CA1309106C - SUBSTITUTED PHENYL .alpha.-FLUOROACRYLATES - Google Patents
SUBSTITUTED PHENYL .alpha.-FLUOROACRYLATESInfo
- Publication number
- CA1309106C CA1309106C CA000539539A CA539539A CA1309106C CA 1309106 C CA1309106 C CA 1309106C CA 000539539 A CA000539539 A CA 000539539A CA 539539 A CA539539 A CA 539539A CA 1309106 C CA1309106 C CA 1309106C
- Authority
- CA
- Canada
- Prior art keywords
- alpha
- fluoroacrylate
- mol
- phenyl
- dimethyl
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Abstract
Abstract of the disclosure:
Substituted phenyl .alpha.-fluoroacrylates Certain esters of .alpha.-fluoroacrylic acid are accessible by hydrolyzing .alpha.-hydroxymethyl .alpha.-fluoromalonic acid esters and subsequently decarboxylating the hydrolysis product The phenyl .alpha.-fluoroacrylates which are substituted on the phenyl radical can be prepared by hydroxymethylating dimethyl .alpha.-fluoromalonate, decarboxylating and dehydrat-ing the resulting dimethyl .alpha.-hydroxymethyl-.alpha.-fluoro-malonate and esterifying the resulting .alpha.-fluoroacrylic acid with substituted phenols. The substituted phenyl .alpha.-fluoroacrylates are colorless liquids or colorless solids which can be polymerized. They are suitable for use as a starting material for the preparation of fluorine polymers.
Substituted phenyl .alpha.-fluoroacrylates Certain esters of .alpha.-fluoroacrylic acid are accessible by hydrolyzing .alpha.-hydroxymethyl .alpha.-fluoromalonic acid esters and subsequently decarboxylating the hydrolysis product The phenyl .alpha.-fluoroacrylates which are substituted on the phenyl radical can be prepared by hydroxymethylating dimethyl .alpha.-fluoromalonate, decarboxylating and dehydrat-ing the resulting dimethyl .alpha.-hydroxymethyl-.alpha.-fluoro-malonate and esterifying the resulting .alpha.-fluoroacrylic acid with substituted phenols. The substituted phenyl .alpha.-fluoroacrylates are colorless liquids or colorless solids which can be polymerized. They are suitable for use as a starting material for the preparation of fluorine polymers.
Description
130qlO6 HOECHST AKTIENGESELLSCHAFT HOE 86/F 136 Dr.DA/mu Substituted phenyl ~-fLuoroacrylates The invention relates to esters of ~-fluoroacrylic acid with substituted phenols, a process for the preparation of these esters and their use.
Esters of ~-fluoroacrylic acid are already known. Thus the phenyl ester of ~-fluoroacrylic acid is prepared by reacting ethyl monofluoroacetate in the presence of sodium ethylate with ethyl oxalate, converting the sodium ~-fluoroacrylate obtained into ~-fluoroacryloyl chloride by means of th;onyl chloride and then esterifying this product with phenol (German Patent No. 2,950,491 = US
Patent No. 4,297,4 6 6)~ It is a disadvantage in this process that ethyl monofluoroacetate, which is highly toxic, has to be employed. Phenyl a-fluoroacrylate can be polymerized and is used for the preparation of poly-mers ~hich, at room temperature, are translucent or transparent or light-transmissive, colorless solids.
Other esters of ~-fluoroacryl;c acid, in particular butyl ~-fluoroacrylate, can be prepared by acid hydrolysis of the appropriate ~-hydroxymethyl-~-fluoromalonate followed by decar~oxylation of the hydrolysis product with simultaneous elimination of alcohol tBritish Patent No.
1,115,287). This method is, however, only descr;bed for Z5 the example of butyl ~-fluoroacrylate; the ester rapidly polymerizes under the influence of light.
Polymers of fluorinated acryl;c acid esters are also kno~n, uh;ch correspond to the formula RHC=CR-CO-OR1 ; ~ 3Q in ~hich R is a hydrogen atom, a methyl group or a halogen atom and R1 is a fluorinated alkyl or aryl radical tUS Patent No. 2,877,207); the fluoroalkyl radical af the aLcohol component is, in particular, a radical con-taining two hydrogen atoms on the carbon atom in the 1-position and no detailed statements at alL are made ~k ., i, .. .. . .
concerning suitable aryl radicals.
It is also known that polymers of ~-halogenoacrylic acid esters with halogen-containing alcohol components are used for the preparation of radiation-sensitive protect-ive layers (US Patent No. 4,259,407). The starting materials used are monomers of the formula H2C = CX-COOR
in which X is a fluorine, chlorine or bromine atom and R represents a fluorinated alkyl, aryl or alkoxy group.
Amongst the polymers cuntaining an aromatic alcohol com-ponent, only poly-(m-trifluoromethylphenyl ~-fluoro-acrylate) is mentioned by name; there is, however, no information at all about any properties of this polymer or the corresponding monomer.
Finally, it is also known that polymers of ~-fluoroacrylic acid esters are suitable as the core material for optical fibers (European published application 0,128~517).
Phenyl ~-fluoroacrylate is the only ester hav;ng an aromatic alcohol component which is shown in terms of a formula, but there ;s no information at a~l on the preparation and properties of this ester.
The object of the invention is to provide esters of ~-fluoroacrylic acid with substituted phenols which can be prepared in an economical manner using starting mater-ials of as low toxicity as possible and which can be polymerized to give products having a high transmittance of light.
The invention relates to phenyl ~-fluoroacrylates of the formula (1) CN2 = C~ - CO - O ~ (~)m : .
l s ~ u ~
in which R denotes a halogenoalkyl group having 1 to 8 carbon atoms and p is o , 1, 2 or 3, X denotes a halogen atom and n is or an integer from 1 to 5 (it being possible for X to denote different halogen atoms if n is greater than 1), Y denotes a hydrogen atom, a cyano group, the radical X or the radical R and m is nought or 1, the sum of n + m + p denoting 1 to 5.
The invention also relates to a process for the prepar-ation of a substituted phenyl ~-fluoroacrylate, which comprises reacting dimethyl ~-fluoromalonate with formal-dehyde in a first process stage, then hydrolyzing, decarboxylating and dehydrating the resulting hydroxy-methylated dimethyl ~-fluoromalonate in a second process stage and subsequently, in a third process stage, esteri-fying the resulting -fluoroacrylic acid tif appropriate in the form of an acid halide) with a phenol o~ the formuls (2) N0 ~ X)n in which X, Y, R, n, m and p have the meaning indicated in formula ~ if appropriate in the form of an alkali metal phenate).
Finally, the invention also relates to the use of sub-stituted phenyl ~-fluoroacrylates of the formula (1) as a starting mater;al for the preparation of polymers contain-;ng fluorine.
The process according to the invention ;s carried out in three stages: dimethyl ~-fluoromalonate is first reacted ~ith formaldehyde to give dimethyl~-hydroxymethyl-~-fluoromalonate, the latter is then hydrolyzed and the hydrolysis product is decarbo~ylated and dehydrated, and finally, the resulting ~-fluoroacrylic acid ;s esterified with a substituted phenol.
In the first process stage, dimethyl ~-fluoromalonate is i,., ~., . ~, --" 1 309 1 06 subjected to hydroxymethylation with formaldehyde.
tDimethyl ~-fluoromalonate is a known compound; see Journal of Fluorine Chenlistry 25 (1984)~ 203 - 212.) The formaldehyde is preferably employed in the form of an aqueous solution having a formaldehyde content of 30 to 40% by weight. The formaldehyde is employed in an amount of 1 to 10 mol, preferably 1.1 to 3 mol (relative to 1 mol of dimethyl ~-fluoromalonate). It is also possible to use paraformaldehyde, hexamethylenetetramine or 1,3,5-trioxane instead of formaldehyde. It is advant-agous to carry out the reaction in the presence of a basic catalyst, which is then used in an amount of 2 to _ . .
S0~ preferably S to 15, mol % (relative to the dimethyl a-fluoromalonate). The catalyst used is, in particular, an alkali metal bicarbonate, for example potassium bi-carbonate and sodium bicarbonate. The reaction is car-ried out at a temperature of S to 40C, preferably 15 to 30C. The dimethyl a-hydroxymethyl-~-fluoromalonate formed is then isolated from the reaction mixture~
preferably by salting out or extraction by means of a water-immiscible organic solvent. A suitable solvent is, above all, an aliphatic chlorinated hydrocarbon having 1 to 4 carbon atoms, ~or example methylene dichloride, chloroform, carbon tetrachloride, 1,1-dichloroethane or 1,Z-d;chloroethane. A combination of salting out and extraction is particularly advantageous; a saturated salt solution (ammonium sulfate or sodium chloride) is then first added to the reaction mixture, and this mixture is then extracted. Dimethyl ~-hydroxymethyl-~-fluoro-malonate is obtained in the form of a colorless solid byevaporating the solvent.
In the second process stage, the dimethyl ~-hydroxymethyl-~-fluoromalonate is hydrolyzed in an aqueous acid medium, and the hydrolysis product is decarboxylated and dehydrated. The reaction is carried out at a pH from -1 to 6, preferably 0 to 2; the acid med;um ;s prepared by means of an aqueous acid solution, preferably a dilute inorganic acid, such as hydrochloric acid or sulfuric -` 1 309 1 06 acid. The reaction temperature is with;n the range from 90 to 110C, preferably 95 to 105C. When the evolution of gas is complete, the reaction mixture is distilled under a pressure of 1013 to 600 mbar, and the distillate is extracted with an organic solvent. The solvent used here is also a water-immiscible solvent, preferably an ether, such as diethyl ether. -fluoro-acrylic acid is obtained in the form of a colorless solid after the solvent has been removed by evaporation. In a preferred variant, the -fluoroacrylic acid is isoLated ;n the form of its ammonium salt. This is effected by passing gaseous ammonia through the solution obtained after the extraction, and then freeing the colorless crystalline precip;tate from the solvent.
- In the third process stage, the ~fluoroacrylic acid is esterified with a substituted phenol. The phenol is employed in an amount of 0.5 to 1~5 mol, preferably 0.8 to 1.2 mol (relative to l mol of ~-fluoroacrylic acid).
In some cases - if the acid is employed in the form of a halide - the phenol is employed in the form of an alkali metal phenate, preferably sodium phenate or potassium phenate. The ~-fluoroacrylic acid is employed for the esterification as such or, preferably, in the form of an acid halide, in particular as ~-fluoroacryl chloride.
The acid halide is prepared by means of a customary halogenating agent, for example oxalyl chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, benzoyl chloride, benzotrichloride~
phosphorus tribromide, sulfur tetrafluoride and, especially, thionyl chloride. The halogenation by means of thionyl-chloride is preferably carried out in the presence of a catalyst, such as dimethyl formamide~ The reaction is carried out in an aromatic hydrocarbon~ for example toluene, xylene and ~rimethylbenzene, as the solvent, and the reaction temperature is w;thin the range from 50 to 100C, preferably 70 to 90C.
The esterification is preferably carried out in a solvent , . ,~ , .. . . . .
and the reaction temperature in this case ;s -10 to 50C, preferably 0 to 25C. The solvent used is a polar organic solvent, in part;cular a symmetr;cal, asymmetrical or cyclic e~her, for example diethyl ether~ dipropyl ether, diisopropyl ether, tert.-butyl methyl ether, tetrahydrofuran and dioxane, and aliphatic halogenated hydrocarbon, preferably a chlorinated hydrocarbon, for example methylene dichloride, chloroform, carbon tetra-chloride, 1,1-dichloroethane and 1,2-dichloroethane, an aromatic halo~enatic hydrocarbon, preferably a chlorinated hydrocarbon, for example chlorobenzene and 1,Z-dichloro-benzene or 1,3-dichlorobenzene, or an aliphatic or aromatic nitrile, for example acetonitrile and benzo-nitrile. The solvent can also be a mixture of several polar solvents. It is expedient to carry out the ester-- ification of the acid halide with the phenol in the presence of an organic base, in particular a trialkyl-amine having 1 to 4 carbon atoms in each of the alkyl groups. The base is employed in an amount of 0.5 to 2 mol, preferably 0.8 to 1.2 mol ~relative to 1 mo; of acid halide)~ The resulting substituted phenyl ~-fluoro-acrylate is isolated from the reaction mixture by distil-lation, preferably under a pressure of 1013 to 200 mbar, or - after the solvent has been removed by distillation -by hot extract;on of the solid residue with a nonpolarsolvent, pre~erably an aliphatic hydrocarbon, such as n-hexane, and subsequent crystallization. It is expedient to carry out the dist;llation in the presence of a customary polymerization inhibitor, for example hydroquinone or hydroquinone monomethyl ether; this is used in an amount of 100 to 500 ppm (relative to ~-fluoroacryloyl halide).
The bottom temperature is within the range from 20 to 100C, preferably 3û to 85C. The phenyl ester is purified further by being distilled again, preferably under reduced pressure, or recrystallized. The substituted phenyl a-fluoro-acrylates according to the invent1on carry 1 to 5, preferably 2 to 5, substituents on the phenyl rad;cal; preferred esters are those which contain, as substi~uents or in the substituent, a fluorine atom or several fluorine atoms.
,, . ~
The esters according to the invention include, for example, the follow;ng compounds: 2- or 3- or 4-fluoro-phenyl a-fluoroacrylate, 2- or 3- or 4-chlorophenyl a-fluoroacrylate, 2- or 3- or 4-bromophenyl a-fluoroacrylate, 2- or 3- or 4 iodophenyl a-fluoroacrylate, 2,3- or 2,4- or 2,5- or 2,6- or 3,4- or 3,5-difluorophenyl a-fluoro-acrylate, 2,3- or 2,4- or 2,5- or 2,6- or 3,4- or 3,5-d;chlorophenyl a-fltloroacrylate, 2- or 3-chlor-4-fluoro-phenyl a-fluoroacrylate, 2-bromo-4-chloro~henyl a-fluoro-acrylate, 4-bromo-2-chlorophenyl -fluoroacrylate, 2,6-d;bromo-4-fluorophenyl a-fluoroacrylate, 4-bromo-2,6-dichlorophenyl a-fluoroacrylate, 2,4-dichloro-6-iodophenyl a-fluoroacrylate, 2,3,4- or 2,3,5- or 2,3,6- or 2,4,5-or 2,4,6- or 3,4,5-trichloro-phenyl a-fluoroacrylate, 2,4,6-tribromophenyl a-fluoroacrylate, 2,4,6-triiodophenyl -fluoroacrylate, 2,3,5,6-tetrafluorophenyl a-fluoro-acrylate, 2,3,4,5-tetrachlorophenyl a-fluoroacrylate, 2,3,5,6-tetrachlorophenyl a-fluoroacrylate, pentafluoro-phenyl a-fluoroacrylate, pentachlorophenyl a-fluoroacrylate, pentabromophenyl a-fluoroacrylate, Z,6-diiodo-4-trifluoro-methylphenyl a-fluoroacrylate, 2- or 3- or 4-trifluoro-methylphenyl a-fluoroacrylate, 2-(heptafluoro-2-propyl)-phe~nyl or 4-~heptafluoro-2-propyl)-phenyl a-fluoroacrylate, 2,6- or 3,5-bis(tr;fluoromethyl)-phenyl a-fluoroacrylate, `25 4-cyanophenyl ~-fluoroacrylate, 2,6-dibromo-4-cyanophenyl a-fluoroacrylate, 2,6-d;chloro-4-cyanophenyl a-fluoro-acrylate, 2,6-difluoro-4-cyanophenyl a-fluoroacrylate, 4-cyano-2,3,5,6-tetrafluorophenyl a-fluoroacrylate, 4-chloro-2,5- ~or 3,5)-difluorophenyl a-fluoroacrylate, 2-30~ chloro-4,5- (or 4,6)-difluorophenyl a-fluoroacrylate, 2,5-~or 2,6- or 3,5-dichloro-4-fluorophenyl a-fluoroacrylate, 2,6- or 3,4-dibromo-3,4 ~or 2,6)-dichlorophenyl a-fluoro-acrylate, 2,4,6-trichloro-3-fluorophenyl a-fluoroacrylate, 2,4- or 2~6-dichloro-3-trifluoromethylphenyl ~-fluoro-acrylate, 2,6-d;bromo-4- ~or 5) -trifluoromethylphenyl ~-~: -fluoroacrylate, 2,4-dibromo-5- ~or 6)-trifluoromethylphenyl a-fluoroacrylate, 2- or 4-bromo-3-: ~or 5)-trifluoromethyl-phenyl -fluoroacrylate, 2,3,6-tribromo,4,5-bisbromo-methylphenyl a-fluoroacrylate, 2,4,5-tribromo-3,6-bis-:
.
(bromomethyl)phenyl ~-fluoroacrylate, 2,4,6-trichloro-3,5-bistchloromethyl)phenyl) ~-fluoroacrylate, 3,4,5-trichloro-2,~-bistchloromethyl)phenyl ~-fluoroacrylate, 2,4,6-trichloro-3-chloromethylphenyl ~-fluoroacrylate, 5 2,4-d;bromo-6-dibromomethylphenyl -fluoroacrylate, 2,6-dibromo-4-dibromomethylphenyl a-fluoroacrylate, 2,3,5,6-tetrachloro-4-chloromethylphenyl ~-fluoroacrylate, 2- or 3-fluoro-4-methylphenyl ~-fluoroacrylate, 3- or 4- or 5-fluoro-2-methylphenyl ~-fluoroacrylate, 2-fluoro-6-10 methylphenyl ~-fluoroacrylater 4-fluoro-3-methylphenyl ~-fluoroacrylate, 2,4,6-trichloro 3,5-dimethylphenyl ~-fluoroacrylate, 2,6-dichloro-3,5-dimethylphenyl ~-fluoro-acrylate, 2,6-dichloro-4-methylphenyl -fluoracrylate~
2,4,6-tribromo-3,5-d;methylphenyl ~-fluoroacrylate, 2,4,6-tribromo-3-methylphenyl ~-fluoroacrylate, 2,3,5,6-tetra-fluoro-4-cyanophenyl -fluoracrylate, 2- or 3- or 4-methylphenyl ~-fluoroacrylate, 2,3- or 2,4- or 2,5- or Z,6- or 3,4- or 3,5-dimethylphenyl -fluoroacrylate, 2,4,6-tr;methylphenyl -fluoroacrylate, 2,3,5,6-tetra-methylphenyl -fluoroacrylate, 2- or 3- or 4-isopropyl-phenyl -fluoroacrylate, 4-isopropyl-3,5-dimethylphenyl ~-fluoroacrylate and 2,3- or 2,5- or 2,6- or 3,4- or 3,5-di;sopropylphenyl ~fluoroacrylate~
The subst;tuted phenyl esters of ~-fluoroacrylic ac;d are colorless liquids or colorless solids at room tem-perature. They are readily polymerizable and are suitable for the preparation of crystal clear, light-transmissive, colorless polymers.
The following examp(es serve to illustrate the invention ;n greater detail. Percentages relate ;n each case to weight.
Example 1 --.
a) 48 g (0.48 mol) of potassium bicarbonate were dissolved in 535 9 ~6.59 mol) of aqueous formaldehyde solution ~37% strength by we;ght) ;n a 4-litre glass flask.
~ 1 30q 1 Oh 841 9 (5.6 mol) of dimethyl a-fluoromalonate were added dropwise to this solution, with stirring, in the course of 3 1/2 hours; the temperature was kept meanwhile within the range from 20 to 25C. Stir-r;ng was continued for 2 hours at the same temperature, and during this time dimethyl a-hydroxymethyl-~-fluoro-malonate was precipitated in the form of a colorless solid. 2,500 9 of an aqueous, saturated solution of ammonium sulfate were then added to the reaction mix-ture, which was then extracted with methylene dichloride. The extraction solution was dried by means of anhydrous sodium sulfate. 906 g (90% of theory) of dimethyl a-hydroxymethyl-a-fluoromalonate were obtained after removing the methylene dichloride by distillation (bath temperature 40C, 25 mbar).
b) 175 9 (0.97 mol) of dimethyl a-hydroxymethyl-~-fluoro-malonate, 750 ml of water and 750 ml of hydrochloric acid ~36% strength by we;ght) were heated at the boil for 2 1/2 hours ;n a 2-l;tre glass flask equipped with a thermometer and stirrer and a Vigreux column fitted with a dist;llat;on head. The temperature of the reaction mixture was 103C. The react;on mixture was then distilled. 1 g of hydroquinone monomethyl ether was added to the distillate and the latter was extracted with diethyl ether, and the extraction solu-tion was dried by means of anhydrous sod;um sulfate.
17 9 (1 mol) of gaseous ammonia were then passed into the solution at room temperature. The colorless pre-cipitate obtained thereby was filtered off, washed with diethyl ether and dried at room temperature under reduced pressure. 70.8 9 t68% of theory) of ammonium a-fluoroacrylate were obtainedO
:
i 35 c~ 100 g (0.~34 mol) of ammon~ium a-fluoroacrylate were dispersed in a m;xture of 600 g of mesitylene and 15 ml of dimethylformamide in a 1-li`tre glass flask and 119 9 (1.0 mol) of thionyl chloride were added in the course of one hour. The resulting m;xture was heated ---` 1 30q 1 06 to a temperature of 80C and was kept at this temperature for 2 hours, with stirring. The liquid obtained after the mixture had coo(ed to room temperature was distilled under reduced pressure, and the fraction obtained up to 100C/160 mbar was distilled again under normal pressure~
67 g (66% of theory) of ~-fluoroacryloyl chloride were obtained, boiling point 65 to 67C.
d) A solution of 1119 (0.5 mol) of potassium pentafluoro-phenate in 250 ml of anhydrous acetonitrile was added dropwise, in the course of 1 hour, at a temperature of 25C and with stirring, to a solution of 54.5 9 (0.502 mol) of ~-fluoroacryloyl chloride in 1nO ml of anhydrous acetone nitrile, and the reaction mixture was then stirred for a further 2 hours at the same temperature. The solid formed was filtered off and washed with 100 ml of anhydrous acetonitrile. The mixture of filtrate and wash solution was distilled, after adding 0.01 g of hydroquinone monomethyl ether.
107.1 g (84% of theory) of penafluorophenyl ~-fluoro-acrylate were obtained, boiling point 41 to 42C
~under 2 mbar).
Example 2 13.9 g ~O~lZ8 mol) of a-fluoroacryloyl chloride (obtained in accordance with example 1c) were added dropwise, at a temperature of 25C, with stirring and in the course o~ 30 m;nutes, to a solution of 30 g (0.0985 mol) of potassium pentachlorophenate in 4ûO ml of anhydrous acetonitrile, and the react;on m;xture was then st;rred for a further 90 m;nutes at the same temperature. The sol;d formed was f;ltered off and washed w;th 20 ml of anhydrous aceto-n;tr;le. After 0.01 g of hydroqu;none monomethyl ether had been added, the volatile constituents in the m;xture of filtrat and washing liquor were distilled off and the residue was recrystallized from boiling n-hexane.
17 g (51% of theory) of pentachlorophenyl ~-fluoroacrylate were obtained, meltlng polnt 90 to 92C.
: ' 1 3nql 06 Example 3 49 g (0.181 mol) of 2,6-dibromo-4-fluorophenol were dis-solved in 150 ml of anhydrous methylene dichloride, and 1~.3 g (0.181 mol) of triethylamine were added to the solution; 20 g (0.184 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were then added dropwise at a temperature of 5C, with stirring and in the course of 30 minutes, and the reaction mixture was stirred for a further 30 minutes at the same temperature.
The solid formed was filtered off and washed with 30 ml of methylene dichloride. The mixture of filtrate and ~ash solution was distilled, after adding 0.01 9 of hydroquinone monomethyl ether. 46 9 (74% of theory) of 2,6 dibromo-4-fluorophenyl ~-fluoroacrylate were obtained, - boiling point 86 to 88C (under 0.4 mbar).
Example 4 2.2 9 (0~02 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were added dropwise, at a temperature of 5C, with stirring and in the course of 5 minutes, to a solution of 7.8 g (0.019 mol) of 2,6-diiodo-4-trifluoromethylphenyl and 2 g (0.02 mol) of triethylamine in 80 ml of anhydrous methylene dichloride, and the reaction m;xture was then stirred for a further 30 minutes at the same temperature. The solid formed ~as filtered off and washed with 1û ml of anhydrous methylene dichloride. After 0~001 g of hydroquinone monomethyl ether had been added, the volatile constituents in the mixture of filtrate and wash solution were removed by distillation, and the residue was recrystaLl;zed from boiling in-hexane. 7 g (76~ of theory) of 2,6-diiodo-4-trifluoromethylphenyl ~-fluoroacrylate were obtained, melting point 93 to 95C.
Exam~le 5 16.2 9 (0.1 mol) of 4-trifluoromethylphenol were dissolved , in 80 ml of anhydrous diethyl ether, and 10.1 9 (0.1 mol) of triethylamine were added in portions to the solut;on;
12 g (0.11 mol) of o~-fluoroacryloyl chloride (obtained in accordance with example 1c) were then added dropw;se, at a temperature of 10C, with stirring, and in the course of 20 minutes, and the reaction mixture was stirred for a further 60 minutes at the same temperature.
The solid formed was filtered off and washed with 20 ml of diethyl ether. The mixture of filtrate and wash sol-ution was distilled, after adding 0.005 9 of hydroquinonemonomethyl ether. 19.5 9 (83~ of theory) of 4-trifluoro-methylphenyl ~-fluoroacrylate were obtained, boiling point 69 to 70C (under 3 mbar).
Example 6 27.5 9 (0.169 mol) of 3-trifluoromethylphenol were dissolved in lOO ml of anhydrous methylene dichloride, and 17.1 9 (0.169 mol) of triethylamine were added in portions to the solution; 20 9 tO.184 mol) of ~-fluoro-acryloyl chloride (obtained in accordance with example 1c) were then added dropwise, at a temperature of 5C, with stirring and in the course of 20 minutes, and the reaction mixture was stirred for a further 60 minutes at the same temperature. The solid formed was filtered off and washed with 30 ml of methylene dichlor;de. The mixture of filtrate and wash solution was distilled, after adding 0.01 9 of hydroquinone monomethyl ether. 27 g (68% of theory) of 3-trifluoromethylphenyl ~-fluoro-acrylate were obtained, boiling point 7~ to 79C (under - 4 mbar).
Example 7 :
26.2 9 (0.1 mol) of 4-perfluoroisopropylphenol were dissolved in 100 ml of anhydrous diethyl ether, and 10~1 g (0.1 molj of triethylamine were added to the solut;on; 12 9 (0.11 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were then added 1 3()ql 06 dropwise, at a temperature of 10C, with stirring and in the course of 15 minutes, and the reaction mixture was stirred for a further 30 minutes at the same temper-ature. The solid formed was filtered off and washed w;th 2û ml of diethyl ether. The mixture of filtrate and wash solution was distil~ed, after adding 0.005 g of hydro-quinone monomethyl ether. 22.9 g (69% of theory) of 4-perfluoroisopropylphenyl a-fluoroacrylate were obtained, boiling point 65 to 66C (under 1 mbar).
Example 8 10 g (0.038 mol) of 2-perflùoroisopropylphenol were dissolved in 30 ml of anhydrous diethyl ether, and 3.9 g (0.038 mol) of triethylamine were added to the solution;
4.3 g (0.039 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were then added dropwise, at a temperature of 10C, with stirring and in the course of 12 minutes, and the reaction mixture was stirred for a further 30 minutes at the same temperature.
The solid formed was filtered off and washed with 10 ml of diethyl ether. The mixture of filtrate and wash sol-ut;on was d;stilled after adding 0.002 g of hydroquinone monomethyl ether. 7 9 ~55~ of theory) of 2-perfluoro-isopropylphenyl a-fluoroacrylate were obtained, boiling point 85C (under 1 mbar).
Example 9 10 9 (0.092 mol) of a-fluoroacryloyl chloride (obtained in accordance with example 1c) were added drop~ise, at a temperature of 5C, with stirring and in the course of 20 minutes, to a solution of 10~7 g (0.09 mol) of 4-cyano-phenol and 9.1 g (0.09 mol) of triethylamine in 150 ml of anhydrous methylene dichloride, and the reaction mixture was then stirred for a further 30 minutes at the same temperatureu The solid formed was filtered off and washed with Z0 ml of anhydrous methylene dichloride.
After 0.005 9 of hydroquinone monometbyl ether had been .:
~ 3~39 1 0 6 added, the volatiLe constituents in the mixture of filtrate and wash solution were removed by distillation, and the residue was recrystallized from boiling n-hexane.
11.2 9 (65% of theory) of 4-cyanophenyl ~-fluoroacrylate were obtained, melting point 78 to 79C.
Example 10 10 g (0.092 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were added dropwise, at a temperature of 5C, with stirring and in the course of 20 minutes, to a solution of 16.7 g (0.089 mol) of 3,5-dichloro-4-hydro~ybenzonitrile and 9 9 (0.089 mol) of triethylamine in Z00 ml of anhydrous methylene dichloride, and the reaction mixture was then stirred for a further 30 minutes at the same temperature. The solid formed was filtered off and washed with 20 ml of anhydrous methylene dichloride. After 0.005 9 of hydroquinone monomethyl ether had been added, the volatile constituents in the mixture of filtrate and wash solution were removed by distillat;on, and the residue was recrystallized from boiling n-heptane. 18.7 9 ~81% of theory) of 2,6-dichloro-4-cyanophenyl ~-fluoroacrylate were obtained, melting point 95 to 99C.
ZS
Example 11 10 g (0.092 mol) ~-fluoroacryloyl chloride (obtained ;n accordance with example 1c) were added dropwise, at a temperature of 5C, with stirring and in the course of S minutes, to a solution of 24.~ 9 (0.09 mol) of 3,5-dibromo-4-hydroxybenzonitrile and 9.1 9 tO.09 mol) of triethylamine in 200 ml of anhydrous methyLene dichloride, and the reaction mixture was then stirred for a further ~5 30 minutes at the same temperature. The solid formed was filtered off and washed w;th 29 ml of anhydrous methylene dichloride. After O.OOS g of hydroquinone monomethyl ether had been added, the volatile constituents in the mixture of fiLtrate and ~ash s~lut1on were removed by ':~
., ``" - 1 309 1 06 distillation, and the residue was recrystallized from boiling n-heptane~ 17~5 9 (55% of theory) of 2,6-dibromo-4-cyanophenyl ~-fluoroacrylate were obtained, melting point 135 to 138C.
:
~: :
Esters of ~-fluoroacrylic acid are already known. Thus the phenyl ester of ~-fluoroacrylic acid is prepared by reacting ethyl monofluoroacetate in the presence of sodium ethylate with ethyl oxalate, converting the sodium ~-fluoroacrylate obtained into ~-fluoroacryloyl chloride by means of th;onyl chloride and then esterifying this product with phenol (German Patent No. 2,950,491 = US
Patent No. 4,297,4 6 6)~ It is a disadvantage in this process that ethyl monofluoroacetate, which is highly toxic, has to be employed. Phenyl a-fluoroacrylate can be polymerized and is used for the preparation of poly-mers ~hich, at room temperature, are translucent or transparent or light-transmissive, colorless solids.
Other esters of ~-fluoroacryl;c acid, in particular butyl ~-fluoroacrylate, can be prepared by acid hydrolysis of the appropriate ~-hydroxymethyl-~-fluoromalonate followed by decar~oxylation of the hydrolysis product with simultaneous elimination of alcohol tBritish Patent No.
1,115,287). This method is, however, only descr;bed for Z5 the example of butyl ~-fluoroacrylate; the ester rapidly polymerizes under the influence of light.
Polymers of fluorinated acryl;c acid esters are also kno~n, uh;ch correspond to the formula RHC=CR-CO-OR1 ; ~ 3Q in ~hich R is a hydrogen atom, a methyl group or a halogen atom and R1 is a fluorinated alkyl or aryl radical tUS Patent No. 2,877,207); the fluoroalkyl radical af the aLcohol component is, in particular, a radical con-taining two hydrogen atoms on the carbon atom in the 1-position and no detailed statements at alL are made ~k ., i, .. .. . .
concerning suitable aryl radicals.
It is also known that polymers of ~-halogenoacrylic acid esters with halogen-containing alcohol components are used for the preparation of radiation-sensitive protect-ive layers (US Patent No. 4,259,407). The starting materials used are monomers of the formula H2C = CX-COOR
in which X is a fluorine, chlorine or bromine atom and R represents a fluorinated alkyl, aryl or alkoxy group.
Amongst the polymers cuntaining an aromatic alcohol com-ponent, only poly-(m-trifluoromethylphenyl ~-fluoro-acrylate) is mentioned by name; there is, however, no information at all about any properties of this polymer or the corresponding monomer.
Finally, it is also known that polymers of ~-fluoroacrylic acid esters are suitable as the core material for optical fibers (European published application 0,128~517).
Phenyl ~-fluoroacrylate is the only ester hav;ng an aromatic alcohol component which is shown in terms of a formula, but there ;s no information at a~l on the preparation and properties of this ester.
The object of the invention is to provide esters of ~-fluoroacrylic acid with substituted phenols which can be prepared in an economical manner using starting mater-ials of as low toxicity as possible and which can be polymerized to give products having a high transmittance of light.
The invention relates to phenyl ~-fluoroacrylates of the formula (1) CN2 = C~ - CO - O ~ (~)m : .
l s ~ u ~
in which R denotes a halogenoalkyl group having 1 to 8 carbon atoms and p is o , 1, 2 or 3, X denotes a halogen atom and n is or an integer from 1 to 5 (it being possible for X to denote different halogen atoms if n is greater than 1), Y denotes a hydrogen atom, a cyano group, the radical X or the radical R and m is nought or 1, the sum of n + m + p denoting 1 to 5.
The invention also relates to a process for the prepar-ation of a substituted phenyl ~-fluoroacrylate, which comprises reacting dimethyl ~-fluoromalonate with formal-dehyde in a first process stage, then hydrolyzing, decarboxylating and dehydrating the resulting hydroxy-methylated dimethyl ~-fluoromalonate in a second process stage and subsequently, in a third process stage, esteri-fying the resulting -fluoroacrylic acid tif appropriate in the form of an acid halide) with a phenol o~ the formuls (2) N0 ~ X)n in which X, Y, R, n, m and p have the meaning indicated in formula ~ if appropriate in the form of an alkali metal phenate).
Finally, the invention also relates to the use of sub-stituted phenyl ~-fluoroacrylates of the formula (1) as a starting mater;al for the preparation of polymers contain-;ng fluorine.
The process according to the invention ;s carried out in three stages: dimethyl ~-fluoromalonate is first reacted ~ith formaldehyde to give dimethyl~-hydroxymethyl-~-fluoromalonate, the latter is then hydrolyzed and the hydrolysis product is decarbo~ylated and dehydrated, and finally, the resulting ~-fluoroacrylic acid ;s esterified with a substituted phenol.
In the first process stage, dimethyl ~-fluoromalonate is i,., ~., . ~, --" 1 309 1 06 subjected to hydroxymethylation with formaldehyde.
tDimethyl ~-fluoromalonate is a known compound; see Journal of Fluorine Chenlistry 25 (1984)~ 203 - 212.) The formaldehyde is preferably employed in the form of an aqueous solution having a formaldehyde content of 30 to 40% by weight. The formaldehyde is employed in an amount of 1 to 10 mol, preferably 1.1 to 3 mol (relative to 1 mol of dimethyl ~-fluoromalonate). It is also possible to use paraformaldehyde, hexamethylenetetramine or 1,3,5-trioxane instead of formaldehyde. It is advant-agous to carry out the reaction in the presence of a basic catalyst, which is then used in an amount of 2 to _ . .
S0~ preferably S to 15, mol % (relative to the dimethyl a-fluoromalonate). The catalyst used is, in particular, an alkali metal bicarbonate, for example potassium bi-carbonate and sodium bicarbonate. The reaction is car-ried out at a temperature of S to 40C, preferably 15 to 30C. The dimethyl a-hydroxymethyl-~-fluoromalonate formed is then isolated from the reaction mixture~
preferably by salting out or extraction by means of a water-immiscible organic solvent. A suitable solvent is, above all, an aliphatic chlorinated hydrocarbon having 1 to 4 carbon atoms, ~or example methylene dichloride, chloroform, carbon tetrachloride, 1,1-dichloroethane or 1,Z-d;chloroethane. A combination of salting out and extraction is particularly advantageous; a saturated salt solution (ammonium sulfate or sodium chloride) is then first added to the reaction mixture, and this mixture is then extracted. Dimethyl ~-hydroxymethyl-~-fluoro-malonate is obtained in the form of a colorless solid byevaporating the solvent.
In the second process stage, the dimethyl ~-hydroxymethyl-~-fluoromalonate is hydrolyzed in an aqueous acid medium, and the hydrolysis product is decarboxylated and dehydrated. The reaction is carried out at a pH from -1 to 6, preferably 0 to 2; the acid med;um ;s prepared by means of an aqueous acid solution, preferably a dilute inorganic acid, such as hydrochloric acid or sulfuric -` 1 309 1 06 acid. The reaction temperature is with;n the range from 90 to 110C, preferably 95 to 105C. When the evolution of gas is complete, the reaction mixture is distilled under a pressure of 1013 to 600 mbar, and the distillate is extracted with an organic solvent. The solvent used here is also a water-immiscible solvent, preferably an ether, such as diethyl ether. -fluoro-acrylic acid is obtained in the form of a colorless solid after the solvent has been removed by evaporation. In a preferred variant, the -fluoroacrylic acid is isoLated ;n the form of its ammonium salt. This is effected by passing gaseous ammonia through the solution obtained after the extraction, and then freeing the colorless crystalline precip;tate from the solvent.
- In the third process stage, the ~fluoroacrylic acid is esterified with a substituted phenol. The phenol is employed in an amount of 0.5 to 1~5 mol, preferably 0.8 to 1.2 mol (relative to l mol of ~-fluoroacrylic acid).
In some cases - if the acid is employed in the form of a halide - the phenol is employed in the form of an alkali metal phenate, preferably sodium phenate or potassium phenate. The ~-fluoroacrylic acid is employed for the esterification as such or, preferably, in the form of an acid halide, in particular as ~-fluoroacryl chloride.
The acid halide is prepared by means of a customary halogenating agent, for example oxalyl chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, benzoyl chloride, benzotrichloride~
phosphorus tribromide, sulfur tetrafluoride and, especially, thionyl chloride. The halogenation by means of thionyl-chloride is preferably carried out in the presence of a catalyst, such as dimethyl formamide~ The reaction is carried out in an aromatic hydrocarbon~ for example toluene, xylene and ~rimethylbenzene, as the solvent, and the reaction temperature is w;thin the range from 50 to 100C, preferably 70 to 90C.
The esterification is preferably carried out in a solvent , . ,~ , .. . . . .
and the reaction temperature in this case ;s -10 to 50C, preferably 0 to 25C. The solvent used is a polar organic solvent, in part;cular a symmetr;cal, asymmetrical or cyclic e~her, for example diethyl ether~ dipropyl ether, diisopropyl ether, tert.-butyl methyl ether, tetrahydrofuran and dioxane, and aliphatic halogenated hydrocarbon, preferably a chlorinated hydrocarbon, for example methylene dichloride, chloroform, carbon tetra-chloride, 1,1-dichloroethane and 1,2-dichloroethane, an aromatic halo~enatic hydrocarbon, preferably a chlorinated hydrocarbon, for example chlorobenzene and 1,Z-dichloro-benzene or 1,3-dichlorobenzene, or an aliphatic or aromatic nitrile, for example acetonitrile and benzo-nitrile. The solvent can also be a mixture of several polar solvents. It is expedient to carry out the ester-- ification of the acid halide with the phenol in the presence of an organic base, in particular a trialkyl-amine having 1 to 4 carbon atoms in each of the alkyl groups. The base is employed in an amount of 0.5 to 2 mol, preferably 0.8 to 1.2 mol ~relative to 1 mo; of acid halide)~ The resulting substituted phenyl ~-fluoro-acrylate is isolated from the reaction mixture by distil-lation, preferably under a pressure of 1013 to 200 mbar, or - after the solvent has been removed by distillation -by hot extract;on of the solid residue with a nonpolarsolvent, pre~erably an aliphatic hydrocarbon, such as n-hexane, and subsequent crystallization. It is expedient to carry out the dist;llation in the presence of a customary polymerization inhibitor, for example hydroquinone or hydroquinone monomethyl ether; this is used in an amount of 100 to 500 ppm (relative to ~-fluoroacryloyl halide).
The bottom temperature is within the range from 20 to 100C, preferably 3û to 85C. The phenyl ester is purified further by being distilled again, preferably under reduced pressure, or recrystallized. The substituted phenyl a-fluoro-acrylates according to the invent1on carry 1 to 5, preferably 2 to 5, substituents on the phenyl rad;cal; preferred esters are those which contain, as substi~uents or in the substituent, a fluorine atom or several fluorine atoms.
,, . ~
The esters according to the invention include, for example, the follow;ng compounds: 2- or 3- or 4-fluoro-phenyl a-fluoroacrylate, 2- or 3- or 4-chlorophenyl a-fluoroacrylate, 2- or 3- or 4-bromophenyl a-fluoroacrylate, 2- or 3- or 4 iodophenyl a-fluoroacrylate, 2,3- or 2,4- or 2,5- or 2,6- or 3,4- or 3,5-difluorophenyl a-fluoro-acrylate, 2,3- or 2,4- or 2,5- or 2,6- or 3,4- or 3,5-d;chlorophenyl a-fltloroacrylate, 2- or 3-chlor-4-fluoro-phenyl a-fluoroacrylate, 2-bromo-4-chloro~henyl a-fluoro-acrylate, 4-bromo-2-chlorophenyl -fluoroacrylate, 2,6-d;bromo-4-fluorophenyl a-fluoroacrylate, 4-bromo-2,6-dichlorophenyl a-fluoroacrylate, 2,4-dichloro-6-iodophenyl a-fluoroacrylate, 2,3,4- or 2,3,5- or 2,3,6- or 2,4,5-or 2,4,6- or 3,4,5-trichloro-phenyl a-fluoroacrylate, 2,4,6-tribromophenyl a-fluoroacrylate, 2,4,6-triiodophenyl -fluoroacrylate, 2,3,5,6-tetrafluorophenyl a-fluoro-acrylate, 2,3,4,5-tetrachlorophenyl a-fluoroacrylate, 2,3,5,6-tetrachlorophenyl a-fluoroacrylate, pentafluoro-phenyl a-fluoroacrylate, pentachlorophenyl a-fluoroacrylate, pentabromophenyl a-fluoroacrylate, Z,6-diiodo-4-trifluoro-methylphenyl a-fluoroacrylate, 2- or 3- or 4-trifluoro-methylphenyl a-fluoroacrylate, 2-(heptafluoro-2-propyl)-phe~nyl or 4-~heptafluoro-2-propyl)-phenyl a-fluoroacrylate, 2,6- or 3,5-bis(tr;fluoromethyl)-phenyl a-fluoroacrylate, `25 4-cyanophenyl ~-fluoroacrylate, 2,6-dibromo-4-cyanophenyl a-fluoroacrylate, 2,6-d;chloro-4-cyanophenyl a-fluoro-acrylate, 2,6-difluoro-4-cyanophenyl a-fluoroacrylate, 4-cyano-2,3,5,6-tetrafluorophenyl a-fluoroacrylate, 4-chloro-2,5- ~or 3,5)-difluorophenyl a-fluoroacrylate, 2-30~ chloro-4,5- (or 4,6)-difluorophenyl a-fluoroacrylate, 2,5-~or 2,6- or 3,5-dichloro-4-fluorophenyl a-fluoroacrylate, 2,6- or 3,4-dibromo-3,4 ~or 2,6)-dichlorophenyl a-fluoro-acrylate, 2,4,6-trichloro-3-fluorophenyl a-fluoroacrylate, 2,4- or 2~6-dichloro-3-trifluoromethylphenyl ~-fluoro-acrylate, 2,6-d;bromo-4- ~or 5) -trifluoromethylphenyl ~-~: -fluoroacrylate, 2,4-dibromo-5- ~or 6)-trifluoromethylphenyl a-fluoroacrylate, 2- or 4-bromo-3-: ~or 5)-trifluoromethyl-phenyl -fluoroacrylate, 2,3,6-tribromo,4,5-bisbromo-methylphenyl a-fluoroacrylate, 2,4,5-tribromo-3,6-bis-:
.
(bromomethyl)phenyl ~-fluoroacrylate, 2,4,6-trichloro-3,5-bistchloromethyl)phenyl) ~-fluoroacrylate, 3,4,5-trichloro-2,~-bistchloromethyl)phenyl ~-fluoroacrylate, 2,4,6-trichloro-3-chloromethylphenyl ~-fluoroacrylate, 5 2,4-d;bromo-6-dibromomethylphenyl -fluoroacrylate, 2,6-dibromo-4-dibromomethylphenyl a-fluoroacrylate, 2,3,5,6-tetrachloro-4-chloromethylphenyl ~-fluoroacrylate, 2- or 3-fluoro-4-methylphenyl ~-fluoroacrylate, 3- or 4- or 5-fluoro-2-methylphenyl ~-fluoroacrylate, 2-fluoro-6-10 methylphenyl ~-fluoroacrylater 4-fluoro-3-methylphenyl ~-fluoroacrylate, 2,4,6-trichloro 3,5-dimethylphenyl ~-fluoroacrylate, 2,6-dichloro-3,5-dimethylphenyl ~-fluoro-acrylate, 2,6-dichloro-4-methylphenyl -fluoracrylate~
2,4,6-tribromo-3,5-d;methylphenyl ~-fluoroacrylate, 2,4,6-tribromo-3-methylphenyl ~-fluoroacrylate, 2,3,5,6-tetra-fluoro-4-cyanophenyl -fluoracrylate, 2- or 3- or 4-methylphenyl ~-fluoroacrylate, 2,3- or 2,4- or 2,5- or Z,6- or 3,4- or 3,5-dimethylphenyl -fluoroacrylate, 2,4,6-tr;methylphenyl -fluoroacrylate, 2,3,5,6-tetra-methylphenyl -fluoroacrylate, 2- or 3- or 4-isopropyl-phenyl -fluoroacrylate, 4-isopropyl-3,5-dimethylphenyl ~-fluoroacrylate and 2,3- or 2,5- or 2,6- or 3,4- or 3,5-di;sopropylphenyl ~fluoroacrylate~
The subst;tuted phenyl esters of ~-fluoroacrylic ac;d are colorless liquids or colorless solids at room tem-perature. They are readily polymerizable and are suitable for the preparation of crystal clear, light-transmissive, colorless polymers.
The following examp(es serve to illustrate the invention ;n greater detail. Percentages relate ;n each case to weight.
Example 1 --.
a) 48 g (0.48 mol) of potassium bicarbonate were dissolved in 535 9 ~6.59 mol) of aqueous formaldehyde solution ~37% strength by we;ght) ;n a 4-litre glass flask.
~ 1 30q 1 Oh 841 9 (5.6 mol) of dimethyl a-fluoromalonate were added dropwise to this solution, with stirring, in the course of 3 1/2 hours; the temperature was kept meanwhile within the range from 20 to 25C. Stir-r;ng was continued for 2 hours at the same temperature, and during this time dimethyl a-hydroxymethyl-~-fluoro-malonate was precipitated in the form of a colorless solid. 2,500 9 of an aqueous, saturated solution of ammonium sulfate were then added to the reaction mix-ture, which was then extracted with methylene dichloride. The extraction solution was dried by means of anhydrous sodium sulfate. 906 g (90% of theory) of dimethyl a-hydroxymethyl-a-fluoromalonate were obtained after removing the methylene dichloride by distillation (bath temperature 40C, 25 mbar).
b) 175 9 (0.97 mol) of dimethyl a-hydroxymethyl-~-fluoro-malonate, 750 ml of water and 750 ml of hydrochloric acid ~36% strength by we;ght) were heated at the boil for 2 1/2 hours ;n a 2-l;tre glass flask equipped with a thermometer and stirrer and a Vigreux column fitted with a dist;llat;on head. The temperature of the reaction mixture was 103C. The react;on mixture was then distilled. 1 g of hydroquinone monomethyl ether was added to the distillate and the latter was extracted with diethyl ether, and the extraction solu-tion was dried by means of anhydrous sod;um sulfate.
17 9 (1 mol) of gaseous ammonia were then passed into the solution at room temperature. The colorless pre-cipitate obtained thereby was filtered off, washed with diethyl ether and dried at room temperature under reduced pressure. 70.8 9 t68% of theory) of ammonium a-fluoroacrylate were obtainedO
:
i 35 c~ 100 g (0.~34 mol) of ammon~ium a-fluoroacrylate were dispersed in a m;xture of 600 g of mesitylene and 15 ml of dimethylformamide in a 1-li`tre glass flask and 119 9 (1.0 mol) of thionyl chloride were added in the course of one hour. The resulting m;xture was heated ---` 1 30q 1 06 to a temperature of 80C and was kept at this temperature for 2 hours, with stirring. The liquid obtained after the mixture had coo(ed to room temperature was distilled under reduced pressure, and the fraction obtained up to 100C/160 mbar was distilled again under normal pressure~
67 g (66% of theory) of ~-fluoroacryloyl chloride were obtained, boiling point 65 to 67C.
d) A solution of 1119 (0.5 mol) of potassium pentafluoro-phenate in 250 ml of anhydrous acetonitrile was added dropwise, in the course of 1 hour, at a temperature of 25C and with stirring, to a solution of 54.5 9 (0.502 mol) of ~-fluoroacryloyl chloride in 1nO ml of anhydrous acetone nitrile, and the reaction mixture was then stirred for a further 2 hours at the same temperature. The solid formed was filtered off and washed with 100 ml of anhydrous acetonitrile. The mixture of filtrate and wash solution was distilled, after adding 0.01 g of hydroquinone monomethyl ether.
107.1 g (84% of theory) of penafluorophenyl ~-fluoro-acrylate were obtained, boiling point 41 to 42C
~under 2 mbar).
Example 2 13.9 g ~O~lZ8 mol) of a-fluoroacryloyl chloride (obtained in accordance with example 1c) were added dropwise, at a temperature of 25C, with stirring and in the course o~ 30 m;nutes, to a solution of 30 g (0.0985 mol) of potassium pentachlorophenate in 4ûO ml of anhydrous acetonitrile, and the react;on m;xture was then st;rred for a further 90 m;nutes at the same temperature. The sol;d formed was f;ltered off and washed w;th 20 ml of anhydrous aceto-n;tr;le. After 0.01 g of hydroqu;none monomethyl ether had been added, the volatile constituents in the m;xture of filtrat and washing liquor were distilled off and the residue was recrystallized from boiling n-hexane.
17 g (51% of theory) of pentachlorophenyl ~-fluoroacrylate were obtained, meltlng polnt 90 to 92C.
: ' 1 3nql 06 Example 3 49 g (0.181 mol) of 2,6-dibromo-4-fluorophenol were dis-solved in 150 ml of anhydrous methylene dichloride, and 1~.3 g (0.181 mol) of triethylamine were added to the solution; 20 g (0.184 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were then added dropwise at a temperature of 5C, with stirring and in the course of 30 minutes, and the reaction mixture was stirred for a further 30 minutes at the same temperature.
The solid formed was filtered off and washed with 30 ml of methylene dichloride. The mixture of filtrate and ~ash solution was distilled, after adding 0.01 9 of hydroquinone monomethyl ether. 46 9 (74% of theory) of 2,6 dibromo-4-fluorophenyl ~-fluoroacrylate were obtained, - boiling point 86 to 88C (under 0.4 mbar).
Example 4 2.2 9 (0~02 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were added dropwise, at a temperature of 5C, with stirring and in the course of 5 minutes, to a solution of 7.8 g (0.019 mol) of 2,6-diiodo-4-trifluoromethylphenyl and 2 g (0.02 mol) of triethylamine in 80 ml of anhydrous methylene dichloride, and the reaction m;xture was then stirred for a further 30 minutes at the same temperature. The solid formed ~as filtered off and washed with 1û ml of anhydrous methylene dichloride. After 0~001 g of hydroquinone monomethyl ether had been added, the volatile constituents in the mixture of filtrate and wash solution were removed by distillation, and the residue was recrystaLl;zed from boiling in-hexane. 7 g (76~ of theory) of 2,6-diiodo-4-trifluoromethylphenyl ~-fluoroacrylate were obtained, melting point 93 to 95C.
Exam~le 5 16.2 9 (0.1 mol) of 4-trifluoromethylphenol were dissolved , in 80 ml of anhydrous diethyl ether, and 10.1 9 (0.1 mol) of triethylamine were added in portions to the solut;on;
12 g (0.11 mol) of o~-fluoroacryloyl chloride (obtained in accordance with example 1c) were then added dropw;se, at a temperature of 10C, with stirring, and in the course of 20 minutes, and the reaction mixture was stirred for a further 60 minutes at the same temperature.
The solid formed was filtered off and washed with 20 ml of diethyl ether. The mixture of filtrate and wash sol-ution was distilled, after adding 0.005 9 of hydroquinonemonomethyl ether. 19.5 9 (83~ of theory) of 4-trifluoro-methylphenyl ~-fluoroacrylate were obtained, boiling point 69 to 70C (under 3 mbar).
Example 6 27.5 9 (0.169 mol) of 3-trifluoromethylphenol were dissolved in lOO ml of anhydrous methylene dichloride, and 17.1 9 (0.169 mol) of triethylamine were added in portions to the solution; 20 9 tO.184 mol) of ~-fluoro-acryloyl chloride (obtained in accordance with example 1c) were then added dropwise, at a temperature of 5C, with stirring and in the course of 20 minutes, and the reaction mixture was stirred for a further 60 minutes at the same temperature. The solid formed was filtered off and washed with 30 ml of methylene dichlor;de. The mixture of filtrate and wash solution was distilled, after adding 0.01 9 of hydroquinone monomethyl ether. 27 g (68% of theory) of 3-trifluoromethylphenyl ~-fluoro-acrylate were obtained, boiling point 7~ to 79C (under - 4 mbar).
Example 7 :
26.2 9 (0.1 mol) of 4-perfluoroisopropylphenol were dissolved in 100 ml of anhydrous diethyl ether, and 10~1 g (0.1 molj of triethylamine were added to the solut;on; 12 9 (0.11 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were then added 1 3()ql 06 dropwise, at a temperature of 10C, with stirring and in the course of 15 minutes, and the reaction mixture was stirred for a further 30 minutes at the same temper-ature. The solid formed was filtered off and washed w;th 2û ml of diethyl ether. The mixture of filtrate and wash solution was distil~ed, after adding 0.005 g of hydro-quinone monomethyl ether. 22.9 g (69% of theory) of 4-perfluoroisopropylphenyl a-fluoroacrylate were obtained, boiling point 65 to 66C (under 1 mbar).
Example 8 10 g (0.038 mol) of 2-perflùoroisopropylphenol were dissolved in 30 ml of anhydrous diethyl ether, and 3.9 g (0.038 mol) of triethylamine were added to the solution;
4.3 g (0.039 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were then added dropwise, at a temperature of 10C, with stirring and in the course of 12 minutes, and the reaction mixture was stirred for a further 30 minutes at the same temperature.
The solid formed was filtered off and washed with 10 ml of diethyl ether. The mixture of filtrate and wash sol-ut;on was d;stilled after adding 0.002 g of hydroquinone monomethyl ether. 7 9 ~55~ of theory) of 2-perfluoro-isopropylphenyl a-fluoroacrylate were obtained, boiling point 85C (under 1 mbar).
Example 9 10 9 (0.092 mol) of a-fluoroacryloyl chloride (obtained in accordance with example 1c) were added drop~ise, at a temperature of 5C, with stirring and in the course of 20 minutes, to a solution of 10~7 g (0.09 mol) of 4-cyano-phenol and 9.1 g (0.09 mol) of triethylamine in 150 ml of anhydrous methylene dichloride, and the reaction mixture was then stirred for a further 30 minutes at the same temperatureu The solid formed was filtered off and washed with Z0 ml of anhydrous methylene dichloride.
After 0.005 9 of hydroquinone monometbyl ether had been .:
~ 3~39 1 0 6 added, the volatiLe constituents in the mixture of filtrate and wash solution were removed by distillation, and the residue was recrystallized from boiling n-hexane.
11.2 9 (65% of theory) of 4-cyanophenyl ~-fluoroacrylate were obtained, melting point 78 to 79C.
Example 10 10 g (0.092 mol) of ~-fluoroacryloyl chloride (obtained in accordance with example 1c) were added dropwise, at a temperature of 5C, with stirring and in the course of 20 minutes, to a solution of 16.7 g (0.089 mol) of 3,5-dichloro-4-hydro~ybenzonitrile and 9 9 (0.089 mol) of triethylamine in Z00 ml of anhydrous methylene dichloride, and the reaction mixture was then stirred for a further 30 minutes at the same temperature. The solid formed was filtered off and washed with 20 ml of anhydrous methylene dichloride. After 0.005 9 of hydroquinone monomethyl ether had been added, the volatile constituents in the mixture of filtrate and wash solution were removed by distillat;on, and the residue was recrystallized from boiling n-heptane. 18.7 9 ~81% of theory) of 2,6-dichloro-4-cyanophenyl ~-fluoroacrylate were obtained, melting point 95 to 99C.
ZS
Example 11 10 g (0.092 mol) ~-fluoroacryloyl chloride (obtained ;n accordance with example 1c) were added dropwise, at a temperature of 5C, with stirring and in the course of S minutes, to a solution of 24.~ 9 (0.09 mol) of 3,5-dibromo-4-hydroxybenzonitrile and 9.1 9 tO.09 mol) of triethylamine in 200 ml of anhydrous methyLene dichloride, and the reaction mixture was then stirred for a further ~5 30 minutes at the same temperature. The solid formed was filtered off and washed w;th 29 ml of anhydrous methylene dichloride. After O.OOS g of hydroquinone monomethyl ether had been added, the volatile constituents in the mixture of fiLtrate and ~ash s~lut1on were removed by ':~
., ``" - 1 309 1 06 distillation, and the residue was recrystallized from boiling n-heptane~ 17~5 9 (55% of theory) of 2,6-dibromo-4-cyanophenyl ~-fluoroacrylate were obtained, melting point 135 to 138C.
:
~: :
Claims (6)
1. A process for the preparation of a phenyl .alpha.-fluoroacrylate, which comprises reacting dimethyl .alpha.-fluoromalonate with formaldehyde in a first process stage, then hydrolyzing, decarboxylating and dehydrating the resulting hydroxymethylated dimethyl .alpha.-fluoromalonate in a second process stage, and subsequently esterifying, in a third process stage the resulting .alpha.-fluoroacrylic acid, (which may be in the form of an acid halide) with a phenol of the formula (2) in which p is 0, 1, 2, or 3, X denotes a halogen atom and n is 0 or an integer from 1 to 5 (X may denote different halogen atoms if n is greater than 1), Y denotes a hydrogen atom, a cyano group, the radical X or a halogenoalkyl group having 1 to 8 carbon atoms and m is 0 or 1, the sum of n + m + p being
2 to 5 (which may be in the form of an alkali metal phenate).
2. The process as claimed in claim 1, wherein the first process stage is carried out at a temperature from 5 to 40°C, the second process stage is carried out at a temperature from 90 to 110°C, and the third process stage is carried out at a temperature from -10 to 50°C.
2. The process as claimed in claim 1, wherein the first process stage is carried out at a temperature from 5 to 40°C, the second process stage is carried out at a temperature from 90 to 110°C, and the third process stage is carried out at a temperature from -10 to 50°C.
3. The process as claimed in claim 1 which further comprises polymerizing the resultant phenyl .alpha.-fluoroacrylate of the formula I to form a fluorine-containing polymer.
4. The process as claimed in claim 2, wherein the dimethyl .alpha.-fluoromalonate and formaldehyde are reacted in a mol ratio of 1:1-10.
5. The process as claimed in claim 4, wherein the second process stage is carried out at a pH of 1 to 6.
6. The process as claimed in claim 5, wherein in the third process stage, the resulting .alpha.-fluoroacrylic acid (which may be in the form of an acid halide) is esterified with a phenol of the formula (2) in a mol ratio of 1:0.5-1.5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863620050 DE3620050A1 (en) | 1986-06-14 | 1986-06-14 | SUBSTITUTED (ALPHA) -FLUORACRYLIC ACID PHENYLESTER |
| DEP3620050.6 | 1986-06-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1309106C true CA1309106C (en) | 1992-10-20 |
Family
ID=6303005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000539539A Expired - Fee Related CA1309106C (en) | 1986-06-14 | 1987-06-12 | SUBSTITUTED PHENYL .alpha.-FLUOROACRYLATES |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0249867B1 (en) |
| JP (1) | JPS62298556A (en) |
| KR (1) | KR950008086B1 (en) |
| CN (1) | CN1014236B (en) |
| AT (2) | ATE71081T1 (en) |
| AU (1) | AU602699B2 (en) |
| CA (1) | CA1309106C (en) |
| DE (2) | DE3620050A1 (en) |
| ES (1) | ES2038617T3 (en) |
| GR (1) | GR3003804T3 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005137A (en) | 1997-06-10 | 1999-12-21 | 3M Innovative Properties Company | Halogenated acrylates and polymers derived therefrom |
| JP4599948B2 (en) * | 2003-09-18 | 2010-12-15 | チッソ株式会社 | α-Fluoroacrylate compound, composition and polymer thereof |
| JP5040259B2 (en) * | 2005-12-08 | 2012-10-03 | Ｊｎｃ株式会社 | Lateral α-substituted acrylate compound and polymer thereof |
| JP5582032B2 (en) * | 2009-02-05 | 2014-09-03 | 三菱レイヨン株式会社 | Method for producing (meth) acrylic acid ester |
| ES2738421T3 (en) * | 2014-06-18 | 2020-01-22 | Saltigo Gmbh | Procedure for the preparation of esters of 2-haloacrylic acid |
| KR20210064190A (en) * | 2018-09-25 | 2021-06-02 | 니폰 제온 가부시키가이샤 | Copolymer and positive resist composition |
| CN114867710A (en) * | 2019-11-14 | 2022-08-05 | 维福(国际)有限公司 | One-step synthesis of 2-fluoroacrylic acid alkyl ester |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5518638A (en) * | 1978-07-27 | 1980-02-08 | Chiyou Lsi Gijutsu Kenkyu Kumiai | Ionized radiation sensitive positive type resist |
| FR2444052A1 (en) * | 1978-12-15 | 1980-07-11 | Onera (Off Nat Aerospatiale) | TRANSPARENT ORGANIC MATERIAL |
| FR2444022A1 (en) * | 1978-12-15 | 1980-07-11 | Onera (Off Nat Aerospatiale) | ACRYLIC MONOMER |
| EP0128517B1 (en) * | 1983-06-10 | 1992-09-02 | Daikin Industries, Limited | Optical material |
| JPS6078940A (en) * | 1983-10-04 | 1985-05-04 | Daikin Ind Ltd | Production of alpha-fluoroacrylic acid ester |
| US4572805A (en) * | 1984-03-27 | 1986-02-25 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | 2,3,5,6-Tetrafluorophenyl (meth) acrylates and method for production thereof |
-
1986
- 1986-06-14 DE DE19863620050 patent/DE3620050A1/en not_active Withdrawn
-
1987
- 1987-06-10 AT AT87108368T patent/ATE71081T1/en not_active IP Right Cessation
- 1987-06-10 EP EP87108368A patent/EP0249867B1/en not_active Expired - Lifetime
- 1987-06-10 ES ES198787108368T patent/ES2038617T3/en not_active Expired - Lifetime
- 1987-06-10 DE DE8787108368T patent/DE3775626D1/en not_active Expired - Fee Related
- 1987-06-11 CN CN87104092A patent/CN1014236B/en not_active Expired
- 1987-06-12 AU AU74181/87A patent/AU602699B2/en not_active Ceased
- 1987-06-12 JP JP62145421A patent/JPS62298556A/en active Pending
- 1987-06-12 KR KR1019870005939A patent/KR950008086B1/en active IP Right Grant
- 1987-06-12 CA CA000539539A patent/CA1309106C/en not_active Expired - Fee Related
- 1987-10-08 AT AT0258787A patent/AT388727B/en not_active IP Right Cessation
-
1992
- 1992-02-13 GR GR920400223T patent/GR3003804T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3620050A1 (en) | 1987-12-17 |
| EP0249867B1 (en) | 1992-01-02 |
| CN1014236B (en) | 1991-10-09 |
| AU602699B2 (en) | 1990-10-25 |
| CN87104092A (en) | 1988-02-10 |
| EP0249867A3 (en) | 1988-12-21 |
| DE3775626D1 (en) | 1992-02-13 |
| AT388727B (en) | 1989-08-25 |
| KR950008086B1 (en) | 1995-07-25 |
| AU7418187A (en) | 1987-12-17 |
| EP0249867A2 (en) | 1987-12-23 |
| ATA258787A (en) | 1989-01-15 |
| ES2038617T3 (en) | 1993-08-01 |
| ATE71081T1 (en) | 1992-01-15 |
| KR880000376A (en) | 1988-03-25 |
| GR3003804T3 (en) | 1993-03-16 |
| JPS62298556A (en) | 1987-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4356296A (en) | Fluorinated diacrylic esters and polymers therefrom | |
| CA1309106C (en) | SUBSTITUTED PHENYL .alpha.-FLUOROACRYLATES | |
| US6359170B1 (en) | Brominated materials | |
| US4076727A (en) | Cyclic acetal acrylates or methacrylates and processes for preparing same | |
| US6028156A (en) | Process for the preparation of poly-(halobenzyl acrylate) | |
| US5266668A (en) | Substituted phenyl α-fluoroacrylates | |
| EP0160379B1 (en) | 2,3,5,6-tetrafluorophenyl (meth)acrylates and their production | |
| JP2509593B2 (en) | Method for producing α-fluoroacrylic acid ester | |
| US4452998A (en) | Fluorinated diacrylic esters | |
| US4145524A (en) | Preparation of heterocyclic block copolymer from perfluoroalkylene oxide α, ω-diamidoximes | |
| US5936111A (en) | Fluorinated amide compounds with a phenyl-Si-unsaturated group | |
| US2508249A (en) | Allyl polyesters of amino alkyl carboxylic acids | |
| US4672098A (en) | Bicyclic acrylic monomers | |
| US4151358A (en) | Ethynyl-substituted bis-naphthalimides | |
| JP2569814B2 (en) | Fluorine-containing diacrylate having sulfonamide bond and method for producing the same | |
| JPS5647431A (en) | Photoconductive polymer and photoconductive material | |
| US3282964A (en) | New alpha-substituted carboxylic acid derivatives | |
| US4841005A (en) | Tricyclodecane derivative | |
| James et al. | Synthesis, polymerization, and copolymerization of aliphatic vinyl azide | |
| JPH06279403A (en) | Fluorine-containing phenylmaleimide | |
| JP3941894B2 (en) | New (meth) acrylate | |
| JPH0251545B2 (en) | ||
| JP2581220B2 (en) | Fluorine-containing diacrylate having ether bond and method for producing the same | |
| JPH02134337A (en) | Fluorine-containing aromatic compound | |
| US4108884A (en) | Hybrid perfluoroalkylene ether thioimidate ester monomers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |