-1,3-dioxacyclopenty halide, alkenyl halide, aralkyl halide, halohydrin or epi methyl phosphite, halohydride with a phosphite of the parent patent that 60 di p-cresyl-4-(2-methyl-2-propyl-1,3-dioxacyclopentyl) is isomeric with a phosphonate of Formula A. The iodides methyl phosphite, and bromides are preferred although there can also be diamyl-4-(2,2-diethyl-1,3-dioxacyclopentyl) methyl employed the chloride. The halides are used in catalytic phosphite, amounts, e.g., 0.5-5 mol percent based on the phosphite diethyl-4-(2-methyl-2-t-butyl-1,3-dioxacyclopentyl) to be arranged in order to reduce the impurities to a mini methyl phosphite, mum. Generally, however, using the Arbuzov rearrange 65 diphenyl-4-(2,2-diheptadecyl-1,3-dioxacyclo-penty) ment, however, some impurities are introduced since the methyl phosphite, R and R2 group can undergo rearrangement (unless they diphenyl-3-(1,4-dioxaspiro-(5,5)-decyl) methyl phosphite, are aryl, haloaryl or tert. alkyl) as well as the dioxolanyl di-o-cresyl-4-(2,2-diphenyl-1,3-dioxacyclopentyl) methyl methyl to form a phosphonate. Additionally a certain phosphite, amount of the alkyl group or the like of the catalyst can 70 diphenyl-4-(2-methyl-2-phenyl-1,3-dioxacyclopentyl) also enter the molecule by direct attachment to the methyl phosphite, phosphorus atom. diethyl-4-(1,3-dioxacyclopentyl) butyl phosphite, The Arbuzov rearrangement can be carried out at ele dipropyl-4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) wated temperature, e.e., 120-200° C. at atmospheric, sub 75 ethoxymethyl phosphite,

3,382,301 29 30 diethyl-4-(2-pentamethylene-1,3-dioxacyclopentyl) dibutyl-5-(2-methyl-2-phenyl-5-ethyl-1,3-dioxacyclo methyl phosphonate, hexyl) methyl phosphonate, diphenyl-4-(2-pentamethylene-1,3-dioxacyclopentyl) dimethyl-5-(2,5-dimethyl-2-phenyl-1,3-dioxacyclo methyl phosphonate, hexyl) methyl phosphonate, ethyl p-cresyl-4-(2-tetramethylene-1,3-dioxacyclopentyl) 5 dimethallyl-5-(2,2-diethyl-5-methyl-1,3-dioxacyclohexyl) methyl phosphonate, methyl phosphonate, dipropyl-4-(2,2-diphenyl-1,3-dioxacyclopentyl) methyl diethyl-5-(2-pentamethylene-5-methyl-1,3-dioxacyclo phosphonate, hexyl) methyl phosphonate, dimethyl-4-(2-methyl-2-phenyl-1,3-dioxacyclopentyl) diphenyl-5-(2-pentamethylene-5-ethyl-1,3-dioxacyclo methyl phosphonate, hexyl) methyl phosphonate, dimethyl-4-(2,2-dimethyl-1,3-dioxacyclopentyl) 10 diphenyl-5-(2-pentamethylene-5-ethyl-1,3-dioxacyclo methoxyethyl phosphonate, hexyl) methyl phosphonate, diphenyl-4-(2,2-dimethyl-1,3-dioxacyclopentyl) methoxy dimethyl-5-(2-cyclohexyl-5-methyl-1,3-dioxacyclohexyl) isopropyl phosphonate, methyl phosphonate, diethyl-4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) 15 diethyl-5-(2,2-diamyl-5-ethyl-1,3-dioxacyclohexyl) methoxy polyethoxy ethyl phosphonte methyl phosphonate, diphenyl-5-(2,2-dimethyl-5-phenyl-1,3-doxacyclohexyl) wherein there are 29 ethoxy groups, methyl phosphonate. phenyl p-cresyl-4-(2-methyl-2-ethyl-1,3-dioxacyclo The compounds of Formula B are prepared by pentyl) methoxy polyisoproxy isopropyl phosphonate 20 hydrolysis of the compounds of Formula A. The hydrol wherein there are 24 isopropyl groups, ysis carried out with the aid of water, preferably with heating e.g., up to 100° C. To hasten hydrolysis there dimethyl-4-(2-methyl-1,3-dioxacyclopentyl) (ethyl) can be added a small amount of acid, e.g., hydrochloric methoxyethyl phosphonate, acid. After hydrolysis is complete, an alkaline material, ethylbutyl-4-(2,2-dimethyl-1,3-dioxacyclopentyl) butyl e.g., sodium hydroxide, sodium carbonate, sodium bi phosphonate, carbonate, potassium hydroxide or potassium carbonate diphenyl-4-(2,2-dimethyl-1,3-dioxacyclopentyl) decyl can be added to neutralize the product. phosphonate, diethyl-4-(2,2-dimethyl-1,3-dioxacyclopentyl) decyl Illustrative of phosphonates within Formula B are phosphonate, dimethyl 2,3-dihydroxypropyl phosphonate O dimethyl-4-(2,2-dimethyl-1,3-dioxacyclopentyl) hexyl I phosphonate, ((CHO)ai CHCHOHCHOH) diphenyl-4-(2-methyl-2-ethyl-1,3-dioxacyclopentyl) diethyl 2,3-dihydroxypropyl phosphonate, butyl phosphonate, methyl ethyl 2,3-dihydroxypropyl phosphonate dipropyl diamyl-4-(1,3-dioxacyclopentyl) butyl phosphonate, 3 5 2,3-dihydroxypropyl phosphonate, di-p-cresyl-4-(2-propyl-1,3-dioxacyclopentyl) butyl diisopropyl 2,3-dihydroxypropyl phosphonate, phosphonate, dibutyl 2,3-dihydroxypropyl phosphonate di sec. butyl diethyl-4-(2,2,5-trimethyl-1,3-dioxacyclopentyl) methyl 2,3-dihydroxypropyl phosphonate dit.butyl 2,3-di phosphonate, hydroxypropyl phosphonate, diphenyl-4-(2,2-dimethyl-5-ethyl-1,3-dioxacyclopentyl) 40 diamyl 2,3-dihydroxypropyl phosphonate, methyl phosphonate, dihexyl 2,3-dihydroxypropyl phosphonate dicyclohexyl diisopropyl-4-(2,4-5-trimethyl-2-ethyl-1,3-dioxacyclo 2,3-dihydroxypropyl phosphonate, pentyl) methyl phosphonate, diheptyl 2,3-dihydroxypropyl phosphonate, diphenyl-5-(2,5-dimethyl-1,3-dioxacyclohexyl) methyl dioctyl 2,3-dihydroxypropyl phosphonate, phosphonate, didecyl 2,3-dihydroxypropyl phosphonate, dimethyl-5-(2-methyl-2,5-diethyl-1,3-dioxacyclohexyl) diisodecyl 2,3-dihydroxypropyl phosphonate, methyl phosphonate, dilaury 2,3-dihydroxypropyl phosphonate, dioctadecyl-5-(2,2-dimethyl-5-propyl-1,3-dioxacyclo dicetyl 2,3-dihydroxypropyl phosphonate, pentyl) methyl phosphonate, dioctadecyl 2,3-dihydroxypropyl phosphonate, diallyl-5-(2,2-dimethyl-5-heptadecyl-1,3-dioxacyclo 50 diallyl 2,3-dihydroxypropyl phosphonate, hexyl) methyl phosphonate, dicrotyl 2,3-dihydroxypropyl phosphonate, diethyl-5-(5-methyl-1,3-dioxacyclohexyl) methyl dimethallyl 2,3-dihydroxypropyl phosphonate, phosphonate, phenyl decyl 2,3-dihydroxypropyl phosphonate, diphenyl-5-(5-ethyl-1,3-dioxacyclohexyl) methyl diphenyl 2,3-dihydroxypropyl phosphonate, phosphonate, dip-cresyl 2,3-dihydroxypropyl phosphonate, dimethyl-5-(2-methyl-5-ethyl-1,3-dioxacyclohexyl) di-o-naphthyl 2,3-dihydroxypropyl phosphonate, methyl phosphonate, di-6-naphthyl 2,3-dihydroxypropyl phosphonate, diphenyl-5-(2-butyl-5-methyl-1,3-dioxacyclohexyl)methyl phosphonate, di-p-chlorophenyl 2,3-dihydroxypropyl phosphonate, dibutyl-5-(2-isobutyl-5-ethyl-1,3-dioxacyclohexyl) 60 di-p-bromophenyl 2,3-dihydroxypropyl phosphonate, methylphosphonate, di 3,5-xylenyl 2,3-dihydroxypropyl phosphonate di-4 diiooctyl-5-(2-phenyl-5-methyl-1,3-dioxacyclohexyl) methylbenzyl 2,3-dihydroxypropyl phosphonate methyl phosphonate, phenyl methyl 2,3-dihydroxypropyl phosphonate, ethyl butyl-5-(2-phenyl-5-ethyl-1,3-dioxacyclohexyl) di-o-cresyl 2,3-dihydroxypropyl phosphonate, methyl phosphonate, 6 5 di-p-butylphenyl 2,3-dihydroxypropyl phosphonate, diphenyl-5-(2-p-methyl-phenyl-5-methyl-1,3-dioxa di 2',4'-dichlorophenyl 2,3-dihydroxypropyl phosphonate, cyclohexyl) methyl phosphonate, diethyl 2,2-di(hydroxymethyl) propyl phosphonate dimethyl-5-(2-o-chlorophenyl-5-ethyl-1,3-dioxacyclo O hexyl) methyl phosphonate, | diethyl-5-(2-m-nitrophenyl-5-methyl-1,3-dioxacyclo 70 colleg hexyl) methyl phosphonate, CBOE CEOH didecyl-5-(2,2-dimethyl-5-ethyl-1,3-dioxacyclohexyl) didecyl 2,2-di-(hydroxymethyl) ethyl phosphonate, methyl phosphonate, diphenyl 2,2-di-(hydroxymethyl) propyl phosphonate, diphenyl-5-(2,2,5-trimethyl-1,3-dioxacyclohexyl) methyl dimethyl 2,2-di-(hydroxymethyl) propyl phosphonate, phosphonate, 75 ethyl amyl 2,3-dihydroxypropyl phosphonate, 3,382,301 3. 32 di-m-cresyl 2,3-dihydroxypropyl phosphonate, moles of 2-methyl-2-ethyl-4-chloromethyl dioxolane with phenyl dodecyl 2,3-dihydroxypropyl phosphonate, 1 mole of tris isodecyl phosphite to produce di-isodecyl di m-chlorophenyl 2,3-dihydroxypropyl phosphonate, 4-(2-methyl-2-ethyl-1,3-dioxyacyclopentyl) methyl phos methyl octyl 2,3-dihydroxypropyl phosphonate, phonate as the product. dibenzyl 2,3-dihydroxypropyl phosphonate, 5 Example IV p-cresyl ethyl 2,3-dihydroxypropyl phosphonate, dimethyl 3-oxa-5,6-dihydroxyhexyl phosphonate, The procedure of Example I was repeated using 1.3 diphenyl 3-oxa-2-methyl-5,6-dihydroxyhexyl phosphonate, moles of 2,2-dimethyl-4-chloromethyl dioxolane with 1 diethyl 2,3-dihydroxypropoxy polyethoxy ethyl phos mole of triallyl phosphite to produce diallyl-4-(2,2-di phonate methyl 1,3-dioxacyclopentyl) methyl phosphonate as the O product. wherein there are 29 ethoxy groups. Example V I(CH5O)2PCHCH(OCH2CH2)2CHCHOHCHOH) The procedure of Example I was repeated using 1.3 CHCHOHCHOH moles of 2,2-dimethyl-4-chloromethyl dioxolane with 1 phenyl p-cresyl 2,3-dihydroxy propoxypolyisoproxy iso 15 mole of triphenyl phosphite to produce diphenyl-4-(2,2- propyl phosphonate wherein there are 24 isopropoxy dimethyl-1,3-dioxacyclopentyl) methyl phosphonate as groups, the product. phenyl p-cresyl 2,3-dihydroxypropyl phosphonate, Example VI dimethyl 2-ethyl-3-oxa-5,6-dihydroxypropyl phosphonate ethyl butyl 5,6-dihydroxyhexyl phosphonate, 20 The procedure of Example I was repeated using 1.3 diphenyl,11,12-dihydroxydodecyl phosphonate, moles of 2,5-dimethyl-2-ethyl-5-chloromethyl m-dioxane diethyl 11,12-dihydroxydodecyl phosphonate, with 1 mole of triethyl phosphite to produce diethyl-5- dimethyl 7,8-dihydroxyoctyl phosphonate, (2,5-dimethyl-2-ethyl-1,3-dioxacyclohexyl) methyl phos diphenyl 5,6-dihydroxylhexyl phosphonate, phonate as the product. diamyl 5,6-dihydroxyhexyl phosphonate, Example VII dip-cresyl 5,6-dihydroxyhexyl phosphonate, 200 grams of dimethyl-4-(2-methyl-2-ethyl-1,3-diox diethyl 2,3-dihydroxybutyl phosphonate, acyclopentyl) methyl phosphite was heated for 7 hours diphenyl 2,3-dihydroxyamyl phosphonate, at 140-150° C. with 1 gram of amyl iodide as a catalyst diisopropyl 2,3-dihydroxybutyl phosphonate, to produce dimethyl-4-(2-methyl-2-ethyl-1,3-dioxacyclo diethyl 2,2-di(hydroxymethyl) propyl phosphonate, 30 pentyl) methyl phosphonate. dioctadecyl 2,2-di (hydroxymethyl) amyl phosphonate dially, Example VIII 2,2-di(hydroxymethyl) eicosanyl phosphonate, 200 grams of dipropyl-4-(2-methyl-2-ethyl-1,3-diox diphenyl 2,2-di(hydroxymethyl) butyl phosphonate, acyclopentyl) ethoxymethyl phosphite was heated for 7 dimethyl 2,2-di-(hydroxymethyl) butyl phosphonate, hours at 140-150° C. with 1 gram of propyl iodide as a dibutyl 2,2-di(hydroxymethyl) butyl phosphonate, catalyst to produce dipropyl-4-(2-methyl-2-ethyl-1,3-diox diisooctyl 2,2-di-(hydroxymethyl) propyl phosphonate, acyclopentyl) ethoxymethyl phosphonate. ethyl butyl 2,2-di-(hydroxymethyl) butyl phosphonate, didecyl 2,2-di(hydroxymethyl) butyl phosphonate, Example IX dimethallyl 2,2-di(hydroxymethyl) propyl phosphonate 40 100 grams of dimethyl-4-(2,2-dimethyl-1,3-dioxacyclo and pentyl) methyl phosphonate was heated for 30 minutes diphenyl 2,2-di(hydroxymethyl)-2-phenyl ethyl phos at 80° C. with an equal weight of water. The reaction phonate. mixture was cooled, neutralized to a pH of 7 with so Example I dium hydroxide and water was removed in a vacuum. The 1 mole of trimethyl phosphite was refluxed for 24 hours filtered product was dimethyl 2,3-dihydroxypropyl phos with 1.3 moles of 2,2-dimethyl-4-chloromethyl dioxolane. phonate. (The 2,2-dimethyl-4-chloromethyldioxolane was prepared Example X from epichlorhydrin and acetone as set forth in Petrov, J. The procedure of Example IX was repeated with 100 Gen. Chem. (USSR) 10, pages 981-96 (1940); Chem. 50 grams of diphenyl-4-(2,2-dimethyl-1,3-dioxacyclopentyl) Abst. 35, 3603 (1941). Titration of 2.0 gram sample of methyl phosphonate and 100 grams of water to produce the reaction mixture with 0.1 Niodine solution in benzene diphenyl 2,3-dihydroxypropyl phosphonate. showed that the reaction was substantially complete. The product was isolated by fractional distillation to give Example XI a 62% yield of dimethyl-4-(2,2-dimethyl-1,3-dioxacyclo 55 The procedure of Example IX was repeated with 100 pentyl) methyl phosphonate as a colorless liquid B.P. grams of diisodecyl-4 (2-methyl-2-ethyl-1,3-dioxacyclo 110-114 C. at 10 mm. having the formula pentyl) methyl phosphonate to produce diisodecyl 2,3-di O hydroxypropyl phosphonate. (CHO)2P CH2CHCH What is claimed is: / N 60 1. O -' RO O R R8 R4 R8 No N || b. H H R2O P-(CHCHo). (CH)--OH &H This compound can also be called dimethyl-5(2,2-di 65 methyl-1,3-dioxyacyclopentyl) methyl phosphonate. where R1 and R2 are selected from the group consisting of Example II alkyl, alkenyl, monocyclic carbocyclic aryl, naphthyl, The procedure of Example I was repeated using 1.3 benzyl, alkyl benzyl, chlorophenyl and bromophenyl; moles of 2,2-dimethyl-4-chloromethyl dioxolane with 1 70 Ra is selected from the group consisting of hydrogen mole of trimethyl phosphite to produce dimethyl-4-(2- and lower alkyl; methyl-2-ethyl-1,3-dioxacyclopentyl) methyl phosphonate R4 and R5 are selected from the group consisting of as the product. hydrogen and alkyl; Example III R8 is selected from the group consisting of hydrogen, The procedure of Example I was repeated using 1.3 alkyl and monocyclic carbocyclic aryl; 3,382,301 33 34 v is an integer of at least zero; alkyl, alkenyl, monocyclic carbocyclic aryl, naphthyl, m is an integer between 1 and 2 inclusive; and benzyl, alkyl benzyl, chlorophenyl and bromophenyl; n is an integer between 1 and 10 inclusive. R is selected from the group consisting of hydrogen 2. Dialkyl 2,3-dihydroxypropylri phosphonate. R15and is alkyl;lower and alkyl; pieInocyclic carbocyclic aryl 2,3-dihydroxypropyl 5 v is an integer of 0 to 100. 4. Monocyclic carbocyclic aryl alkyl 2,3-dihydroxy propyl phosphonate. References Cited Rodd: “Chemistry, of Carbon Compounds,' Elsevier 5. - Publishing Co., New York, vol. IV, Part A, p. 332, Rio R. CIOH (1957). P-(CHCHo).P- CEO),C CH- CHARLES B. PARKER, Primary Examiner. R2O RCH2OH. where 15 A. H. SUTTO, Assistant Examiner. R1 and R2 are selected from the group consisting of