JP4667035B2 - Process for producing 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester - Google Patents
Process for producing 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester Download PDFInfo
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- JP4667035B2 JP4667035B2 JP2004370449A JP2004370449A JP4667035B2 JP 4667035 B2 JP4667035 B2 JP 4667035B2 JP 2004370449 A JP2004370449 A JP 2004370449A JP 2004370449 A JP2004370449 A JP 2004370449A JP 4667035 B2 JP4667035 B2 JP 4667035B2
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 title claims description 72
- 238000000034 method Methods 0.000 title claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 29
- -1 α-substituted acrylic anhydride Chemical class 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 9
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- QAJCOMPEAMJMEB-UHFFFAOYSA-N 1,1,1-trifluoro-2-(trifluoromethyl)pentane-2,4-diol Chemical compound CC(O)CC(O)(C(F)(F)F)C(F)(F)F QAJCOMPEAMJMEB-UHFFFAOYSA-N 0.000 description 12
- 239000012925 reference material Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 229950000688 phenothiazine Drugs 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VHSCQANAKTXZTG-UHFFFAOYSA-N 1,1,1-trifluoro-2-(trifluoromethyl)pent-4-en-2-ol Chemical compound FC(F)(F)C(C(F)(F)F)(O)CC=C VHSCQANAKTXZTG-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 0 *C(C(C(F)(F)F)(C(F)(F)F)O)C(*)=O Chemical compound *C(C(C(F)(F)F)(C(F)(F)F)O)C(*)=O 0.000 description 1
- WCBPJVKVIMMEQC-UHFFFAOYSA-N 1,1-diphenyl-2-(2,4,6-trinitrophenyl)hydrazine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 WCBPJVKVIMMEQC-UHFFFAOYSA-N 0.000 description 1
- 150000000185 1,3-diols Chemical class 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- HXSIAJREWWAACY-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoyl chloride Chemical compound FC(F)(F)C(=C)C(Cl)=O HXSIAJREWWAACY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004358 Butane-1, 3-diol Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- BKNBVEKCHVXGPH-UHFFFAOYSA-N anthracene-1,4,9,10-tetrol Chemical compound C1=CC=C2C(O)=C3C(O)=CC=C(O)C3=C(O)C2=C1 BKNBVEKCHVXGPH-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、次世代フォトレジストに対応するモノマーとして有用な化合物である一般式［１］ The present invention is a compound represented by the general formula [1] that is a useful compound as a monomer corresponding to a next-generation photoresist.
で表される１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルの製造方法に関する。 It is related with the manufacturing method of 1,1-bis (trifluoromethyl) -1,3-diols acrylic acid ester represented by these.
１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルは、次世代レジスト材料のモノマーとして有望な化合物であり、該モノマーを構成要素として含有するレジストは光の透過性、表面吸着性に優れていることが知られている（特許文献１）。 1,1-bis (trifluoromethyl) -1,3-diols acrylic esters are promising compounds as monomers for next-generation resist materials, and resists containing such monomers as constituents are light-transmissive. It is known that the surface adsorbability is excellent (Patent Document 1).
特許文献１において、式［１］の化合物を包含するα、β−不飽和エステルの一般的合成方法として、式［２］の化合物 In Patent Document 1, as a general synthesis method of an α, β-unsaturated ester including a compound of the formula [1], a compound of the formula [2]
を包含するアルコール体と、アクリル酸またはアクリル酸クロリドを反応させる方法に言及がなされている。 Reference is made to a method of reacting an alcohol comprising acryl with acrylic acid or acrylic acid chloride.
また本発明における中間体化合物である、一般式［２］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオール類は、以下の２つの工程（工程Ａ、工程Ｂ）を組み合わせて合成できることが知られている(特許文献２)。
［工程Ａ］：式［３］で示されるヘキサフルオロアセトン
The 1,1-bis (trifluoromethyl) -1,3-diols represented by the general formula [2], which is an intermediate compound in the present invention, has the following two steps (step A and step B). It is known that they can be combined and synthesized (Patent Document 2).
[Step A]: Hexafluoroacetone represented by the formula [3]
と、一般式［４］で示されるカルボニル化合物 And a carbonyl compound represented by the general formula [4]
とを無触媒で、160℃に加熱することにより、一般式［５］で表される化合物 And a compound represented by the general formula [5] by heating to 160 ° C. without using any catalyst
を得る工程。
［工程Ｂ］：工程Ａで得られた、式［５］の化合物を、イソプロパノールを溶媒として、アルミニウムイソプロポキシドで還元することにより、一般式［６］で表される化合物
Obtaining.
[Step B]: A compound represented by the general formula [6] obtained by reducing the compound of the formula [5] obtained in the step A with aluminum isopropoxide using isopropanol as a solvent.
を得る工程。
[但し、式中のR3は水素原子、炭素数１〜７のアルキル基である。R4は水素、炭素数１〜４のアルキル基、炭素数１〜４のアルケニル基、ナフチル基、チエニル基、フルフリル基、または置換されたフェニル基である。]
[Wherein R 3 is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R 4 is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, a naphthyl group, a thienyl group, a furfuryl group, or a substituted phenyl group. ]
特許文献１には、式［１］を包含する化合物の一般的合成方法が記載されているが、アクリル酸、アクリル酸クロリドを用いた場合（本願明細書の比較例１〜３）には、95℃以上の比較的高い温度が必要で、このことにより副生物の生成が顕著であり目的物の選択率が低い。また、比較例３に記載したように、脱酸剤に2-メチル-2-ブテンを用いた場合には47時間もの長時間、110℃で加熱するために副生物の生成が特に顕著であり、目的物の選択率が低い等の問題があった。 Patent Document 1 describes a general method for synthesizing a compound including the formula [1], but when acrylic acid or acrylic acid chloride is used (Comparative Examples 1 to 3 in the present specification), A relatively high temperature of 95 ° C. or higher is required, and as a result, the formation of by-products is remarkable and the selectivity of the target product is low. Further, as described in Comparative Example 3, when 2-methyl-2-butene was used as the deoxidizer, by-product formation was particularly noticeable because it was heated at 110 ° C. for a long time of 47 hours. There was a problem that the selectivity of the target product was low.
また、特許文献１では、広い概念の式［１］で表される化合物の合成方法としての記述がなされているだけで、好ましい反応条件についての記載はない。 In addition, Patent Document 1 only describes a method for synthesizing a compound represented by the broad concept formula [1], and does not describe preferable reaction conditions.
特許文献２には、式［２］を包含する化合物の合成方法が記載されているが、ヘキサフルオロアセトン［３］と、ケトン類［４］とを無触媒で、160℃に加熱するため、4MPa程度の高い圧力がかかり、この圧力に耐える反応装置が必要となる。また、一般式［５］で表される化合物を、イソプロパノールを溶媒として、アルミニウムイソプロポキシドで還元し、１，３−ジオール類［６］を得るため、溶媒、後処理により発生する含有機排水等を大量に排出するという問題があった。 Patent Document 2 describes a method for synthesizing a compound including the formula [2]. In order to heat hexafluoroacetone [3] and ketones [4] to 160 ° C. without catalyst, A high pressure of about 4 MPa is applied, and a reactor that can withstand this pressure is required. In addition, the compound represented by the general formula [5] is reduced with aluminum isopropoxide using isopropanol as a solvent to obtain 1,3-diols [6]. There was a problem of discharging a large amount of etc.
そこで、本発明の目的は、上記のような問題が生じない１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルの製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing 1,1-bis (trifluoromethyl) -1,3-diols acrylic acid ester which does not cause the above problems.
本発明者らはかかる従来技術の問題点に鑑み、工業的規模での製造に適した１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルの製造法を確立するべく、鋭意検討を行なった。その結果、式［２］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオール類を、式［７］で示されるα−置換アクリル酸無水物 In view of the problems of the prior art, the present inventors establish a method for producing 1,1-bis (trifluoromethyl) -1,3-diol acrylic acid ester suitable for production on an industrial scale. Therefore, we conducted an intensive study. As a result, the 1,1-bis (trifluoromethyl) -1,3-diols represented by the formula [2] was converted into the α-substituted acrylic anhydride represented by the formula [7].
と反応させることにより、式［１］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルが、特許文献１記載の方法に比べ穏和に、しかも収率良く製造できることを見出した。 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester represented by the formula [1] is milder than the method described in Patent Document 1, and the yield is We found that it can be manufactured well.
特に、添加剤を添加し、α−置換アクリル酸無水物を、１，１−ビス（トリフルオロメチル）−１，３−ジオールと反応させると0〜80℃という穏和な条件で目的物の１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルを収率良く製造できることを見出した。このように穏和な条件で目的とするα−置換アクリル酸無水物を製造できるということは、分離の難しい不純物の生成を抑制し、目的物の選択性を向上する上で重要である。この反応に使用される添加剤としては、メタンスルホン酸、エタンスルホン酸、p−トルエンスルホン酸、ベンゼンスルホン酸、トリフルオロメタンスルホン酸等有機スルホン酸類、ＢＦ3，ＢＣｌ3，無水フッ化水素等のルイス酸類の群から選ばれる少なくとも一種の酸が好ましい。 In particular, when an additive is added and an α-substituted acrylic anhydride is reacted with 1,1-bis (trifluoromethyl) -1,3-diol, 1 of the target product is obtained under mild conditions of 0 to 80 ° C. It was found that 1,2-bis (trifluoromethyl) -1,3-diols acrylic ester can be produced with good yield. The ability to produce the target α-substituted acrylic anhydride under such mild conditions is important for suppressing the generation of impurities that are difficult to separate and improving the selectivity of the target product. Additives used in this reaction include organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, BF 3 , BCl 3 , anhydrous hydrogen fluoride, etc. At least one acid selected from the group of Lewis acids is preferred.
さらに本発明者らは、上記反応の原料である、式［２］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオール類の製造方法として、一般式［８］で示される含フッ素不飽和アルコール Furthermore, the present inventors have shown in general formula [8] as a method for producing 1,1-bis (trifluoromethyl) -1,3-diols represented by formula [2], which is a raw material for the above reaction. Fluorine-containing unsaturated alcohol
を濃硫酸と反応させた後、水で加水分解する新規方法を見出した。本方法によれば、特許文献２の方法と異なり、常圧での実施も可能で、穏和な条件で収率良く、容易に式［２］の化合物を得ることができることを見出した。この方法を「第１工程」とし、得られた一般式［２］の１，１−ビス（トリフルオロメチル）−１，３−ジオール類をさらに、式［７］で示されるα−置換アクリル酸無水物と反応させる上記方法を「第２工程」とし、両者を組み合わせることによって、工業的に比較的入手の容易な、一般式［８］で示される含フッ素不飽和アルコールを出発物質として、有用な化合物である一般式［１］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルを、有利に製造できることがわかった。 Was found to be a novel method of reacting with concentrated sulfuric acid and then hydrolyzing with water. It was found that according to this method, unlike the method of Patent Document 2, it can be carried out at normal pressure, and the compound of the formula [2] can be easily obtained in a good yield under mild conditions. This method is referred to as “first step”, and the obtained 1,1-bis (trifluoromethyl) -1,3-diol of the general formula [2] is further converted to an α-substituted acryl represented by the formula [7]. The above-mentioned method of reacting with an acid anhydride is referred to as “second step”, and by combining the two, a fluorine-containing unsaturated alcohol represented by the general formula [8], which is relatively easily obtained industrially, is used as a starting material. It was found that the 1,1-bis (trifluoromethyl) -1,3-diols acrylic acid ester represented by the general formula [1], which is a useful compound, can be advantageously produced.
すなわち本発明は、次の２工程によりなる、式［１］で表される１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステル That is, the present invention comprises 1,2-bis (trifluoromethyl) -1,3-diol acrylic acid ester represented by the formula [1], comprising the following two steps.
の製造方法を提供する。
第１工程：一般式［８］で示される含フッ素不飽和アルコール
A manufacturing method is provided.
First step: Fluorine-containing unsaturated alcohol represented by the general formula [8]
を濃硫酸と反応させた後、水と接触させて加水分解し、式［２］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオール Is reacted with concentrated sulfuric acid, hydrolyzed by contact with water, and 1,1-bis (trifluoromethyl) -1,3-diol represented by the formula [2]
を得る工程。
第２工程：一般式［７］で示されるα−置換アクリル酸無水物
Obtaining.
Second step: α-substituted acrylic anhydride represented by general formula [7]
を、第１工程で得られた、式［２］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオール 1,1-bis (trifluoromethyl) -1,3-diol represented by the formula [2] obtained in the first step
と反応させ、式［１］で表される１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルを得る工程。 And a step of obtaining 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester represented by the formula [1].
[但し、式中のR1は水素原子、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、またはパーフルオロエチル基である。R2は水素原子、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、またはパーフルオロエチル基である。]
また、本発明は、R1およびR2が上記のうち特定の官能基であることを特徴とする、上記１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルを提供する。
[Wherein R 1 represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a fluoromethyl group, a difluoromethyl group, a trimethyl group, It is a fluoromethyl group or a perfluoroethyl group. R 2 represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, or a peroxy group. It is a fluoroethyl group. ]
Further, the present invention provides the above 1,1-bis (trifluoromethyl) -1,3-diol acrylic acid ester, wherein R 1 and R 2 are specific functional groups among the above. provide.
さらに本発明は、上記反応を特定の条件下で行うことを特徴とする、上記１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルを提供する。 Furthermore, the present invention provides the 1,1-bis (trifluoromethyl) -1,3-diol acrylic acid ester characterized in that the reaction is carried out under specific conditions.
本発明のスキームを次に示す。 The scheme of the present invention is shown below.
本発明によれば、１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルを従来の方法よりも効率よく、選択的に製造することができる。このため本発明は、工業的な規模で１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルを製造するための優れた方法である。 According to the present invention, 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester can be selectively produced more efficiently than conventional methods. Therefore, the present invention is an excellent method for producing 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester on an industrial scale.
本発明の基質において、生成物１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルの有用性の観点から、R1が水素原子であり、R2が水素原子、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、またはトリフルオロメチル基である組み合わせが好ましい。中でも、R1が水素原子でありかつR2がメチル基である場合、R1及びR2が水素原子である場合、R1が水素原子であり、かつR2がトリフルオロメチル基である場合が特に好ましい。 In the substrate of the present invention, from the viewpoint of the usefulness of the product 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester, R 1 is a hydrogen atom, R 2 is a hydrogen atom, Combinations that are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, or trifluoromethyl are preferred. Among them, when R 1 is a hydrogen atom and R 2 is a methyl group, when R 1 and R 2 are hydrogen atoms, when R 1 is a hydrogen atom and R 2 is a trifluoromethyl group Is particularly preferred.
以下、本発明につき、さらに詳細に説明する。本発明の方法は、第１工程、第２工程のいずれにおいても、バッチ式反応装置において実施することができる。以下においてその反応条件を述べるが、それぞれの反応装置において、当業者が容易に調節しうる程度の反応条件の変更を妨げるものではない。 Hereinafter, the present invention will be described in more detail. The method of the present invention can be carried out in a batch reactor in either the first step or the second step. The reaction conditions will be described below, but this does not prevent changes in the reaction conditions that can be easily adjusted by those skilled in the art in each reaction apparatus.
まず、第１工程について説明する。第１工程は、一般式［８］で示される含フッ素不飽和アルコールを濃硫酸と反応させた後、水と接触させて加水分解し、式［２］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオールを得る工程である。なお、本工程に用いられる「濃硫酸」とは、濃度が概ね８０％以上の硫酸を意味し、９０％以上の硫酸が好適に使用され、９５％以上の硫酸が特に好ましく使用できる。濃硫酸としては、市販の濃硫酸（例えば９５％硫酸、９８％硫酸）を好適に使用することができる。 First, the first step will be described. In the first step, the fluorine-containing unsaturated alcohol represented by the general formula [8] is reacted with concentrated sulfuric acid, and then hydrolyzed by contacting with water to obtain 1,1-bis (trimethyl) represented by the formula [2]. In this step, fluoromethyl) -1,3-diol is obtained. The “concentrated sulfuric acid” used in this step means sulfuric acid having a concentration of approximately 80% or higher, 90% or higher sulfuric acid is preferably used, and 95% or higher sulfuric acid is particularly preferably used. As the concentrated sulfuric acid, commercially available concentrated sulfuric acid (for example, 95% sulfuric acid, 98% sulfuric acid) can be suitably used.
第１工程に使用する原料の、一般式［８］で表される含フッ素不飽和アルコールは、対応するグリニャール試薬とヘキサフルオロアセトンとの反応等により合成できる（J. Photopolym. Sci. Technol., Vol. 13, No. 4, 2000, p.657）。 The fluorine-containing unsaturated alcohol represented by the general formula [8], which is a raw material used in the first step, can be synthesized by a reaction of a corresponding Grignard reagent and hexafluoroacetone (J. Photopolym. Sci. Technol., Vol. 13, No. 4, 2000, p.657).
第１工程の生成物である一般式［２］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオール類を得るために使用する濃硫酸の量は、基質の含フッ素不飽和アルコール1.0モルに対して通常1.0〜5.0モルであり、1.0〜4.0モルが好ましく、1.0〜3.0モルがより好ましい。基質の含フッ素不飽和アルコール1.0モルに対して濃硫酸の量が1.0モル未満では、反応の選択率、目的物の収率共に低下し、5.0モルを超えると、反応に関与しない濃硫酸の量が増加するため、経済的に好ましくない。 The amount of concentrated sulfuric acid used to obtain the 1,1-bis (trifluoromethyl) -1,3-diols represented by the general formula [2], which is the product of the first step, depends on whether the substrate contains fluorine. It is 1.0-5.0 mol normally with respect to 1.0 mol of saturated alcohol, 1.0-4.0 mol is preferable and 1.0-3.0 mol is more preferable. If the amount of concentrated sulfuric acid is less than 1.0 mol with respect to 1.0 mol of the fluorine-containing unsaturated alcohol of the substrate, both the selectivity of the reaction and the yield of the target product decrease, and if it exceeds 5.0 mol, the amount of concentrated sulfuric acid not involved in the reaction This is not economically preferable.
また、濃硫酸と基質の含フッ素不飽和アルコールを混合する際の温度は、通常−30〜100℃であり、−20〜80℃が好ましく、−10℃〜50℃がより好ましい。−30℃未満では過冷却となり設備、エネルギー等経済的に好ましくない。また、100℃を超えると基質の含フッ素不飽和アルコールの異性化もしくは分解が起こることから好ましくない。 Moreover, the temperature at the time of mixing concentrated sulfuric acid and the fluorine-containing unsaturated alcohol of a substrate is normally -30-100 degreeC, -20-80 degreeC is preferable, and -10 degreeC-50 degreeC is more preferable. If it is less than −30 ° C., it is supercooled, which is not preferable in terms of facilities and energy. Moreover, when it exceeds 100 degreeC, since isomerization or decomposition | disassembly of the fluorine-containing unsaturated alcohol of a substrate occurs, it is unpreferable.
濃硫酸と基質の含フッ素不飽和アルコールを混合することにより得られる硫酸エステルを加水分解するために添加する水の量は、基質の含フッ素不飽和アルコール1モルに対して通常1〜100モルであり、1〜80モルが好ましく、1〜60モルがより好ましい。含フッ素不飽和アルコール1モルに対して水の量が1.0モル未満では、加水分解が十分に進行せず目的物の収率が低下し、100モルを超えると反応に関与しない水の量が増加するため生成した１，１−ビス（トリフルオロメチル）−１，３−ジオール類の単離等の操作上不利益となる。 The amount of water added to hydrolyze the sulfuric ester obtained by mixing concentrated sulfuric acid with the substrate fluorine-containing unsaturated alcohol is usually 1 to 100 mol per mol of substrate fluorine-containing unsaturated alcohol. Yes, 1 to 80 mol is preferable, and 1 to 60 mol is more preferable. If the amount of water is less than 1.0 mol with respect to 1 mol of fluorine-containing unsaturated alcohol, hydrolysis does not proceed sufficiently and the yield of the target product decreases, and if it exceeds 100 mol, the amount of water not involved in the reaction increases. Therefore, it is disadvantageous in operation such as isolation of 1,1-bis (trifluoromethyl) -1,3-diols produced.
加水分解する際の温度は、通常0〜200℃であり、20〜150℃が好ましく、50℃〜120℃がより好ましい。0℃未満では反応速度が遅く、実用的製造法とはならない。また、200℃を超えると生成した１，１−ビス（トリフルオロメチル）−１，３−ジオール類の分解等が起こることから好ましくない。 The temperature at the time of hydrolysis is usually 0 to 200 ° C, preferably 20 to 150 ° C, and more preferably 50 ° C to 120 ° C. If it is less than 0 ° C., the reaction rate is slow and it is not a practical production method. Moreover, when it exceeds 200 degreeC, since decomposition | disassembly etc. of the produced | generated 1, 1-bis (trifluoromethyl) -1,3-diol occur, it is unpreferable.
なお、この加水分解工程では、水と濃硫酸（未反応分）を接触させることになるため、強い発熱が起こる。このため、水に対し、上記硫酸エステルを含む混合物を逐次添加するなどの操作方法をとることが望ましく、反応基の冷却、攪拌を行い、温度管理には十分注意する必要がある。 In this hydrolysis step, since water and concentrated sulfuric acid (unreacted component) are brought into contact with each other, strong heat generation occurs. For this reason, it is desirable to take an operation method such as sequentially adding the mixture containing the sulfate ester to water, and it is necessary to cool and stir the reactive group and to pay sufficient attention to temperature control.
第１工程の反応時間に特別の制限はなく、反応基質が十分混合し、目的反応が十分進行する反応時間を適宜設定することができる。「濃硫酸との反応」、「加水分解反応」とも、試薬の混合を終了して、内部の液体温度が安定した後、２時間程度の攪拌を継続するのは、好ましい一例である。 There is no special restriction | limiting in the reaction time of a 1st process, The reaction substrate can fully set and the reaction time for which target reaction fully advances can be set suitably. In both the “reaction with concentrated sulfuric acid” and the “hydrolysis reaction”, it is a preferable example to continue the stirring for about 2 hours after the mixing of the reagents is completed and the internal liquid temperature is stabilized.
第１工程の反応に使用される反応器は、四フッ化エチレン樹脂、クロロ−トリフルオロエチレン樹脂、フッ化ビニリデン樹脂、ＰＦＡ樹脂、ガラスなどを内部にライニングしたもの、もしくはグラス容器が好ましい。 The reactor used for the reaction in the first step is preferably a glass container or a container in which tetrafluoroethylene resin, chloro-trifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass or the like is lined.
生成した１，１−ビス（トリフルオロメチル）−１，３−ジオール類は、通常の分液操作またはエーテル等の有機溶媒による抽出により単離することができる。また、必要に応じて単離した１，１−ビス（トリフルオロメチル）−１，３−ジオール類を蒸留により、更に精製することも可能である。 The produced 1,1-bis (trifluoromethyl) -1,3-diols can be isolated by ordinary liquid separation operation or extraction with an organic solvent such as ether. Further, the 1,1-bis (trifluoromethyl) -1,3-diols isolated as necessary can be further purified by distillation.
次に第２工程につき、説明する。第２工程は、式［２］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオールを、式［７］で示されるα−置換アクリル酸無水物とを反応させることにより、本発明の目的物である、一般式［１］で示される１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルを得る工程である。 Next, the second step will be described. In the second step, 1,1-bis (trifluoromethyl) -1,3-diol represented by the formula [2] is reacted with an α-substituted acrylic anhydride represented by the formula [7]. This is a step of obtaining 1,1-bis (trifluoromethyl) -1,3-diols acrylic acid ester represented by the general formula [1], which is an object of the present invention.
第２工程に使用するα−置換アクリル酸無水物の量は、１，１−ビス（トリフルオロメチル）−１，３−ジオール類1.0モルに対して通常0.5〜5.0モルであり、0.7〜3.0モルが好ましく、1.0〜2.0モルがより好ましい。１，１−ビス（トリフルオロメチル）−１，３−ジオール類1.0モルに対してα−置換アクリル酸無水物の量が0.5モル未満では反応の転化率、目的物の収率が共に十分でなく、5.0モルを超えると反応に関与しないα−置換アクリル酸無水物が増加し、廃棄の手間から経済的に好ましくない。 The amount of α-substituted acrylic anhydride used in the second step is usually 0.5 to 5.0 moles per 1.0 mole of 1,1-bis (trifluoromethyl) -1,3-diols, and 0.7 to 3.0. Mole is preferable, and 1.0 to 2.0 mol is more preferable. If the amount of α-substituted acrylic anhydride is less than 0.5 mol relative to 1.0 mol of 1,1-bis (trifluoromethyl) -1,3-diols, both the conversion rate of the reaction and the yield of the target product are sufficient. If the amount exceeds 5.0 mol, α-substituted acrylic anhydride that does not participate in the reaction increases, which is economically undesirable from the point of disposal.
第２工程において、反応を促進するために添加剤を添加することができる。使用される添加剤としてはメタンスルホン酸、エタンスルホン酸、p−トルエンスルホン酸、ベンゼンスルホン酸、トリフルオロメタンスルホン酸等有機スルホン酸類、ＢＦ3，ＢＣｌ3，無水フッ化水素等のルイス酸類の群から選ばれる少なくとも一種の酸が、好適に用いられる。メタンスルホン酸、エタンスルホン酸、p−トルエンスルホン酸、ベンゼンスルホン酸、トリフルオロメタンスルホン酸等有機スルホン酸類が特に好ましい。本反応に使用する添加剤の量は基質の１，１−ビス（トリフルオロメチル）−１，３−ジオール類1.0モルに対して0.01〜2.0モルあり、0.02〜1.8モルが好ましく、0.05〜1.5モルがより好ましい。基質の１，１−ビス（トリフルオロメチル）−１，３−ジオール類1.0モルに対して添加剤の量が0.01モル未満では反応の転化率、目的物の収率共に低下し、2.0モルを超えると反応に関与しない添加剤の量が増加するため経済的に好ましくない。 In the second step, additives can be added to promote the reaction. Additives used include organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and Lewis acids such as BF 3 , BCl 3 , and anhydrous hydrogen fluoride. At least one acid selected from is preferably used. Organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid and trifluoromethanesulfonic acid are particularly preferred. The amount of the additive used in this reaction is 0.01 to 2.0 mol, preferably 0.02 to 1.8 mol, preferably 0.05 to 1.5 mol, relative to 1.0 mol of 1,1-bis (trifluoromethyl) -1,3-diol as a substrate. Mole is more preferred. If the amount of the additive is less than 0.01 mol with respect to 1.0 mol of 1,1-bis (trifluoromethyl) -1,3-diol as the substrate, both the conversion rate of the reaction and the yield of the target product are reduced. Exceeding this is not economically preferable because the amount of the additive not involved in the reaction increases.
本反応を実施する際の反応温度は、添加剤を添加しない場合は通常、80〜200℃、好ましくは100〜180℃、さらに好ましくは120〜160℃で実施する。この場合、80℃未満では反応速度が極めて遅く、200℃を超えると原料のα−置換アクリル酸無水物もしくは生成物の１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルが重合することがあるから好ましくない。添加剤を添加する場合は、通常0〜80℃、好ましくは10〜70℃、さらに好ましくは20〜60℃で実施する。この場合、0℃未満では反応速度が遅く実用的製造法とはならない。また、80℃を超えると副反応が進行し易くなり、目的物の１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルの選択率が低下することがあるから好ましくない。本発明においては、添加剤を加えた方が低い温度で十分な反応性が得られ、選択率が向上するので好ましい。すなわち、メタンスルホン酸、エタンスルホン酸、p−トルエンスルホン酸、ベンゼンスルホン酸、トリフルオロメタンスルホン酸等の添加剤を系内に共存させ、２０〜６０℃の温度範囲で、反応を実施することは、本工程の特に好ましい態様である。 When this reaction is carried out, the reaction temperature is usually from 80 to 200 ° C, preferably from 100 to 180 ° C, more preferably from 120 to 160 ° C when no additive is added. In this case, the reaction rate is very slow below 80 ° C., and when it exceeds 200 ° C., the raw material α-substituted acrylic anhydride or the product 1,1-bis (trifluoromethyl) -1,3-diols acrylic acid This is not preferable because a series ester may be polymerized. When adding an additive, it is 0-80 degreeC normally, Preferably it is 10-70 degreeC, More preferably, it implements at 20-60 degreeC. In this case, if it is less than 0 ° C., the reaction rate is too slow to be a practical production method. Further, if the temperature exceeds 80 ° C., side reactions are likely to proceed, and the selectivity of the target 1,1-bis (trifluoromethyl) -1,3-diol acrylic acid ester may be reduced. Absent. In the present invention, it is preferable to add an additive because sufficient reactivity can be obtained at a low temperature and the selectivity is improved. That is, it is possible to carry out the reaction in the temperature range of 20 to 60 ° C. by coexisting additives such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and trifluoromethanesulfonic acid in the system. This is a particularly preferred embodiment of this step.
本反応は、無溶媒でも進行するが反応の均一性、反応後の操作性を考慮すると溶媒を使用するのが望ましい。使用可能な溶媒の種類に特別な制限はないが、ベンゼン、トルエン、キシレン、メシチレン等の芳香族化合物、ジエチルエーテル、メチル−ｔ−ブチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン等のエーテル系溶媒、塩化メチレン、クロロホルム、四塩化炭素等のハロゲン系溶媒が好ましく、これらは単独で用いても、複数の溶媒を併用しても良い。 This reaction proceeds even without solvent, but it is desirable to use a solvent in consideration of the uniformity of the reaction and the operability after the reaction. There are no particular restrictions on the type of solvent that can be used, but aromatic compounds such as benzene, toluene, xylene, and mesitylene, ether solvents such as diethyl ether, methyl-t-butyl ether, diisopropyl ether, and tetrahydrofuran, methylene chloride, and chloroform And halogen-based solvents such as carbon tetrachloride are preferable, and these may be used alone or in combination with a plurality of solvents.
本反応に使用する溶媒の量は１，１−ビス（トリフルオロメチル）−１，３−ジオール類1gに対して通常0.1〜100gであり、0.5〜50gが好ましく、1.0〜20gがより好ましい。溶媒量が１，１−ビス（トリフルオロメチル）−１，３−ジオール類1gに対して0.1g未満では溶媒を使用するメリットを十分に引き出せない。100gを超えると生産性の観点から経済的に好ましくない。 The amount of the solvent used in this reaction is usually 0.1 to 100 g, preferably 0.5 to 50 g, more preferably 1.0 to 20 g based on 1 g of 1,1-bis (trifluoromethyl) -1,3-diols. If the amount of the solvent is less than 0.1 g with respect to 1 g of 1,1-bis (trifluoromethyl) -1,3-diol, the merit of using the solvent cannot be sufficiently obtained. If it exceeds 100 g, it is not economically preferable from the viewpoint of productivity.
第２工程の反応においてα−置換アクリル酸無水物もしくは生成物（１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステル）が重合することを防止することを目的として重合禁止剤の共存させて行なっても良く、通常は重合禁止剤を使用することが望ましい。使用する重合禁止剤はヒドロキノン、メトキノン、２，５−ジ−ｔ−ブチルヒドロキノン、1,2,4−トリヒドロキシベンゼン、2,5−ビステトラメチルブチルヒドロキノン、ロイコキニザリン、ノンフレックスＦ、ノンフレックスＨ、ノンフレックスＤＣＤ、ノンフレックスＭＢＰ、オゾノン３５、フェノチアジン、テトラエチルチウラム ジスルフィド、1,1−ジフェニル−2−ピクリルヒドラジル、1,1−ジフェニル−2−ピクリルヒドラジン、Q−1300、Q−1301から選ばれる少なくとも一種の化合物である。上記の重合禁止剤は市販品であり容易に入手可能である。 For the purpose of preventing polymerization of α-substituted acrylic anhydride or product (1,1-bis (trifluoromethyl) -1,3-diol acrylic acid ester) in the reaction of the second step. It may be carried out in the presence of a polymerization inhibitor, and it is usually desirable to use a polymerization inhibitor. Polymerization inhibitors used are hydroquinone, methoquinone, 2,5-di-t-butylhydroquinone, 1,2,4-trihydroxybenzene, 2,5-bistetramethylbutylhydroquinone, leucoquinizarin, nonflex F, nonflex H Nonflex DCD, Nonflex MBP, Ozonon 35, Phenothiazine, Tetraethylthiuram disulfide, 1,1-diphenyl-2-picrylhydrazyl, 1,1-diphenyl-2-picrylhydrazine, Q-1300, Q-1301 Is at least one compound selected from the group consisting of The above polymerization inhibitors are commercially available products and can be easily obtained.
本発明に使用する重合禁止剤の量は原料の１，１−ビス（トリフルオロメチル）−１，３−ジオール類1.0モルに対して通常0.00001〜0.1モルであり、0.0001〜0.05モルが好ましく、0.001〜0.01モルがより好ましい。重合禁止剤の量が原料の１，１−ビス（トリフルオロメチル）−１，３−ジオール類1.0モルに対して0.1モルを超えても重合を防止する能力に大きな差異はなく、そのため、経済的に好ましくない。 The amount of the polymerization inhibitor used in the present invention is usually 0.00001 to 0.1 mol, preferably 0.0001 to 0.05 mol, relative to 1.0 mol of 1,1-bis (trifluoromethyl) -1,3-diol as a raw material, 0.001-0.01 mol is more preferable. Even if the amount of the polymerization inhibitor exceeds 0.1 mol with respect to 1.0 mol of 1,1-bis (trifluoromethyl) -1,3-diol as a raw material, there is no significant difference in the ability to prevent polymerization. Is not preferable.
第２工程の反応に使用される反応器は、四フッ化エチレン樹脂、クロロ−トリフルオロエチレン樹脂、フッ化ビニリデン樹脂、ＰＦＡ樹脂、ガラスなどを内部にライニングしたもの、グラス容器、もしくはステンレスで製作したものが好ましい。 The reactor used for the second step reaction is made of tetrafluoroethylene resin, chloro-trifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass lined inside, glass container, or stainless steel. Is preferred.
本発明を実施する方法は限定されるものではないが、望ましい態様の一例につき、詳細を述べる。
1)第１工程：１，１−ビス（トリフルオロメチル）−１，３−ジオール類の製造
反応条件に耐えられる反応器に濃硫酸を入れ、攪拌しながら必要な場合には外部より冷却または加熱し、所定の温度で原料の含フッ素不飽和アルコール［８］を加える。所定の温度にて撹拌し、反応を進行させる。サンプリング等により原料の消費をモニタリングし、原料が消費されたら、徐々に水を加え、所定の温度に加熱する。サンプリング等により原料の消費をモニタリングし、反応が終了したのを確認し、反応液を冷却するのが好ましい。本発明の方法で製造された一般式［２］で表される１，１−ビス（トリフルオロメチル）−１，３−ジオール類は公知の方法を適用して精製されるが、例えば、反応液をエーテル等の溶媒により抽出し、溶媒を留去することにより粗有機物が得られる。得られた粗有機物はカラムクロマトグラフィーや蒸留等の精製を行うことで高純度の１，１−ビス（トリフルオロメチル）−１，３−ジオール類とすることができる。
2)第２工程：１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルの製造
反応条件に耐えられる反応器に溶媒、原料の１，１−ビス（トリフルオロメチル）−１，３−ジオール類、α−置換アクリル酸無水物、重合禁止剤及び添加剤を加え、攪拌しながら外部より加熱して反応を進行させる。サンプリング等により原料の消費をモニタリングし、反応が終了したのを確認し、反応液を冷却するのが好ましい。本発明の方法で製造された一般式［１］で表される１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルは公知の方法を適用して精製されるが、例えば、反応液を水、炭酸水素ナトリウム水溶液、食塩水の順で処理し、さらに溶媒を留去することで粗有機物が得られる。得られた粗有機物はカラムクロマトグラフィーや蒸留等の精製を行うことで、高純度の１，１−ビス（トリフルオロメチル）−１，３−ジオール類アクリル酸系エステルとすることができる。
Although the method for carrying out the present invention is not limited, details will be described with respect to an example of a desirable embodiment.
1) First step: Production of 1,1-bis (trifluoromethyl) -1,3-diols Concentrated sulfuric acid is placed in a reactor that can withstand the reaction conditions, and is cooled from the outside if necessary while stirring. Heat and add the raw fluorine-containing unsaturated alcohol [8] at a predetermined temperature. Stir at a predetermined temperature to allow the reaction to proceed. The consumption of the raw material is monitored by sampling or the like, and when the raw material is consumed, water is gradually added and heated to a predetermined temperature. It is preferable to monitor the consumption of the raw material by sampling or the like, confirm that the reaction is completed, and cool the reaction solution. The 1,1-bis (trifluoromethyl) -1,3-diols represented by the general formula [2] produced by the method of the present invention are purified by applying a known method. The liquid is extracted with a solvent such as ether, and the solvent is distilled off to obtain a crude organic material. The obtained crude organic substance can be made into high-purity 1,1-bis (trifluoromethyl) -1,3-diols by performing purification such as column chromatography or distillation.
2) Second step: Production of 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester Established in a reactor that can withstand the reaction conditions, 1,1-bis (trifluoromethyl) as a solvent and raw material ) -1,3-diols, α-substituted acrylic anhydride, polymerization inhibitor and additives are added, and the reaction is allowed to proceed by heating from outside while stirring. It is preferable to monitor the consumption of the raw material by sampling or the like, confirm that the reaction is completed, and cool the reaction solution. The 1,1-bis (trifluoromethyl) -1,3-diol acrylic acid ester represented by the general formula [1] produced by the method of the present invention is purified by applying a known method. For example, the reaction solution is treated in the order of water, aqueous sodium hydrogen carbonate solution and brine, and the solvent is distilled off to obtain a crude organic material. The obtained crude organic substance can be made into a highly pure 1,1-bis (trifluoromethyl) -1,3-diol acrylic acid ester by performing purification such as column chromatography or distillation.
以下、実施例により本発明を詳細に説明するがこれらの実施態様に限られない。ここで、組成分析値の「％」とは、反応混合物の一部を採取するか、必要に応じて有機成分をジエチルエーテル等により抽出し、これをガスクロマトグラフィーによって測定して得られた、溶媒成分を除く有機成分の「面積％」を表す。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not restricted to these embodiments. Here, “%” of the composition analysis value was obtained by collecting a part of the reaction mixture or extracting the organic component with diethyl ether or the like as necessary, and measuring this by gas chromatography. “Area%” of the organic component excluding the solvent component is represented.
［実施例１］第１工程
滴下ロート、還流冷却器及び温度計を備えた1000mLの四つ口フラスコに四フッ化エチレン樹脂で被覆された撹拌子及び濃硫酸141.3g（1.44 mol）を入れ、かくはん機で撹拌しながら氷水浴中０〜５℃に冷却した。これに、1,1,1−トリフルオロ−2−(トリフルオロメチル)ペンタ−4−エン−2−オール151.2g（0.72mol）を滴下ロートより０〜５℃で滴下した。滴下終了後、ゆっくりと２０〜２５℃に昇温し、この温度で２時間撹拌した後、水623.9g（34.7mol）を加え、オイルバスにより内温 ９０〜９５℃に加熱した。２時間後、組成をガスクロマトグラフィーにより測定したところ、目的とする1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオール91.1%、原料の1,1,1−トリフルオロ−2−(トリフルオロメチル)ペンタ−4−エン−2−オール2.3%、その他6.6%であった。反応液を冷却後、ジイソプロピルエーテル250gで2回抽出した。得られた溶液を硫酸マグネシウム50gで乾燥し、硫酸マグネシウムを濾別した。濾液を蒸留装置に仕込み、ジイソプロピルエーテルを留去した後、減圧蒸留（35Torr＝4.67kPa）を行い、85〜87℃の留分を集めたところ、130.5gの1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオールが得られた。ガスクロマトグラフィーにより組成を調べたところ、目的物である1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオールが100%であった。収率は79.4%であった。
1H NMR (溶媒：CDCl3, 基準物質：TMS)；δ6.62(s, 1H), 4.44(m, 1H), 2.79(d, J=3.90Hz, 1H), 2.04(m, 2H), 1.30(d, J=6.10Hz, 3H)
19F NMR（溶媒：CDCl3, 基準物質：CCl3F）;δ-76.2(q, J=10.7Hz, 3F), -80.0(q, J=10.7Hz, 3F)。
[Example 1] First step A 1000 mL four-necked flask equipped with a dropping funnel, a reflux condenser and a thermometer was charged with a stirrer coated with tetrafluoroethylene resin and 141.3 g (1.44 mol) of concentrated sulfuric acid. The mixture was cooled to 0 to 5 ° C. in an ice water bath while stirring with a stirrer. To this, 151.2 g (0.72 mol) of 1,1,1-trifluoro-2- (trifluoromethyl) pent-4-en-2-ol was added dropwise at 0 to 5 ° C. from a dropping funnel. After completion of the dropwise addition, the temperature was slowly raised to 20 to 25 ° C., and the mixture was stirred at this temperature for 2 hours. Then, 623.9 g (34.7 mol) of water was added and heated to an internal temperature of 90 to 95 ° C. with an oil bath. After 2 hours, the composition was measured by gas chromatography. As a result, the target 1,1-bis (trifluoromethyl) butane-1,3-diol 91.1%, the raw material 1,1,1-trifluoro-2- (Trifluoromethyl) pent-4-en-2-ol was 2.3% and the others were 6.6%. The reaction mixture was cooled and extracted twice with 250 g of diisopropyl ether. The obtained solution was dried with 50 g of magnesium sulfate, and magnesium sulfate was filtered off. The filtrate was charged into a distillation apparatus, diisopropyl ether was distilled off, vacuum distillation (35 Torr = 4.67 kPa) was performed, and a fraction at 85 to 87 ° C was collected. As a result, 130.5 g of 1,1-bis (trifluoromethyl) was collected. ) Butane-1,3-diol was obtained. When the composition was examined by gas chromatography, the target 1,1-bis (trifluoromethyl) butane-1,3-diol was 100%. The yield was 79.4%.
1 H NMR (solvent: CDCl 3 , reference material: TMS); δ6.62 (s, 1H), 4.44 (m, 1H), 2.79 (d, J = 3.90Hz, 1H), 2.04 (m, 2H), 1.30 (d, J = 6.10Hz, 3H)
19 F NMR (solvent: CDCl 3 , reference material: CCl 3 F); δ-76.2 (q, J = 10.7 Hz, 3F), -80.0 (q, J = 10.7 Hz, 3F).
［実施例２］第２工程
温度計、還流冷却器を備えた1000mLの三口フラスコに四フッ化エチレン樹脂で被覆された撹拌子及び1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオール100.0g（0.44mol）、メタクリル酸無水物74.6g（0.48mol）、メタンスルホン酸4.23g（0.044mol）、トルエン400g、及びフェノチアジン0.5gを入れ、かくはん機で撹拌しながらオイルバスにより50℃で加熱還流した。4時間後、反応液をガスクロマトグラフィーにより測定したところ、副生したメタクリル酸を除くと目的とする4,4,4−トリフルオロ−3−ヒドロキシ−1−メチル−３−(トリフルオロメチル)ブチル メタクリレートが94.5%、原料の1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオールが1.6%、メタクリル酸無水物が2.0%、その他が1.9%であった。
[Example 2] Second Step A stirrer coated with a tetrafluoroethylene resin on a 1000 mL three-necked flask equipped with a thermometer and a reflux condenser, and 1,1-bis (trifluoromethyl) butane-1,3- Add diol 100.0g (0.44mol), methacrylic anhydride 74.6g (0.48mol), methanesulfonic acid 4.23g (0.044mol), toluene 400g, and phenothiazine 0.5g. And heated at reflux. After 4 hours, when the reaction solution was measured by gas chromatography, the desired 4,4,4-trifluoro-3-hydroxy-1-methyl-3- (trifluoromethyl) was removed when the by-product methacrylic acid was removed. Butyl methacrylate was 94.5%, raw material 1,1-bis (trifluoromethyl) butane-1,3-diol was 1.6%, methacrylic anhydride was 2.0%, and others were 1.9%.
反応液を水200gで２回洗浄した後、分液し得られた有機層を硫酸マグネシウム30gで乾燥し、硫酸マグネシウムを濾過により除去した。濾液に重合禁止剤としてフェノチアジンを0.7g添加し、溶媒留去をした後、減圧蒸留（8Torr＝1.07kPa）を行い、80〜82℃の留分を集めたところ、77.5gの4,4,4−トリフルオロ−3−ヒドロキシ−1−メチル−３−(トリフルオロメチル)ブチル 2−メタクリレートが得られた。ガスクロマトグラフィーにより組成を調べたところ、目的物である4,4,4−トリフルオロ−3−ヒドロキシ−1−メチル−３−(トリフルオロメチル)ブチル メタクリレートが98.2%、原料の1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオールが0.2%、その他が1.6%であった。収率は58.8%であった。
1H NMR (溶媒：CDCl3, 基準物質：TMS)；δ6.16(q, J=0.98Hz, 1H), 5.96(bs, 1H), 5.66(q, J=1.46Hz, 1H), 5.13-5.20(m, 1H), 2.24-2.36(m, 2H), 1.94(dd, J=1.46Hz,0.98Hz,3H), 1.44(d, J=6.34Hz, 3H)
19F NMR（溶媒：CDCl3, 基準物質：CCl3F）;δ-77.03(q, J=9.67Hz, 3F), -79.25(q, J=9.67Hz, 3F)。
The reaction solution was washed twice with 200 g of water, and the organic layer obtained by liquid separation was dried with 30 g of magnesium sulfate, and magnesium sulfate was removed by filtration. 0.7 g of phenothiazine as a polymerization inhibitor was added to the filtrate, the solvent was distilled off, and distillation under reduced pressure (8 Torr = 1.07 kPa) was performed. When a fraction at 80 to 82 ° C was collected, 77.5 g of 4,4, 4-Trifluoro-3-hydroxy-1-methyl-3- (trifluoromethyl) butyl 2-methacrylate was obtained. When the composition was examined by gas chromatography, it was found that the target product 4,4,4-trifluoro-3-hydroxy-1-methyl-3- (trifluoromethyl) butyl methacrylate was 98.2%, the raw material 1,1- Bis (trifluoromethyl) butane-1,3-diol was 0.2% and the others were 1.6%. The yield was 58.8%.
1 H NMR (solvent: CDCl 3 , reference material: TMS); δ6.16 (q, J = 0.98Hz, 1H), 5.96 (bs, 1H), 5.66 (q, J = 1.46Hz, 1H), 5.13- 5.20 (m, 1H), 2.24-2.36 (m, 2H), 1.94 (dd, J = 1.46Hz, 0.98Hz, 3H), 1.44 (d, J = 6.34Hz, 3H)
19 F NMR (solvent: CDCl 3 , reference material: CCl 3 F); δ-77.03 (q, J = 9.67 Hz, 3F), −79.25 (q, J = 9.67 Hz, 3F).
本実施例に明らかなように、本方法では５０℃という穏和な条件で高い反応率、選択率で、目的物が生成しており、副生物（「その他」）の生成が下記比較例に比べて格段に少ない。 As is apparent from this example, the target product was produced at a high reaction rate and selectivity under a mild condition of 50 ° C. in this method, and the by-product (“others”) was produced compared to the following comparative example. And very little.
［比較例１］
温度計及び還流冷却器を備えた1000mLの四口フラスコに四フッ化エチレン樹脂で被覆された撹拌子及び1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオール100.0g（0.44mol）、トルエン300g、2,6−ジメチルピリジン58.7g（0.48mol）、メタクリル酸クロリド68.99g（0.66mol）及びノンフレックスＭＢＰ0.5gを入れ、かくはん機で撹拌しながら、オイルバスにより内温 95〜100℃に加熱した。6時間後、組成をガスクロマトグラフィーにより測定したところ、目的とする4,4,4−トリフルオロ−3−ヒドロキシ−1−メチル−３−(トリフルオロメチル)ブチル メタクリレートが89.0%、原料の1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオールが1.9%、その他が9.1%であった。
1H NMR (溶媒：CDCl3, 基準物質：TMS)；δ6.16(q, J=0.98Hz, 1H), 5.96(bs, 1H), 5.66(q, J=1.46Hz, 1H), 5.13-5.20(m, 1H), 2.24-2.36(m, 2H), 1.94(dd, J=1.46Hz,0.98Hz,3H), 1.44(d, J=6.34Hz, 3H)
19F NMR（溶媒：CDCl3, 基準物質：CCl3F）;δ-77.03(q, J=9.67Hz, 3F), -79.25(q, J=9.67Hz, 3F)。
[Comparative Example 1]
A 1000 mL four-necked flask equipped with a thermometer and a reflux condenser and a stirrer coated with tetrafluoroethylene resin and 1,1-bis (trifluoromethyl) butane-1,3-diol 100.0 g (0.44 mol) , 300 g of toluene, 58.7 g (0.48 mol) of 2,6-dimethylpyridine, 68.99 g (0.66 mol) of methacrylic acid chloride and 0.5 g of non-flex MBP were added, and the internal temperature was 95 to 100 using an oil bath while stirring with a stirrer. Heated to ° C. After 6 hours, the composition was measured by gas chromatography, and it was found that the desired 4,4,4-trifluoro-3-hydroxy-1-methyl-3- (trifluoromethyl) butyl methacrylate was 89.0%, 1,1-bis (trifluoromethyl) butane-1,3-diol was 1.9% and the others were 9.1%.
1 H NMR (solvent: CDCl 3 , reference material: TMS); δ6.16 (q, J = 0.98Hz, 1H), 5.96 (bs, 1H), 5.66 (q, J = 1.46Hz, 1H), 5.13- 5.20 (m, 1H), 2.24-2.36 (m, 2H), 1.94 (dd, J = 1.46Hz, 0.98Hz, 3H), 1.44 (d, J = 6.34Hz, 3H)
19 F NMR (solvent: CDCl 3 , reference material: CCl 3 F); δ-77.03 (q, J = 9.67 Hz, 3F), −79.25 (q, J = 9.67 Hz, 3F).
［比較例２］
温度計、水分定量受器及び還流冷却器を備えた1000mLの三口フラスコに四フッ化エチレン樹脂で被覆された撹拌子及び1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオール100.0g（0.44mol）、メタクリル酸45.5g（0.53mol）、メタンスルホン酸42.3g（0.44mol）、トルエン400g、及びフェノチアジン0.5gを入れ、かくはん機で撹拌しながらオイルバスにより120℃で加熱還流した。6時間後、水分定量受器に反応により生成した水約8mLが分離された。反応液をガスクロマトグラフィーにより測定したところ、目的とする4,4,4−トリフルオロ−3−ヒドロキシ−1−メチル−３−(トリフルオロメチル)ブチル メタクリレートが92.4%、原料の1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオールが1.9%、その他が5.2%であった。
1H NMR (溶媒：CDCl3, 基準物質：TMS)；δ6.16(q, J=0.98Hz, 1H), 5.96(bs, 1H), 5.66(q, J=1.46Hz, 1H), 5.13-5.20(m, 1H), 2.24-2.36(m, 2H), 1.94(dd, J=1.46Hz,0.98Hz,3H), 1.44(d, J=6.34Hz, 3H)
19F NMR（溶媒：CDCl3, 基準物質：CCl3F）;δ-77.03(q, J=9.67Hz, 3F), -79.25(q, J=9.67Hz, 3F)。
[Comparative Example 2]
A 1000 mL three-necked flask equipped with a thermometer, a moisture meter and a reflux condenser, a stirrer coated with tetrafluoroethylene resin and 1,1-bis (trifluoromethyl) butane-1,3-diol 100.0 g (0.44 mol), 45.5 g (0.53 mol) of methacrylic acid, 42.3 g (0.44 mol) of methanesulfonic acid, 400 g of toluene, and 0.5 g of phenothiazine were added and heated to reflux at 120 ° C. with an oil bath while stirring with a stirrer. After 6 hours, about 8 mL of water produced by the reaction was separated in the moisture meter. When the reaction solution was measured by gas chromatography, the target 4,4,4-trifluoro-3-hydroxy-1-methyl-3- (trifluoromethyl) butyl methacrylate was 92.4%, and 1,1- Bis (trifluoromethyl) butane-1,3-diol was 1.9% and the others were 5.2%.
1 H NMR (solvent: CDCl 3 , reference material: TMS); δ6.16 (q, J = 0.98Hz, 1H), 5.96 (bs, 1H), 5.66 (q, J = 1.46Hz, 1H), 5.13- 5.20 (m, 1H), 2.24-2.36 (m, 2H), 1.94 (dd, J = 1.46Hz, 0.98Hz, 3H), 1.44 (d, J = 6.34Hz, 3H)
19 F NMR (solvent: CDCl 3 , reference material: CCl 3 F); δ-77.03 (q, J = 9.67 Hz, 3F), −79.25 (q, J = 9.67 Hz, 3F).
［比較例３］
還流冷却器を備えた500mLの4つ口フラスコに四フッ化エチレン樹脂で被覆された撹拌子及び1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオール60.03g（0.265mol）、トルエン230g、2-メチル-2-ブテン37.24g（0.531mol）、ノンフレックスＭＢＰ0.30g、アクリル酸クロリド36.04g（0.398mol）を入れ、かくはん機で撹拌しながらオイルバスにより110℃で加熱還流した。47時間後、ガスクロマトグラフィーにより測定したところ、目的の4,4,4−トリフルオロ−3−ヒドロキシ−1−メチル−３−(トリフルオロメチル)ブチル アクリレートが87.6%、原料の1,1−ビス(トリフルオロメチル)ブタン−1,3−ジオールが1.0%、その他が11.4%であった。反応液を室温まで冷却後、水100gを滴下し、洗浄後二層分離を行った。
1H NMR（溶媒：CDCl3，基準物質：TMS）；δ6.48(1H, dd, J=17.2Hz, 1.2Hz)， 6.11(1H,dd, J=17.2Hz, 10.4Hz)， 5.94(1H, dd, J=10.4Hz, 1.2Hz)， 5.83(1H, bs)， 5.22-5.13(1H, m)， 2.36-2.23(2H, m)， 1.44(1H, d, J=6.4Hz)
19F NMR（溶媒：CDCl3,基準物質：CCl3F）；δ-77.0(3F, q, J=12.4Hz)， -79.4(3F, q, J=12.4Hz)。
[Comparative Example 3]
A 500 mL four-necked flask equipped with a reflux condenser and a stirrer coated with tetrafluoroethylene resin, 60.03 g (0.265 mol) of 1,1-bis (trifluoromethyl) butane-1,3-diol, toluene 230 g, 37.24 g (0.531 mol) of 2-methyl-2-butene, 0.30 g of nonflex MBP, and 36.04 g (0.398 mol) of acrylic acid chloride were added, and the mixture was heated to reflux at 110 ° C. with an oil bath while stirring with a stirrer. After 47 hours, as measured by gas chromatography, the target 4,4,4-trifluoro-3-hydroxy-1-methyl-3- (trifluoromethyl) butyl acrylate was 87.6%, the starting 1,1- Bis (trifluoromethyl) butane-1,3-diol was 1.0% and the others were 11.4%. After cooling the reaction solution to room temperature, 100 g of water was added dropwise, and after washing, two-layer separation was performed.
1 H NMR (solvent: CDCl 3 , reference material: TMS); δ6.48 (1H, dd, J = 17.2Hz, 1.2Hz), 6.11 (1H, dd, J = 17.2Hz, 10.4Hz), 5.94 (1H , dd, J = 10.4Hz, 1.2Hz), 5.83 (1H, bs), 5.22-5.13 (1H, m), 2.36-2.23 (2H, m), 1.44 (1H, d, J = 6.4Hz)
19 F NMR (solvent: CDCl 3 , reference material: CCl 3 F); δ-77.0 (3F, q, J = 12.4 Hz), -79.4 (3F, q, J = 12.4 Hz).
［比較例４］
温度計及び還流冷却器を備えた1000mLの三口フラスコに四フッ化エチレン樹脂で被覆された撹拌子および1,1−ビス（トリフルオロメチル）ブタン−1,3−ジオール150g (0.66mol)、2−トリフルオロメチルアクリル酸クロリド126.9g (0.80mol)、2,6−ジメチルピリジン78.3g (0.73 mol)、トルエン260g及びノンフレックスＭＢＰ0.75gを入れ、かくはん機で撹拌しながらオイルバスにより50℃で加熱した。2時間後、反応液をガスクロマトグラフィーにより測定したところ、目的とする4,4,4−トリフルオロ−3−ヒドロキシ−1−メチル−3−（トリフルオロメチル）ブチル 2−（トリフルオロメチル）アクリレートが85.7%、原料の1,1−ビス（トリフルオロメチル）ブタン−1,3−ジオールが2.1%、その他が12.2%であった。
1H NMR （溶媒：CDCl3, 基準物質：TMS）；δ6.79 (d, J=1.46 Hz, 1H), 6.51 (d, J=1.46 Hz, 1H), 5.33−5.40 (m, 1H), 4.65 (bs, 1H), 2.25−2.42 (m, 2H), 1.46 (d, J=6.34 Hz, 3H)
19F NMR （溶媒：CDCl3, 基準物質：CCl3F）；δ‐65.92 (s, 3F), ‐77.20 (q, J=9.66 Hz, 3F), ‐79.09 (q, J=9.66 Hz, 3F)
比較例１〜４の何れも、反応終了時の目的物の選択率は、実施例２よりも低く、構造の特定されない不純物の副生が多かった。
[Comparative Example 4]
A 1000 mL three-necked flask equipped with a thermometer and a reflux condenser was stirred with a tetrafluoroethylene resin-coated stir bar and 1,1-bis (trifluoromethyl) butane-1,3-diol 150 g (0.66 mol), 2 -Add 126.9 g (0.80 mol) of trifluoromethylacrylic chloride, 78.3 g (0.73 mol) of 2,6-dimethylpyridine, 260 g of toluene and 0.75 g of nonflex MBP, and stir with a stirrer at 50 ° C with an oil bath. Heated. After 2 hours, the reaction mixture was measured by gas chromatography, and the desired 4,4,4-trifluoro-3-hydroxy-1-methyl-3- (trifluoromethyl) butyl 2- (trifluoromethyl) was obtained. The acrylate content was 85.7%, the raw material 1,1-bis (trifluoromethyl) butane-1,3-diol was 2.1%, and the others were 12.2%.
1 H NMR (solvent: CDCl 3 , reference material: TMS); δ 6.79 (d, J = 1.46 Hz, 1H), 6.51 (d, J = 1.46 Hz, 1H), 5.33-5.40 (m, 1H), 4.65 (bs, 1H), 2.25−2.42 (m, 2H), 1.46 (d, J = 6.34 Hz, 3H)
19 F NMR (solvent: CDCl 3, standard substance: CCl 3 F); δ- 65.92 (s, 3F), -77.20 (q, J = 9.66 Hz, 3F), -79.09 (q, J = 9.66 Hz, 3F )
In all of Comparative Examples 1 to 4, the selectivity of the target product at the end of the reaction was lower than that in Example 2, and there were many by-products of impurities whose structure was not specified.
Claims (10)
第１工程：一般式［８］で示される含フッ素不飽和アルコール
第２工程：一般式［７］で示されるα−置換アクリル酸無水物
［但し、式中のＲ１は水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、またはパーフルオロエチル基である。Ｒ２は水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、またはパーフルオロエチル基である。］ 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester represented by the formula [1] consisting of the following two steps
First step: Fluorine-containing unsaturated alcohol represented by the general formula [8]
Second step: α-substituted acrylic anhydride represented by general formula [7]
[Wherein R 1 represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a fluoromethyl group, a difluoromethyl group, a trimethyl group, It is a fluoromethyl group or a perfluoroethyl group. R 2 represents a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, or per It is a fluoroethyl group. ]
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| JP2000191590A (en) * | 1998-12-24 | 2000-07-11 | Nof Corp | Production of (meth)acrylic acid phenyl ester |
| JP2003040840A (en) * | 2001-07-24 | 2003-02-13 | Central Glass Co Ltd | Fluorine-containing polymerizable monomer and polymer using the same |
| US20030224283A1 (en) * | 2002-05-31 | 2003-12-04 | International Business Machines Corporation | Photoresist composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210045439A (en) | 2018-08-14 | 2021-04-26 | 샌트랄 글래스 컴퍼니 리미티드 | Distillation purification method of fluorinated polymerizable monomer |
| US11597696B2 (en) | 2018-08-14 | 2023-03-07 | Central Glass Company, Limited | Method for purifying polymerizable fluoromonomer by distillation |
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| JP2005206587A (en) | 2005-08-04 |
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