CN115974684B - A kind of chiral borneol ester and the synthesis method of chiral borneol - Google Patents
A kind of chiral borneol ester and the synthesis method of chiral borneol Download PDFInfo
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- CN115974684B CN115974684B CN202211677307.6A CN202211677307A CN115974684B CN 115974684 B CN115974684 B CN 115974684B CN 202211677307 A CN202211677307 A CN 202211677307A CN 115974684 B CN115974684 B CN 115974684B
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- borneol
- chiral
- acid
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- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 title claims abstract description 219
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 title claims abstract description 215
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 229940116229 borneol Drugs 0.000 title claims abstract description 213
- -1 borneol ester Chemical class 0.000 title claims abstract description 69
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 title abstract description 170
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 111
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- 239000004327 boric acid Substances 0.000 claims abstract description 42
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims description 64
- 230000007935 neutral effect Effects 0.000 claims description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000005194 fractionation Methods 0.000 claims description 23
- 239000007795 chemical reaction product Substances 0.000 claims description 21
- 230000002194 synthesizing effect Effects 0.000 claims description 21
- NDUIFQPPDDOKRN-UHFFFAOYSA-N 4,6,6-trimethylbicyclo[3.1.1]hept-4-ene Chemical group C1CC(C)=C2C(C)(C)C1C2 NDUIFQPPDDOKRN-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 11
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 11
- 239000011975 tartaric acid Substances 0.000 claims description 11
- 235000002906 tartaric acid Nutrition 0.000 claims description 11
- 235000015165 citric acid Nutrition 0.000 claims description 10
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 7
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- 229960002510 mandelic acid Drugs 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 150000001637 borneol derivatives Chemical class 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 5
- 239000002994 raw material Substances 0.000 abstract description 11
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 3
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- 238000010992 reflux Methods 0.000 description 64
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 55
- 238000010438 heat treatment Methods 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 38
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 38
- 229930006978 terpinene Natural products 0.000 description 37
- 150000003507 terpinene derivatives Chemical class 0.000 description 37
- 239000002131 composite material Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 30
- 238000007670 refining Methods 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 238000005886 esterification reaction Methods 0.000 description 20
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- 229930006727 (-)-endo-fenchol Natural products 0.000 description 19
- IAIHUHQCLTYTSF-MRTMQBJTSA-N Fenchyl alcohol Chemical compound C1C[C@]2(C)[C@H](O)C(C)(C)[C@H]1C2 IAIHUHQCLTYTSF-MRTMQBJTSA-N 0.000 description 19
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 19
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 19
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 19
- 229930006739 camphene Natural products 0.000 description 19
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 description 19
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 19
- 230000032050 esterification Effects 0.000 description 19
- IAIHUHQCLTYTSF-UHFFFAOYSA-N fenchyl alcohol Natural products C1CC2(C)C(O)C(C)(C)C1C2 IAIHUHQCLTYTSF-UHFFFAOYSA-N 0.000 description 19
- 229940087305 limonene Drugs 0.000 description 19
- 235000001510 limonene Nutrition 0.000 description 19
- 229940116411 terpineol Drugs 0.000 description 19
- 238000007599 discharging Methods 0.000 description 18
- 238000006386 neutralization reaction Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- 238000011084 recovery Methods 0.000 description 18
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 17
- 238000001914 filtration Methods 0.000 description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 14
- 241000723346 Cinnamomum camphora Species 0.000 description 13
- 229930008380 camphor Natural products 0.000 description 13
- 229960000846 camphor Drugs 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- KGEKLUUHTZCSIP-HOSYDEDBSA-N [(1s,4s,6r)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate Chemical compound C1C[C@]2(C)[C@H](OC(=O)C)C[C@H]1C2(C)C KGEKLUUHTZCSIP-HOSYDEDBSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 229960001367 tartaric acid Drugs 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000000344 soap Substances 0.000 description 9
- DTGKSKDOIYIVQL-NQMVMOMDSA-N (+)-Borneol Natural products C1C[C@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-NQMVMOMDSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- IWYDHOAUDWTVEP-UHFFFAOYSA-M mandelate Chemical compound [O-]C(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-M 0.000 description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 6
- 229940049920 malate Drugs 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- PKKVIPFBICXMFP-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-hydroxypropanoate Chemical compound C1CC2(C)C(OC(=O)C(O)C)CC1C2(C)C PKKVIPFBICXMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- FAFMZORPAAGQFV-UHFFFAOYSA-N Isobornyl propionate Chemical compound C1CC2(C)C(OC(=O)CC)CC1C2(C)C FAFMZORPAAGQFV-UHFFFAOYSA-N 0.000 description 4
- ILUAVCBOWYHFAI-UHFFFAOYSA-N bornyl valerate Chemical compound C1CC2(C)C(OC(=O)CCCC)CC1C2(C)C ILUAVCBOWYHFAI-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 4
- 229940070765 laurate Drugs 0.000 description 4
- 229940099690 malic acid Drugs 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-M nonanoate Chemical compound CCCCCCCCC([O-])=O FBUKVWPVBMHYJY-UHFFFAOYSA-M 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 4
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
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- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
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- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 2
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012069 chiral reagent Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 229960001270 d- tartaric acid Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- YPGCWEMNNLXISK-UHFFFAOYSA-N hydratropic acid Chemical compound OC(=O)C(C)C1=CC=CC=C1 YPGCWEMNNLXISK-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a chiral borneol ester and a synthesis method of chiral borneol, and relates to the technical field of fine chemical production. The invention uses a catalyst composed of alpha-hydroxy carboxylic acid and boric acid to catalyze the reaction of pinene and carboxylic acid, can synthesize chiral borneol ester, and can obtain chiral borneol by saponification of the synthesized chiral borneol ester. The method has low cost of raw materials, easy preparation of the catalyst, and the synthesized chiral borneol ester and borneol products, and can be widely applied to medicines and daily chemical products.
Description
Technical Field
The invention relates to the technical field of fine chemical production, in particular to chiral borneol ester and a synthesis method of chiral borneol.
Background
Borneol with a molecular formula of C 10H18 O, also called borneol or 2-camphol, is white semitransparent crystal and has a similar camphor smell. The dextro borneol is leaf-shaped or hexagonal flaky crystal; melting point 208 ℃, boiling point 212 ℃, relative density 1011 (20/4 ℃), specific rotation +37 (ethanol); dissolved in ethanol, diethyl ether and benzene. The levorotatory borneol is a hexagonal flaky crystal; melting point 208.6deg.C, boiling point 210 ℃ (779 mmHg), relative density 1.1011 (20/4deg.C); dissolved in ethanol, diethyl ether, acetone and benzene. The racemized borneol is a leaf-shaped crystal; melting point 210.5 deg.C, easy sublimation, relative density 1.011 (20/4 deg.C); dissolved in ethanol, diethyl ether and benzene. Camphor is formed upon oxidation. Borneolum Syntheticum can be reduced by camphor in ethanol solution with sodium metal; or is prepared by esterifying pinene with oxalic acid in the presence of a catalyst and hydrolyzing. Borneol is widely used for preparing rosemary and lavender type essence and is used in traditional Chinese medicine and Chinese ink.
The commercial synthetic borneol is prepared by using alpha-pinene and dehydrated oxalic acid in turpentine as raw materials, catalyzing and condensing the raw materials into borneol oxalate, and saponifying the borneol oxalate with caustic soda, and contains byproducts such as isoborneol, camphor and the like as racemate.
The synthesis method of chiral borneol comprises the following steps: tan Ruiquan et al, in the published papers of "trial production of synthetic D-borneol" (Guangzhou chemical, 1987) and "pilot production of new technology of direct catalytic hydration synthetic borneol" (forest chemical and industry, 1988), disclose that D-borneol is obtained by directly reacting alpha-pinene with water by using Nanya turpentine as raw material and GC-82 solid acid as catalyst. However, the catalyst of the process is expensive, the consumption is large, the loss is large, the material handling capacity is large, and the power consumption is large. The technology for preparing borneol by a pinene direct hydration method has no synthetic route capable of replacing the traditional esterification-saponification method using oxalic acid in industry. In addition, most of researches are directed to technical routes for synthesizing chiral borneol by asymmetric hydrogenation of camphor. The most mature research on asymmetric camphora synthesis of borneol is the alkali metal/NH 3 method. Huffman et al reported in paper "Dissolvingmetal reduction of cyclic ketones" (J Org Chem,1979,44 (4): 594-599) that the chemical asymmetric reduction of camphor in liquid ammonia resulted in a yield of 95% and an e.e. value of 85%, but the preparation had to be carried out at ultra-low temperature (-33-78 ℃), and the preparation conditions were severe, which was difficult to produce industrially. Secondly, the alkali metal/absolute ethanol and alkali metal/THF system also achieve a certain achievement when being used for asymmetric reduction of camphor, such as Wang Ninghui, and the like, and the research in the paper "chiral synthesis of dextroborneol by camphor" (the university of Chinese by fuqiao: nature science edition, 2006,27 (1): 89-91) considers that the ratio of the dextroborneol obtained by the absolute ethanol system is 80 percent, and the ratio of the dextroborneol obtained by the THF system is lower than 72 percent, and the dextrobornol modified lithium aluminum hydride is used as a chiral reagent to reduce the camphor into the dextroborneol, so as to obtain the dextroborneol with the conversion rate of 82.4 percent, the yield of 24.55 percent and the relative optical rotation of 69.2 percent. Huang Yingfen, and the like, in the paper 'natural brain powder secondary reduction refining dextroborneol', a detailed study is carried out on camphor reduction by using a metal sodium/absolute ethyl alcohol system, and the study shows that the conversion rate of camphor can reach 98.9 percent, and the borneol yield is 81.7 percent. Jiao Anxia, et al, found in the paper "RaneyNi modified with D-tartaric acid catalyzed asymmetric hydrogenation of camphor to borneol" (the university of fuqiao, shuo paper, 2011) that tartaric acid modified RaneyNi had a great improvement in optical selectivity, however, the catalyst activity was greatly reduced after modification, resulting in lower conversion.
The synthesis method of chiral borneol ester comprises the following steps: zhang Pinghui et al, in the paper, "synthesis of and characterization of the ester of the binary borneol oxalate" (fine chemical. 2014,31 (11)), disclose that the esterification of natural borneol with oxalic acid occurs to produce the ester of the binary borneol oxalate under the catalysis of meta-titanic acid or boric anhydride. Dong Zhe et al, in published paper "Enzymatic lipophilization of d-borneol extracted from Cinnamomumcamphora chvar.Borneol seed"(LWT-Food Science and TechnologyVolume148,2021), disclose the synthesis of borneol oleate from d-borneol and oleic acid using lipase catalysis. Chinese patent application CN03127103.0 discloses a 2-phenyl-propionic acid borneol ester derivative and a synthesis method thereof, and the purpose of selectively inhibiting COX-2 is achieved by further improving the borneol serving as a core structure through the reaction of 2-phenyl-propionic acid and the derivative thereof with borneol under the action of a catalyst. Chinese patent application CN201410482083.2 discloses a method for preparing d-borneol acetate from natural d-borneol. The method takes natural D-borneol and acetic anhydride as raw materials, takes P 2O5 or P 2O5-H3PO4 as a catalyst, the dosage of the catalyst is 5-10% of the mass of the natural borneol, the reaction temperature is 55-75 ℃, the esterification is carried out for 4-10 hours under normal pressure, and the D-borneol acetate is obtained after purification. Chinese patent application CN201711203302.9 discloses that natural borneol is used as raw material, and is condensed with fatty acid under the condition of condensing agent to obtain fatty acid borneol ester. The condensing agent is selected from N, N '-Diisopropylcarbodiimide (DIC), N' -Dicyclohexylcarbodiimide (DCC), 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl) or N, N-bis (2, 6-diisopropylphenyl) carbodiimide (DIPPC).
In summary, the problems existing in the synthesis of chiral borneol esters and chiral borneol at present are mainly as follows: the direct hydration method of pinene and water has lower yield and low selectivity of borneol, and the industry fails to replace the esterification-saponification method synthesis process. The camphor is hydrogenated to synthesize the chiral borneol, natural camphor is used as a raw material, the reaction condition is harsh, and industrialization is difficult. The synthesis of chiral borneol esters requires natural borneol as a raw material, and has high cost. In the prior art, when pinene is used as a starting material to synthesize borneol ester, a chiral borneol ester product is often difficult to obtain.
Disclosure of Invention
The invention aims to provide chiral borneol ester and a synthesis method of chiral borneol, which are used for solving the problems existing in the prior art and realizing simple and green synthesis of the chiral borneol ester and the chiral borneol.
In order to achieve the above object, the present invention provides the following solutions:
The invention provides a method for synthesizing chiral borneol ester, which comprises the following steps:
Mixing pinene, carboxylic acid and a catalyst at normal pressure and 60-120 ℃ for reaction, cooling a reaction product to room temperature after the reaction is finished, washing to be neutral, and separating and purifying to obtain the chiral borneol ester; wherein the reaction time is 2-30 h.
The mass ratio of the pinene to the carboxylic acid to the catalyst is 100 (33-300) to 0.1-50.
The catalyst is a mixture of alpha-hydroxy carboxylic acid and boric acid in a mass ratio of (0-30): 1.
The method also comprises the step of catalyst recovery after the reaction is finished: after the reaction is finished, the product is cooled to room temperature, the catalyst is filtered out, and the dried catalyst is reused.
The reaction product is washed with water to neutrality or neutralized with aqueous sodium carbonate solution and then washed with water.
Further, the carboxylic acid is a C2-C18 fatty acid.
Further, the alpha-hydroxycarboxylic acid is one of lactic acid, mandelic acid, tartaric acid, citric acid or malic acid.
Further, when the carboxylic acid is an alpha-hydroxycarboxylic acid and is the same as the type of the alpha-hydroxycarboxylic acid in the catalyst, the mass ratio of the alpha-hydroxycarboxylic acid to boric acid in the catalyst is 0:1.
Further, the catalyst is added in an amount of 0.5 to 30% by mass of the carboxylic acid.
Further, the separation and purification mode comprises vacuum fractionation.
The invention uses vacuum fractionation to separate and purify the reaction product, and the vacuum fractionation process removes byproducts in the product.
The by-products include camphene, limonene, terpinene, fenchyl alcohol, isoborneol, and terpineol.
Recrystallizing by solvent to obtain refined chiral alpha-hydroxy acid borneol ester product; the solvent is one or more of methanol, ethanol, ethyl acetate, acetone, tetrahydrofuran, dimethyl carbonate and diethyl carbonate.
Further, the activated carbon is used for decoloring treatment after the vacuum fractionation.
The specific steps of the vacuum fractionation are as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1-2h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 10-13:1;
and S4, heating to keep the temperature of a tower kettle at 130-150 ℃, keeping the temperature of a tower top at 95-105 ℃ and the reflux ratio at 15-20:1, collecting fenchyl alcohol, isobornyl and terpineol, and obtaining chiral borneol ester from the tower kettle.
The invention also provides a method for synthesizing the chiral borneol, which is characterized in that the chiral borneol ester prepared by the method is subjected to saponification reaction to obtain the chiral borneol.
In the present invention, the solvent may be used for saponification after dissolution (rapid reaction) or direct saponification distillation (long time).
Further, the saponification reaction comprises the following steps: dissolving the chiral borneol ester in an organic solvent, adding alkali liquor at 50-60 ℃, separating soap, and removing the organic solvent in a reaction system to obtain the chiral borneol.
More specifically: dissolving the chiral borneol ester in ethanol or acetone, controlling the temperature at 50-60 ℃, stirring, dripping alkali solution, and separating soap; washing the separated soap with the solvent and combining the washing solution with the chiral borneol-containing ethanol or acetone solution; distilling to recover solvent to obtain chiral borneol.
The invention discloses the following technical effects:
1. The invention adopts alpha-hydroxy carboxylic acid and boric acid to form a composite catalyst, and catalyzes pinene and carboxylic acid to react to prepare chiral borneol ester.
2. The chiral borneol ester product prepared by the invention has wide application: the short-chain fatty acid borneol ester can be used as perfume, and the medium-chain fatty acid borneol ester can be used as green solvent and plasticizer. For example, the freezing point of long-chain fatty acid borneol ester is lower than-18 ℃ and far lower than that of long-chain fatty acid methyl ester, and the long-chain fatty acid borneol ester can effectively reduce the glass transition temperature (Tg) as a plasticizer of PVC materials. Because long-chain fatty acid borneol ester has a double-ring structure at one end of the molecule, the anti-solvent extraction performance of the long-chain fatty acid borneol ester is superior to that of dioctyl phthalate.
3. The invention uses alpha-hydroxy carboxylic acid to react with pinene to prepare chiral alpha-hydroxy carboxylic acid borneol ester, which expands the variety of borneol ester. The catalyst is boric acid, the dosage is small, and the esterification reaction can be smoothly carried out by adding the catalyst with the mass of 0.5-30% of the alpha-hydroxy carboxylic acid. Since boric acid is capable of binding with hydroxyl groups to form complexes, the catalytic action is that of alpha-hydroxycarboxylic acids with boric acid.
4. In the prior art, when catalysts such as concentrated sulfuric acid, p-toluenesulfonic acid, sodium bisulfate, titanium sulfate, solid acid and the like are used, the borneol acetate obtained by the reaction of pinene and acetic acid is racemic, and the borneol acetate obtained by the method has optical activity.
5. According to the invention, the alpha-hydroxy acid and boric acid complex is used as a catalyst to catalyze pinene and carboxylic acid to react to synthesize borneol ester, so that the knowledge of people on the alpha-hydroxy acid and boric acid complex is expanded.
6. The method of the invention obtains the chiral borneol ester, and the chiral borneol can be obtained after saponification reaction, and compared with the traditional camphora chiral hydrogenation synthesized borneol, the method has the advantages of cheap raw materials, simple process and low cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a mass spectrum of borneol synthesized in example 2;
FIG. 2 is an infrared spectrum of borneol synthesized in example 2;
FIG. 3 is a nuclear magnetic resonance spectrum of borneol synthesized in example 2;
FIG. 4 is a nuclear magnetic carbon spectrum of borneol synthesized in example 2.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw material content used in the embodiment of the invention can have a wider range. The product composition can be qualitatively determined by GC-MS, infrared and nuclear magnetic hydrogen spectroscopy. Relative content determination of volatizable products, see "GBT11538-2006 general method for essential oil capillary column determination". The optical rotation of the product can be measured by an optical rotation meter.
The analytical instrument adopted in the embodiment of the invention is as follows: aglient 7890A gas chromatograph, agilent, USA; chromatographic column: AT-35, quartz capillary column (60 m. Times.0.25 mm. Times.0.25 μm).
GC analysis conditions: carrier gas, high-purity nitrogen; programming temperature: 70 ℃ (2 min), rising to 150 ℃ at 50 ℃/min, staying for 3min, rising to 230 ℃ at 30 ℃/min, staying for 5min; sample inlet temperature: the total flow is 130.5ml/min at the temperature of 250 ℃, the split ratio is 50:1, and the spacer is purged for 3ml/min; FID detection, detecting port temperature: the hydrogen flow rate is 40ml/min at 250 ℃, the air is 450ml/min, and the nitrogen is blown at 25ml/min. The sample injection amount is 0.2ul.
An area normalization method is adopted. The conversion of pinene was approximated by subtracting the GC content of pinene in the product from the GC content of pinene in the feed.
Specifically, pinene conversion= (GC content of pinene in the raw material-GC content of pinene in the product)/GC content of pinene in the raw material.
Example 1
Synthesizing chiral borneol acetate:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), acetic acid and a composite catalyst into a reaction device according to the mass ratio of 100:180:32, stirring at normal pressure and the temperature of 60 ℃ for reaction for 15h; the composite catalyst is malic acid and boric acid, and the mass ratio of the malic acid to the boric acid is 10:1;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
s5, heating to maintain the temperature of the tower kettle at 140-150 ℃, maintaining the temperature of the tower top at 100-105 ℃ and collecting borneol acetate at a reflux ratio of 22-25:1.
After the reaction, the conversion rate of pinene was 98.5%, the GC content of borneol in the product was 4.7%, and the GC content of borneol acetate was 33%. The GC content of the product after refining borneol acetate is 95 percent, and the specific optical rotation is-36 degrees.
Example 2
Synthesizing chiral borneol acetate and borneol:
(1) And (3) synthesis reaction: adding (+) -pinene (GC content 98%), acetic acid and a composite catalyst into a reaction device according to the mass ratio of 100:150:20, stirring at normal pressure and the temperature of 60 ℃ for reaction for 15h; the composite catalyst is mandelic acid and boric acid, and the mass ratio of the mandelic acid to the boric acid is 5:1;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: neutralizing the reaction product obtained in the step (2) with a sodium carbonate aqueous solution, and then washing with water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
s5, heating to maintain the temperature of the tower kettle at 140-150 ℃, maintaining the temperature of the tower top at 100-105 ℃ and collecting borneol acetate at a reflux ratio of 22-25:1.
After the reaction, the conversion rate of pinene was 98.7%, the GC content of borneol in the product was 3.5%, and the GC content of borneol acetate was 35%. The GC content of the product after refining borneol acetate is 94.8 percent, and the specific rotation is +35 degrees.
Dissolving borneol acetate in ethanol, controlling the temperature at 50-60 ℃, stirring, dripping alkali liquor, and reacting for 2h; after ethanol is distilled and recovered, crude borneol is separated by adding water, and the crude borneol is dissolved by absolute ethanol and recrystallized to obtain the borneol with the GC content of 99 percent and the specific optical rotation of +34 degrees.
FIGS. 1 to 4 are respectively a mass spectrum, an infrared spectrum, a nuclear magnetic hydrogen spectrum and a nuclear magnetic carbon spectrum of the synthetic borneol of example 2.
Example 3
Synthesizing chiral borneol propionate:
(1) And (3) synthesis reaction: adding (+) -pinene (GC content 98%), propionic acid and a composite catalyst into a reaction device according to the mass ratio of 100:150:25, stirring at normal pressure and the temperature of 60 ℃, and reacting for 18h; the composite catalyst is mandelic acid and boric acid, and the mass ratio of the mandelic acid to the boric acid is 5:3;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
And S5, heating to maintain the temperature of the tower bottom at 140-150 ℃, maintaining the temperature of the tower top at 100-105 ℃ and collecting the borneol propionate at a reflux ratio of 22-25:1.
After the reaction, the conversion rate of pinene was 95.1%, the GC content of borneol in the product was 3.2%, and the GC content of borneol propionate was 45%. The GC content of the refined borneol propionate is 96.8 percent, and the specific rotation is +33 degrees.
Example 4
Synthesizing chiral borneol butyrate:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), butyric acid and a composite catalyst into a reaction device according to the mass ratio of 100:190:35, stirring at normal pressure and the temperature of 60 ℃ for reaction for 20h; the composite catalyst is tartaric acid and boric acid, and the mass ratio of the tartaric acid to the boric acid is 5:4;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
S5, heating to maintain the temperature of the tower kettle at 140-150 ℃, maintaining the temperature of the tower top at 100-105 ℃ and collecting borneol butyrate at a reflux ratio of 22-25:1.
After the reaction, the conversion rate of pinene was 95.1%, the GC content of borneol in the product was 2.5%, and the GC content of borneol butyrate was 42%. The GC content of the product after refining the borneol butyrate is 96.5 percent, and the specific rotation is-34 degrees.
Example 5
Synthesizing chiral borneol valerate:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), valeric acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:35, stirring at normal pressure and the temperature of 60 ℃ for reaction for 20 hours; the composite catalyst is citric acid and boric acid, and the mass ratio of the citric acid to the boric acid is 5:4;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
And S5, heating to maintain the temperature of the tower kettle at 140-150 ℃, maintaining the temperature of the tower top at 100-105 ℃ and collecting the borneol valerate at a reflux ratio of 22-25:1.
After the reaction, the conversion rate of pinene was 95.1%, the GC content of borneol in the product was 2.7%, and the GC content of borneol valerate was 41%. The GC content of the product after refining the borneol valerate is 95 percent, and the specific rotation is-37 degrees.
Example 6
Synthesizing chiral borneol caproate:
(1) And (3) synthesis reaction: adding (+) -pinene (GC content 98%), caproic acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:50, stirring at normal pressure and the temperature of 60 ℃ for 24 hours; the composite catalyst is lactic acid and boric acid, and the mass ratio of the composite catalyst to the boric acid is 5:3;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: neutralizing the reaction product obtained in the step (2) with a sodium carbonate aqueous solution, and then washing with water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
S5, heating to maintain the temperature of the tower kettle at 140-150 ℃, maintaining the temperature of the tower top at 105-110 ℃ and collecting the borneol caproate at a reflux ratio of 22-25:1.
After the reaction, the conversion rate of pinene was 95.1%, the GC content of borneol in the product was 2.4%, and the GC content of borneol caproate was 42%. The GC content of the product after refining the borneol caproate is 95 percent, and the specific optical rotation is +36 degrees.
Example 7
Synthesizing chiral borneol heptanoate:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), heptanoic acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:45, stirring at normal pressure and the temperature of 70 ℃ for 24 hours; the composite catalyst is glycolic acid and boric acid, and the mass ratio of the composite catalyst to the boric acid is 5:5;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
S5, heating to maintain the temperature of the tower kettle at 145-155 ℃, maintaining the temperature of the tower top at 105-110 ℃ and collecting borneol heptanoate at a reflux ratio of 22-25:1.
After the reaction, the conversion rate of pinene was 93.7%, the GC content of borneol in the product was 3.4%, and the GC content of borneol heptanoate was 40%. The GC content of the product after refining the borneol heptanoate is 94 percent, and the specific rotation is-32 degrees.
Example 8
Synthesizing chiral borneol octoate:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), octanoic acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:45, stirring at normal pressure, and reacting at 70 ℃ for 24 hours; the composite catalyst is lactic acid and boric acid, and the mass ratio of the composite catalyst to the boric acid is 5:5;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
S5, heating to maintain the temperature of the tower kettle at 150-155 ℃, maintaining the temperature of the tower top at 108-112 ℃ and the reflux ratio at 22-25:1, and collecting the borneol octoate.
After the reaction, the conversion rate of pinene was 93.7%, the GC content of borneol in the product was 3.7%, and the GC content of borneol octoate was 39%. The GC content of the product after refining the borneol octoate is 94.5 percent, and the specific rotation is minus 32 degrees.
Example 9
Synthesizing chiral borneol pelargonate:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), pelargonic acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:35, stirring at normal pressure and the temperature of 80 ℃ for 24 hours; the composite catalyst is tartaric acid and boric acid, and the mass ratio of the tartaric acid to the boric acid is 5:4;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
S3, heating to keep the temperature of a tower kettle at 115-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
s5, heating to maintain the temperature of the tower kettle at 155-160 ℃, maintaining the temperature of the tower top at 110-112 ℃ and collecting the borneol pelargonate at a reflux ratio of 22-25:1.
After the reaction, the conversion rate of pinene was 93.7%, the GC content of borneol in the product was 4.7%, and the GC content of borneol pelargonate was 40%. The GC content of the product after refining the borneol pelargonate is 94 percent, and the specific rotation is-31 degrees.
Example 10
Synthesizing chiral capric acid borneol ester:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), decanoic acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:35, stirring at normal pressure and the temperature of 90 ℃ for 24 hours; the composite catalyst is tartaric acid and boric acid, and the mass ratio of the tartaric acid to the boric acid is 5:4;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: neutralizing the reaction product obtained in the step (2) with a sodium carbonate aqueous solution, and then washing with water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
S3, heating to keep the temperature of a tower kettle at 115-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 12-13:1;
s4, heating to maintain the temperature of the tower kettle at 130-145 ℃, maintaining the temperature of the tower top at 95-100 ℃ and a reflux ratio of 18-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
S5, heating to maintain the temperature of the tower kettle at 155-160 ℃, maintaining the temperature of the tower top at 112-115 ℃ and the reflux ratio at 23-25:1, and collecting the capric borneol ester.
After the reaction, the conversion rate of pinene was 93.7%, the GC content of borneol in the product was 4.1%, and the GC content of borneol decanoate was 39.6%. The GC content of the product after refining the capric acid borneol ester is 95 percent and the specific optical rotation is-30 degrees.
Example 11
Synthesizing chiral laurate and borneol:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), lauric acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:35, stirring at normal pressure and the temperature of 90 ℃ for reaction for 30 hours; the composite catalyst is tartaric acid and boric acid, and the mass ratio of the tartaric acid to the boric acid is 5:4;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
S3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 2 hours, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 10-13:1;
S4, heating to keep the temperature of the tower kettle at 130-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
and S5, conveying the chiral borneol ester in the tower kettle to a decoloring kettle, adding 2% of active carbon by mass, controlling the temperature at 70 ℃, stirring for 1h, and separating the active carbon by a filter press to obtain a refined chiral borneol ester product.
After the reaction was completed, the conversion of pinene was 93.7%, the GC content of borneol in the product was 4.1%, and the GC content of borneol laurate was 42.6%. The GC content of the product after refining the borneol laurate is 95 percent, and the specific optical rotation is-30 degrees.
Dissolving borneol laurate in acetone, controlling the temperature at 50-60 ℃, stirring, dripping alkali solution, and separating soap; washing the separated soap with acetone, and combining the washing solution with the acetone solution containing chiral borneol; distilling to recover solvent to obtain chiral borneol. Dissolving the obtained chiral borneol in acetone for recrystallization, dissolving the obtained borneol in acetone, and recrystallizing to obtain borneol with GC content of 99% and specific optical rotation of-30 °.
Example 12
Synthesizing chiral borneol myristate:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), myristic acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:45, stirring at normal pressure and the temperature of 90 ℃ for reaction for 30 hours; the composite catalyst is citric acid and boric acid, and the mass ratio of the citric acid to the boric acid is 5:4;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 10-13:1;
S4, heating to keep the temperature of the tower kettle at 130-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
and S5, conveying the chiral borneol ester in the tower kettle to a decoloring kettle, adding 2% of active carbon by mass, controlling the temperature at 70 ℃, stirring for 1h, and separating the active carbon by a filter press to obtain a refined chiral borneol ester product.
After the reaction was completed, the conversion of pinene was 93.7%, the GC content of borneol in the product was 3.7%, and the GC content of borneol myristate was 42.3%. The GC content of the product after refining the borneol myristate is 95 percent, and the specific optical rotation is-29 degrees.
Example 13
Synthesizing chiral borneol palmitate and borneol:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), palmitic acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:45, stirring at normal pressure, and reacting at 100 ℃ for 30 hours; the composite catalyst is citric acid and boric acid, and the mass ratio of the citric acid to the boric acid is 5:4;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
S3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 2 hours, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 10-13:1;
S4, heating to keep the temperature of the tower kettle at 130-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
And S5, conveying the chiral borneol ester in the tower kettle to a decoloring kettle, adding 3% of active carbon by mass, controlling the temperature at 70 ℃, stirring for 1h, and separating the active carbon by a filter press to obtain a refined chiral borneol ester product.
After the reaction was completed, the conversion of pinene was 93.7%, the GC content of borneol in the product was 3.7%, and the GC content of borneol palmitate was 42.3%. The GC content of the product after refining the borneol palmitate is 95 percent, and the specific optical rotation is-29 degrees.
Dissolving borneol palmitate in ethanol, controlling the temperature at 50-60 ℃, stirring, dripping alkali solution, and separating soap; washing the separated soap with ethanol, and combining the washing solution with the ethanol solution containing chiral borneol; distilling to recover solvent to obtain chiral borneol. Dissolving the obtained chiral borneol in acetone for recrystallization, dissolving the obtained borneol in acetone, and recrystallizing to obtain borneol with GC content of 99% and specific optical rotation of-30 °.
Example 14
Synthesizing chiral borneol stearate and borneol:
(1) And (3) synthesis reaction: adding (+) -pinene (GC content 98%), stearic acid and a composite catalyst into a reaction device according to the mass ratio of 100:200:45, stirring at normal pressure and the temperature of 120 ℃ for reaction for 30 hours; the composite catalyst is citric acid and boric acid, and the mass ratio of the citric acid to the boric acid is 5:4;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The product refinement in step (4) comprises the steps of:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1h, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 10-13:1;
S4, heating to keep the temperature of the tower kettle at 130-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
And S5, conveying the chiral borneol ester in the tower kettle to a decoloring kettle, adding 3% of active carbon by mass, controlling the temperature at 70 ℃, stirring for 1h, and separating the active carbon by a filter press to obtain a refined chiral borneol ester product.
After the reaction, the conversion rate of pinene was 93.7%, the GC content of borneol in the product was 3.5%, and the GC content of borneol stearate was 42.9%. The GC content of the refined borneol stearate is 92 percent, and the specific optical rotation is +28 degrees.
Dissolving borneol stearate in ethanol, controlling the temperature at 50-60 ℃, stirring, dripping alkali solution, and separating soap; washing the separated soap with ethanol, and combining the washing solution with the ethanol solution containing chiral borneol; distilling to recover solvent to obtain chiral borneol. Dissolving the obtained chiral borneol in acetone for recrystallization, dissolving the obtained borneol in acetone, and recrystallizing to obtain borneol with GC content of 99% and specific optical rotation of +30°.
Example 15
Synthesizing chiral borneol malate and chiral borneol:
(1) And (3) synthesis reaction: adding (+) -pinene (GC content 98%), malic acid and boric acid into a reaction device according to the mass ratio of 100:110:1, stirring at normal pressure and the temperature of 70 ℃ for reaction for 30 hours;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) The neutral esterified product obtained in the step (3) is subjected to vacuum fractionation, and the steps are as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
S3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1.5 hours, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 10-13:1;
S4, heating to keep the temperature of the tower kettle at 130-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
S5, conveying the chiral borneol ester in the tower kettle to a decoloring kettle, adding activated carbon with the mass of 2.5%, controlling the temperature at 70 ℃, stirring for 1h, and separating the activated carbon by a filter press to obtain a decoloring chiral borneol ester product. Dissolving the decolorized borneol malate with ethanol at room temperature, and recrystallizing to obtain refined borneol malate product.
After the reaction, the conversion rate of pinene was 93.7%, and the content of borneol malate was 35.9%. The content of refined borneol malate is 98%. Saponifying the borneol malate, and distilling with steam to obtain chiral borneol with specific optical rotation of +30 deg.
Example 16
Synthesizing chiral borneol mandelate and borneol:
(1) And (3) synthesis reaction: adding (-) -pinene (GC content 98%), mandelic acid and boric acid into a reaction device according to the mass ratio of 100:200:10, stirring at normal pressure and the temperature of 70 ℃ for reaction for 30 hours;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) The neutral esterified product obtained in the step (3) is subjected to vacuum fractionation, and the steps are as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
S3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 1.5 hours, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 10-13:1;
S4, heating to keep the temperature of the tower kettle at 130-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
s5, conveying the chiral borneol ester in the tower kettle to a decoloring kettle, adding activated carbon with the mass of 2.5%, controlling the temperature at 70 ℃, stirring for 1h, and separating the activated carbon by a filter press to obtain a decoloring chiral borneol ester product. Dissolving the decolorized borneol mandelate with acetone at room temperature, and recrystallizing to obtain refined borneol mandelate product.
After the reaction, the conversion rate of pinene was 93.7%, the GC content of borneol in the product was 3.5%, and the content of borneol mandelate was 38.9%. The content of refined borneol mandelate was 97%. Saponifying the borneol mandelate, and distilling with steam to obtain chiral borneol with specific optical rotation of-31 deg.
Dissolving borneol mandelate in acetone, controlling the temperature at 50-60 ℃, stirring, dripping alkali solution, and carrying out saponification reaction for 1h; washing the separated sodium salt with acetone, and combining the washing solution with the acetone solution containing chiral borneol; distilling to recover solvent to obtain chiral borneol. The borneol is dissolved by acetone and recrystallized, and the borneol with GC content of 99 percent can be prepared, and the specific optical rotation is-31 degrees.
Example 17
Synthesizing chiral lactic acid borneol ester and borneol:
(1) And (3) synthesis reaction: adding (+) -pinene (GC content 98%), lactic acid and boric acid into a reaction device according to the mass ratio of 100:200:25, stirring at normal pressure and the temperature of 70 ℃ for reaction for 30 hours;
(2) And (3) catalyst recovery: after the reaction is finished, cooling the product to room temperature, filtering out the catalyst, and reusing the dried catalyst;
(3) And (3) neutralizing and washing: washing the reaction product obtained in the step (2) to be neutral by water to obtain a neutral esterification product;
(4) Refining: and (3) carrying out vacuum fractionation on the neutral esterified product obtained in the step (3) to obtain a refined chiral borneol ester product.
The process is as follows:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the esterified product after neutralization and water washing to a rectifying tower kettle;
S3, heating to keep the temperature of a tower kettle at 110-120 ℃, keeping the temperature of a tower top at 80-95 ℃, refluxing for 2 hours, and collecting camphene, limonene, terpinene and terpinene at a reflux ratio of 10-13:1;
S4, heating to keep the temperature of the tower kettle at 130-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting fenchyl alcohol, isobornyl and terpineol;
And S5, conveying the chiral borneol ester in the tower kettle to a decoloring kettle, adding 3% of active carbon by mass, controlling the temperature at 70 ℃, stirring for 1h, and separating the active carbon by a filter press to obtain a decoloring chiral borneol ester product. Dissolving the decolorized borneol lactate with acetone at room temperature, and recrystallizing to obtain refined borneol lactate product.
After the reaction, the conversion rate of pinene was 93.7%, the GC content of borneol in the product was 4.6%, and the content of borneol lactate was 40.9%. The content of refined borneol lactate is 98%. The lactic acid borneol ester is saponified, and the chiral borneol with 98 percent GC content is obtained by steam distillation, and the specific optical rotation is +30 degrees.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (4)
1. A method for synthesizing chiral borneol esters, comprising the steps of:
Mixing pinene, carboxylic acid and a catalyst at normal pressure and 60-120 ℃ for reaction, cooling a reaction product to room temperature after the reaction is finished, washing to be neutral, and separating and purifying to obtain the chiral borneol ester;
The mass ratio of the pinene to the carboxylic acid to the catalyst is 100 (33-300) (0.1-50);
The catalyst is a mixture of alpha-hydroxycarboxylic acid and boric acid in a mass ratio of (0-30): 1;
the pinene is (-) -pinene or (+) -pinene;
the carboxylic acid is C2-C18 fatty acid;
the alpha-hydroxycarboxylic acid is one of lactic acid, mandelic acid, tartaric acid, citric acid or malic acid.
2. The method according to claim 1, wherein when the carboxylic acid is an α -hydroxycarboxylic acid and is the same as the kind of α -hydroxycarboxylic acid in the catalyst, the mass ratio of α -hydroxycarboxylic acid to boric acid in the catalyst is 0:1.
3. The method according to claim 2, wherein the catalyst is added in an amount of 0.5 to 30% by mass of the carboxylic acid.
4. The method of claim 1, wherein the means for separating and purifying comprises vacuum fractionation.
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| Complexation of Boronic Acid with Chiral α-Hydroxycarboxylic Acids and the Ability of the Complexes to Catalyze α-Hydroxycarboxylic Acid Esterification;Zhonglei Meng et al.;Molecules;20231220;第29卷(第43期);8-10 * |
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