JP4929663B2 - Method for producing polymerizable compound - Google Patents
Method for producing polymerizable compound Download PDFInfo
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- JP4929663B2 JP4929663B2 JP2005284097A JP2005284097A JP4929663B2 JP 4929663 B2 JP4929663 B2 JP 4929663B2 JP 2005284097 A JP2005284097 A JP 2005284097A JP 2005284097 A JP2005284097 A JP 2005284097A JP 4929663 B2 JP4929663 B2 JP 4929663B2
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- 150000001875 compounds Chemical class 0.000 title claims description 99
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- -1 sulfonyloxy group Chemical group 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 14
- 150000002367 halogens Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 48
- 239000002904 solvent Substances 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 17
- 239000012044 organic layer Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000004973 liquid crystal related substance Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000149 argon plasma sintering Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- AZYTZQYCOBXDGY-UHFFFAOYSA-N 2-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=CC=N1 AZYTZQYCOBXDGY-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 1
- 0 *C1(*)OCC(*)(CO)CO1 Chemical compound *C1(*)OCC(*)(CO)CO1 0.000 description 1
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JEQDSBVHLKBEIZ-UHFFFAOYSA-N 2-chloropropanoyl chloride Chemical compound CC(Cl)C(Cl)=O JEQDSBVHLKBEIZ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- RUUJECRHYIYRSH-UHFFFAOYSA-N CCC1(CO)COC(C)(C)OC1 Chemical compound CCC1(CO)COC(C)(C)OC1 RUUJECRHYIYRSH-UHFFFAOYSA-N 0.000 description 1
- KVIYAWSINJHNEG-UHFFFAOYSA-N CCCCCCCCCC(OCC(CC)(CO)COC(C=C)=O)=N Chemical compound CCCCCCCCCC(OCC(CC)(CO)COC(C=C)=O)=N KVIYAWSINJHNEG-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940115457 cetyldimethylethylammonium bromide Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VHDPPDRSCMVFAV-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH+](C)C VHDPPDRSCMVFAV-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- PTLZMJYQEBOHHM-UHFFFAOYSA-N oxiran-2-ylmethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC1CO1 PTLZMJYQEBOHHM-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JUKPJGZUFHCZQI-UHFFFAOYSA-N undecanoyl chloride Chemical compound CCCCCCCCCCC(Cl)=O JUKPJGZUFHCZQI-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は新規重合性化合物の製造方法に関し、更に詳しくは、幅広い温度範囲において低電圧駆動が可能で電気光学特性に優れる光散乱型液晶デバイスの調光層形成材料に好適に使用できる重合性化合物の製造方法に関する。 The present invention relates to a method for producing a novel polymerizable compound, and more specifically, a polymerizable compound that can be suitably used as a light control layer forming material for a light-scattering liquid crystal device that can be driven at a low voltage in a wide temperature range and has excellent electro-optical characteristics. It relates to the manufacturing method.
情報化社会の進展に伴い、情報通信材料の需要がますます高まっている。特に、光散乱型の液晶デバイスは、偏光板が不要なことや視野角依存性が少ないことから、広告板、装飾表示板、時計、コンピューター、プロジェクション、デジタルペーパー、携帯用情報端末、光シャッター、などに用いる液晶表示素子又は光学素子として大きく期待されている。 With the development of the information society, the demand for information and communication materials is increasing. In particular, light-scattering liquid crystal devices do not require polarizing plates and have little viewing angle dependency, so advertising boards, decorative display boards, watches, computers, projections, digital paper, portable information terminals, optical shutters, It is highly expected as a liquid crystal display element or an optical element used for the above.
光散乱型液晶デバイスとして、ラジカル重合性組成物と液晶組成物とからなる調光層形成材料に光照射又は加熱して得られる、ポリマーマトリックスと液晶組成物とからなる調光層を有する液晶デバイスが知られている。
該デバイスには、使用する液晶化合物の種類には左右されず、−２０℃から７０℃程度の幅広い温度範囲において駆動電圧の変化が小さいこと、且つ、駆動電圧の絶対値は２０Ｖ以下であることが求められている。特に液晶駆動方式がＴＦＴ駆動の場合は１０Ｖ以下の低電圧化と不純物の除去が不可欠であり、これらの特性を満たすような、重合性化合物の開発が進められており、次の一般式（E）で模式的に表されるような側鎖型ラジカル重合性化合物が開発されている。
A liquid crystal device having a light control layer comprising a polymer matrix and a liquid crystal composition, which is obtained by irradiating or heating a light control layer forming material comprising a radical polymerizable composition and a liquid crystal composition as a light scattering liquid crystal device. It has been known.
The device does not depend on the type of liquid crystal compound used, and the change in drive voltage is small in a wide temperature range of about -20 ° C to 70 ° C, and the absolute value of the drive voltage is 20 V or less. Is required. In particular, when the liquid crystal driving method is TFT driving, it is indispensable to lower the voltage to 10 V or less and to remove impurities, and the development of a polymerizable compound that satisfies these characteristics is in progress, and the following general formula (E Side-chain type radically polymerizable compounds as schematically represented by) have been developed.
当該側鎖型ラジカル重合性化合物の製造は、従来次に示すようなグリシジルエーテルを用いて行われていた（特許文献１及び２参照。）。
The production of the side chain radically polymerizable compound has heretofore been performed using glycidyl ether as shown below (see Patent Documents 1 and 2).
又、側鎖型ラジカル重合性化合物の製造方法としては、多価水酸基化合物と脂肪酸および、アクリル酸を同時に混合してエステル化反応を行うことによる製造方法が開示されている（特許文献３参照。）。しかしながら、当該引用文献記載の製造方法では目的物以外の構造が多量に生成してしまい、最終生成物に不純物が混入するため重合性液晶組成物として必要とされる特性を得ることがでず、液晶デバイスを構成した際の品質に大きなばらつきを生じる問題があった。特にＴＦＴ駆動用の光散乱型液晶デバイスにおいては不純物の混入を最小限に抑える必要があり、製造工程において目的化合物以外の類似構造体、極性不純物等は取り除く必要がある。しかしながら、当該引用文献記載の製造方法により得られた混合物から目的とする化合物のみを効率よく取り出すことは困難であり、製造効率を大幅に低下させる問題があった。
このような状況下、側鎖型ラジカル重合性化合物を効率的に製造する方法として、次に示すようなオキセタン誘導体を用いる方法が開発された（特許文献４参照。）。
Moreover, as a manufacturing method of a side chain type radically polymerizable compound, the manufacturing method by mixing a polyhydric hydroxyl compound, a fatty acid, and acrylic acid simultaneously, and performing esterification is disclosed (refer patent document 3). ). However, in the production method described in the cited document, a structure other than the target product is produced in a large amount, and impurities required to be mixed into the final product cannot obtain the characteristics required as a polymerizable liquid crystal composition. There has been a problem that the quality of the liquid crystal device varies greatly. In particular, in a light-scattering liquid crystal device for driving a TFT, it is necessary to minimize the mixing of impurities, and it is necessary to remove similar structures other than the target compound, polar impurities, and the like in the manufacturing process. However, it is difficult to efficiently extract only the target compound from the mixture obtained by the production method described in the cited document, and there is a problem that production efficiency is greatly reduced.
Under such circumstances, a method using an oxetane derivative as shown below has been developed as a method for efficiently producing a side chain type radically polymerizable compound (see Patent Document 4).
本発明が解決しようとする課題は、側鎖型ラジカル重合性化合物効率的な製造方法を提供することにある。 The problem to be solved by the present invention is to provide an efficient method for producing a side chain type radical polymerizable compound.
本願発明者らは、側鎖型ラジカル重合性化合物の製造方法に関して様々な検討を行った結果、特定の構造を有するアルコール誘導体を用いて製造を行うことにより前述の課題を解決できることを見出し本願発明を完成するに至った。
本願発明は、一般式（１）
As a result of various studies on the production method of the side chain type radical polymerizable compound, the present inventors have found that the above-mentioned problems can be solved by producing an alcohol derivative having a specific structure. It came to complete.
The present invention provides a general formula (1)
本発明の製造方法により側鎖型ラジカル重合性化合物を効率的に製造することが可能となる。当該重合性化合物を構成部材とする光散乱型液晶デバイスは、幅広い温度範囲においても低電圧駆動可能であることから表示素子として有用である。 The production method of the present invention makes it possible to efficiently produce a side chain type radically polymerizable compound. The light scattering liquid crystal device comprising the polymerizable compound as a constituent member is useful as a display element because it can be driven at a low voltage even in a wide temperature range.
本願発明の製造方法は、一般式（１）で表される化合物に、一般式（２）、一般式（３）及び一般式（３）で表される化合物を反応させることを特徴とするものである。一般式（２）、一般式（３）及び一般式（３）で表される化合物の反応の順番はどの化合物から始めることは可能である。しかし、中間体の精製のし易さの点から、一般式（１）で表される化合物に、一般式（２）で表されるハロゲン化合物、カルボン酸又はこれらの誘導体を反応させることにより一般式（６） The production method of the present invention is characterized in that the compound represented by the general formula (1) is reacted with the compound represented by the general formula (2), the general formula (3) and the general formula (3). It is. The order of reaction of the compounds represented by the general formula (2), the general formula (3), and the general formula (3) can be started from any compound. However, from the viewpoint of ease of purification of the intermediate, the compound represented by the general formula (1) is generally reacted with the halogen compound represented by the general formula (2), a carboxylic acid or a derivative thereof. Formula (6)
一般式（１）で表されるトリメチロールプロパン誘導体と一般式（２）で表される化合物により一般式（６）で表される化合物を生成する反応は、トリエチルアミン、ピリジン等の塩基性化合物存在下行うことが好ましい。反応溶媒には原料アルコールとの溶解性が高い溶媒を選択する。溶解性の小さい溶媒を用い原料アルコールが分散された状態で反応を行うと、ジアルキル体、トリアルキル体が多く生成してしまうので好ましくない。反応温度は室温付近で実施することが好ましく、一般式（２）で表される化合物の滴下速度を抑えることが好ましい。
反応の際副生するジアルキル体、トリアルキル体は、ヘキサン、ヘプタン等の炭化水素系溶媒とジメチルスルホキシド（以下ＤＭＳＯと略す）やＮ，Ｎ−ジメチルホルムアミド（以下ＤＭＦと略す）、メタノールなどの極性溶媒による２液分離により、炭化水素系溶媒側に移行するため、（目的物は極性溶媒に移行）容易に除去することができる。その後極性溶媒から目的物を抽出する。、更に再結晶又は蒸留により高純度の一般式（６）で表されるジアルコール誘導体を得ることができる。
特にヘキサン又はヘプタンとメタノール又はメタノール／水混合溶媒との組み合わせは、分離能が高いだけでなく、分離後の溶媒除去が容易であり好適である。
The reaction for producing the compound represented by the general formula (6) from the trimethylolpropane derivative represented by the general formula (1) and the compound represented by the general formula (2) is a basic compound such as triethylamine or pyridine. It is preferable to perform the following. A solvent having high solubility with the raw material alcohol is selected as the reaction solvent. It is not preferable to carry out the reaction in a state in which the raw material alcohol is dispersed using a solvent having low solubility because a large amount of dialkyl and trialkyl forms are generated. The reaction temperature is preferably about room temperature, and it is preferable to suppress the dropping rate of the compound represented by the general formula (2).
Dialkyl and trialkyl compounds by-produced in the reaction are polar solvents such as hexane, heptane and other hydrocarbon solvents, dimethyl sulfoxide (hereinafter abbreviated as DMSO), N, N-dimethylformamide (hereinafter abbreviated as DMF), methanol, and the like. Since it moves to the hydrocarbon solvent side by two-liquid separation with a solvent, the target product can be easily removed (transfer to a polar solvent). Thereafter, the target product is extracted from the polar solvent. Furthermore, a dialcohol derivative represented by the general formula (6) having a high purity can be obtained by recrystallization or distillation.
In particular, a combination of hexane or heptane and methanol or a methanol / water mixed solvent is preferable because it not only has a high resolution, but also facilitates removal of the solvent after the separation.
又、一般式（１）で表される化合物の二つの水酸基を環状アセタール誘導体として保護した後、一般式（２）で表される化合物を反応させその後環状アセタールを外すことにより一般式（６）で表される化合物を得る工程を経由することも好ましい。
この場合、保護に用いるケトン誘導体は特に制限はないが、入手の容易さ、価格の点から炭素原子数１０以下のケトン誘導体が好ましく、アセトン、メチルエチルケトン等が好適である。
保護工程を加えた場合、中間体の環状アセタール誘導体は具体的には、一般式（８）
Further, after protecting the two hydroxyl groups of the compound represented by the general formula (1) as a cyclic acetal derivative, the compound represented by the general formula (2) is reacted, and then the cyclic acetal is removed to remove the general formula (6). It is also preferable to go through a step of obtaining a compound represented by:
In this case, the ketone derivative used for protection is not particularly limited, but a ketone derivative having 10 or less carbon atoms is preferable from the viewpoint of availability and cost, and acetone, methyl ethyl ketone, and the like are preferable.
When the protection step is added, the intermediate cyclic acetal derivative is specifically represented by the general formula (8)
特に、Ｙ１が単結合を表す場合、保護工程を経由する方法が好ましい。
In particular, when Y 1 represents a single bond, a method through a protection step is preferable.
一般式（１）で表されるトリメチロールプロパン誘導体とアルキルハライドを直接エーテル化反応させるとジアルキル体、トリアルキル体が生成することがあり、目的物の収率が十分向上しないこともある。この場合、一般式（１）で表されるトリメチロールプロパン誘導体をアセトン、ジメトキシプロパン等を用いて、二つの水酸基を保護した後、エーテル下反応を行うことが好ましい。
保護基の導入は、アセトン（Ｒ５＝Ｒ６＝メチル基）又は２，２−ジメトキシプロパン（Ｒ５＝Ｒ６＝メチル基）の場合、ｐ−トルエンスルホン酸等の酸触媒存在下で実施することが好ましい。この場合の反応溶媒には種々の有機溶媒を用いることが可能であり、代表的な溶媒としてトルエン、ＤＭＦ、ＴＨＦ、アセトニトリル等が挙げられるが、反応時間、収率の点でアセトニトリルが好ましい。
アセトンを用いて水酸基を保護する場合は、反応後にアセトンを水洗で取り除かないと溶媒留去中に脱保護反応が起きてしまい収率が低下するため、保護基を導入した化合物が水との溶解性が高く、水洗によりアセトンのみを効率的に除去することができない場合は、２，２−ジメトキシプロパンによる保護が好ましい。
When the trimethylolpropane derivative represented by the general formula (1) is directly etherified with an alkyl halide, a dialkyl or trialkyl form may be produced, and the yield of the target product may not be sufficiently improved. In this case, the trimethylolpropane derivative represented by the general formula (1) is preferably protected with ether after using acetone, dimethoxypropane or the like to protect the two hydroxyl groups.
In the case of acetone (R 5 = R 6 = methyl group ) or 2,2-dimethoxypropane (R 5 = R 6 = methyl group), the protective group is introduced in the presence of an acid catalyst such as p-toluenesulfonic acid. It is preferable to do. Various organic solvents can be used as the reaction solvent in this case, and typical solvents include toluene, DMF, THF, acetonitrile, and the like. Acetonitrile is preferred in terms of reaction time and yield.
When protecting the hydroxyl group with acetone, if the acetone is not removed by washing with water after the reaction, the deprotection reaction will occur during the distillation of the solvent and the yield will be reduced. In the case where the property is high and only acetone cannot be efficiently removed by washing with water, protection with 2,2-dimethoxypropane is preferred.
一般式（８）で表される化合物とアルキルハライドの反応による一般式（８）で表される化合物 Compound represented by general formula (8) by reaction of compound represented by general formula (8) and alkyl halide
保護基の除去は、酸性条件下溶媒中で行う一般的な方法を用いることができるが、エタノール等のアルコール中で希塩酸等を用い、加熱条件下行う方法が好ましい。保護基を除去することにより、一般式（６）で表される化合物を得ることができ前述の２液分離により、同様に純度の高い中間体を得ることができる。
The removal of the protecting group can be performed by a general method performed in a solvent under acidic conditions, but a method performed under heating conditions using dilute hydrochloric acid or the like in an alcohol such as ethanol is preferable. By removing the protecting group, the compound represented by the general formula (6) can be obtained, and an intermediate having a high purity can be obtained by the above-described two-liquid separation.
一般式（６）で表される化合物に、一般式（３）で表される化合物及び一般式（４）で表される化合物を順次反応させるが、反応の効率を考慮すると一般式（３）で表される化合物を反応させて一般式（７）で表される化合物を得た後、一般式（４）で表される化合物を反応させることが好ましい。
一般式（７）で表される化合物の製造は、一般式（６）及び一般式（３）で表される化合物を酸触媒によるエステル化又は１，３−ジシクロヘキシルカルボジイミド（ＤＣＣ）、Ｎ−エチル−Ｎ’−（３−ジメチルアミノプロピル）カルボジイミド（ＷＳＣ）等の脱水縮合剤によるエステル化により行うことができるが、反応収率の点で脱水縮合剤を用いることが好ましい。
アクリル酸誘導体の替わりにアクリル酸塩化物（一般式（３）においてＸ２がハロゲンを表す場合。）を、アミン触媒存在下に反応させることも可能であるが、アクリル酸誘導体を用いる場合がよりジアクリル体の生成を抑えることが可能であることから好ましい。
アクリル酸塩化物を用いる場合、アクリル酸塩化物の反応性が、出発物質である一般式（６）より生成した一般式（７）でより高い問題がある。この場合、反応系内にテトラブチルアンモニウムブロミド、セチルジメチルエチルアンモニウムブロミド等の相関移動触媒を用いるとジアクリル体の生成を抑制することができる。
また、アクリル酸および、アクリル酸塩化物の代わりにクロロプロピオン酸、クロロプロピオン酸クロリドを用いて、脱塩酸によりアクリル化することも可能である。
このように合成した反応物は前記と同様な極性−非極性の２液分離、若しくはシリカゲルカラムにより容易に精製することができる。
The compound represented by the general formula (6) is sequentially reacted with the compound represented by the general formula (3) and the compound represented by the general formula (4). In consideration of the efficiency of the reaction, the general formula (3) It is preferable to react the compound represented by General Formula (4) after reacting the compound represented by General Formula (7).
The compound represented by the general formula (7) is produced by esterifying the compound represented by the general formula (6) and the general formula (3) with an acid catalyst or 1,3-dicyclohexylcarbodiimide (DCC), N-ethyl. Although it can be performed by esterification with a dehydrating condensing agent such as —N ′-(3-dimethylaminopropyl) carbodiimide (WSC), it is preferable to use a dehydrating condensing agent in terms of reaction yield.
An acrylic acid chloride (when X 2 represents halogen in the general formula (3)) can be reacted in the presence of an amine catalyst instead of the acrylic acid derivative, but the acrylic acid derivative is more often used. It is preferable because the production of diacrylic body can be suppressed.
When an acrylate is used, the reactivity of the acrylate is higher in the general formula (7) generated from the general formula (6) as a starting material. In this case, when a phase transfer catalyst such as tetrabutylammonium bromide or cetyldimethylethylammonium bromide is used in the reaction system, the production of diacrylic body can be suppressed.
It is also possible to acrylate by dehydrochlorination using acrylic acid and chloropropionic acid or chloropropionic acid chloride instead of acrylic acid chloride.
The reaction product thus synthesized can be easily purified by the same polar-nonpolar two-liquid separation as described above, or a silica gel column.
一般式（７）で表される化合物に一般式（４）で表される化合物を反応させることにより最終物である一般式（５）を製造する。この場合、一般式（４）で表される化合物の内カルボン酸誘導体を前述の脱水縮合剤存在下エステル化するか、一般式（４）で表される化合物の内カルボン酸ハライドを用いて目的とする一般式（５）で表される化合物を製造することができる。この場合においても、脱水縮合剤を用いることがより好ましい。
更に、ヘキサン、ヘプタン等の炭化水素系溶媒とＤＭＳＯ、ＤＭＦ、メタノールなどの極性溶媒による２液分離により、目的物を炭化水素系溶媒側に移行させ、原料、カルボジイミド、副生する尿素化合物を容易に除去できる。特にヘキサン又はヘプタンとメタノール又はメタノール／水混合溶媒との組み合わせは、分離能が高いだけでなく、分離後の溶媒除去が容易であり好適である。
By reacting the compound represented by the general formula (7) with the compound represented by the general formula (4), the general formula (5) as the final product is produced. In this case, the inner carboxylic acid derivative of the compound represented by the general formula (4) is esterified in the presence of the aforementioned dehydration condensing agent, or the inner carboxylic acid halide of the compound represented by the general formula (4) is used for the purpose. A compound represented by the general formula (5) can be produced. Even in this case, it is more preferable to use a dehydrating condensing agent.
Furthermore, by two-liquid separation using a hydrocarbon solvent such as hexane and heptane and a polar solvent such as DMSO, DMF, and methanol, the target product is transferred to the hydrocarbon solvent side, and raw materials, carbodiimide, and by-product urea compounds are easily obtained. Can be removed. In particular, a combination of hexane or heptane and methanol or a methanol / water mixed solvent is preferable because it not only has a high resolution, but also facilitates removal of the solvent after the separation.
一般式（１）において、Ｒ１は炭素原子数１から１０のアルキル基が好ましく、更に炭素原子数１から４の直鎖アルキル基がより好ましい。一般式（１）に示されるトリヒドロキシメチルアルカン化合物は、対応するアルデヒド化合物とパラホルムによる縮合反応により得ることができる。
一般式（２）において、Ｒ２は炭素原子数５から２０の直鎖又は分岐アルキル基が好ましく、更に炭素原子数５〜１４の直鎖アルキル、炭素原子数８〜１８の分岐アルキル基がより好ましい。具体的には、ｎ−ヘキシル基、２−エチルヘキシル基、ｎ−オクチル基、ｎ−ウンデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−オクタデシル基、２−ｎ−ヘプチルノニル基、イソミリスチル基、２−エチルヘキシル基、ブトキシエチル基、ヘキシロキシエチル基、ｎ−ブトキシエトキシメチル基、シクロヘキシル基、ポリエチレングリコールモノエーテル基、４−オクチルシクロヘキシル基等があげられる。
一般式（２）において、Ｙ１はカルボニル基又は単結合を表し、Ｘ１は水酸基、置換スルホニルオキシ基又はハロゲンを表すが、Ｙ１がカルボニル基であり、Ｘ１がハロゲンである化合物、又はＹ１が単結合であり、Ｘ１がハロゲンである化合物による製造方法が、低コスト化の観点から好ましい。
In the general formula (1), R 1 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a linear alkyl group having 1 to 4 carbon atoms. The trihydroxymethylalkane compound represented by the general formula (1) can be obtained by a condensation reaction with a corresponding aldehyde compound and paraform.
In the general formula (2), R 2 is preferably a linear or branched alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 5 to 14 carbon atoms, or a branched alkyl group having 8 to 18 carbon atoms. preferable. Specifically, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-octadecyl group, 2-n-heptylnonyl group, isomristyl group 2-ethylhexyl group, butoxyethyl group, hexyloxyethyl group, n-butoxyethoxymethyl group, cyclohexyl group, polyethylene glycol monoether group, 4-octylcyclohexyl group and the like.
In General Formula (2), Y 1 represents a carbonyl group or a single bond, X 1 represents a hydroxyl group, a substituted sulfonyloxy group, or a halogen, Y 1 is a carbonyl group, and X 1 is a halogen, or A production method using a compound in which Y 1 is a single bond and X 1 is halogen is preferable from the viewpoint of cost reduction.
一般式（３）において、Ｒ３は水素又はメチル基を表すが、反応性の高さから水素がより好ましい。
一般式（３）において、Ｒ４は単結合であるか又は炭素原子数が１から２であることが好ましく、Ｙ２は酸素原子、Ｙ３は単結合又はカルボニル基、Ｘ３は水酸基が好ましい。具体的な化合物としては、アクリル酸、アクリル酸ダイマー、又はヒドロキシエチルアクリレートが挙げられる。
一般式（４）において、Ｒ５は炭素原子数５〜２６のアルキレン基又はアルカントリイル基が好ましく、炭素原子数５〜２２のアルキレン基がより好ましい。Ｙ４はカルボニル基、Ｘ３は水酸基又はハロゲンが好ましい。具体的な化合物としては、アジピン酸、スベリン酸、セバシン酸、長鎖二塩基酸、およびこれらの酸塩化物が挙げられる。
In the general formula (3), R 3 represents hydrogen or a methyl group, and hydrogen is more preferable because of high reactivity.
In the general formula (3), R 4 is preferably a single bond or preferably having 1 to 2 carbon atoms, Y 2 is an oxygen atom, Y 3 is a single bond or a carbonyl group, and X 3 is preferably a hydroxyl group. . Specific compounds include acrylic acid, acrylic acid dimer, or hydroxyethyl acrylate.
In the general formula (4), R 5 is preferably an alkylene group having 5 to 26 carbon atoms or an alkanetriyl group, and more preferably an alkylene group having 5 to 22 carbon atoms. Y 4 is preferably a carbonyl group, and X 3 is preferably a hydroxyl group or a halogen. Specific examples of the compound include adipic acid, suberic acid, sebacic acid, long-chain dibasic acid, and acid chlorides thereof.
一般式（８）において、Ｒ５及びＲ６はそれぞれ独立して炭素原子数１から５のアルキル基が好ましく、更に炭素原子数１から２がより好ましい。 In the general formula (8), R 5 and R 6 are each independently preferably an alkyl group having 1 to 5 carbon atoms, and more preferably 1 to 2 carbon atoms.
このようにして得られた一般式（５）で表される重合性化合物と液晶組成物との組成物は、光散乱型液晶デバイス用の調光層形成材料として特に有用である。 The composition of the polymerizable compound represented by the general formula (5) and the liquid crystal composition thus obtained is particularly useful as a light control layer forming material for a light scattering liquid crystal device.
以下に、本発明の実施例を示し、本発明を更に具体的に説明する。しかしながら、本発明はこれらの実施例に限定されるものではない。なお、以下の実施例において「％」は特に断りのない限り「質量％」を表す。
（実施例１） 式（Ｍ−１）で表される化合物の製造
（実施例１−１）
撹拌装置、及び温度計を備えた反応容器にトリメチロールプロパン１００ｇ （７５０ミリモル）とＰ−トルエンスルホン酸ピリジニウム塩１．９ｇ（７．４５ミリモル） 、アセトニトリル５００ｍｌを仕込み室温で攪拌した。次いで、２，２−ジメトキシプロパン １１６．４ｇ（１．１２モル）をゆっくり滴下した。滴下終了後、室温で２時間撹拌して、原料が消失したのを確認して反応を終了する。反応液を濃縮し、トリメチロールプロパンが保護された式（１０）で表される化合物を１３５ｇ合成した。
Examples of the present invention will be shown below, and the present invention will be described more specifically. However, the present invention is not limited to these examples. In the following examples, “%” represents “% by mass” unless otherwise specified.
Example 1 Production of Compound Represented by Formula (M-1) (Example 1-1)
A reaction vessel equipped with a stirrer and a thermometer was charged with 100 g (750 mmol) of trimethylolpropane, 1.9 g (7.45 mmol) of P-toluenesulfonic acid pyridinium salt, and 500 ml of acetonitrile and stirred at room temperature. Next, 116.4 g (1.12 mol) of 2,2-dimethoxypropane was slowly added dropwise. After completion of the dropwise addition, the mixture is stirred at room temperature for 2 hours, and the reaction is terminated after confirming that the raw materials have disappeared. The reaction solution was concentrated to synthesize 135 g of the compound represented by the formula (10) in which trimethylolpropane was protected.
次いで、撹拌装置、及び温度計を備えた反応容器に、上記で合成した式（１０）で表される化合物 130g（０．７５モル）、1-ブロモヘキサン １８４．８ｇ（１．１２モル）とセチルヂメチルアンモニウムブロミド１４．１ｇ、ＤＭＳＯ １Ｌを仕込む。反応容器を室温で攪拌しながら５０％水酸化カリウム水溶液 １３０ｇをゆっくり滴下した。滴下終了後、室温で１時間撹拌後、更に６０℃で２時間攪拌して反応を完結させた。原料が消失したのを確認して反応を終了させ、反応液に酢酸エチル １Ｌ、ｎ−ヘキサン ５００ｍｌを加えて、純水、食塩水で洗浄し、有機層を濃縮して式（１１）で表される化合物の粗生物を１８０ｇ得た。
Next, in a reaction vessel equipped with a stirrer and a thermometer, 130 g (0.75 mol) of the compound represented by the formula (10) synthesized above, 184.8 g (1.12 mol) of 1-bromohexane, Charge 14.1 g of cetyldimethylammonium bromide and 1 L of DMSO. While stirring the reaction vessel at room temperature, 130 g of 50% aqueous potassium hydroxide solution was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour and further stirred at 60 ° C. for 2 hours to complete the reaction. After confirming the disappearance of the raw materials, the reaction was terminated, and 1 L of ethyl acetate and 500 ml of n-hexane were added to the reaction solution, washed with pure water and brine, and the organic layer was concentrated and represented by formula (11). 180 g of a crude product of the resulting compound was obtained.
更に、撹拌装置、及び温度計を備えた反応容器に、上記で合成した式（１１）で表される化合物 １８０ｇ 、テトラヒドロフラン（以下ＴＨＦと略す）４００ｍｌ、１０％塩酸水溶液 ４００ｍｌ、を加え、６５℃で２時間攪拌する。反応終了後、ＴＨＦを留去して、酢酸エチル１Ｌを加え、純水 飽和食塩水で洗浄した。有機層の溶媒を留去した後にｎ−ヘキサン６００ｍｌに溶解させ、メタノール／水の４／１（体積比）混合溶液７００ｍｌで２回抽出した。メタノール／水層からメタノールを留去した後、酢酸エチル １Ｌを加え、純水、飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥、溶媒を留去、更に蒸留により精製を行い式（１２）で表される化合物を８０ｇ得た。
Furthermore, 180 g of the compound represented by the formula (11) synthesized above, 400 ml of tetrahydrofuran (hereinafter abbreviated as THF), 400 ml of 10% hydrochloric acid aqueous solution were added to a reaction vessel equipped with a stirrer and a thermometer at 65 ° C. For 2 hours. After completion of the reaction, THF was distilled off, 1 L of ethyl acetate was added, and the mixture was washed with pure water and saturated brine. After the solvent of the organic layer was distilled off, it was dissolved in 600 ml of n-hexane and extracted twice with 700 ml of a methanol / water 4/1 (volume ratio) mixed solution. After distilling off methanol from the methanol / water layer, 1 L of ethyl acetate was added, washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was further purified by distillation. 80 g of the compound represented by 12) was obtained.
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：３．７０（ｍ，２Ｈ），３．５９（ｍ，２Ｈ），３．４２（ｍ，４Ｈ），２．９３（ｓ，２Ｈ），１．５９（ｍ，２Ｈ），１．３８−１．２６（ｍ，８Ｈ），０．９２−０．８０（ｍ，６Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：７５．０，７１．９，６５．８，４２．７，３１．５，２９．４，２９．１，２５．７，２３．０，２２．５，２２．５，１３．９，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ−１
（実施例１−４）
次いで、撹拌装置、及び温度計を備えた反応容器に、上記で合成した式（１２）で表される化合物を５０ｇ（０．２３モル）、アクリル酸 ２４．７ｇ、ジメチルアミノピリジン ４．１５ｇ、塩化メチレン ５００ｍｌを仕込んだ。窒素ガスの雰囲気下でジイソプロピルカルボジイミド４３．２ｇ（０．３４モル）を室温でゆっくり滴下した。滴下終了後、更に２時間撹拌した後、４０℃で２時間反応させた。反応液をろ過した後、ろ液に塩化メチレン２００ｍｌ、１０％塩酸水溶液 ７００ｍｌを加え洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（１３）で表される化合物３５ｇを得た。
1 H-NMR (solvent: deuterated chloroform): δ: 3.70 (m, 2H), 3.59 (m, 2H), 3.42 (m, 4H), 2.93 (s, 2H), 1 .59 (m, 2H), 1.38-1.26 (m, 8H), 0.92-0.80 (m, 6H)
13 C-NMR (solvent: deuterated chloroform): δ: 75.0, 71.9, 65.8, 42.7, 31.5, 29.4, 29.1, 25.7, 23.0, 22 .5, 22.5, 13.9, 7.4
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm −1
(Example 1-4)
Next, in a reaction vessel equipped with a stirrer and a thermometer, 50 g (0.23 mol) of the compound represented by the formula (12) synthesized above, 24.7 g of acrylic acid, 4.15 g of dimethylaminopyridine, 500 ml of methylene chloride was charged. Under an atmosphere of nitrogen gas, 43.2 g (0.34 mol) of diisopropylcarbodiimide was slowly added dropwise at room temperature. After completion of dropping, the mixture was further stirred for 2 hours, and then reacted at 40 ° C. for 2 hours. After filtering the reaction solution, the filtrate was washed with 200 ml of methylene chloride and 700 ml of 10% hydrochloric acid aqueous solution and further washed with saturated brine, and the organic layer was distilled off with anhydrous sodium sulfate. Purification was performed with a silica gel column (weight ratio) to obtain 35 g of a compound represented by the formula (13).
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４３（ｄ，１Ｈ），６．１２（ｑ，１Ｈ），５．８５（ｄ，１Ｈ），４．２０（ｓ，２Ｈ），３．５７（ｄ，２Ｈ），３．４４（ｍ，４Ｈ），２．８９（ｍ，１Ｈ），１．５５（ｍ，２Ｈ），１．３８−１．２６（ｍ，８Ｈ），０．９２−０．８０（ｍ，６Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１６６．３，１３０．８，１２８．２，１２７．９，７４．２，７１．９，６６．１，６４．５，４２．２，３１．７，２９．７，２５．７，２２．９，２２．５，１３．９，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ−１
（実施例１−５）
更に、撹拌装置、及び温度計を備えた反応容器に、上記で合成した式（１３）で表される化合物 ３５ｇ（０．１２モル）セバシン酸 １２．９ｇ（０．０６モル）、ピロリジノピリジン ２．２７ｇ、塩化メチレン ３００ｍｌを仕込んだ。窒素ガスの雰囲気下で反応容器を０〜５℃に冷却してジイソプロピルカルボジイミド１９．３ｇ（０．１５モル）をゆっくり滴下した。滴下終了後、室温で４時間反応させた。反応液に塩化メチレン２００ｍｌ、１０％塩酸水溶液 ７００ｍｌを加え洗浄し、更に飽和食塩水で洗浄し有機層の溶媒を留去した後に、ｎ−ヘキサン５００ｍｌを加え、メタノール／水の４／１（体積比）混合溶液５００ｍｌで洗浄した。更に有機層を純水、飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥、溶媒を留去、更に５倍量（重量比）のシリカゲルカラムにより精製を行い目的の化合物（Ｍ−１）を３８．７ｇを得た。
1 H-NMR (solvent: deuterated chloroform): δ: 6.43 (d, 1H), 6.12 (q, 1H), 5.85 (d, 1H), 4.20 (s, 2H), 3 .57 (d, 2H), 3.44 (m, 4H), 2.89 (m, 1H), 1.55 (m, 2H), 1.38-1.26 (m, 8H),. 92-0.80 (m, 6H)
13 C-NMR (solvent: deuterated chloroform): δ: 166.3, 130.8, 128.2, 127.9, 74.2, 71.9, 66.1, 64.5, 42.2, 31 .7, 29.7, 25.7, 22.9, 22.5, 13.9, 7.4
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm −1
(Example 1-5)
Furthermore, in a reaction vessel equipped with a stirrer and a thermometer, 35 g (0.12 mol) of the compound represented by the formula (13) synthesized above, 12.9 g (0.06 mol) of sebacic acid, pyrrolidinopyridine 2.27 g and 300 ml of methylene chloride were charged. Under a nitrogen gas atmosphere, the reaction vessel was cooled to 0 to 5 ° C., and 19.3 g (0.15 mol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction was allowed to proceed at room temperature for 4 hours. The reaction solution was washed by adding 200 ml of methylene chloride and 700 ml of 10% aqueous hydrochloric acid, and further washed with saturated saline, and the solvent of the organic layer was distilled off. Then, 500 ml of n-hexane was added, and 4/1 (volume by volume of methanol / water). Ratio) Washed with 500 ml of the mixed solution. Further, the organic layer was washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and further purified with a 5-fold amount (weight ratio) silica gel column to obtain the target compound (M-1 ) Was obtained 38.7 g.
（物性値）
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４１（ｄ，２Ｈ），６．１２（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１１（ｓ，４Ｈ），４．０５（ｓ，４Ｈ），３．３５（ｔ，４Ｈ），３．２９（ｓ，４Ｈ），２．３１（ｔ，４Ｈ），１．６２（ｍ，４Ｈ），１．６−１．４７（ｍ，８Ｈ），１．２５（ｍ，２０Ｈ），０．９２−０．８（ｍ，１２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．６，１６５．９，１３０．６，１２８．３，７１．６，７０．３，６４．７，６４．４，４１．５，３４．３，３１．９，２９．６−２９．０，２５．７，２５．０，２３．０，２２．６，１４．０，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
（実施例２） 式（Ｍ−２）で表される化合物の製造
（実施例２−１）
トリメチロールプロパン（１モル）と２，２−ジメトキシプロパン（１．５モル）、ｐ−トルエンスルホン酸（０．０１モル）を用い、実施例１−１と同様にして式（１４）で表される化合物を得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.11 (s, 4H), 4 .05 (s, 4H), 3.35 (t, 4H), 3.29 (s, 4H), 2.31 (t, 4H), 1.62 (m, 4H), 1.6-1. 47 (m, 8H), 1.25 (m, 20H), 0.92-0.8 (m, 12H)
13 C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.6, 128.3, 71.6, 70.3, 64.7, 64.4, 41.5, 34 3, 31.9, 29.6-29.0, 25.7, 25.0, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
(Example 2) Production of a compound represented by the formula (M-2) (Example 2-1)
Using trimethylolpropane (1 mol), 2,2-dimethoxypropane (1.5 mol), and p-toluenesulfonic acid (0.01 mol), it is represented by the formula (14) in the same manner as in Example 1-1. The compound obtained was obtained.
式（１４）で表される化合物（１モル）と１−ブロモデカン（１．５モル）、テトラブチルアンモニウムブロミド（０．０３モル）を用い、実施例１−２及び１−３と同様にして式（１５）で表される化合物を得た。
Using the compound represented by the formula (14) (1 mol), 1-bromodecane (1.5 mol), and tetrabutylammonium bromide (0.03 mol), in the same manner as in Examples 1-2 and 1-3. A compound represented by the formula (15) was obtained.
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：３．７０（ｍ，２Ｈ），３．５９（ｍ，２Ｈ），３．４２（ｍ，４Ｈ），２．９３（ｓ，２Ｈ），１．５９（ｍ，２Ｈ），１．３８−１．２６（ｍ，１６Ｈ），０．９２−０．８０（ｍ，６Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：７５．０，７１．９，６５．８，４２．７，３１．５，２９．４，２９．１，２５．７，２３．０，２２．５，２２．５，１３．９，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ−１
（実施例２−３）
得られた式（１５）で表される化合物（１モル）とアクリル酸（１．２モル）を用い、実施例１−４と同様にして式（１６）で表される化合物を得た。
1 H-NMR (solvent: deuterated chloroform): δ: 3.70 (m, 2H), 3.59 (m, 2H), 3.42 (m, 4H), 2.93 (s, 2H), 1 .59 (m, 2H), 1.38-1.26 (m, 16H), 0.92-0.80 (m, 6H)
13 C-NMR (solvent: deuterated chloroform): δ: 75.0, 71.9, 65.8, 42.7, 31.5, 29.4, 29.1, 25.7, 23.0, 22 .5, 22.5, 13.9, 7.4
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm −1
(Example 2-3)
The compound represented by the formula (16) was obtained in the same manner as in Example 1-4, using the compound represented by the formula (15) (1 mol) and acrylic acid (1.2 mol).
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４３（ｄ，１Ｈ），６．１２（ｑ，１Ｈ），５．８５（ｄ，１Ｈ），４．２０（ｓ，２Ｈ），３．５７（ｄ，２Ｈ），３．４４（ｍ，４Ｈ），２．８９（ｍ，１Ｈ），１．５５（ｍ，２Ｈ），１．３８−１．２６（ｍ，１６Ｈ），０．９２−０．８０（ｍ，６Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１６６．３，１３０．８，１２８．２，１２７．９，７４．２，７１．９，６６．１，６４．５，４２．２，３１．７，２９．７，２５．７，２２．９，２２．５，１３．９，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ−１
（実施例２−４）
得られた式（１６）で表される化合物とアジピン酸を用い、実施例１−５と同様にして式（Ｍ−２）で表される重合性化合物を得た。
1 H-NMR (solvent: deuterated chloroform): δ: 6.43 (d, 1H), 6.12 (q, 1H), 5.85 (d, 1H), 4.20 (s, 2H), 3 .57 (d, 2H), 3.44 (m, 4H), 2.89 (m, 1H), 1.55 (m, 2H), 1.38-1.26 (m, 16H),. 92-0.80 (m, 6H)
13 C-NMR (solvent: deuterated chloroform): δ: 166.3, 130.8, 128.2, 127.9, 74.2, 71.9, 66.1, 64.5, 42.2, 31 .7, 29.7, 25.7, 22.9, 22.5, 13.9, 7.4
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm −1
(Example 2-4)
Using the obtained compound represented by the formula (16) and adipic acid, a polymerizable compound represented by the formula (M-2) was obtained in the same manner as in Example 1-5.
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４１（ｄ，２Ｈ），６．１２（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１１（ｓ，４Ｈ），４．０５（ｓ，４Ｈ），３．３５（ｔ，４Ｈ），３．２９（ｓ，４Ｈ），２．３１（ｔ，４Ｈ），１．６２（ｍ，４Ｈ），１．６−１．４７（ｍ，８Ｈ），１．２５（ｍ，２８Ｈ），０．９２−０．８（ｍ，１２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．６，１６５．９，１３０．６，１２８．３，７１．６，７０．３，６４．７，６４．４，４１．５，３４．３，３１．９，２９．６−２９．０，２５．７，２５．０，２３．０，２２．６，１４．０，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
（実施例３） 式（Ｍ−３）で表される化合物の製造
（実施例３−１）
撹拌装置、及び温度計を備えた反応容器にトリメチロールプロパン２２０ｇ （１．６４モル）とトリエチルアミン７２．７ｇ（０．７２モル）、ＴＨＦ １．２Ｌを仕込んだ。反応容器を５℃以下に保ち、ｎ−デカノイルクロリド１２５ｇ（０．６６モル）を滴下ロートでゆっくり滴下した。滴下終了後、室温で3時間攪拌後、４０℃で１時間撹拌して反応を完結させた。反応液に酢酸エチル８００ｍｌ、ｎ−ヘキサン２００ｍｌ、加えて１０％塩酸水溶液１Ｌで洗浄後、水洗、飽和食塩水で洗浄した。有機層を濃縮した後、ｎ−ヘプタン１．２Ｌに溶解させ、メタノール／水の４／１（体積比）混合溶液１．２Ｌで抽出した。メタノール／水層からメタノールを留去して、酢酸エチル１Ｌ、ｎ-ヘキサン ２００ｍｌ、純水１Ｌ加えて水洗する。有機層を無水硫酸ナトリウムで乾燥、溶媒を留去して粗生成物を１４５ｇ得た。ｎ−ヘプタン ３００ｍｌで再結晶を2回行い、式（１７）で表される化合物を１３５ｇ得た。
1 H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.11 (s, 4H), 4 .05 (s, 4H), 3.35 (t, 4H), 3.29 (s, 4H), 2.31 (t, 4H), 1.62 (m, 4H), 1.6-1. 47 (m, 8H), 1.25 (m, 28H), 0.92-0.8 (m, 12H)
13 C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.6, 128.3, 71.6, 70.3, 64.7, 64.4, 41.5, 34 3, 31.9, 29.6-29.0, 25.7, 25.0, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
Example 3 Production of Compound Represented by Formula (M-3) (Example 3-1)
A reaction vessel equipped with a stirrer and a thermometer was charged with 220 g (1.64 mol) of trimethylolpropane, 72.7 g (0.72 mol) of triethylamine, and 1.2 L of THF. The reaction vessel was kept at 5 ° C. or lower, and 125 g (0.66 mol) of n-decanoyl chloride was slowly dropped with a dropping funnel. After completion of dropping, the mixture was stirred at room temperature for 3 hours and then stirred at 40 ° C. for 1 hour to complete the reaction. The reaction solution was washed with 800 ml of ethyl acetate, 200 ml of n-hexane, and 1 L of a 10% aqueous hydrochloric acid solution, followed by washing with water and saturated brine. The organic layer was concentrated, dissolved in 1.2 L of n-heptane, and extracted with 1.2 L of a methanol / water 4/1 (volume ratio) mixed solution. Methanol is distilled off from the methanol / water layer, and 1 L of ethyl acetate, 200 ml of n-hexane and 1 L of pure water are added and washed. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain 145 g of a crude product. Recrystallization was performed twice with 300 ml of n-heptane to obtain 135 g of a compound represented by the formula (17).
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：４．２２（ｓ，２Ｈ），３．５８（ｍ，４Ｈ），２．７４（ｍ，２Ｈ），２．３７（ｔ，２H），１．６２（ｍ，２Ｈ），１．３８−１．２６（ｍ，１４Ｈ），０．９２−０．８０（ｍ，６Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：６５．９，６４．１，４２．９，３４．３，３１．８，２９．４，２９．１，２５．０，２２．６，２２．５，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ−１
（実施例３−２）
次いで、撹拌装置、及び温度計を備えた反応容器に上記で合成した式（１７）で表される化合物１１０ｇ（０．３８モル）、アクリル酸 ４１．２ｇ（０．５７モル）、ジメチルアミノピリジン ７ｇ、塩化メチレン８００ｍｌを仕込んだ。窒素ガスの雰囲気下でジイソプロピルカルボジイミド７２ｇ（０．５７モル）を室温でゆっくり滴下した。滴下終了後、更に２時間撹拌した後、４０℃で２時間反応させた。反応液をろ過した後、ろ液に塩化メチレン５００ｍｌ、１０％塩酸水溶液 １Ｌを加えて洗浄、更に飽和食塩水で洗浄した。有機層を無水硫酸ナトリウムで乾燥溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（１８）で表される化合物７８ｇを得た。
1 H-NMR (solvent: deuterated chloroform): δ: 4.22 (s, 2H), 3.58 (m, 4H), 2.74 (m, 2H), 2.37 (t, 2H), 1 .62 (m, 2H), 1.38-1.26 (m, 14H), 0.92-0.80 (m, 6H)
13 C-NMR (solvent: deuterated chloroform): δ: 65.9, 64.1, 42.9, 34.3, 31.8, 29.4, 29.1, 25.0, 22.6, 22 .5, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm −1
(Example 3-2)
Next, 110 g (0.38 mol) of the compound represented by the formula (17) synthesized above in a reaction vessel equipped with a stirrer and a thermometer, 41.2 g (0.57 mol) of acrylic acid, dimethylaminopyridine 7 g and 800 ml of methylene chloride were charged. Under an atmosphere of nitrogen gas, 72 g (0.57 mol) of diisopropylcarbodiimide was slowly added dropwise at room temperature. After completion of dropping, the mixture was further stirred for 2 hours, and then reacted at 40 ° C. for 2 hours. After the reaction solution was filtered, 500 ml of methylene chloride and 1 L of a 10% hydrochloric acid aqueous solution were added to the filtrate for washing, and further washed with a saturated saline solution. The organic layer was purified by a 5-fold amount (weight ratio) silica gel column after distilling off the dry solvent with anhydrous sodium sulfate to obtain 78 g of a compound represented by the formula (18).
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４４（ｄ，１Ｈ），６．１２（ｑ，１Ｈ），５．８４（ｄ，１Ｈ），４．１６（ｓ，２Ｈ），４．０５（ｓ，２Ｈ），３．４４（ｄ，２Ｈ），２．４９（ｓ，１Ｈ），２．３２（ｔ，２Ｈ），１．６２（ｍ，２Ｈ），１．４３（ｑ，２Ｈ），１．３８−１．２６（ｍ，１２Ｈ），０．９２−０．８０（ｍ，６Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７４．１，１６６．３，１３１．１，１２８．２，１２７．９，６３．９，６３．７，６２．２，４２．６，３４．２，３１．７，３１．５，２９．７−２９．０，２４．９，２２．６，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ−１
（実施例３−３）
更に撹拌装置、及び温度計を備えた反応容器に上記で合成した式（１８）で表される化合物７８ｇ（０．２７７モル）、長鎖二塩基酸ＩＰＳ−２２（岡村製油社製）５１．３ｇ（０．１３８モル）、ピロリジノピリジン２ｇ、塩化メチレン１Ｌを仕込んだ。窒素ガスの雰囲気下で反応容器を０〜５℃に冷却してジイソプロピルカルボジイミド４２ｇ（０．３３モル）をゆっくり滴下した。滴下終了後、室温で４時間反応させた。反応液に塩化メチレン２００ｍｌ、１０％塩酸水溶液 ７００ｍｌを加え洗浄し、更に飽和食塩水で洗浄し有機層の溶媒を留去した後に、ｎ−ヘキサン１Ｌを加え、メタノール／水の４／１（体積比）混合溶液６００ｍｌで２回洗浄した。更に有機層を純水、飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥、溶媒を留去、更に５倍量（重量比）のシリカゲルカラムにより精製を行い目的の化合物（Ｍ−３）を９８．５ｇを得た。
1 H-NMR (solvent: deuterated chloroform): δ: 6.44 (d, 1H), 6.12 (q, 1H), 5.84 (d, 1H), 4.16 (s, 2H), 4 .05 (s, 2H), 3.44 (d, 2H), 2.49 (s, 1H), 2.32 (t, 2H), 1.62 (m, 2H), 1.43 (q, 2H), 1.38-1.26 (m, 12H), 0.92-0.80 (m, 6H)
13 C-NMR (solvent: deuterated chloroform): δ: 174.1, 166.3, 131.1, 128.2, 127.9, 63.9, 63.7, 62.2, 42.6, 34 2, 31.7, 31.5, 29.7-29.0, 24.9, 22.6, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm −1
(Example 3-3)
Furthermore, 78 g (0.277 mol) of the compound represented by the formula (18) synthesized above in a reaction vessel equipped with a stirrer and a thermometer, long-chain dibasic acid IPS-22 (manufactured by Okamura Oil Co., Ltd.) 3 g (0.138 mol), 2 g of pyrrolidinopyridine, and 1 L of methylene chloride were charged. Under a nitrogen gas atmosphere, the reaction vessel was cooled to 0 to 5 ° C., and 42 g (0.33 mol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction was allowed to proceed at room temperature for 4 hours. The reaction solution was washed with 200 ml of methylene chloride and 700 ml of a 10% aqueous hydrochloric acid solution, further washed with saturated saline, and the solvent of the organic layer was distilled off. Then, 1 L of n-hexane was added, and 4/1 (volume by volume of methanol / water). Ratio) Washed twice with 600 ml of the mixed solution. Further, the organic layer was washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and further purified with a 5 times amount (weight ratio) silica gel column to obtain the target compound (M-3 ) Was obtained.
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４２（ｄ，２Ｈ），６．１２（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１２（ｓ，４Ｈ），４．０４（ｓ，８Ｈ），２．３２（ｔ，８Ｈ），１．６２（ｍ，８Ｈ），１．５８（ｍ，４Ｈ），１．３８−１．２５（ｍ，４８Ｈ），０．９１−８０（ｍ，１８Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．５，１６５．７，１３１．１，１２７．９，６４．０，６３．７，４０．６，３４．２，３１．８，２９．７−２９．０，２６．８，２４．９，２３．０，２２．６，１４．０，１０．７，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
（実施例４） 式（Ｍ−４）で表される化合物の製造
（実施例４−１）
トリメチロールプロパン（２．５モル）及びウンデカノイルクロリド（１モル）を用い実施例３−１と同様にして式（１９）で表される化合物を得た。
1 H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H), 4 .04 (s, 8H), 2.32 (t, 8H), 1.62 (m, 8H), 1.58 (m, 4H), 1.38-1.25 (m, 48H),. 91-80 (m, 18H)
13 C-NMR (solvent: deuterated chloroform): δ: 173.5, 165.7, 131.1, 127.9, 64.0, 63.7, 40.6, 34.2, 31.8, 29 .7-29.0, 26.8, 24.9, 23.0, 22.6, 14.0, 10.7, 7.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
(Example 4) Production of compound represented by formula (M-4) (Example 4-1)
A compound represented by the formula (19) was obtained in the same manner as in Example 3-1, using trimethylolpropane (2.5 mol) and undecanoyl chloride (1 mol).
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：４．２２（ｓ，２Ｈ），３．５８（ｍ，４Ｈ），２．７４（ｍ，２Ｈ），２．３７（ｔ，２H），１．６２（ｍ，２Ｈ），１．３８−１．２６（ｍ，１６Ｈ），０．９２−０．８０（ｍ，６Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：６５．９，６４．１，４２．９，３４．３，３１．８，２９．４，２９．１，２５．０，２２．６，２２．５，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ−１
（実施例４−２）
化合物（１９）（１モル）及びアクリル酸（１．２モル）を用い実施例３−２と同様にして式（２０）で表される化合物を得た。
1 H-NMR (solvent: deuterated chloroform): δ: 4.22 (s, 2H), 3.58 (m, 4H), 2.74 (m, 2H), 2.37 (t, 2H), 1 .62 (m, 2H), 1.38-1.26 (m, 16H), 0.92-0.80 (m, 6H)
13 C-NMR (solvent: deuterated chloroform): δ: 65.9, 64.1, 42.9, 34.3, 31.8, 29.4, 29.1, 25.0, 22.6, 22 .5, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm −1
(Example 4-2)
A compound represented by the formula (20) was obtained in the same manner as in Example 3-2 using the compound (19) (1 mol) and acrylic acid (1.2 mol).
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４４（ｄ，１Ｈ），６．１２（ｑ，１Ｈ），５．８４（ｄ，１Ｈ），４．１６（ｓ，２Ｈ），４．０５（ｓ，２Ｈ），３．４４（ｄ，２Ｈ），２．４９（ｓ，１Ｈ），２．３２（ｔ，２Ｈ），１．６２（ｍ，２Ｈ），１．４３（ｑ，２Ｈ），１．３８−１．２６（ｍ，１４Ｈ），０．９２−０．８０（ｍ，６Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７４．１，１６６．３，１３１．１，１２８．２，１２７．９，６３．９，６３．７，６２．２，４２．６，３４．２，３１．７，３１．５，２９．７−２９．０，２４．９，２２．６，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ−１
（実施例４−２）
化合物（２０）及びスベリン酸を用い実施例３−３と同様にして式（Ｍ−４）で表される化合物を得た。
1 H-NMR (solvent: deuterated chloroform): δ: 6.44 (d, 1H), 6.12 (q, 1H), 5.84 (d, 1H), 4.16 (s, 2H), 4 .05 (s, 2H), 3.44 (d, 2H), 2.49 (s, 1H), 2.32 (t, 2H), 1.62 (m, 2H), 1.43 (q, 2H), 1.38-1.26 (m, 14H), 0.92-0.80 (m, 6H)
13 C-NMR (solvent: deuterated chloroform): δ: 174.1, 166.3, 131.1, 128.2, 127.9, 63.9, 63.7, 62.2, 42.6, 34 2, 31.7, 31.5, 29.7-29.0, 24.9, 22.6, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm −1
(Example 4-2)
A compound represented by the formula (M-4) was obtained in the same manner as in Example 3-3 using the compound (20) and suberic acid.
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４１（ｄ，２Ｈ），６．１２（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１２（ｓ，４Ｈ），４．０４（ｓ，８Ｈ），２．３２（ｔ，８Ｈ），１．６２（ｍ，８Ｈ），１．５８（ｍ，４Ｈ），１．２５（ｍ，３２Ｈ），０．９２−０．８（ｍ，１２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．６，１６５．９，１３０．６，１２８．３，７１．６，７０．３，６４．７，６４．４，４１．５，３４．３，３１．９，２９．６−２９．０，２５．７，２５．０，２３．０，２２．６，１４．０，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
（比較例）
本願発明に係る化合物に類似する化合物に関して、従来の方法で製造を行った。
撹拌装置、冷却管及び温度計を備えた四つ口フラスコに、ラウリン酸グリシジルエステル２５７ｇ（１．０モル）、アクリル酸１０８ｇ（１．５モル）、ｐ−メトキシフェノール１５０mg及び触媒としてＮ，Ｎ−ジメチルベンジルアミン１．３１ｇを入れ、８０℃で撹拌した。次に、反応液を１１０℃にゆっくり昇温し、同温度に保ちながら、１０時間撹拌して反応を完結させた。次に、５％水酸化ナトリウム溶液３００mlで洗浄し、更に、純水及び飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた後、有機溶媒を留去して、酸価０．８の淡褐色透明液状生成物を得た。
次に、撹拌装置、窒素導入管、冷却管及び温度計を備えた四つ口フラスコに、上記液状生成物３３．０ｇ、ｐ−メトキシフェノール２０mg、４−ジメチルアミノピリジン３．１ｇ、セバシン酸１０．１ｇ（０．０５モル）及びテトラヒドロフラン５００mlを加え、窒素気流下で、水氷バスを用いて５℃に保った。次に、ジシクロヘキシルカルボジイミド２０．６ｇ（０．１モル）のテトラヒドロフラン１００ml溶液を１時間かけてゆっくり滴下した。滴下終了後、水氷バスを外し、室温で２４時間撹拌して反応を完結させた。反応終了後、析出したジシクロヘキシル尿素を濾別し、濃縮した。濃縮液をトルエン２００mlに溶解させ、純水及び飽和食塩水で洗浄した後、有機層を無水硫酸ナトリウムで乾燥させた。有機層の溶媒を減圧留去し、濃縮液をシリカゲルクロマトグラフィー（濃縮液に対して４０倍量のシリカゲルを使用）を用いて精製して、次式
1 H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H), 4 .04 (s, 8H), 2.32 (t, 8H), 1.62 (m, 8H), 1.58 (m, 4H), 1.25 (m, 32H), 0.92-0. 8 (m, 12H)
13 C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.6, 128.3, 71.6, 70.3, 64.7, 64.4, 41.5, 34 3, 31.9, 29.6-29.0, 25.7, 25.0, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
(Comparative example)
A compound similar to the compound according to the present invention was produced by a conventional method.
In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 257 g (1.0 mol) of glycidyl laurate, 108 g (1.5 mol) of acrylic acid, 150 mg of p-methoxyphenol and N, N as a catalyst -1.31 g of dimethylbenzylamine was added and stirred at 80 ° C. Next, the reaction solution was slowly heated to 110 ° C. and stirred for 10 hours to complete the reaction while maintaining the same temperature. Next, it was washed with 300 ml of 5% sodium hydroxide solution, and further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. 8 light brown transparent liquid product was obtained.
Next, in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a condenser tube and a thermometer, 33.0 g of the above liquid product, 20 mg of p-methoxyphenol, 3.1 g of 4-dimethylaminopyridine, 10 sebacic acid 10 0.1 g (0.05 mol) and 500 ml of tetrahydrofuran were added, and the mixture was kept at 5 ° C. using a water ice bath under a nitrogen stream. Next, a solution of 20.6 g (0.1 mol) of dicyclohexylcarbodiimide in 100 ml of tetrahydrofuran was slowly added dropwise over 1 hour. After completion of the dropwise addition, the water ice bath was removed and the reaction was completed by stirring at room temperature for 24 hours. After completion of the reaction, the precipitated dicyclohexylurea was filtered off and concentrated. The concentrated solution was dissolved in 200 ml of toluene, washed with pure water and saturated brine, and then the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified using silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution).
比較例の方法では、最終工程におけるカラム精製において、４０倍量ものシリカゲルを使用しなければならないのに対して、本願発明の方法では５倍量と大幅に少ない量で精製が可能であった。更に、生成物の純度も本願発明の方法で製造された物が優れていた。
In the method of the comparative example, 40 times the amount of silica gel must be used in the column purification in the final step, whereas in the method of the present invention, purification was possible in a significantly small amount of 5 times. Further, the product produced by the method of the present invention was excellent in the purity of the product.
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