CN100577630C - Adamantane derivative and process for producing the same - Google Patents
Adamantane derivative and process for producing the same Download PDFInfo
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- CN100577630C CN100577630C CN200580003712A CN200580003712A CN100577630C CN 100577630 C CN100577630 C CN 100577630C CN 200580003712 A CN200580003712 A CN 200580003712A CN 200580003712 A CN200580003712 A CN 200580003712A CN 100577630 C CN100577630 C CN 100577630C
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- Prior art keywords
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- adamantane
- adamantane derivative
- general formula
- alkyl
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical class C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title abstract description 4
- -1 adamantane compound Chemical class 0.000 claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 239000002904 solvent Substances 0.000 claims description 44
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 18
- 239000006227 byproduct Substances 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 10
- 238000010168 coupling process Methods 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 3
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 11
- 239000011347 resin Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 5
- 229940052761 dopaminergic adamantane derivative Drugs 0.000 abstract description 4
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 abstract description 3
- 238000000206 photolithography Methods 0.000 abstract description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 52
- 239000000047 product Substances 0.000 description 50
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000000203 mixture Substances 0.000 description 32
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 24
- 150000001721 carbon Chemical group 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 19
- 238000004817 gas chromatography Methods 0.000 description 18
- 238000004587 chromatography analysis Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 239000006200 vaporizer Substances 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000000710 polymer precipitation Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000006266 etherification reaction Methods 0.000 description 7
- 230000002779 inactivation Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 230000006103 sulfonylation Effects 0.000 description 7
- 238000005694 sulfonylation reaction Methods 0.000 description 7
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical class O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- ZZXUWRKAAKRMEK-UHFFFAOYSA-N C12CC3CC(CC(C1)C3)C2.CC=CC(=O)O Chemical class C12CC3CC(CC(C1)C3)C2.CC=CC(=O)O ZZXUWRKAAKRMEK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WIJGTIIKQPGTSQ-UHFFFAOYSA-N adamantane;prop-2-enoic acid Chemical class OC(=O)C=C.C1C(C2)CC3CC1CC2C3 WIJGTIIKQPGTSQ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 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 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000005905 mesyloxy group Chemical group 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- FRYHCSODNHYDPU-UHFFFAOYSA-N ethanesulfonyl chloride Chemical compound CCS(Cl)(=O)=O FRYHCSODNHYDPU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Abstract
Disclosed are an adamantane derivative having a structure represented by the general formula , an adamantane derivative (II) having a structure represented by the general formula (II), and a process for producing these adamantane derivatives. An adamantane compound in the form of an alcohol is reacted with a sulfonyl compound to give an adamantane derivative (II), which is then reacted with an alcohol to give an adamantane derivative . The adamantane derivative and the adamantane derivative (II) each having a structure represented by the general formula and the general formula (II) are novel adamantyl (meth) acrylate compounds, and are useful as monomers for functional resins such as photosensitive resins in the field of photolithography.
Description
Technical field
[0001] the present invention relates to new adamantane derivative and preparation method thereof.More particularly, the present invention relates to can be used as functional resin, (methyl) vinylformic acid adamantane esters of replacing of (methyl) the vinylformic acid adamantane esters that replaces of the new alkoxyl group that uses of the monomer of the photosensitive resin in the photolithography field and alkane sulfonyloxy for example, and effectively prepare described various diamantane
Background technology
[0002] four cyclohexane rings condense into a cage shape form in the structure of diamantane, and it is a kind of height symmetry and stable compound.A kind of derivative of known diamantane can be used as the raw material of medicine for example because of its specific function or the raw material of high function Industrial materials uses.Attempted using this derivative to make CD base material, optical fiber, lens etc., because this derivative has for example optical property and thermotolerance (patent documentation 1 and patent documentation 2).
In addition, also attempt to use the raw material of the resin that the diamantane ester uses as photoresist material, to utilize its acid sensitivity, (patent documentations 3) such as anti-dry etching, UV-light transmissibilitys.
Meanwhile, the miniaturization of semiconducter device makes progress in recent years.Interrelate with this progress, in the lithography step of preparation semiconducter device, proposed further miniaturization requirement.Therefore, for using and used short-wavelength light such as KrF, ArF or F
2The photoresist material material that excimer laser laser adapts forms the whole bag of tricks of fine pattern and studies.In addition, the new photoresist material material that can adapt with the short-wavelength light that will use such as above-mentioned excimer laser laser wish to appear.A kind of hydroxyl of having introduced has been well-known (patent documentation 4) with the adhering monomer that improves silicon substrate.Wish to have a kind of photoresist material material to have unknown before this functional functional group.
[0003] patent documentation 1: Japanese Patent Application Publication, No. puts down into 6 (1994)-305044
Patent documentation 2: Japanese Patent Application Publication, No. puts down into 9 (1997)-302077
Patent documentation 3: Japanese Patent Application Publication, No. puts down into 4 (1992)-39665
Patent documentation 4: Japanese Patent Application Publication, No. is clear and 63 (1988)-33350
Summary of the invention
[0004] the present invention forms under these circumstances, an object of the present invention is to provide a kind of functional resin new adamantane derivative that the monomer that keeps flat the photosensitive resin in the print field uses and preparation method thereof of for example taking a picture that can be used as.
[0005] inventor has made extensive studies for realizing above purpose.Found that, having (methyl) vinylformic acid diamantane ester that (methyl) vinylformic acid diamantane ester that the alkoxyl group of special construction replaces and mesyloxy replace is new compound, be suitable for above-mentioned purpose, and these compounds can react as raw material by the pure form with corresponding adamantyl effectively all and prepare.
The present invention finishes on the basis of these discoveries.
[0006] promptly, the invention provides following adamantane derivative and preparation method thereof.
[1] a kind of adamantane derivative is characterized in that containing the structure that general formula (I) is represented:
Wherein R represents hydrogen atom, methyl or CF
3Group, each Y representative has alkyl, halogen atom or the hydroxyl of 1-10 carbon atom, perhaps two Y coupling formation=O, and a plurality of Y can be same to each other or different to each other R
1Representative has the alkyl or cycloalkyl of 1-10 carbon atom, can contain heteroatoms and/or itrile group in the part of its structure, and k represents 0 to 14 integer, and m and n represent 0 to 4 integer independently of one another.
[2], wherein there is substituting group except that Y at bridgehead position according to a kind of adamantane derivative of above-mentioned [1].
[3] according to a kind of adamantane derivative of above-mentioned [1] or [2], R wherein
1Represent a group that has with 0 adjacent tertiary carbon atom.
[0007] [4] a kind of adamantane derivative is characterized in that, it comprises the structure of general formula (II) representative:
Wherein R represents hydrogen atom, methyl or CF
3Group, R
2Representative has alkyl, phenyl, alkyl phenyl or the CF of 1-10 carbon atom
3Group, each Y representative has alkyl, halogen atom or the hydroxyl of 1-10 carbon atom, and perhaps two Y coupling formation=O, and a plurality of Y can be same to each other or different to each other, and k represents 0 to 14 integer, and m and n represent 0 to 4 integer independently of one another.
[0008] [5] are according to a kind of adamantane derivative of above [4], wherein R
2Represent methylidene.
[6] a kind of preparation has the method for adamantane derivative of the structure of general formula (II) representative:
Wherein R represents hydrogen atom, methyl or CF
3Group, R
2Representative has alkyl, phenyl, alkyl phenyl or the CF of 1 to 10 carbon atom
3Group; each Y representative has alkyl, halogen atom or the hydroxyl of 1 to 10 carbon atom; perhaps two Y couplings form=0; and a plurality of Y can be same to each other or different to each other; the integer of k representative from 0 to 14; m and n represent 0 to 4 integer independently of one another, the method is characterized in that, react comprising the adamantane derivative of the pure form of general formula (III) the expression a kind of sulfonyl compound with general formula (N) expression:
Wherein equal with the above-mentioned implication of R, Y, K, m and n is identical,
R wherein
2Representative has alkyl, phenyl, alkyl phenyl or the CF of 1 to 10 carbon atom
3Group, X representation hydroxy or halogen atom.
[0009] [7] according to a kind of method for preparing adamantane derivative of above [6], the specific inductivity of sulfonyl compound under 20 ℃ of the adamantane compound of the pure form of its formula of (III) representative and general formula (IV) representative be 8 or littler organic solvent in react to each other.
[8] according to the method for preparing adamantane derivative of above [6] or [7], the sulfonyl compound of its formula of (IV) representative comprises methylsulfonyl halogenide.
[9] according to each the method for preparing adamantane derivative in above [6] to [8]; wherein; after the sulfonyl compound that the pure form adamantane compound and the general formula (IV) of general formula (III) representative are represented reacts to each other; after reaction is finished with reaction product and liquid separation; the poor solvent that adds by-product polymer in this reaction product in reaction product is removed the precipitation of the by-product polymer that is generated.
[10] according to the method for preparing adamantane derivative of above [9], wherein the poor solvent of by-product polymer comprises methyl alcohol.
[11] method of the adamantane derivative of a kind of preparation general formula (I) representative:
[0010]
Wherein R represents hydrogen atom, methyl or CF
3Group, each Y representative has alkyl, halogen atom or the hydroxyl of 1 to 10 carbon atom, perhaps two Y coupling form=O, and a plurality of Y can be same to each other or different to each other R
1Representative has the alkyl or cycloalkyl of 1 to 10 carbon atom, and in the part of its structure, can contain heteroatoms and/or itrile group, k represents 0 to 14 integer, m and n represent 0 to 4 integer independently of one another, the method is characterized in that a kind of adamantane derivative and alcohol reaction that comprise general formula (II) representative:
R wherein
2Representative has alkyl, phenyl, alkyl phenyl or the CF of 1 to 10 carbon atom
3Group, R, Y, k, m and n all have above-mentioned identical meanings.
[12] according to a kind of method for preparing adamantane derivative of above [11], wherein (methyl) vinylformic acid 3-mesyloxy-1-adamantane esters and this alcohol react.
[13] according to the method for preparing adamantane derivative of above [11] or [12], wherein this alcohol comprises the tertiary alcohol.
Implement optimal mode of the present invention
[0011] hereinafter, the The compounds of this invention of general formula (I) representative is called adamantane derivative (I), and the The compounds of this invention of general formula (II) representative is called adamantane derivative (II).These adamantane derivatives are new compound.
Below these adamantane derivatives and preparation method thereof will be described.
At first, adamantane derivative of the present invention (I) is have (methyl) vinylformic acid adamantane esters that the alkoxyl group of the structure of general formula (I) representative replaces a kind of.
[0012]
[0013] in general formula (I), R represents hydrogen atom, methyl or trifluoromethyl, and each Y representative has alkyl, halogen atom or the hydroxyl of 1 to 10 carbon atom, perhaps two Y coupling formation=O.A plurality of Y can be same to each other or different to each other.R
1Representative has the alkyl of 1 to 10 carbon atom, and can contain heteroatoms and/or itrile group in the part of its structure.The integer of k representative from 0 to 14, m and n represent integer 0 or bigger independently of one another, and perhaps preferably 0 or 1.When m represents 0 and n when representing 0, be shown as oxygen directly and the structure of adamantyl bonding.
At above each Y and R
1In, there is the example of the alkyl of 1 to 10 carbon atom to comprise methyl, ethyl, various propyl group, various butyl, various amyl group, various hexyl, various heptyl, various octyl group, various nonyl and various decyl.These groups are straight or branched all.This alkyl can be by replacements such as halogen atom, hydroxyls.In addition, R
1Also representation ring alkyl.Work as R
1When the alkyl or cycloalkyl of representative contained heteroatoms and/or itrile group in the part of its structure, the irregularity that this derivative appears on the resist pattern side when using as ultraviolet curable resin further reduced.
[0014] R
1Specific examples can comprise following group.With primary carbon atom bonded R
1Example comprise methyl, ethyl, 1-propyl group, 1-butyl, 1-amyl group, 3-methyl isophthalic acid-butyl, 2-methyl-1-butene base, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, cyclohexyl methyl, 1-adamantyl methyl, 3-methylol-1-adamantyl methyl, 2-hydroxyl-1-ethyl, 2,3-dihydroxypropyl, 2,2,2-three (methylol) ethyl and 2-chloro-1-ethyl.
With secondary carbon(atom) bonded R
1Example comprise 2-propyl group, 2-butyl, 2-amyl group, 3-methyl-2-butyl, 3,3-dimethyl-2-butyl, cyclohexyl, 2-adamantyl, 4-oxo-2-adamantyl, 1-methoxyl group-2-propyl group and 1,3-dihydroxyl-2-propyl group.
With tertiary carbon atom bonded R
1Example comprise 2-methyl-2-propyl group (tertiary butyl), 2-methyl-2-butyl (tert-pentyl), 2,3-dimethyl-2-butyl (uncle's hexyl), 1-adamantyl, 3-hydroxyl-1-adamantyl, 4-oxo-1-adamantyl, perfluor-1-adamantyl, perfluor-3-hydroxyl-1-adamantyl, 1-methylcyclohexyl, 1-ethyl cyclopentyl and 2-methyl-2-adamantyl.
[0015] considers R from effectiveness as this derivative of novel substance
1Preferred representative has the group with 0 adjacent tertiary carbon atom.Wherein, R
1The preferred tertiary butyl, tert-pentyl or the uncle's hexyl represented.In addition, preferably there is the substituting group except that Y at bridgehead position.
In each Y, the example of halogen atom comprises fluorine, chlorine, bromine and iodine.
[0016] the particularly preferred examples for compounds of above-mentioned general formula (I) representative comprises: methacrylic acid uncle 3-pentyloxy-1-adamantane esters, vinylformic acid 3-tert.-butoxy-1-adamantane esters, 2-trifluoromethyl acrylate uncle 3-pentyloxy-1-adamantane esters, methacrylic acid uncle 3-hexyloxy-1-adamantane esters, methacrylic acid uncle 3-pentyloxy methyl isophthalic acid-adamantane esters, vinylformic acid 3-tert.-butoxy methyl isophthalic acid-adamantane esters, 2-trifluoromethyl acrylate uncle 3-pentyloxy methyl isophthalic acid-adamantane esters, methacrylic acid 3-tert.-butoxy perfluor-1-adamantane esters and vinylformic acid uncle 3-pentyloxy perfluor-1-adamantane esters.
[0017] adamantane derivative (II) below will be described.Adamantane derivative of the present invention (II) is have (methyl) vinylformic acid adamantane esters that the sulfonyloxy of the structure of general formula (II) representative replaces a kind of.
[0018]
[0019] in general formula (II), R represents hydrogen atom, methyl or CF
3Group, R
2Representative has alkyl, phenyl, alkyl phenyl or the CF of 1 to 10 carbon atom
3Group, each Y representative has alkyl, halogen atom or the hydroxyl of 1 to 10 carbon atom, and perhaps two Y couplings form=0.A plurality of Y can be same to each other or different to each other.K represents 0 to 14 integer, and m and n represent 0 to 4 integer independently of one another.When m represents 0 and n when representing 0, be shown as the direct bonded structure of a kind of oxygen and adamantyl.
At above R
2In, there is the example of the alkyl of 1 to 10 carbon atom to comprise above-mentioned group.The example of alkyl phenyl comprises aminomethyl phenyl, ethylphenyl and propyl group phenyl.
[0020] example of the adamantane derivative (II) of above-mentioned general formula (II) representative preferably includes the wherein compound of the following group of R2 representative:
Methacrylic acid 3-mesyloxy-1-adamantane esters,
Acrylate 3-mesyloxy-1-adamantane esters,
2-trifluoromethyl acrylate 3-mesyloxy-1-adamantane esters,
Methacrylic acid 1-mesyloxy-4-adamantane esters,
Vinylformic acid 1-mesyloxy-4-adamantane esters,
2-trifluoromethyl acrylate 1-mesyloxy-4-adamantane esters,
Methacrylic acid 3-mesyloxy methyl isophthalic acid-adamantyl methyl ester,
Vinylformic acid 3-mesyloxy methyl isophthalic acid-adamantyl methyl ester,
2-trifluoromethyl acrylate 3-mesyloxy-1-adamantyl methyl ester,
Methacrylic acid 3-mesyloxy perfluor-1-adamantane esters and
Vinylformic acid 3-mesyloxy perfluor-1-adamantane esters.
[0021] a kind of preferred method for preparing adamantane derivative (I) and adamantane derivative (II) below will be described.
At first, the adamantane compound of the pure form by general formula (III) representative and the sulfonyl compound reaction of general formula (IV) representative prepare adamantane derivative (II).
(methyl) vinylformic acid adamantane esters that comprises hydroxyl as the example of the adamantane compound of the pure form of the general formula (III) of raw material representative, methacrylic acid 3-hydroxyl-1-adamantane esters for example, vinylformic acid 3-hydroxyl-1-adamantane esters, 2-trifluoromethyl acrylate 3-hydroxyl-1-adamantane esters, methacrylic acid 3-methylol-1-adamantyl methyl esters, vinylformic acid 3-methylol-1-adamantyl methyl esters, 2-trifluoromethyl acrylate 3-methylol-1-adamantyl methyl esters, methacrylic acid 3-hydroxyl perfluor-1-adamantane esters and vinylformic acid 3-hydroxyl perfluor-1-adamantane esters.
[0022] secondly, in the sulfonyl compound of general formula (IV) representative, from the viewpoint of reactive behavior, X preferably represents halogen atom rather than hydroxyl, considers from industrial point of view, especially preferably represents the chlorine atom.The example of this sulfonyl compound comprises methylsulfonyl chloride, ethyl sulfonyl chloride, third SULPHURYL CHLORIDE, Tosyl chloride and trifluoromethanesulfchloride chloride.Wherein, methylsulfonyl chloride preferably.
The feed ratio of the sulfonyl compound of the adamantane compound of the pure form of general formula (III) representative and general formula (IV) representative preferably make the quantity of the sulfonyl compound that adds with respect to the 1mol adamantane compound in 1 to 1.5mol scope.
[0023] in this reaction, uses a kind of alkali as catalyzer usually, and use solvent as required.
The example of alkali comprises: sodium amide, triethylamine, Tributylamine, trioctylamine, pyridine, N, accelerine, 1,5-diazabicylo [4.3.0] nonene-5 (DBN), 1,8-diazabicylo [5.4.0] undecylene (DBU), sodium hydroxide, potassium hydroxide, sodium hydride, salt of wormwood, silver suboxide, sodium methylate and potassium tert.-butoxide.Can only use a kind of in these catalyzer, also in them two or more can be merged and use.
[0024] in this reaction, uses a kind of solvent usually.Preferably use under temperature of reaction for solubleness and be 0.5% quality or higher as (methyl) vinylformic acid adamantane esters of raw-material various hydroxyls, or preferably 5% quality or higher solvent.It is 0.5% quality or higher that the quantity of solvent should make the concentration of (methyl) vinylformic acid adamantane esters of hydroxyl in the reaction blended, or 5% quality or higher preferably.At this moment, it is preferably dissolved to be in the adamantane derivative of suspended state.In addition, the moisture content in the solvent is preferably removed before use.The specific examples of this solvent comprises: alkyl solvent, for example normal hexane and normal heptane; Ether solvent, for example ether and tetrahydrofuran (THF); Halogen radical solvent, for example methylene dichloride and tetracol phenixin; Dimethyl sulfoxide (DMSO) and N, dinethylformamide (sulfoxide).Can only use a kind of in these solvents, also can use two or more the mixture in them.
[0025] wherein, preferably use 20 ℃ specific inductivity be 8 or littler organic solvent as solvent.Use the solvent of this class low-k to make desired adamantane derivative (II), but also suppressed the generation of polymkeric substance, thereby improved processing property with high yield.The specific examples of these solvents comprises: alkyl solvent, for example toluene, normal hexane, normal heptane and hexanaphthene; Ester group solvent, for example ethyl acetate; And the mixed solvent of these solvents and ether solvent such as ether and tetrahydrofuran (THF).Can only use a kind of in these solvents, also can use two or more the mixture in them.
When using above-mentioned solvent with low-k as solvent, after reaction, remove and desalt by washing, can utilize Crystallization Separation to go out adamantane derivative (II) then.
[0026] temperature of reaction that adopts usually is from-200 ℃ to 200 ℃.As long as temperature of reaction is in this scope, speed of response does not just reduce, and the reaction times can be not long yet.In addition, the quantity of the polymkeric substance that generates as by product can not increase.Temperature of reaction is preferably-200 to 100 ℃ scope, perhaps more preferably-50 ℃ to 50 ℃.
Usually the reaction pressure that adopts is pressed absolute manometer at last in 0.01 to 10MPa scope.Reaction pressure in this scope is economical, because the reaction pressure in this scope does not need special pressure-resistant apparatus.Reaction pressure is preferably in the scope from standard atmosphere pressure to 1MPa.
Reaction times is generally 1 minute to 24 hours, and preferred 5 minutes to 6 hours, perhaps more preferably from 30 minutes to 6 hours.
[0027] R in the sulfonyl compound of general formula (II) representative
2During for methyl, can utilize following method with adamantane derivative and separation of by-products: after reaction is finished with reaction product and liquid separation; The poor solvent that in reaction product, adds the by-product polymer in this reaction product; Remove the precipitation of the by-product polymer that is produced.In this situation, can use methyl alcohol, ethanol, ether etc. as poor solvent, wherein methyl alcohol preferably.
Specifically, in reaction mixture, add water so that make methylsulfonyl halogen inactivation after reaction is finished.Steaming subsequently desolventizes, and the wash residual thing is removed catalyzer.Then, add the poor solvent of by-product polymer in the residue, methyl alcohol for example is so that the by-product polymer precipitation.For example utilize filtration method to remove after the precipitation, distillate poor solvent.Subsequently, with for example ether solvent recrystallization of residue of steaming except poor solvent.The result can obtain wherein R with high purity
2The target adamantane derivative (II) of represent methylidene.
Be the purification of target reaction product, can adopt methods such as distillation, crystallization, post separation.Suggestion is selected purification process according to the character of product and the kind of impurity.
[0028] adamantane derivative (I) can obtain as follows: the sulfonyl halogen compound of adamantane compound and general formula (IV) representative of the pure form of general formula (III) representative is reacted, obtain adamantane derivative (II); Make adamantane derivative (II) and a kind of alcohol reaction.Or, can be in advance with this sulfonyl halogen compound etherificate, this resultant can finally change into (methyl) acrylate.
That is, a kind of method for preparing adamantane derivative (I) comprises: the step of the sulfonyloxy halide reaction of the adamantane compound of the pure form of general formula (III) representative and following general formula (IV) representative:
[0029]
R wherein
2Have and above-mentioned identical implication, X represents halogen atom, and the result forms the sulfonyloxy form of following general formula (II) representative:
[0030]
Wherein R, R
2, Y, k, m all have and the above-mentioned identical implication (the first step: the sulfonylation step) with n; With
[0031] step of the alcohol reaction of this sulphonyl oxygen form and logical formula V representative:
R
1-OH (V)
R wherein
1Have and above-mentioned identical implication, the result generates target adamantane derivative (I) (second step: etherification step).Hereinafter these steps will be described successively.
[0032] (1) the first step (sulfonylation step)
The sulphonyl oxyhalogenation compound that uses in the first step is similar to the sulfonyl compound of above-mentioned general formula (IV) representative, and this sulfonyloxy form is similar to the above-mentioned adamantane derivative (II) of general formula (II) representative.Therefore, this sulfonyloxy form (II) can be used and the above method similar methods preparation for preparing adamantane derivative (II).
[0033] (2) second steps (etherification step)
Second step was the step that the sulfonyloxy form (II) and the alcohol reaction of logical formula V representative generate target adamantane derivative (I).(methyl) vinylformic acid adamantane esters that any mesyloxy replaces, for example (methyl) vinylformic acid 3-mesyloxy-1-adamantane esters all is suitable as sulphonyl oxygen form (II) and uses.
Above-described any one all can be used as R in the alcohol of logical formula V representative
1Use, do not associate, preferably have the tertiary alcohol with 0 adjacent tertiary carbon atom, for example the trimethyl carbinol, tertiary amyl alcohol or uncle's hexanol as the suitability of the present invention of novel substance.Feed ratio should make that the quantity of the alcohol of adding is in 1 to 1.5mol scope with respect to the sulphonyl oxygen form (II) that obtains in the 1mol the first step.
[0034] in this reaction, uses a kind of alkali as catalyzer usually, and use solvent as required.
The example of alkali comprises: sodium amide, triethylamine, Tributylamine, trioctylamine, pyridine, N, accelerine, 1,5-diazabicylo [4.3.0] nonene-5 (DBN), 1,8-diazabicylo [5.4.0] undecylene-7 (DBU), sodium hydroxide, potassium hydroxide, sodium hydride, salt of wormwood, silver suboxide, sodium methylate and butanols potassium.Can only use a kind of in these catalyzer, also in them two or more can be merged and use.
[0035] solvent that uses in etherification step is 0.5% quality or higher to the solubleness of sulphonyl oxygen form (II) under temperature of reaction preferably, or is preferably 5% quality or higher.Should to make the concentration of sulphonyl oxygen form (II) in the reaction mixture be 0.5% quality or higher to the quantity of suggestion solvent, perhaps 5% quality or higher preferably.At this moment, it is preferably dissolved to be in the sulphonyl oxygen form (II) of suspended state.In addition, preferably remove moisture in desolvating before the use.The specific examples of this solvent comprises: alkyl solvent, for example normal hexane and normal heptane; Ether solvent, for example ether and tetrahydrofuran (THF); Halogen radical solvent, for example methylene dichloride and tetracol phenixin; Dimethyl sulfoxide (DMSO); And N, dinethylformamide (sulfoxide).Can only use a kind of in these solvents, also can use two or more the mixture in them.
[0036] temperature of reaction that adopts usually is in-200 to 200 ℃ scope.As long as temperature of reaction is in this scope, speed of response does not just reduce, and the reaction times can be not long.In addition, the quantity of the polymkeric substance that generates as by product does not increase.Temperature of reaction is preferably in 100 to 150 ℃ scope.
According to absolute pressure, the reaction pressure that adopts is in 0.01 to 10MPa scope usually.Reaction pressure in this scope is economical, because the reaction pressure in this scope does not need special pressure-resistant apparatus.Reaction pressure is preferably in the scope from standard atmosphere pressure to 10MPa.
Reaction times was generally 1 to 48 hour.
[0037] target compound can carry out purifying and separate as follows: use alkali aqueous solution, for example sodium bicarbonate aqueous solution is hydrolyzed into unreacted sulphonyl oxygen form (II) and the corresponding pure form of general formula (III), adsorbs this alcohol form with silica gel or similar substance.
Resulting compound can utilize for example gas chromatography (GC), liquid phase chromatography (LC), gas chromatography-mass spectrography (GC-MS), nuclear magnetic resonance spectrum (NMR), infrared spectra (IR) or the evaluation of fusing point device.
Embodiment
[0038] below, will utilize embodiment for a more detailed description to the present invention.But the present invention is not subjected to the restriction of these embodiment fully.
The dielectric constant values of solvent is according to the Japanese synthetic organic chemistry editor of association " SolventPocketbook New Edition " (ohmaha, Ltd.) and the numerical value among " Solvent Handbook " (koudan-sha Scientific) of Shoeo Asahara etc., the value of the specific inductivity of mixed solvent (embodiment 10) is the numerical value that calculates on the basis of additivity rule.
[0039] [embodiment 1] (preparation of adamantane derivative (I))
Synthesizing of the methacrylic acid uncle 3-pentyloxy-1-adamantane esters of following structural formula representative:
[0040]
[0041] (1) sulfonylation step
One 2 liters glass reactor has whipping appts, to wherein adding 118.16g (500mmol) methacrylic acid 3-hydroxyl-1-adamantane esters (ADAMANTANE HM, Idemitsu Kosan Co., Ltd. make), 104.5ml (750mmol) anhydrous triethylamine and 1 liter of anhydrous tetrahydrofuran (THF).This mixture is cooled to 0 ℃ and stir in water-bath.In mixture, add 46.4ml (600mmol) methylsulfonyl chloride, stirred 5 minutes, carry out gas chromatographic analysis subsequently.The result confirms to have obtained methacrylic acid 3-mesyloxy-1-adamantane esters, and transformation efficiency is 92.6%, selectivity 99.8%.In this resultant, add 50ml water so that unreacted methylsulfonyl chloride inactivation is removed tetrahydrofuran (THF) with vaporizer.Resultant is transferred in one 2 liters the separating funnel,, washes this mixture 2 times with water, removed triethylamine salt and 1.01g polymkeric substance to wherein adding 600ml ether and 550ml water twice.In resultant, add 12.0g (100mmol) anhydrous magnesium sulfate and dewater, remove by filter sal epsom then.Make the resultant evaporation in the mode of removing ether, carry out vapor-phase chromatography (GC) subsequently and analyze and gpc analysis.The result confirms to have obtained methacrylic acid 3-mesyloxy-1-adamantane esters, output 156.26g, and purity is 91.3% (GC) or 97.8% (GPC).
[0042] (2) etherification step.
One 2 liters glass reactor is equipped with whipping appts.The product that obtains in above (1) is packed in the reactor, add the anhydrous 2-methyl of 750.0ml (6849mmol)-2-butanols, 80.0ml (535mmol) anhydrous 1,8-diazabicylo [5.4.0]-7-undecylene (DBU) and 0.30g (2000ppm, quality) methoxyl group benzoquinones stirs this mixture.Oil bath temperature is set at 120 ℃, refluxed 36 hours.In addition, per 6 hours orders add 0.03g (200rpm, quality) methoxyl group benzoquinones.Gas chromatographic analysis confirms to have obtained target product, transformation efficiency 86.9%.Selectivity 99.8%.For the methacrylic acid 3-mesyloxy-1-diamantane ester that will not get transformed into methacrylic acid 3-hydroxyl-1-adamantane esters transforms, add the saturated sodium bicarbonate aqueous solution of 100ml, stir this mixture.With this mixture 60 ℃ of restir 8 hours.Utilize vaporizer to remove 2-methyl-2-butanols.Resultant transferred in one 2 liters the separating funnel, add 600m ether and 550ml water secondary in resultant, this mixture washes secondary with water, removes DBU salt.Add 12.0g (100mmol) anhydrous magnesium sulfate and dewater in resultant, subsequent filtration is removed sal epsom.Resultant is evaporated in the mode of removing ether, carry out gas chromatographic analysis subsequently.The result confirms to have obtained target product, output 149.1g, purity 80.7%.This target product is dissolved in 1 liter of hexane, solution is filtered and with the 100g silica decoloration that has adsorbed methacrylic acid 3-hydroxyl-1-adamantane esters.Utilize vaporizer to remove normal hexane, obtain the water white liquid of 81.0g.It is 99.8% target product that gas chromatographic analysis has confirmed to obtain purity.List below
1H-NMR,
13C-NMR and GC-MS data.
[0043] nuclear magnetic resonance spectroscopy (NMR): CDCl
3
1H-NMR (500MHz): 0.85 (t, J=7.7Hz, 3H, o); 1.21 (s, 6H, m); 1.43 (q, J=7.4Hz, 2H, n); (1.48 m, 2H, h or i); (1.80 br-s, 4H, f or j); 1.85 (s, 3H, a); (1.97 d, J=11.5Hz, f or j); (2.08 d, J=11.9Hz, f or j); 2.20 (s, 2H, g); (2.25 s, 2H, h or i); 5.43 (s, b
1); 5.96 (s, b
2),
13C-NMR (126MHz): 8.62 (o); 18.27 (a); (29.04 h or m); (31.39 m or h); (35.07 g or i or n); (37.49 g or i or n); (40.06 f or j); (43.90 j or f); (48.96 g or i or n); (73.35 e or k or l); (76.42 e or k or l); (81.54 e or k or l); 124.31 (b); 137.85 (c); 166.28 (d)
[0044]
[0045] gaschromatographic mass spectrometric analysis (GC-MS):
EI?291(M
+-CH
3，0.05％)，219(M
+-C
5H
11O，100％)。133(25.6％)，69(98.6％)，41(26.1％)
[0046] [embodiment 2] (preparation of adamantane derivative (I))
Synthesizing of methacrylic acid 3-(2-the hydroxyl-oxethyl)-1-adamantane esters of following structural formula representative:
[0047]
[0048] (1) sulfonylation step
Add the 100ml ether to the methacrylic acid 3-mesyloxy that obtains according to the mode identical-1-adamantane esters, the temperature of mixture is cooled to 0 ℃, subsequently recrystallization with the sulfonylation step of embodiment 1.The result obtains the 115.13g white solid.Gas chromatographic analysis and gpc analysis confirm to obtain methacrylic acid 3-mesyloxy-1-adamantane esters that purity is 99.1% (GC) or 98.9% (GPC).
[0049] (2) etherification step
One 2 liters glass reactor has whipping appts.The product that obtains in above (1) is packed in the reactor.(19,725mmol) no water glycol and 76.0ml (545mmol) anhydrous triethylamine stirs this mixture to add 1100.0ml to reactor.Oil bath temperature is set at 80 ℃, heated 2 hours.Gas chromatographic analysis confirms to have obtained target product, and transformation efficiency is 99.9%, selectivity 99.8%.Reaction solution is transferred in one 2 liters the separating funnel, adds 600ml ether and 200ml water, the extraction organic layer.Add 700ml 1N dilute hydrochloric acid in resultant, mixture washes with water.In addition, add 700ml water in resultant, mixture washes with water, removes triethylamine salt.Adding 12.0g (100mmol) anhydrous magnesium sulfate in resultant dewaters.Remove sal epsom with filtering subsequently.Resultant is evaporated in the mode of removing ether, carry out gas chromatographic analysis and gpc analysis subsequently.The result confirms to have obtained target product, output 91.96g, and purity is 99.5 (GC) or 99.4% (GPC).
1H-NMR,
13C-NMR, GC-MS and fusing point data are listed as follows.
[0050] nuclear magnetic resonance spectroscopy (NMR), CDCl
3
1H-NMR(500MHz)：1.52(d，J＝12.8Hz，2H)；1.60(d，J＝12.8Hz，2H)；1.70(d，J＝11.3Hz，2H)；1.78(d，J＝11.3Hz，2H)；1.89(s，3H，a)；2.05(d，J＝11.3Hz，2H)；2.13(d，J＝11.2Hz，2H)；2.17(s，2H，g)；2.36(br-s，2H)；2.48(q，J＝4.0Hz，1H)；3.54(t，J＝4.6Hz，2H，l)；3.68(q，J＝5.0Hz，2H，m)；5.49(q，J＝1.5Hz，b
1)；5.96(s，b
2)
13C-NMR (127MHz): 18.18 (a); 30.84 (h); 34.97 (i); (40.04 f or j); (40.40 j or f); 45.11 (g); (61.48 l or m); (62.06 m or l); 74.28 (k); 81.19 (e); 124.54 (b); 137.59 (c); 166.28 (d)
[0051]
[0052] gaschromatographic mass spectrometric analysis (GC-MS):
EI
281(M
++1，0.02％)，280(M
+，0.16％)，263(0.05％)，262(0.26％)，220(11.0％)，219(40.3％)，195(8.7％)，194(37.1％)，134(24.0％)，133(21.7％)，69(100％)
Fusing point: DSC, 50.0 to 54.5 ℃
[0053] [embodiment 3] (preparation of adamantane derivative (I))
Synthesizing of methacrylic acid 3-(2-the methoxyl group)-1-methyl ethoxy-1-adamantane esters of following structural formula representative:
[0054]
[0055] (1) sulfonylation step
According to the mode identical with embodiment 2, obtaining purity is methacrylic acid 3-mesyloxy-1-adamantane esters of 99.1% (GC) or 98.9% (GPC).
(2) etherification step
One 2 liters glass reactor has whipping appts.The product that obtains in above (1) is packed in the reactor.In reactor, add the anhydrous 1-methoxyl group of 1100.0ml (11254mmol)-2-propyl alcohol and 76.0ml (545mmol) anhydrous triethylamine, stir this mixture.Oil bath temperature is set in 80 ℃, heated 2 hours.Gas chromatographic analysis confirms to have obtained target product, and transformation efficiency is 99.8%, selectivity 99.8%.Reaction solution is transferred in one 2 liters the separating funnel, in resultant, adds 600ml ether and 200ml water, organic phase is extracted.Add 700ml 1N dilute hydrochloric acid in resultant, this mixture washes with water.Then, add 700ml water in resultant, this mixture washes with water, thereby removes triethylamine salt.In resultant, add 12.0g (100mmol) anhydrous magnesium sulfate and dewater, filter then and remove sal epsom.
Resultant is evaporated in the mode of removing ether, then carry out stratographic analysis and gpc analysis.The result confirms to have obtained target product, output 106.40g, purity 99.6% (GC) or 99.5% (GPC).
1H-NMR,
13C0NMR, GC-MS and fusing point data are listed as follows respectively.
[0056] nuclear magnetic resonance spectroscopy (NMR): CDCl
3
1H-NMR (500MHz): 1.21 (o); (1.48 m, 2H, h or i); (1.80 br-s, 4H, f or j); 1.85 (s, 3H, a); (1.97 d, f or j); (2.08 d, f or j); 2.20 (s, 2H, g); 3.24 (s, 3H, p); 3.34 (l); 3.50 (m); 5.43 (s, b
1); 5.96 (s, b
2)
13C-NMR (127MHz): 17.7 (o); 18.3 (a); 29.0 (h); (37.5 g or i); (40.1 f or j); (43.9 j or f); (49.0 g or i); 54.2 (p); 67.9 (l); (75.4 e or k); (76.42 e or k); 80.6 (m); 124.3 (b); 137.9 (c); 166.3 (d)
[0057]
[0058] gaschromatographic mass spectrometric analysis (GC-MS):
EI
263(M
+-CH
2OCH
3，11.1％)，220(16.7％)，219(100％)，133(25.3％)，73(12.2％)，69(99.4％)，45(10.4％)，41(19.9％)
[0059] [embodiment 4] (preparation of adamantane derivative (1))
Synthesizing of methacrylic acid 3-(2-cyano group the oxyethyl group)-1-adamantane esters of following structural formula representative:
[0060]
[0061] (1) sulfonylation step
According to the mode identical, obtain methacrylic acid 3-mesyloxy-1-adamantane esters with the purity of 99.1% (GC) or 98.9% (GPC) with embodiment 2.
(2) etherification step
One 2 liters glass reactor has whipping appts.The product that obtains in above (1) is packed in the reactor.Add anhydrous 3-hydroxypropionitrile of 1100.0ml (16110mmol) and 76.0ml (545mmol) anhydrous triethylamine to reactor, stir this mixture.Oil bath temperature is set at 80 ℃, heated 2 hours.Gas chromatographic analysis confirms to have obtained target product, and transformation efficiency is 99.8%, and selectivity is 99.8%.Reaction solution is transferred in 2 liters of separating funnels, in resultant, adds 600ml ether and 200ml water, organic layer is extracted.Add 700ml 1N dilute hydrochloric acid in resultant, this mixture washes with water.Then, add 700ml water in this resultant, this mixture washes with water, thereby removes triethylamine salt.In resultant, add 12.0g (100mmol) anhydrous magnesium sulfate and dewater, remove by filter sal epsom then.
Resultant is evaporated in the mode of removing ether, carry out gas chromatographic analysis and gpc analysis subsequently, the result confirms to have obtained target product, output 95.9g, purity 98.5% (GC) or 99.0% (GPC).
1H-NMR,
13C-NMR, the data of GC-MS and fusing point are listed as follows.
[0062] nuclear magnetic resonance spectroscopy (NMR): CDCl
3
1H-NMR (500MHz): 1.48 (m, 2H, h or i); (1.80 br-s, 4H, f or j); 1.85 (s, 3H, a); (1.97 d, f or j); (2.08 d, f or j); 2.20 (s, 2H, g); 2.58 (m); 3.74 (l); 5.43 (s, b
1); 5.96 (s, b
2)
13C-NMR (127MHz): 19.6 (m); 18.3 (a); 29.0 (h); (37.5 g or i); (40.1 f or j); (43.9 j or f); (49.0 g or i); 61.0 (l); (75.4 e or k); (76.42 e or k); 117.7 (n); 124.3 (b); 137.9 (c); 166.3 (d)
[0063]
[0064] gaschromatographic mass spectrometric analysis (GC-MS):
EI
290(M
++1，0.18％)，289(M
+，1.4％)，204(43.1％)，203(100％)，148(76.9％)，135(39.3％)，92(78.3％)，69(88.6％)，41(69.9％)
[0065] [embodiment 5] (poor solvent is used in the preparation of adamantane derivative (II) during separation)
Synthesizing of the methacrylic acid 3-mesyloxy-1-adamantane esters of following structural formula representative:
[0066]
[0067] one 2 liters glass reactor is equipped with whipping appts and dropping funnel.In reactor, add 118.16g (500mmol) methacrylic acid 3-hydroxyl-1-adamantane esters (ADAMANTATE HM, Idemitsu, Kosan Co., Ltd. make), 104.5ml (750mmol) anhydrous triethylamine and 1 liter of anhydrous tetrahydro furan are cooled to 0 ℃ and stir with mixture in water-bath.Dripped 46.4ml (600mmol) methylsulfonyl chloride in 1 hour in mixture, restir 1 hour carries out gas chromatographic analysis subsequently.The result confirms methacrylic acid 3-hydroxyl-1-adamantane esters, and oneself transforms fully, and the selectivity with 99.5% obtains target product.In biology, add 50ml water so that unreacted methylsulfonyl chloride inactivation utilizes vaporizer to remove tetrahydrofuran (THF).Resultant is transferred in 2 liters of separating funnels, in resultant, adds 600ml ether and 550ml water secondary, wash this mixture secondary with water and remove triethylamine salt.Utilize vaporizer from reactant, to remove after the ether, in resistates, add 300ml methyl alcohol and make polymer precipitation, remove by filter the 31.44g polymkeric substance.After removing methyl alcohol in the filtrate with vaporizer, in resultant, add the 200ml ether and 12.0g (100mmol) anhydrous magnesium sulfate dewaters.Remove by filter sal epsom then.Utilize vaporizer to remove ether in the resultant, carry out gas chromatographic analysis and gpc analysis subsequently.The result confirms to have obtained target product, output 115.37g, purity 98.2% (GC) or 98.7% (GPC).Add the 50ml ether, the temperature of mixture is cooled to-20 ℃, subsequently recrystallization.The result obtains the 102.21g white solid.Gas chromatographic analysis confirms to obtain the target product of purity 98.9%.
The analytical results of compound is as follows.
[0068] nuclear magnetic resonance spectroscopy (NMR): CDCl
3
1H-NMR (500MHz): 1.55 (g); 1.85 (c); 2.04 to 2.06 (f or i); 2.13 to 2.16 (f or i); 2.18 (h); (2.39 f or i); (2.58 f or i); 2.97 (k); 5.47 to 5.48 (a2); 5.98 (a1)
13C-NMR (127MHz): 18.3 (c); 31.5 (k); (34.3 f or h or i); (39.5 f or h or i); 40.9 (g); (41.7 f or h or i); (46.6 f or h or i); 80.6 (j); 90.3 (e); 125.0 (a); 137.4 (b); 166.2 (d)
Gaschromatographic mass spectrometric analysis (GC-MS): EI
315(M
++1，2.％)，314(M
+，11.4％)，149(78.8％)，133(82.6％)，69(100％)
[0069] [embodiment 6] (preparation of adamantane derivative (II), organic solvent of use low-k during reaction)
The glass reactor of a 200ml has whipping appts, dropping funnel and thermometer.In this reactor, add 10.0g (42mmol) ADAMANTATE HM (Idemitsu KosanCo., Ltd. make, methacrylic acid 3-hydroxyl-1-adamantane esters), 8.8ml (63mmol) triethylamine and 84.0ml toluene, with the reactor submergence in 25 ℃ water-bath and stir.In 35 minutes, in mixture, drip 4.0ml (50mmol) methylsulfonyl chloride, restir 25 minutes.In resultant, add 10ml water and make unreacted methylsulfonyl chloride inactivation.Take out a part of reaction solution and carry out GPC mensuration, so that determine the output ratio of target product and polymkeric substance.Remaining reaction solution is transferred in the 200ml separating funnel, and resultant is washed with 40ml, and organic layer is washed with hydrochloric acid and the 50ml of 50ml1mmol/ml successively then.In the liquid separation operating process, there is not polymer precipitation.In resultant, add 6.0g (50mmol) anhydrous magnesium sulfate and dewater, remove by filter sal epsom then.Filtrate distilled in vaporizer remove toluene, then the thickness product that forms is cooled to 0 ℃, subsequently recrystallization.After with the washing of a small amount of normal hexane, this crystal of filtering separation, drying under reduced pressure until the crystal constant weight, thereby obtains adamantane derivative (methacrylic acid 3-mesyloxy-1-adamantane esters) as target product.The result that table 1 is listed comprises: with respect to adamantane compound as raw material, and the productive rate of target product (mol%); The purity (quality %) of the target product that records with vapor-phase chromatography; With measure the output of the polymkeric substance obtain according to GPC than (quality %).
[0070] not [embodiment 6-1] (organic solvent of low-k is not used in the preparation of adamantane derivative (II) during reaction)
The glass reactor of a 200ml is equipped with whipping appts, dropping funnel and thermometer.In reactor, add 10.0g (42mmol) ADAMANTATE HM (Idemitsu Kosan Co., Ltd. makes, methacrylic acid 3-hydroxyl-1-adamantane esters), 8.8ml (63mmol) triethylamine and 84ml tetrahydrofuran (THF).The reactor submergence is stirred in 25 ℃ water-bath.Introversive this mixture dripped 4.0ml (50mmol) methylsulfonyl chloride, restir 25 minutes in 35 minutes.In resultant, add 10ml water so that unreacted methylsulfonyl chloride inactivation.Get a part of reaction solution and carry out GPC mensuration to determine the output ratio between target product and the polymkeric substance.Remaining reaction solution is transferred in the 300ml separating funnel, adds 100ml ether and 40ml water, washes this mixture with water.This moment polymer precipitation and sticking on the separating funnel.In addition, the piston of separating funnel is aggregated thing and stops up when separating organic layer and water layer, therefore separates consuming time and trouble.Use this organic layer of salt pickling of 50ml 1mmol/ml then, then wash with 50ml.Adding 6.0g (50mmol) anhydrous magnesium sulfate in resultant dewaters.Subsequent filtration is removed sal epsom, and filtrate is evaporated in the mode that steaming desolventizes in vaporizer.Then the thickness product that generates is cooled to 0 ℃, crystallization immediately.After with a small amount of normal hexane washing, the filtering separation crystal, drying under reduced pressure, constant until crystal weight, so obtain target product.The result that table 1 is listed comprises: the productive rate of target product; Purity with the target product of gas chromatography determination; And the output ratio of the polymkeric substance that obtains according to GPC.
[0071] [embodiment 7] (preparation of adamantane derivative (H), organic solvent of use low-k during reaction)
The glass reactor of a 200ml is equipped with whipping appts, dropping funnel and thermometer.In this reactor, add 10.0g (42mmol) ADAMANTATE HM (Idemitsu KosanCo., Ltd. make, methacrylic acid 3-hydroxyl-1-adamantane esters), 8.8ml (63mmol) triethylamine and 42ml toluene are cooled to 5 ℃ and stirring with this mixture in ice bath.In 3 minutes, in mixture, drip 4.0ml (50mmol) methylsulfonyl chloride, restir 5 minutes.In resultant, add 10ml water and make unreacted methylsulfonyl chloride inactivation.Get a part of reaction solution and carry out GPC mensuration to determine the output ratio of target product and polymkeric substance.Remaining reaction liquid then is transferred in the 200ml separating funnel, to wherein adding this resultant of 40ml water washing, uses hydrochloric acid and the 50ml washing organic layer of 50ml 1mmol/ml then successively.In the liquid separation operating process, there is not polymer precipitation.In resultant, add 6.0g (50mmol) anhydrous magnesium sulfate and dewater, remove by filter sal epsom then.Filtrate is distilled in vaporizer and is removed toluene.Temperature with the thickness product that generates is cooled to 0 ℃ then, carries out crystallization subsequently.After a small amount of normal hexane washing, the filtering separation crystal, drying under reduced pressure is constant until crystal weight, thereby obtains target product.Table 1 is listed following result: with respect to adamantane derivative as raw material, and the productive rate of target product (mol%); Purity (quality %) with the target product of gas chromatography determination; And measure the output of the polymkeric substance obtain than (quality %) according to GPC.
[0072] not [embodiment 7-1] (solvent of low-price electricity constant is not used in the preparation of adamantane derivative (II) during reaction)
The glass reactor of a 200ml is equipped with whipping appts, dropping funnel and thermometer.In reactor, add 10.0g (42mmol) ADAMANTATE HM (Idemitsu KosanCo., Ltd. make, methacrylic acid 3-hydroxyl-1-adamantane esters), 8.8ml (63mmol) triethylamine and 42ml tetrahydrofuran (THF) are cooled to 5 ℃ and stirring with mixture in ice bath.Added 4.0ml (50mmol) methylsulfonyl chloride, restir 5 minutes in 3 minutes in introversive this mixture.In resultant, add 10ml water so that unreacted methylsulfonyl chloride inactivation.Get a part of reaction liquid and carry out GPC mensuration, so that determine the output ratio of target product and polymkeric substance.Remaining reaction solution is transferred in the separating funnel of a 300ml, adds 100ml ether and 40ml water, washes this mixture with water.This moment polymer precipitation and sticking on the separating funnel.Then, wash this organic layer with 1mmol/ml hydrochloric acid and the 50ml of 50ml successively.Adding 6.0g (50mmol) anhydrous magnesium sulfate in resultant dewaters.Subsequent filtration is removed sal epsom.Filtrate is distilled in vaporizer except that desolvating.Then the thickness product that forms is cooled to 0 ℃, then carries out crystallization.After with a small amount of normal hexane washing, the filtering separation crystal, its drying under reduced pressure is constant until crystal weight, thus obtain target product.Table 1 has been listed following result; The productive rate of target product; Purity with the target product of gas chromatography determination; And the output ratio of measuring the polymkeric substance that obtains according to GPC.
[0073] not [embodiment 7-2] (organic solvent of low-k is not used in the preparation of adamantane derivative (II) during reaction)
Obtain target product according to the mode identical, just the toluene among the embodiment 7 is changed into methylene dichloride with embodiment 7.During liquid separation, be settled out polymkeric substance.Table 1 has been listed following result: the productive rate of target product; Purity with the target product of gas chromatography determination; And the output ratio of measuring the polymkeric substance that obtains according to GPC.
[0074] [embodiment 8] (preparation of adamantane derivative (II), organic solvent of use low-k during reaction)
Obtain target product according to the mode identical with embodiment 7, just the quantity 42ml with the toluene among the embodiment 7 changes into 84ml.In liquid separation process, there is not polymer precipitation.Table 1 has been listed following result: the productive rate of target product; Purity with the target product of gas chromatography determination; And measure the polymkeric substance output ratio obtain according to GPC.
[0075] [embodiment 9] (preparation of adamantane derivative (II), organic solvent of use low-k during reaction)
Obtain target product according to the mode identical, just toluene is changed into glycol diacetate with quantity with embodiment 7.During liquid separation, there is not polymer precipitation.Table 1 has been listed following result: the productive rate of target product; Purity with the target product of gas chromatography determination; And the output ratio of measuring the polymkeric substance that obtains according to GPC.
[0076] [embodiment 10] (preparation of adamantane derivative, organic solvent of use low-k during reaction)
Obtain target product according to the mode identical with embodiment 7, just the consumption with toluene changes the mixed solvent of being made up of hexanaphthene and the 22ml tetrahydrofuran (THF) of 22ml.In liquid separation process, there is not polymer precipitation.Table 1 has been listed following result: the productive rate of target product; Purity with the target product of gas chromatography determination; And the output ratio of measuring the polymkeric substance that obtains according to GPC.
Industrial usability
[0078] adamantane derivative of the present invention (I) and the general formula (II) of general formula (I) expression The adamantane derivative of the present invention (II) of expression all is new (methyl) acrylic acid adamantyl Ester compounds can be used as monomer and is used for functional resin, for example in the lithoprinting field Ultraviolet curable resin.
Expect adamantane derivative of the present invention (I) can to the exposure after surface roughness (LER: Appear at the scrambling on the resist side surface; LWR: by directly over bending when seeing circuit Property plays and reduces effect, and for for example PEB (heat of doing for the acid diffusion that exposure is produced Processing) temperature dependency has improved action.
In addition, adamantane derivative of the present invention (II) and as one of resist mixed liquor component Photogenerated acid propellant (PAG) between compatibility be considered to improvement. The result is passable Form uniform film, and expect the surface roughness (LER: anti-of this film after can reducing to expose The scrambling that occurs on the erosion agent side; LWR: by directly over bendability when seeing circuit).
Moreover adamantane derivative (I) and adamantane derivative (II) all can utilize the present invention The method of these adamantane derivatives of preparation make with high yield. Particularly, at the preparation Buddha's warrior attendant The dielectric constant that is included in 20 ℃ in the method for alkane derivatives (II) is 8 or lower organic molten React in the agent, this can suppress the generation of polymer, thereby has improved operating characteristics, and can With effective and industrial this derivative that advantageously makes.
Claims (15)
1. adamantane derivative is characterized in that containing the structure of general formula (I) representative:
Wherein R represents hydrogen atom, methyl or CF
3Group, each Y representative has the alkyl or the halogen atom of 1 to 10 carbon atom, perhaps two Y coupling formation=O, and a plurality of Y can be same to each other or different to each other R
1Representative has the alkyl or cycloalkyl of 1 to 10 carbon atom, and can contain heteroatoms and/or itrile group in its part-structure, the integer of k representative from 0 to 14, and m and n represent from 0 to 4 integer independently of one another.
2. according to the adamantane derivative of claim 1, wherein there is substituting group except that Y at bridgehead position
And/or
3. according to the adamantane derivative of claim 1 or 2, R wherein
1Represent a group with tertiary carbon atom adjacent with O.
4. adamantane derivative, the structure of (II) representative that it is characterized in that having general formula:
Wherein R represents hydrogen atom, methyl or CF
3Group, R
2Represent alkyl, phenyl, alkyl phenyl or a CF that 1 to 10 carbon atom is arranged
3Group, each Y are represented alkyl, halogen atom or a hydroxyl that 1 to 10 carbon atom is arranged, and perhaps two Y coupling formation=O, and a plurality of Y can be same to each other or different to each other, the integer of k representative from 0 to 14, and m and n represent from 0 to 4 integer independently of one another.
5. according to the adamantane derivative of claim 4, R wherein
2Represent methylidene.
6. method of adamantane derivative for preparing the structure of (II) representative that has general formula:
Wherein R represents hydrogen atom, methyl or CF
3Group, R
2Representative has alkyl, phenyl, alkyl phenyl or the CF of 1 to 10 carbon atom
3Group; each Y representative has alkyl, halogen atom, the hydroxyl of 1 to 10 carbon atom; perhaps two Y coupling formation=O; and a plurality of Y can be same to each other or different to each other; the integer of k representative from 0 to 14; m and n represent from 0 to 4 integer independently of one another, the method is characterized in that, react comprising the adamantane compound of the pure form that makes general formula (III) representative and the sulfonyl compound of general formula (IV) representative:
Wherein R, Y, k, m and n respectively have as above-mentioned identical implication,
R wherein
2Represent alkyl, phenyl, alkyl phenyl or a CF that 1 to 10 carbon atom is arranged
3Group, X representation hydroxy or halogen atom.
7. according to the method for preparing adamantane derivative of claim 6, the sulfonyl compound of the adamantane compound of the pure form of its formula of (III) representative and general formula (IV) representative 20 ℃ dielectric constant values be 8 or lower organic solvent in react to each other.
8. according to the method for preparing adamantane derivative of claim 6 or 7, the sulfonyl compound of its formula of (IV) representative is a methylsulfonyl halogenide.
9. according to the method for preparing adamantane derivative of claim 6 or 7; wherein; the sulfonyl compound of the adamantane compound of the pure form of general formula (III) representative and general formula (IV) representative reacts to each other; after reaction is finished with reaction product and liquid separation; the poor solvent that in reaction product, adds the by-product polymer in the reaction product, the precipitation of removing the by-product polymer of generation.
10. according to the method for preparing adamantane derivative of claim 9, wherein the poor solvent of this by-product polymer is a methyl alcohol.
11. method for preparing the adamantane derivative of general formula (I) representative:
Wherein R represents hydrogen atom, methyl or CF
3Group, each Y representative has alkyl, halogen atom or the hydroxyl of 1 to 10 carbon atom, perhaps two Y coupling formation=O, and also a plurality of Y can be same to each other or different to each other R
1Representative has the alkyl or cycloalkyl of 1 to 10 carbon atom, and can in its part-structure, contain heteroatoms and/or itrile group, the integer of k representative from 0 to 14, m and n represent from 0 to 4 integer independently of one another, the method is characterized in that, react comprising the adamantane derivative that makes general formula (II) representative and a kind of alcohol:
R wherein
2Representative has alkyl, phenyl, alkyl phenyl or the CF of 1 to 10 carbon atom
3Group, R, Y, k, m and n respectively have and above-mentioned identical implication.
12. according to the method for preparing adamantane derivative of claim 11, wherein (methyl) vinylformic acid 3-mesyloxy-1-adamantane esters reacts with alcohol.
13. according to the method for preparing adamantane derivative of claim 11 or 12, wherein this alcohol is the tertiary alcohol.
14. the method for preparing adamantane derivative according to Claim 8; wherein; the sulfonyl compound of the adamantane compound of the pure form of general formula (III) representative and general formula (IV) representative reacts to each other; after reaction is finished with reaction product and liquid separation; the poor solvent that in reaction product, adds the by-product polymer in the reaction product, the precipitation of removing the by-product polymer of generation.
15. according to the method for preparing adamantane derivative of claim 14, wherein the poor solvent of this by-product polymer is a methyl alcohol.
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| JP4594695B2 (en) * | 2004-10-08 | 2010-12-08 | 出光興産株式会社 | Method for producing adamantane derivative |
| JP2006089412A (en) | 2004-09-24 | 2006-04-06 | Idemitsu Kosan Co Ltd | Adamantane derivative, method for producing the same and photosensitive material for photoresist |
| JP4494161B2 (en) * | 2004-10-14 | 2010-06-30 | 東京応化工業株式会社 | POLYMER COMPOUND, POSITIVE RESIST COMPOSITION AND METHOD FOR FORMING RESIST PATTERN |
| JP4979915B2 (en) * | 2005-09-09 | 2012-07-18 | 東京応化工業株式会社 | Polymer compound, negative resist composition, and resist pattern forming method |
| JP2007284368A (en) * | 2006-04-14 | 2007-11-01 | Daicel Chem Ind Ltd | Methacrylic or acrylic monomer and resin for protective layer of resist resin |
| JP2007284381A (en) * | 2006-04-18 | 2007-11-01 | Daicel Chem Ind Ltd | Methacrylic or acrylic monomer for photoresist, polymer compound from the same, and resin composition for photoresist |
| JP6252157B2 (en) * | 2013-12-16 | 2017-12-27 | 住友化学株式会社 | Resist composition and method for producing resist pattern |
| CN113307967A (en) * | 2020-02-27 | 2021-08-27 | 北京大学 | Polyaramide material containing adamantyl groups, and preparation method and application thereof |
| CN111978239A (en) * | 2020-08-26 | 2020-11-24 | 阜阳欣奕华材料科技有限公司 | Compound and photosensitive resin composition |
| CN114479046B (en) * | 2021-12-27 | 2022-11-25 | 北京理工大学 | Adamantane functionalized polyether carbonate material, preparation method and application thereof |
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| US6391520B1 (en) * | 1998-05-25 | 2002-05-21 | Daicel Chemical Industries, Ltd. | Compounds for photoresist and resin composition for photoresist |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4434358B2 (en) * | 1998-05-25 | 2010-03-17 | ダイセル化学工業株式会社 | Photoresist compound and photoresist resin composition |
| JP3390702B2 (en) * | 1999-08-05 | 2003-03-31 | ダイセル化学工業株式会社 | Polymer compound for photoresist and resin composition for photoresist |
| JP4275284B2 (en) * | 2000-02-25 | 2009-06-10 | 株式会社東芝 | Polymer compound for photoresist and resin composition for photoresist |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391520B1 (en) * | 1998-05-25 | 2002-05-21 | Daicel Chemical Industries, Ltd. | Compounds for photoresist and resin composition for photoresist |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1914147A (en) | 2007-02-14 |
| JP4429754B2 (en) | 2010-03-10 |
| JP2005220066A (en) | 2005-08-18 |
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