# US 5,703,270 A · Method for preparing a vinyl compound having a hydroxy group > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,703,270 A - Document ID: US5703270A - Status: Granted - Kind: A - Application number: 08/394,013 - Filed: 1995-02-22 - Granted: 1997-12-30 - Earliest claimed: 1994-02-25 - Assignees: Nippon Shokubai Co., Ltd. - Inventors: Koichi Nakagawa; Mitsuaki Makino; Yuichi Kita - Web page: https://patentgrep.com/patent/US5703270A ## CPC - C07C 253/30: by reactions not involving the formation of cyano groups - C07C 45/72: by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups - C07C 45/75: Reactions with formaldehyde - C07C 67/343: by increase in the number of carbon atoms - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract A vinyl compound having a hydroxy group of the formula (1) ##STR1## wherein R is a hydrogen atom or an organic residue, X is a --CN group, a --COR.sub.0 group or a --COOR.sub.0 group and R.sub.0 is a hydrogen atom or an organic residue, is prepared by reacting a vinyl compound of the formula (2) ##STR2## wherein X is a --CN group, a --COR.sub.0 group or a --COOR.sub.0 group and R.sub.0 is a hydrogen atom or an organic residue, with an aldehyde series compound in the presence of a tertiary amine compound, and water in a sufficient amount for forming an aqueous phase upon the completion of the reaction. In this method, since the aqueous phase is formed upon the completion of the reaction, the organic phase including the vinyl compound having a hydroxy group and the aqueous phase including the tertiary amine compound can be easily separated. ## Claims ### Claim 1 A method for preparing a vinyl compound having a hydroxy group of the formula (1) ##STR5## wherein R is derived from an aldehyde series compound selected from the group consisting of formaldehyde, acetoaldehyde, propionaldehyde, butylaldehyde, valeraldehyde, isobutylaldehyde, pivalynaldehyde, cyclohexylaldehyde, cyclohexenealdehyde, benzaldehyde, tolualdehyde, anisaldehyde, furfural, trioxane, paraacetoaldehyde, and an oxymethylene compound of the formula HO(CH.sub.2 O).sub.p Y wherein Y is a hydrogen atom, a straight-chain or branched-chain alkyl group of 1 to 8 carbons, or an optionally substituted cycloalkyl group of 3 to 10 carbons, and p is an integer of from 1 to 100; X is a --COOR.sub.0 group and R.sub.0 is a hydrogen atom or an organic residue selected from the group consisting of an alkyl group of 1 to 18 carbons, a cycloalkyl group of 3 to 10 carbons, an aryl group, a hydroxyalkyl group of 1 to 8 carbons, a --(CH.sub.2).sub.m NR.sub.1 R.sub.2 group, a --(CH).sub.2 N.sup.+ R.sub.1 R.sub.2 R.sub.3.M.sup.- group or a --(C.sub.2 H.sub.4 O).sub.n R.sub.4 group, wherein R.sub.1, R.sub.2 and R.sub.3 respectively represent straight-chain or branched-chain alkyl groups of 1 to 8 carbons, m is an integer of from 2 to 5, M.sup.- is Cl.sup.-, Br.sup.-, CH.sub.3 COOO.sup.-, HCOO.sup.-, 1/2SO.sub.4.sup.2-, 1/3 PO.sub.4.sup.3-, R.sub.4 is a straight-chain or branched-chain alkyl group of 1 to 18 carbons and n is an integer of from 1 to 80, comprising the step of: reacting a vinyl compound of the formula (2) ##STR6## wherein X is a --COOR.sub.0 group; with an aldehyde series compound selected from the group consisting of formaldehyde, acetoaldehyde, propionaldehyde, butylaldehyde, valeraldehyde, isobutylaldehyde, pivalynaldehyde, cyclohexylaldehyde, cyclohexenealdehyde, benzaldehyde, tolualdehyde, anisaldehyde, furfural, trioxane, paraacetoaldehyde, and an oxymethylene compound of the formula HO(CH.sub.2 O).sub.p Y wherein Y is a hydrogen atom, a straight-chain or branched-chain alkyl group of 1 to 8 carbons, or an optionally substituted cycloalkyl group of 3 to 10 carbons, and p is an integer of from 1 to 100; in a presence of a tertiary amine compound and water in a sufficient amount for obtaining an aqueous phase upon completion of the reaction. ### Claim 2 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said sufficient amount is a sufficient amount of said water for obtaining an aqueous phase throughout from start to completion of the reaction. ### Claim 3 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein a mole ratio of said vinyl compound to said aldehyde compound is not less than 2. ### Claim 4 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein a mole ratio of said vinyl compound to said aldehyde compound is in a range of 2.5-15. ### Claim 5 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein a mole ratio of said vinyl compound to said aldehyde compound is in a range of 2.5-8. ### Claim 6 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein a mole ratio of said tertiary amine compound to said aldehyde series compound is in a range of 0.2-2. ### Claim 7 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein a mole ratio of said tertiary amine compound to said aldehyde series compound is in a range of 0.2-1. ### Claim 8 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein a mole ratio of said tertiary amine compound to said aldehyde series compound is in a range of 0.4-0.8. ### Claim 9 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said vinyl compound is an acrylate compound. ### Claim 10 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said vinyl compound is at least one member selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. ### Claim 11 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said aldehyde series compound is at least one member selected from the group consisting of formaldehyde, paraformaldehyde and acetaldehyde. ### Claim 12 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said aldehyde series compound is in the form of a 20-50% by weight of aqueous solution. ### Claim 13 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said aldehyde series compound is in the form of a 20-50% by weight aqueous methanol solution. ### Claim 14 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said tertiary amine compound is an N-methylalkylamine compound. ### Claim 15 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said tertiary amine compound is an N-methylalkylamine having a boiling point of not higher than 100.degree. C. at atmospheric pressure. ### Claim 16 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said tertiary amine compound is an N,N-dimethylalkylamine having a boiling point of not higher than 100.degree. C. at atmospheric pressure. ### Claim 17 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said tertiary amine compound is a trimethyl amine. ### Claim 18 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said tertiary amine compound is in the form of a 5-80% by weight aqueous solution. ### Claim 19 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said tertiary amine compound is in the form of a 20-60% by weight of aqueous solution. ### Claim 20 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein a reaction temperature is in a range of 10.degree.-150.degree. C. ### Claim 21 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said step is performed in a presence of a water-insoluble solvent. ### Claim 22 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said step is performed in a presence of a polymerization inhibitor. ### Claim 23 (depends on 22) The method for preparing a vinyl compound having a hydroxy group according to claim 22, wherein a ratio of said polymerization inhibitor to said vinyl compound is in a range of 0.01-1% by weight. ### Claim 24 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, wherein said step is performed in the presence of oxygen. ### Claim 25 (depends on 1) The method for preparing a vinyl compound having a hydroxy group according to claim 1, further comprising the step of: separating an organic phase including said vinyl compound having a hydroxy group from the aqueous phase after the reaction is completed. ### Claim 26 (depends on 25) The method for preparing a vinyl compound having a hydroxy group according to claim 25, further comprising the step of: recovering said tertiary amine compound from said aqueous phase after the step of separating said organic phase from said aqueous phase. ### Claim 27 (depends on 25) The method for preparing a vinyl compound having a hydroxy group according to claim 25, further comprising the step of: recovering said tertiary amine compound from said aqueous phase by heating said aqueous phase under basic conditions after the step of separating said organic phase from said aqueous phase. ### Claim 28 (depends on 27) The method for preparing a vinyl compound having a hydroxy group according to claim 27, wherein said aqueous phase is heated to 30.degree.-150.degree. C. ### Claim 29 (depends on 27) The method for preparing a vinyl compound having a hydroxy group according to claim 27, wherein said step for recovering said tertiary amine compound includes a step of collecting vapor of said tertiary amine compound with water. ### Claim 30 (depends on 27) The method for preparing a vinyl compound having a hydroxy group according to claim 27, wherein said step for recovering said tertiary amine compound includes a step of making vapor of said tertiary amine compound. ### Claim 31 (depends on 27) The method for preparing a vinyl compound having a hydroxy group according to claim 27, wherein said aqueous phase is made basic by at least one alkaline material selected from the group consisting of an alkali metal hydroxide, alkaline-earth metal hydroxide, alkali metal carbonate and alkali metal acetate. ### Claim 32 (depends on 31) The method for preparing a vinyl compound having a hydroxy group according to claim 31, wherein said alkaline material is at least one member selected from the group consisting of sodium hydroxide and potassium hydroxide. ### Claim 33 (depends on 31) The method for preparing a vinyl compound with hydroxy group according to claim 31, wherein said alkaline material is used in an amount sufficient to bring a pH of said aqueous phase to not less than 8.0. ### Claim 34 (depends on 25) The method for preparing a vinyl compound having a hydroxy group according to claim 25, further comprising the step of: extracting said organic phase from an aqueous phase after said step of separating said organic phase from said aqueous phase. ### Claim 35 (depends on 25) The method for preparing a vinyl compound having a hydroxy group according to claim 25, further comprising the step of: distilling said organic phase after said step of separating said organic phase from said aqueous phase. ### Claim 36 (depends on 25) The method for preparing a vinyl compound having a hydroxy group according to claim 25, further comprising the step of: recovering unreacted vinyl compound from said organic phase after said step of separating said organic phase from said aqueous phase. ### Claim 37 (depends on 25) The method for preparing a vinyl compound having a hydroxy group according to claim 25, further comprising the step of: washing said organic phase with an acid solution after said step of separating said organic phase from said aqueous phase. ### Claim 38 (depends on 37) The method for preparing a vinyl compound having a hydroxy group according to claim 37, further comprising the step of: adding washing solution to said aqueous phase after said step of washing. ### Claim 39 (depends on 37) The method for preparing a vinyl compound having a hydroxy group according to claim 37, further comprising the step of: washing said organic phase with water after said step of washing said organic phase with the acid solution. ### Claim 40 (depends on 37) The method for preparing a vinyl compound having a hydroxy group according to claim 37, wherein said acid is at least one member selected from the group consisting of sulfuric acid, phosphoric acid, sulfurous acid, ammonium hydrogensulfate and ammonium hydrogenphosphate. ### Claim 41 (depends on 37) The method for preparing a vinyl compound having a hydroxy group according to claim 37, wherein said acid is a carboxylic acid. ### Claim 42 (depends on 37) The method for preparing a vinyl compound having a hydroxy group according to claim 37, wherein said acid is at least one member selected from the group consisting of (meth)acrylic acid, maleic acid, fumaric acid, maleic anhydride, oxalic acid, succinic acid and citric acid. ### Claim 43 (depends on 37) The method for preparing a vinyl compound with hydroxy group according to claim 37, wherein said acid solution is used in an amount sufficient to bring a pH of a washing solution after being separated from the organic phase to not more than 7.0.