CA1053690A - Unsaturated phosphorus containing carboxylic acid derivatives - Google Patents
Unsaturated phosphorus containing carboxylic acid derivativesInfo
- Publication number
- CA1053690A CA1053690A CA239,930A CA239930A CA1053690A CA 1053690 A CA1053690 A CA 1053690A CA 239930 A CA239930 A CA 239930A CA 1053690 A CA1053690 A CA 1053690A
- Authority
- CA
- Canada
- Prior art keywords
- carboxylic acid
- carbon atoms
- formula
- methyl
- carried out
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
Abstract
NOVEL UNSATURATED PHOSPHORUS CONTAINING CARBOXYLIC ACID
DERIVATIVES
Abstract of the disclosure:
Carboxylic acid derivatives of the formula (I)
DERIVATIVES
Abstract of the disclosure:
Carboxylic acid derivatives of the formula (I)
Description
The present invention relates to novel unsaturated phos-phorus containing carboxylic acid derivatives.
Unsaturated phosphorus containing carboxylic acid deri-vatives of the formula CH3 ~ 0 0 ~ ( 2)n C I C~2 CH3 Rl where R1 is hydrogen or methyl and n is 1, 2 or 3, are already known (German Offenlegungsschrift No. 2 052 569). They are derivatives of tertiary phosphine oxides which have good flame retarding properties. Starting product for their preparation is generally dimethylchlorophosphine which, simultaneously with methyldichlorophosphine, is obtained in the industrial--scsle process of reacting methyl chloride with phosphorus at abc~t 350C (German Auslegeschrift No. 1 568 928). A similar fl~meproofing application as described above for dimethylch~oro-phosphine is unknown hitherto for methyldichlorophosphine, which makes the above use of dimethylchl.orophosphine unecono-mic.
The present invention now provides novel phosphorus con-taining carboxylic acid derivatives of the formula (I) R X o ~11 11 ~2 ~ -~O-~-C=CH (I) wherein R1 and R2 are alkyl having a to~al of up to 8 carbon atoms, preferably lower alkyl each having from 1 to 4 carbon , . :
, - ` :
HO~ 74lF 302 1~353~90 atoms; R3 is hydrogen or methyl; X is oxygen or sulfur, pre-ferably oxygen; Y is linear or branched alkylene having up to 6, preferably from 1 to 3 carbon atoms.
The present invention provides furthermore a process fDr th~ prep~ration of cnmpollndQ of forml~la (T ~ j whi rh c.omnrl S~S
reacting alcohols of the formula (II) > p _ y - OH (II) wherein R1, R2, X and Y are as defined above, with compounds of the formula ~II) Z - CO - C = CH2 (III) wh~re Z is halogen, perferably chlorine; and R3 is as defined above, in the presence of an inert solvent.
The acylation according to the invention of alcohols of formula (II) with acrylic or methacrylic acid halides of formula (III) is carried out in known manner, preferably in the presence of a hydrogen halide - binding compound, for ex-ample a tertiary amine such as triethylamine or pyridine, at temperatures of from -30 to +100C, preferably from 20 to 70C.
The hydrogen halide-binding compound is used in equimolar amounts relative to the acid halide of formula (III), or in a . slight excess of up to about 10%.
29 It is furthermore preferable to use one of the polymeri--.
~OE 74/F ~02 10536~0 ~ation inhibitors known for acrylic acid derivatives, for example phenothiazine, hydroquinone, hydroquinone-monomethyl ether and/or metal salt inhibitors. The amount of inhibitor is chosen within the usual range, for example from 0.01 to 1 wcight ~-, relat ~e to 'he ccmpo~.d of fc mula (III). The presence of active polymerization inhibitors is important also for the optional distillation work-up of the crude reaction mixture.
The starting compounds of formula (II) and ~II) are gene-rally used in about equimolar amounts; the acid~ halide of formula (III) optionally being in a slight excess of up to 10~. The oonversion of the reactants is carried out with ex-clusion of water.
The reaction is advantageously carried out as follows:
the alcohol of formula (II) and the tertiary amine optionally us~d in the inert solvent are introduced first into the re-actor at room temperature, and the acid chloride of formula (Iï) is added dropwise, while the batch is continuously and thoroughly intermixed, for example by means of an agitator.
The reaction temperature is not critical and may rise within the abovementioned temperature range, that is, up to 100C because of the reaction heat set free during the re-action~and this may be advantageous for the course of the re-action. The starting compounds of formula (II) are easily ob-tainable. For example, hydroxymethyl-alkylphosphinic acid esters are prepared by addition of paraformaldehyde on alkgl-phosphonous acid esters according to the process of German Offenlegungsschrift No. 2 226 406. 2-Hydroxyethyl-alkylphos-29 phinic acid es~rs are obtained with good yields from 2-acetoxy-10536~0 ethyl-alkylphos~hinic acid esters according to the process of German Offenlegungsschrift No. 2 335 852, and 3-hydroxypropyl-alkylphosphinic acid esters may be prepared in analogous manner.
Typical phosphorus containing carboxylic acid derivatives G~ ~ ormula ~I~ a.c for examp e: tho acryl ^ a-~ ~ethacryl~ _ acid esters of methylhydroxymethylphosphinic acid methyl, ethyl, propyl or isobutyl ester; ethyl-hydroxymethylphosphinic acid methyl, ethyl, propyl, or isobutyl ester; methyl-2-hydroxy-ethylphosphinic acid isobutyl ester; methyl-2-hydroxyethyl-thiophosphinic acid isobutyl estér; propyl-2-hydroxyethylphos-phinic acid propyl ester; methyl-(2-hydroxy-2-methylethyl)-phosphinic acid methyl, ethyl,propyl, n-butyl, isobutyl or pentyl ester; methyl-3-hydroxypropylphosphinic acid isobutyl ester; butyl-3-hydroxypropylphosphinic acid isopropyl ester.
As inert solvents there may be used for example those so vents which are usually employed for esterification and/or es~;er interchange, such as benzene, toluene, xylene, chloro-belzene, carbon tetrachloride, chloroform, diisopropyl ether, acetonitrile or mixtures of such compounds. The amount of inert solvent is not critical and depends advantageously on the agitabllity of the reaction batch after complete reaction, in which the hydrogen halide-binding compound optionally used precipitates generally as a hydrohalide in the form of crystals.
Therefore, the inert solvent is generally used in a weight amount of up to 10 times, preferably from 2 to 5 times, that of the alcohol of formula (II). Xylene or toluene are the preferred inert solvents.
Because of their unsaturated carbon-carbon bonds, the 29 novel carboxylic acid derivatives of formula (I) are suitable . . ~
' ~-1~353~90 as monomers or comonomers for the preparation of polymers. For example, by copolymerization with monomers such as acrylic derivatives, styrene or vinyl compounds, flame retarding poly-mers having improved dyeability and antistatic properties are ~ U. C~uiy~e~ n~i~iing ~I acryi~nitriie, vinyi chloride, vinyl bromide and/or vinylidene chloride and compounds of formula (I) have surprisingly good flame retarding proper-ties. Furthermore, filaments and fibers made from these co-polymers have an unexpected high thérmostability, that is, their tendency to yellowi~g under thermal strain is consider-abl~ reduced as compared to the state of the art.
By ester interchange of the phosphinic acid ester groups OR2 (preferably in the case of R2 being alkyl having from 1 to 4 carbon atomsJ especially methyl or ethyl) with glycols such as ethylene glycol, diethylene glycol, propylene glycol or higher ~lycols, the polymers obtained may also be cross-link-ed. When using methyldichlorophosphine as starting material, the phosphinic acid esters of formula (I) are more easily ob-tainable than the analogous tertiary phosphine oxides, which require the use of dimethylchlorophosphine as starting sub-stance. Contrary to dimethylchlorophosphine, methyldichloro-phosphine is easily manufactured on an industrial scale, since it may be obtained in known manner and as exclusive product by reaction of methane with PCl3 at 600C.
The following examples illustrate the inv2ntion.
E X A M P ~ E 1:
252 g (1.52 mol) of methylhydroxymethylphosphinic acid isobutyl ester, 153 g (1.52 mol) of triethyl~mine and 1 g of 29 phenothiazine are dissolved in toluene and, with agitation and 1~536gO
slight cooling, 137.5 g (1.52 mol) of acrylic acid chloride are added dropwise at 20 - 30C. Agitation is continued for 15 hours. After one further hour, the triethylamine hydro-chloride precipitated is suction-filtered. After having distil-led off the solvent and after addition of polymerization in-hibitors, the filtrate is distilled in vacuo. 185 g of ~ , `P - CH2 - O - C - CH = CH2, (CH3)2CHCH20 boiling point 95 - 98C at 0.1 mm Hg, are obtained, which corresponds to a yield of 55.5% of the theoretical yield.
Analvsis found: C 49.3%; H 7.7%; P 14.0%
calculated: C 49.1~; H 7.72%; P 14.1%.
E X A M P_~ E 2:
500 g t2.78 mol) of methyl-2-hydroxyethylphosphinic acid isobutyl ester,281 g (2.78 mol) of triethylamine and 1.5 g of phenothiazine are dissolved in 1.67 l of toluene and, with ~igorous agitation and without cooling, 252 g (2.78 mol) of acrylic acid chloride are added dropwise. The temperature rises to 50C. After the chloride is added, agitation is continued for 15 hours. Subsequently, the batch is cooled to 10C, and the triethylamine hydrochloride precipitated is eliminated by suction-filtration. After having distilled off the sol~ent in a water jet vacuum and after addition of poly~
merization inhibitors, the residue is distilled in vacuo.
29 485 g of , HOE 74/F ~02 lOS3690 CH O
3 "
/ P - CH2 - CH2 - O - C - CH = CH2 (CH3)2CHCH20 0 bolllng point i45~C at 2mm Hg, are oblaine~, which CUL re3pUlldS
to a yield of 75% of the theoretical yield.
Analysis:
found: C 51.4%; H 8.10%; P 13.0 %
calculated: C 51.3%; H 8.12~; P 13.25%.
E X A M P ~ E 3:
188 g (1.04 mol) of methyl-2-hydroxyethylphosphinic acid isobutyl ester, 105 g (1.04 mol) of triethylamine and 0.5 g of phenothiazine are dissolved in 620 ml of toluene and, with vigrorous agitation and without cooling, 109 g (1.04 mol) of methacrylic acid chloride are added dropwise. The temperature rises to 50 - 60C. After the chloride is-added, agitation is continued for 10-hours, and the batch is cooled to -10C.
The triethylamine hydrochloride precipitated in the form of crystals is eliminated by suction-filtration, and the filtrate is substantially liberated from the toluene at 120C and 35 mm Hg. After addition of polymerization inhibitors, the residue is distilled in vacuo. 220 g of CH O
~ ., / PcH2cH2oc - C = CH2 ; (~H3)2CHcH2 O CH3 boiling point 125 - 131 C at O.45 mm Xg, are obtained, which 29 corresponds to a yield of 85%.
1~536~0 Analysis:
found: C 53~2~o; H 8~47%; P 12~5%
calculated: C 53~6~; H 8.5 %; P 12.4%
E X A M P ~ E 4:
75 g (0.3~5 molj of methyl-~2-hydroxy-2-methylelhyl)-phosphinic acid isobutyl ester, 39 g of triethylamine (0~385 mol) and 0. 3 g of phenothiazine are dissolve in toluene and, with sl$ght cooling, 35 g (0.385 mol) of acrylic acid chloride are added dropwise. Agitation is continued for 12 hours.
After a further hour, methylene chloride is added, and the tri-ethylamine hydrochloride is suction-filtered. The filtrate, after having eliminated the solvent and added polymerization inhibitors, is distilled under reduced pressure.~~ 57~5 g of .
CH O O
- 3 ~ " .-/ P - CH2 - CHOC - CH = CH2 (CH3)2CHCH20 CH3 boiling point 95 - 100C at 0.1 mm Hg, are obtained, which corresponds to a yield of 60% of the theoretical yield.
Anal~sis:
found: C 53.4%; H 8.5~; P 12.5%;
calculated: C 5~.6~; H 8.5%; P 12.4%.
E X A M P ~ E 5:
196 g ( 1 mol) of methyl-2-hydroxyethylthiophosphinic acid isobutyl ester, 101 g of triethylamine (1 mol) and 0.4 g of phenotiazine are dissolved in 500 ml of toluene and, with vigo-rous agitativn and without cooling, 104.5 g (1 mol) of meth-29 acrylic acid chloride are added dropwise. The temperature _ g _ .
- . :
. ' , . ' ~ . . , ' -.
.. . . .. .. . :
10536~0 rises to 50C. Agitation is continued for 5 hours, and the batch is abandoned overnight. Subsequently, it is cooled, and the triethylamine hydrochloride is suction-filtered. The filtrate is stirred with water, the organic phase is separat-ed and dried with Na2~u4. After having distilled OII ihe sol-vent at room temperature and 1mm Hg, the residue, after addi-tion of polymerization inhibitors, is distilled in a thin-lay-er evaporator at 180C and 0.5 mm Hg. 200 g of CH S
3 "
/ PCH2CH20C - ,CH = CH2 (CH3)2CHCH20 CH3 are obtained which corresponds to a yield of 76~ of the theo-retical yield.
Anal~$is:
fo~nd: C 50.0%; H 7.90%; P 11.3%; S 12.05%
ca}^ulated: C 50.0%; H 7.95%; P 11.75%; S 12.13%.
E X A M P k E 6:
1ûû g (0.66 mol) of methyl-2- hydroxyethylphosphinic acid ethyl ester, 66.8 g (0.66 mol) of triethylamine and 0.3 g of phenothiazine are dissolved in a mixture of toluene and methy-lene chloride, and, with vigorous agitation and cooling, 69 g (0.66 mol) of methacrylic acid chloride are added dropwise.
After this addition is complete, agitation is continued for 1 hour, the batch is then cooled to 0C, and is distilled in vacuo. 116 g of CH O O
3 ~ " "
P - CH2 - CH2 - - C - C = CH2 ~9 H5C2 CH3 , .
.. . .
1~536~0 boiling point 147C at 1.2 mm Hg, are obtained, which corres~
ponds to a yield of 80% of the theoretical yield.
Anal~sis:
found: C 49.2%; H 7.8%; P 14.1%;
ca'~ulatcd: ~ 4~.1~o; E 7.8%; P 13.9~;
. . , . . . .. : . :
.
:
' ' ' '' ' ' ~ .
...
" ' '' , ' '
Unsaturated phosphorus containing carboxylic acid deri-vatives of the formula CH3 ~ 0 0 ~ ( 2)n C I C~2 CH3 Rl where R1 is hydrogen or methyl and n is 1, 2 or 3, are already known (German Offenlegungsschrift No. 2 052 569). They are derivatives of tertiary phosphine oxides which have good flame retarding properties. Starting product for their preparation is generally dimethylchlorophosphine which, simultaneously with methyldichlorophosphine, is obtained in the industrial--scsle process of reacting methyl chloride with phosphorus at abc~t 350C (German Auslegeschrift No. 1 568 928). A similar fl~meproofing application as described above for dimethylch~oro-phosphine is unknown hitherto for methyldichlorophosphine, which makes the above use of dimethylchl.orophosphine unecono-mic.
The present invention now provides novel phosphorus con-taining carboxylic acid derivatives of the formula (I) R X o ~11 11 ~2 ~ -~O-~-C=CH (I) wherein R1 and R2 are alkyl having a to~al of up to 8 carbon atoms, preferably lower alkyl each having from 1 to 4 carbon , . :
, - ` :
HO~ 74lF 302 1~353~90 atoms; R3 is hydrogen or methyl; X is oxygen or sulfur, pre-ferably oxygen; Y is linear or branched alkylene having up to 6, preferably from 1 to 3 carbon atoms.
The present invention provides furthermore a process fDr th~ prep~ration of cnmpollndQ of forml~la (T ~ j whi rh c.omnrl S~S
reacting alcohols of the formula (II) > p _ y - OH (II) wherein R1, R2, X and Y are as defined above, with compounds of the formula ~II) Z - CO - C = CH2 (III) wh~re Z is halogen, perferably chlorine; and R3 is as defined above, in the presence of an inert solvent.
The acylation according to the invention of alcohols of formula (II) with acrylic or methacrylic acid halides of formula (III) is carried out in known manner, preferably in the presence of a hydrogen halide - binding compound, for ex-ample a tertiary amine such as triethylamine or pyridine, at temperatures of from -30 to +100C, preferably from 20 to 70C.
The hydrogen halide-binding compound is used in equimolar amounts relative to the acid halide of formula (III), or in a . slight excess of up to about 10%.
29 It is furthermore preferable to use one of the polymeri--.
~OE 74/F ~02 10536~0 ~ation inhibitors known for acrylic acid derivatives, for example phenothiazine, hydroquinone, hydroquinone-monomethyl ether and/or metal salt inhibitors. The amount of inhibitor is chosen within the usual range, for example from 0.01 to 1 wcight ~-, relat ~e to 'he ccmpo~.d of fc mula (III). The presence of active polymerization inhibitors is important also for the optional distillation work-up of the crude reaction mixture.
The starting compounds of formula (II) and ~II) are gene-rally used in about equimolar amounts; the acid~ halide of formula (III) optionally being in a slight excess of up to 10~. The oonversion of the reactants is carried out with ex-clusion of water.
The reaction is advantageously carried out as follows:
the alcohol of formula (II) and the tertiary amine optionally us~d in the inert solvent are introduced first into the re-actor at room temperature, and the acid chloride of formula (Iï) is added dropwise, while the batch is continuously and thoroughly intermixed, for example by means of an agitator.
The reaction temperature is not critical and may rise within the abovementioned temperature range, that is, up to 100C because of the reaction heat set free during the re-action~and this may be advantageous for the course of the re-action. The starting compounds of formula (II) are easily ob-tainable. For example, hydroxymethyl-alkylphosphinic acid esters are prepared by addition of paraformaldehyde on alkgl-phosphonous acid esters according to the process of German Offenlegungsschrift No. 2 226 406. 2-Hydroxyethyl-alkylphos-29 phinic acid es~rs are obtained with good yields from 2-acetoxy-10536~0 ethyl-alkylphos~hinic acid esters according to the process of German Offenlegungsschrift No. 2 335 852, and 3-hydroxypropyl-alkylphosphinic acid esters may be prepared in analogous manner.
Typical phosphorus containing carboxylic acid derivatives G~ ~ ormula ~I~ a.c for examp e: tho acryl ^ a-~ ~ethacryl~ _ acid esters of methylhydroxymethylphosphinic acid methyl, ethyl, propyl or isobutyl ester; ethyl-hydroxymethylphosphinic acid methyl, ethyl, propyl, or isobutyl ester; methyl-2-hydroxy-ethylphosphinic acid isobutyl ester; methyl-2-hydroxyethyl-thiophosphinic acid isobutyl estér; propyl-2-hydroxyethylphos-phinic acid propyl ester; methyl-(2-hydroxy-2-methylethyl)-phosphinic acid methyl, ethyl,propyl, n-butyl, isobutyl or pentyl ester; methyl-3-hydroxypropylphosphinic acid isobutyl ester; butyl-3-hydroxypropylphosphinic acid isopropyl ester.
As inert solvents there may be used for example those so vents which are usually employed for esterification and/or es~;er interchange, such as benzene, toluene, xylene, chloro-belzene, carbon tetrachloride, chloroform, diisopropyl ether, acetonitrile or mixtures of such compounds. The amount of inert solvent is not critical and depends advantageously on the agitabllity of the reaction batch after complete reaction, in which the hydrogen halide-binding compound optionally used precipitates generally as a hydrohalide in the form of crystals.
Therefore, the inert solvent is generally used in a weight amount of up to 10 times, preferably from 2 to 5 times, that of the alcohol of formula (II). Xylene or toluene are the preferred inert solvents.
Because of their unsaturated carbon-carbon bonds, the 29 novel carboxylic acid derivatives of formula (I) are suitable . . ~
' ~-1~353~90 as monomers or comonomers for the preparation of polymers. For example, by copolymerization with monomers such as acrylic derivatives, styrene or vinyl compounds, flame retarding poly-mers having improved dyeability and antistatic properties are ~ U. C~uiy~e~ n~i~iing ~I acryi~nitriie, vinyi chloride, vinyl bromide and/or vinylidene chloride and compounds of formula (I) have surprisingly good flame retarding proper-ties. Furthermore, filaments and fibers made from these co-polymers have an unexpected high thérmostability, that is, their tendency to yellowi~g under thermal strain is consider-abl~ reduced as compared to the state of the art.
By ester interchange of the phosphinic acid ester groups OR2 (preferably in the case of R2 being alkyl having from 1 to 4 carbon atomsJ especially methyl or ethyl) with glycols such as ethylene glycol, diethylene glycol, propylene glycol or higher ~lycols, the polymers obtained may also be cross-link-ed. When using methyldichlorophosphine as starting material, the phosphinic acid esters of formula (I) are more easily ob-tainable than the analogous tertiary phosphine oxides, which require the use of dimethylchlorophosphine as starting sub-stance. Contrary to dimethylchlorophosphine, methyldichloro-phosphine is easily manufactured on an industrial scale, since it may be obtained in known manner and as exclusive product by reaction of methane with PCl3 at 600C.
The following examples illustrate the inv2ntion.
E X A M P ~ E 1:
252 g (1.52 mol) of methylhydroxymethylphosphinic acid isobutyl ester, 153 g (1.52 mol) of triethyl~mine and 1 g of 29 phenothiazine are dissolved in toluene and, with agitation and 1~536gO
slight cooling, 137.5 g (1.52 mol) of acrylic acid chloride are added dropwise at 20 - 30C. Agitation is continued for 15 hours. After one further hour, the triethylamine hydro-chloride precipitated is suction-filtered. After having distil-led off the solvent and after addition of polymerization in-hibitors, the filtrate is distilled in vacuo. 185 g of ~ , `P - CH2 - O - C - CH = CH2, (CH3)2CHCH20 boiling point 95 - 98C at 0.1 mm Hg, are obtained, which corresponds to a yield of 55.5% of the theoretical yield.
Analvsis found: C 49.3%; H 7.7%; P 14.0%
calculated: C 49.1~; H 7.72%; P 14.1%.
E X A M P_~ E 2:
500 g t2.78 mol) of methyl-2-hydroxyethylphosphinic acid isobutyl ester,281 g (2.78 mol) of triethylamine and 1.5 g of phenothiazine are dissolved in 1.67 l of toluene and, with ~igorous agitation and without cooling, 252 g (2.78 mol) of acrylic acid chloride are added dropwise. The temperature rises to 50C. After the chloride is added, agitation is continued for 15 hours. Subsequently, the batch is cooled to 10C, and the triethylamine hydrochloride precipitated is eliminated by suction-filtration. After having distilled off the sol~ent in a water jet vacuum and after addition of poly~
merization inhibitors, the residue is distilled in vacuo.
29 485 g of , HOE 74/F ~02 lOS3690 CH O
3 "
/ P - CH2 - CH2 - O - C - CH = CH2 (CH3)2CHCH20 0 bolllng point i45~C at 2mm Hg, are oblaine~, which CUL re3pUlldS
to a yield of 75% of the theoretical yield.
Analysis:
found: C 51.4%; H 8.10%; P 13.0 %
calculated: C 51.3%; H 8.12~; P 13.25%.
E X A M P ~ E 3:
188 g (1.04 mol) of methyl-2-hydroxyethylphosphinic acid isobutyl ester, 105 g (1.04 mol) of triethylamine and 0.5 g of phenothiazine are dissolved in 620 ml of toluene and, with vigrorous agitation and without cooling, 109 g (1.04 mol) of methacrylic acid chloride are added dropwise. The temperature rises to 50 - 60C. After the chloride is-added, agitation is continued for 10-hours, and the batch is cooled to -10C.
The triethylamine hydrochloride precipitated in the form of crystals is eliminated by suction-filtration, and the filtrate is substantially liberated from the toluene at 120C and 35 mm Hg. After addition of polymerization inhibitors, the residue is distilled in vacuo. 220 g of CH O
~ ., / PcH2cH2oc - C = CH2 ; (~H3)2CHcH2 O CH3 boiling point 125 - 131 C at O.45 mm Xg, are obtained, which 29 corresponds to a yield of 85%.
1~536~0 Analysis:
found: C 53~2~o; H 8~47%; P 12~5%
calculated: C 53~6~; H 8.5 %; P 12.4%
E X A M P ~ E 4:
75 g (0.3~5 molj of methyl-~2-hydroxy-2-methylelhyl)-phosphinic acid isobutyl ester, 39 g of triethylamine (0~385 mol) and 0. 3 g of phenothiazine are dissolve in toluene and, with sl$ght cooling, 35 g (0.385 mol) of acrylic acid chloride are added dropwise. Agitation is continued for 12 hours.
After a further hour, methylene chloride is added, and the tri-ethylamine hydrochloride is suction-filtered. The filtrate, after having eliminated the solvent and added polymerization inhibitors, is distilled under reduced pressure.~~ 57~5 g of .
CH O O
- 3 ~ " .-/ P - CH2 - CHOC - CH = CH2 (CH3)2CHCH20 CH3 boiling point 95 - 100C at 0.1 mm Hg, are obtained, which corresponds to a yield of 60% of the theoretical yield.
Anal~sis:
found: C 53.4%; H 8.5~; P 12.5%;
calculated: C 5~.6~; H 8.5%; P 12.4%.
E X A M P ~ E 5:
196 g ( 1 mol) of methyl-2-hydroxyethylthiophosphinic acid isobutyl ester, 101 g of triethylamine (1 mol) and 0.4 g of phenotiazine are dissolved in 500 ml of toluene and, with vigo-rous agitativn and without cooling, 104.5 g (1 mol) of meth-29 acrylic acid chloride are added dropwise. The temperature _ g _ .
- . :
. ' , . ' ~ . . , ' -.
.. . . .. .. . :
10536~0 rises to 50C. Agitation is continued for 5 hours, and the batch is abandoned overnight. Subsequently, it is cooled, and the triethylamine hydrochloride is suction-filtered. The filtrate is stirred with water, the organic phase is separat-ed and dried with Na2~u4. After having distilled OII ihe sol-vent at room temperature and 1mm Hg, the residue, after addi-tion of polymerization inhibitors, is distilled in a thin-lay-er evaporator at 180C and 0.5 mm Hg. 200 g of CH S
3 "
/ PCH2CH20C - ,CH = CH2 (CH3)2CHCH20 CH3 are obtained which corresponds to a yield of 76~ of the theo-retical yield.
Anal~$is:
fo~nd: C 50.0%; H 7.90%; P 11.3%; S 12.05%
ca}^ulated: C 50.0%; H 7.95%; P 11.75%; S 12.13%.
E X A M P k E 6:
1ûû g (0.66 mol) of methyl-2- hydroxyethylphosphinic acid ethyl ester, 66.8 g (0.66 mol) of triethylamine and 0.3 g of phenothiazine are dissolved in a mixture of toluene and methy-lene chloride, and, with vigorous agitation and cooling, 69 g (0.66 mol) of methacrylic acid chloride are added dropwise.
After this addition is complete, agitation is continued for 1 hour, the batch is then cooled to 0C, and is distilled in vacuo. 116 g of CH O O
3 ~ " "
P - CH2 - CH2 - - C - C = CH2 ~9 H5C2 CH3 , .
.. . .
1~536~0 boiling point 147C at 1.2 mm Hg, are obtained, which corres~
ponds to a yield of 80% of the theoretical yield.
Anal~sis:
found: C 49.2%; H 7.8%; P 14.1%;
ca'~ulatcd: ~ 4~.1~o; E 7.8%; P 13.9~;
. . , . . . .. : . :
.
:
' ' ' '' ' ' ~ .
...
" ' '' , ' '
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A carboxylic acid derivative of the formula I
(I) wherein R1 and R2 represent alkyl radicals having a total of up to 8 carbon atoms; R3 represents hydrogen or methyl; X
represents oxygen or sulfur; and Y represents a linear or branched alkylene having up to 6 carbon atoms.
(I) wherein R1 and R2 represent alkyl radicals having a total of up to 8 carbon atoms; R3 represents hydrogen or methyl; X
represents oxygen or sulfur; and Y represents a linear or branched alkylene having up to 6 carbon atoms.
2. A carboxylic acid derivative as claimed in claim 1 in which R1 and R2 are lower alkyl each having from 1 to 4 carbon atoms.
3. A carboxylic acid derivative as claimed in claim 1 or claim 2 in which Y is an alkylene chain having from 1 to 3 carbon atoms.
4. A process for the preparation of a carboxylic acid derivative of the formula I
wherein R1 and R2 represent alkyl radicals having a total of up to 8 carbon atoms; R3 represents hydrogen or methyl; X rep-resents oxygen or sulfur; and Y represents a linear or branched alkylene having up to 6 carbon atoms, in which an alcohol of the formula II
(II) wherein R1, R2, X and Y are as defined above, is reacted with a compound of the formula III
(III) wherein Z represents halogen, and R3 is as defined above, in the presence of an inert solvent.
wherein R1 and R2 represent alkyl radicals having a total of up to 8 carbon atoms; R3 represents hydrogen or methyl; X rep-resents oxygen or sulfur; and Y represents a linear or branched alkylene having up to 6 carbon atoms, in which an alcohol of the formula II
(II) wherein R1, R2, X and Y are as defined above, is reacted with a compound of the formula III
(III) wherein Z represents halogen, and R3 is as defined above, in the presence of an inert solvent.
5. A process as claimed in claim 4 in which Z repre-sents chlorine.
6. A process as claimed in claim 4 in which the reac-tion is carried out in the presence of a compound which acts as a polymerization inhibitor for the acryl or methacryl group.
7. A process as claimed in claim 4, claim 5 or claim 6 in which the reaction is carried out in the presence of a hydrogen halide-binding compound.
8. A process as claimed in claim 4, claim 5 or claim 6 in which the reaction is carried out in the presence of a tertiary amine as a hydrogen halide-binding compound.
9. A process as claimed in claim 4, claim 5 or claim 6 in which the inert solvent is toluene or xylene.
10. A process as claimed in claim 4, claim 5 or claim 6 in which the reaction is carried out at a temperature of from -30 to +100°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2449466A DE2449466C2 (en) | 1974-10-19 | 1974-10-19 | New unsaturated phosphorus-containing carboxylic acid derivatives and processes for their preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1053690A true CA1053690A (en) | 1979-05-01 |
Family
ID=5928547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA239,930A Expired CA1053690A (en) | 1974-10-19 | 1975-10-17 | Unsaturated phosphorus containing carboxylic acid derivatives |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5626676B2 (en) |
| AT (1) | AT334398B (en) |
| BE (1) | BE834672A (en) |
| CA (1) | CA1053690A (en) |
| CH (1) | CH616431A5 (en) |
| DE (1) | DE2449466C2 (en) |
| DK (1) | DK467675A (en) |
| ES (1) | ES441741A1 (en) |
| FR (1) | FR2288097A1 (en) |
| GB (1) | GB1472699A (en) |
| IE (1) | IE41812B1 (en) |
| IT (1) | IT1043463B (en) |
| LU (1) | LU73602A1 (en) |
| NL (1) | NL7512062A (en) |
| SE (1) | SE7511677L (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2841941A1 (en) * | 1978-09-27 | 1980-04-17 | Hoechst Ag | ORGANIC PHOSPHORUS COMPOUNDS WITH 3-HYDROXYALKYLPHOSPHINIC ACID ESTER GROUPS |
| DE2918161A1 (en) * | 1979-05-05 | 1980-11-13 | Bayer Ag | PHOSPHONOMAL ACID ESTER AND METHOD FOR THE PRODUCTION THEREOF |
| DE102006012881A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Limited | Phosphorus-containing mixtures, a process for their preparation and their use |
| DE102006012878A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Limited | Phosphorus-containing mixtures, a process for their preparation and their use |
| JP2008222677A (en) * | 2007-03-15 | 2008-09-25 | Chisso Corp | Flame retardant, polymer composition using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES396221A1 (en) * | 1970-10-27 | 1974-04-16 | Hoechst Ag | Phosphorus-containing unsaturated carboxylic acid derivatives |
-
1974
- 1974-10-19 DE DE2449466A patent/DE2449466C2/en not_active Expired
-
1975
- 1975-10-13 ES ES441741A patent/ES441741A1/en not_active Expired
- 1975-10-14 NL NL7512062A patent/NL7512062A/en not_active Application Discontinuation
- 1975-10-15 CH CH1340675A patent/CH616431A5/en not_active IP Right Cessation
- 1975-10-17 FR FR7531811A patent/FR2288097A1/en active Granted
- 1975-10-17 AT AT791175A patent/AT334398B/en not_active IP Right Cessation
- 1975-10-17 JP JP12448775A patent/JPS5626676B2/ja not_active Expired
- 1975-10-17 GB GB4271675A patent/GB1472699A/en not_active Expired
- 1975-10-17 IE IE2261/75A patent/IE41812B1/en unknown
- 1975-10-17 LU LU73602A patent/LU73602A1/xx unknown
- 1975-10-17 DK DK467675A patent/DK467675A/en unknown
- 1975-10-17 CA CA239,930A patent/CA1053690A/en not_active Expired
- 1975-10-17 SE SE7511677A patent/SE7511677L/en unknown
- 1975-10-17 IT IT28410/75A patent/IT1043463B/en active
- 1975-10-20 BE BE161076A patent/BE834672A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL7512062A (en) | 1976-04-21 |
| IT1043463B (en) | 1980-02-20 |
| JPS5180823A (en) | 1976-07-15 |
| BE834672A (en) | 1976-04-20 |
| AT334398B (en) | 1976-01-10 |
| ATA791175A (en) | 1976-05-15 |
| FR2288097A1 (en) | 1976-05-14 |
| FR2288097B1 (en) | 1979-01-05 |
| DK467675A (en) | 1976-04-20 |
| JPS5626676B2 (en) | 1981-06-19 |
| SE7511677L (en) | 1976-04-20 |
| IE41812B1 (en) | 1980-03-26 |
| GB1472699A (en) | 1977-05-04 |
| ES441741A1 (en) | 1977-03-16 |
| LU73602A1 (en) | 1976-08-19 |
| IE41812L (en) | 1976-04-19 |
| CH616431A5 (en) | 1980-03-31 |
| DE2449466C2 (en) | 1982-07-15 |
| DE2449466A1 (en) | 1976-04-29 |
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