JP2009046415A - エステルの製造法 - Google Patents
エステルの製造法 Download PDFInfo
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- JP2009046415A JP2009046415A JP2007213235A JP2007213235A JP2009046415A JP 2009046415 A JP2009046415 A JP 2009046415A JP 2007213235 A JP2007213235 A JP 2007213235A JP 2007213235 A JP2007213235 A JP 2007213235A JP 2009046415 A JP2009046415 A JP 2009046415A
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- dialkylamino
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- pyridine
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- 150000002148 esters Chemical class 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 25
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 5
- -1 pyridine compound Chemical class 0.000 claims description 13
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229940088594 vitamin Drugs 0.000 claims description 3
- 239000011782 vitamin Substances 0.000 claims description 3
- 235000013343 vitamin Nutrition 0.000 claims description 3
- 229930003231 vitamin Natural products 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229940105990 diglycerin Drugs 0.000 claims description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 4
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 125000004122 cyclic group Chemical group 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 150000003722 vitamin derivatives Chemical class 0.000 claims 2
- 235000001014 amino acid Nutrition 0.000 claims 1
- 150000001720 carbohydrates Chemical class 0.000 claims 1
- 238000000053 physical method Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 abstract description 7
- 229960000549 4-dimethylaminophenol Drugs 0.000 abstract description 2
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
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- PGZVFRAEAAXREB-UHFFFAOYSA-N 2,2-dimethylpropanoyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC(=O)C(C)(C)C PGZVFRAEAAXREB-UHFFFAOYSA-N 0.000 description 7
- NZNMSOFKMUBTKW-UHFFFAOYSA-N Cyclohexanecarboxylic acid Natural products OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 4
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- 229910002027 silica gel Inorganic materials 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000011627 DL-alpha-tocopherol Substances 0.000 description 2
- 235000001815 DL-alpha-tocopherol Nutrition 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229960000984 tocofersolan Drugs 0.000 description 2
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- ZYJPUMXJBDHSIF-NSHDSACASA-N (2s)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-3-phenylpropanoic acid Chemical compound CC(C)(C)OC(=O)N[C@H](C(O)=O)CC1=CC=CC=C1 ZYJPUMXJBDHSIF-NSHDSACASA-N 0.000 description 1
- 0 *c(cncc1*)c1N(*)* Chemical compound *c(cncc1*)c1N(*)* 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FREZLSIGWNCSOQ-UHFFFAOYSA-N 3-methylbutanoyl 3-methylbutanoate Chemical compound CC(C)CC(=O)OC(=O)CC(C)C FREZLSIGWNCSOQ-UHFFFAOYSA-N 0.000 description 1
- 208000035657 Abasia Diseases 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-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
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 229940107161 cholesterol Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000008160 pyridoxine Nutrition 0.000 description 1
- 239000011677 pyridoxine Substances 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229930002330 retinoic acid Natural products 0.000 description 1
- 235000020944 retinol Nutrition 0.000 description 1
- 229960003471 retinol Drugs 0.000 description 1
- 239000011607 retinol Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 229960001727 tretinoin Drugs 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Pyrane Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
【解決手段】無溶媒もしくは非極性溶媒中、触媒量の化学式(1)で表される4−(N,N−ジアルキルアミノ)ピリジン系化合物存在下、触媒量の化学式(1)で表される4−(N,N−ジアルキルアミノ)ピリジン系化合物以外の塩基を全く使用することなく酸無水物とアルコールとを反応させ、エステルを製造する。
【選択図】なし
Description
第4版実験化学講座22.有機合成IV p50 実験例1・38
実施例1 l-メントールピバル酸エステルの合成
1H NMR (300 MHz, CDCl3) δ 0.75 (d, J = 7.0 Hz, 3H), 0.80-1.11 (m, 3H), 0.89 (d, J = 6.8 Hz, 3H), 0.90 (d, J = 6.8 Hz, 3H), 1.19 (s, 9H), 1.30−1.44 (m, 1H), 1.44−1.56 (m, 1H), 1.62−1.72 (m, 2H), 1.82−2.00 (m, 2H), 4.62 (dt, J = 4.4, 10.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 16.0, 20.8, 22.0, 23.2, 26.1, 27.1, 31.3, 34.3, 38.7, 40.7, 47.0, 73.7, 178.0.
実施例2 dl-α-トコフェロールリノール酸エステルの合成
dl-α-トコフェロール 2.15 g (5 mmol)、リノール酸 1.71 mL (5.5 mmol)、無水ピバル酸 1.12 mL (5.5 mmol)、DMAP 3.1 mg (0.5 mol%) を 50 ℃、27 時間反応させた。反応終了後、ピバル酸を減圧留去し、ショートシリカゲルカラム(展開溶媒:ヘキサン-酢酸エチル 100:1)で精製し、標題化合物を収率 88% で得た。
1H NMR (300 MHz, CDCl3) δ 0.78-0.94 (m, 15H), 0.98-1.62 (m, 36H), 1.23 (s, 3H), 1.79 (m, 4H), 1.92−2.16 (m, 4H), 1.96 (s, 3H), 2.01 (s, 3H), 2.09 (s, 3H), 2.58 (t, J = 7.2 Hz, 4H), 2.78 (t, J = 5.7 Hz, 2H), 5.28-5.45 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 11.8, 12.1, 12.9, 14.1, 19.5, 19.6, 19.7, 20.5, 21.0, 22.5, 22.6, 22.7, 24.4, 24.8, 25.1, 25.6, 27.1, 27.2, 27.9, 29.1, 29.2, 29.3, 29.3, 31.5, 31.6, 32.6, 32.7, 34.1, 37.2, 37.3, 37.4, 37.5, 39.3, 74.9, 117.2, 122.9, 124.8, 126.6, 127.8, 128.0, 129.9, 130.1, 140.4, 149.2, 172.3.
l-メントール 156 mg (1 mmol)、シクロヘキサンカルボン酸 136 μL (1.1 mmol)、無水ピバル酸 223 μL (1.1 mmol)、DMAP 0.61 mg (0.5 mol%)を 50 ℃、15 時間反応させた。反応終了後、ピバル酸を減圧留去し、ショートシリカゲルカラム(展開溶媒:ヘキサン-酢酸エチル 100:1)で精製し、標題化合物を収率 92% で得た。
1H NMR (300 MHz, CDCl3) δ 0.74 (d, J = 7.0 Hz, 3H), 0.80-2.00 (m, 19H), 0.89 (d, J = 7.0 Hz, 3H), 0.90 (d, J = 6.4 Hz, 3H), 2.26 (tt, J = 3.7, 11.0 Hz, 1H), 4.65 (tt, J = 4.2, 10.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 16.1, 22.0, 23.3, 24.2, 25.4, 25.5, 25.8, 26.1, 29.0, 29.1, 31.3, 34.3, 40.9, 43.5, 47.1, 73.5, 175.7.
n-オクタノール 157 μL (1 mmol)、N-(tert-ブチルオキシカルボニル)-L-フェニルアラニン 292 mg (1.1 mmol)、無水ピバル酸 223 μL (1.1 mmol)、DMAP 0.61 mg (0.5 mol%)を 50 ℃、24 時間反応させた。反応終了後、ピバル酸を減圧留去し、ショートシリカゲルカラム(展開溶媒:ヘキサン-酢酸エチル 20:1)で精製し、標題化合物を収率 92% で得た。光学純度を損なうことなく生成物を与えた。
1H NMR (300 MHz, CDCl3) δ 0.89 (t, J = 6.9 Hz, 3H), 1.18-1.46 (m, 10H), 1.42 (s, 9H), 1.51-1.65 (m, 2H), 3.01-3.16 (m, 2H), 4.08 (t, J = 6.9 Hz, 2H), 4.57 (q, J = 8.4 Hz, 1H), 4.98 (br d, J = 8.7 Hz, 1H), 7.10-7.33 (m, 5H); 13C NMR (75 MHz, CDCl3) δ 14.0, 22.6, 25.8, 27.0, 28.2, 28.4, 29.1, 31.7, 38.4, 54.4, 65.5, 79.8, 126.9, 128.4, 129.3, 136.0, 155.0, 171.2.
l-メントール 781 mg (5 mmol)、シクロヘキサンカルボン酸 682 μL (5.5 mmol)、無水ピバル酸 1.12 mL (5.5 mmol)、ポリスチレン樹脂担持型DMAP (10 mol%-DMAP unit) を室温で 24 時間反応させた。反応終了後、デカンテーションにより上澄み液を取り出し、1H NMRにより収率を算出した。残渣に l-メントール 781 mg (5 mmol)、シクロヘキサンカルボン酸 682 μL (5.5 mmol)、無水ピバル酸 1.12 mL (5.5 mmol)を加え同じ条件下で反応させるという操作を繰り返した。
収率は以下の通りであった。
Claims (5)
- アルコールが、2〜22の炭素原子を含む脂肪あるいは合成アルコール、グリセリン、ジグリセリンポリグリセリン、糖質又はビタミンであることを特徴とする請求項1又は2に記載のエステルの製造法。
- カルボン酸が、2〜22の炭素原子を含む脂肪酸、アミノ酸、ビタミン又はヒドロキシカルボン酸であることを特徴とする請求項2に記載のエステルの製造法。
- 反応温度が−20〜120℃であることを特徴とする請求項1又は2に記載のエステルの製造法。
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CN101857545A (zh) * | 2010-06-02 | 2010-10-13 | 昆明云大医药开发有限公司 | 一种单薄荷酯的合成方法 |
WO2015068770A1 (ja) * | 2013-11-11 | 2015-05-14 | 国立大学法人名古屋大学 | カルボン酸アミドの製法 |
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