CN107188781A - A kind of method that isopulegol is prepared by citronellal - Google Patents
A kind of method that isopulegol is prepared by citronellal Download PDFInfo
- Publication number
- CN107188781A CN107188781A CN201710406113.5A CN201710406113A CN107188781A CN 107188781 A CN107188781 A CN 107188781A CN 201710406113 A CN201710406113 A CN 201710406113A CN 107188781 A CN107188781 A CN 107188781A
- Authority
- CN
- China
- Prior art keywords
- formula
- isopulegol
- citronellal
- sulfonic acid
- benzene sulfonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 title claims abstract description 177
- ZYTMANIQRDEHIO-KXUCPTDWSA-N isopulegol Chemical compound C[C@@H]1CC[C@@H](C(C)=C)[C@H](O)C1 ZYTMANIQRDEHIO-KXUCPTDWSA-N 0.000 title claims abstract description 143
- 239000001871 (1R,2R,5S)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Substances 0.000 title claims abstract description 92
- 229940095045 isopulegol Drugs 0.000 title claims abstract description 92
- 229930003633 citronellal Natural products 0.000 title claims abstract description 89
- 235000000983 citronellal Nutrition 0.000 title claims abstract description 89
- ZYTMANIQRDEHIO-UHFFFAOYSA-N neo-Isopulegol Natural products CC1CCC(C(C)=C)C(O)C1 ZYTMANIQRDEHIO-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- -1 aryl benzene sulfonic acid Chemical compound 0.000 claims abstract description 39
- 150000001399 aluminium compounds Chemical class 0.000 claims abstract description 31
- 229940092714 benzenesulfonic acid Drugs 0.000 claims abstract description 20
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- 239000003054 catalyst Substances 0.000 claims description 65
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 38
- 239000000725 suspension Substances 0.000 claims description 32
- 239000012074 organic phase Substances 0.000 claims description 29
- 239000003446 ligand Substances 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008346 aqueous phase Substances 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Chemical group 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 claims description 6
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 229940041616 menthol Drugs 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical group [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229940117360 ethyl pyruvate Drugs 0.000 claims description 2
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052700 potassium Chemical group 0.000 claims description 2
- 239000011591 potassium Chemical group 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical class CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000002304 perfume Substances 0.000 claims 1
- 235000013599 spices Nutrition 0.000 claims 1
- 239000004577 thatch Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 53
- ZYTMANIQRDEHIO-LPEHRKFASA-N (1r,2s,5s)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Chemical compound C[C@H]1CC[C@@H](C(C)=C)[C@H](O)C1 ZYTMANIQRDEHIO-LPEHRKFASA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000284 extract Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 240000004784 Cymbopogon citratus Species 0.000 description 4
- 235000017897 Cymbopogon citratus Nutrition 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JGVWYJDASSSGEK-UHFFFAOYSA-N 5-methyl-2-propan-2-ylidenecyclohexan-1-ol Chemical compound CC1CCC(=C(C)C)C(O)C1 JGVWYJDASSSGEK-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 244000246386 Mentha pulegium Species 0.000 description 2
- 235000016257 Mentha pulegium Nutrition 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- ZYTMANIQRDEHIO-UTLUCORTSA-N (1s,2s,5r)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Chemical compound C[C@@H]1CC[C@@H](C(C)=C)[C@@H](O)C1 ZYTMANIQRDEHIO-UTLUCORTSA-N 0.000 description 1
- KTDIUYZQGDFHPC-UHFFFAOYSA-N 2,6-bis(2-chlorophenyl)benzenesulfonic acid Chemical compound ClC1=C(C=CC=C1)C1=C(C(=CC=C1)C1=C(C=CC=C1)Cl)S(=O)(=O)O KTDIUYZQGDFHPC-UHFFFAOYSA-N 0.000 description 1
- HQNBBUMWLBWREG-UHFFFAOYSA-N 2,6-dinaphthalen-2-ylbenzenesulfonic acid Chemical compound C1=C(C=CC2=CC=CC=C12)C1=C(C(=CC=C1)C1=CC2=CC=CC=C2C=C1)S(=O)(=O)O HQNBBUMWLBWREG-UHFFFAOYSA-N 0.000 description 1
- ZEJOWBKCKMRKNW-UHFFFAOYSA-N 2,6-diphenylbenzenesulfonic acid Chemical compound C1(=CC=CC=C1)C1=C(C(=CC=C1)C1=CC=CC=C1)S(=O)(=O)O ZEJOWBKCKMRKNW-UHFFFAOYSA-N 0.000 description 1
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FJOMMMRMXCHMCN-UHFFFAOYSA-N CCN(CC)[Si](C)(C)CN(C)C Chemical compound CCN(CC)[Si](C)(C)CN(C)C FJOMMMRMXCHMCN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2252—Sulfonate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that isopulegol is prepared by citronellal, citronellal cyclisation is prepared into isopulegol in the presence of aryl benzene sulfonic acid base aluminium compound, aryl benzene sulfonic acid base aluminium compound is prepared from by the aluminium compound of the aryl benzene sulfonic acid part of formula (I) and the aluminium compound of formula (II) and/or formula (III)；(R1)3‑pAIHp(II)、MAIH4(III), the cyclization mild condition, preferably 5 15 DEG C of reaction temperature, reaction enantioselectivity is 90% 99%, and conversion ratio can reach 80 99.9%.
Description
Technical field
The present invention relates to a kind of method that isopulegol is prepared by citronellal, belong to organic chemical synthesis field.
Background technology
Menthol is a kind of important aromachemicals, and the demand to menthol was continuously increased in the last few years, current peppermint
The source of alcohol is divided into naturally isolated and artificial synthesized, the yield of the natural menthol of the limitation such as climate and geography and unstable, people
The advantages of isopulegol of work synthesis is because price is relatively cheap, yield is steady, mouthfeel is stable is increasingly by the joyous of market
Meet.Isopulegol is the important intermediate of artificial synthesized menthol, and the conventional method for obtaining isopulegol is to use lemongrass
Aldehyde is cyclized to prepare under Louis acid catalysis, and generally yield be four kinds of correspondence bodies form of mixtures, i.e., different Hu is thin
Lotus alcohol, iso- isopulegol, new-isopulegol, new iso- isopulegol.
Highly Stereoslective Preparation of l-Isopulegol；Synthesis, 1978 (2)；
The method that zinc bromide catalysis citronellal cyclisation prepares isopulegol is reported in 147-148.But when using the catalyst, obtain
The yield obtained is about 92%, and its enantioselectivity (ratio of isopulegol and other isopulegol isomers) then only reaches
To 94/6, and bromide ion requires harsh to equipment corrosion resistance.
EP1225163A is described to be cyclized using three (2,6- diphenyl phenol) aluminium as catalyst citronellal and prepared
The method of isopulegol.Although under the catalyst action, its enantioselectivity (L- (-)-n- isopulegol with it is other
The ratio of isopulegol isomers) 99.7/0.3 is reached, but be due to the catalyst and unstable, it is impossible to recycling causes
The shortcomings of cost is too high is so be difficult to large-scale industrial production.
CN101723809A, which is described, uses Diarylphenoxy aluminum compounds anti-as catalyst progress citronellal cyclisation
Should be come the method for preparing isopulegol.Yield and enantioselectivity are deposited in operation obviously higher than zinc bromide
The shortcomings of reaction temperature is low, part removal process is cumbersome.
Accordingly, it would be desirable to develop, a kind of reaction condition is gentle, L- (-)-n- isopulegol reaction enantioselectivity is high
The method for preparing isopulegol, realizes the large-scale industrial production of isopulegol.
The content of the invention
It is an object of the invention to provide a kind of method that isopulegol is prepared by citronellal, aryl benzene sulfonic acid base aluminium is used
Compound prepares isopulegol as catalyst, catalysis citronellal cyclisation, and reaction condition is gentle, and enantio-selectivity is high, fits
For industrialized production and application.
In order to realize above goal of the invention, the technical solution adopted by the present invention is as follows：
A kind of method that isopulegol is prepared by citronellal, comprises the following steps：In catalyst aryl benzene sulfonic acid base aluminium
In the presence of compound, citronellal occurs cyclization and prepares isopulegol；
The aryl benzene sulfonic acid base aluminium compound is by the aryl benzene sulfonic acid part including formula (I) and the aluminium compound of formula (II)
And/or the aluminium compound of formula (III) is prepared from；
(R1)3-pAIHp
(II)
MAIH4
(III)
Wherein Ar1、Ar2Can with it is identical or different and separately be selected from C6-C12Heteroaryl or C6-Cl5Aryl
And optionally containing 1-3 substituent on aryl, the substituent selected from halogeno-group, trihalomethyl group, methoxyl group, acetyl group,
Dimethylamino, diethylamino, trimethyl silicon substrate, triethyl group silicon substrate, cyano group, nitro；Preferably, the Ar1With Ar2Respectively
Independently selected from phenyl, betanaphthyl, 3- trifluoromethyls, chlorphenyl, 3- isopropyl phenyls；
R1It is C1-C5Alkyl；P is 0-3 integer；M is lithium, sodium or potassium.
In the present invention, in the aryl benzene sulfonic acid part, Ar1With Ar2Group of the selection with big steric hindrance, can be in sulfonic acid
Primitive period encloses the suitable steric hindrance of construction, and it is suitable that the catalyst with big steric group can have with the formation of reactant citronellal
The reaction transition state of steric hindrance, so as to reduce the isopulegol diastereo-isomerism such as different isopulegol, neoisopulegol
The generation of body, prevents citronellal intermolecular reaction, is conducive to citronellal intramolecular cyclization, improves reaction selectivity.In its part
It is sulfonic to exist so that catalyst has good water solubility, using the property that sulfonic group sodium salt is soluble in water, in reaction knot
Part can be caused to be separated from reaction system by the way of sodium hydrate aqueous solution alkali cleaning after beam, can entering with high-recovery
Row recovery, is conducive to the recycling of part, and larger simplifies technological process.
In the present invention, the aryl benzene sulfonic acid part of formula (I) may be selected from but be not limited to following part：
In the present invention, the aluminium compound of described formula (II) is preferably trimethyl aluminium and/or triethyl aluminum；Described formula
(III) aluminium compound is preferably lithium aluminium hydride reduction..
In the present invention, the aryl benzene sulfonic acid part of the formula (I) and the aluminium compound of formula (II) and/or the aluminium of formula (III)
The mol ratio of compound is 10:1 to 3:1, preferably 4:1 to 3:1.
In the present invention, the preparation method of the catalyst aryl benzene sulfonic acid base aluminium compound comprises the following steps：
Under inert gas shielding, the aryl benzene sulfonic acid part of formula (I) is dissolved in solvent, the aryl benzene sulfonic acid of formula (I) is obtained
Ligand solution；
The aluminium compound of formula (II) and/or the aluminium compound of formula (III) are diluted using solvent, the aluminium containing formula (II) is obtained
The aluminum compound solution of compound and/or formula (III)；
Proportionally, the aluminum compound solution of the aluminium compound containing formula (II) and/or formula (III) is slowly added dropwise to formula
(I) in aryl benzene sulfonic acid ligand solution, catalyst solution or catalyst suspension are formed.
During the reaction of the aluminium compound of formula (II) and/or the aluminium compound of formula (III) and the aryl benzene sulfonic acid part of formula (I)
Between be 0.5-6h, preferably 0.5-2h.
In the present invention, in the method for preparing catalyst, reaction system needs to carry out in atmosphere of inert gases, described lazy
Property gas includes but is not limited to nitrogen and/or argon gas, preferably high pure nitrogen and/or high-purity argon gas, wherein, oxygen content is less than
20ppm(v/v)。
In the present invention, in the method for preparing catalyst, aryl benzene sulfonic acid part and diluting type for dissolving formula (I)
(II) aluminium compound and/or the solvent of the aluminium compound of formula (III) is selected from alkane, aromatic hydrocarbons, halogenated hydrocarbons, ethers and esters solvent
One or more, preferably one kind or many in n-hexane, normal heptane, toluene, dimethylbenzene, tetrahydrofuran and dichloromethane
Plant, more preferably toluene and/or dimethylbenzene.
In the present invention, during citronellal prepares isopulegol, the catalyst is with catalyst solution or catalysis
Agent form of suspension is added to reaction system, and the mass concentration of catalyst is 1-50wt%, preferably 10-25wt%.
In the present invention, during citronellal prepares isopulegol, the addition manner of catalyst is in inert gas atmosphere
Under enclosing, catalyst solution is added in substrate, catalyst adding procedure is completed after being uniformly mixed.The inert gas includes
But nitrogen and/or argon gas, preferably high pure nitrogen and/or high-purity argon gas are not limited to, wherein, oxygen content is less than 20ppm (v/v).
It is described to prepare different Hu for being catalyzed citronellal cyclisation during citronellal prepares isopulegol in the present invention
The consumption of the catalyst of menthol, with the molar amount of aluminium atom in catalyst aryl benzene sulfonic acid base aluminium compound, is 0.1mol%
To 10mol%, preferably 0.5mo1% to 5mo1%, the mole based on citronellal.
In the present invention, the reaction temperature that the catalysis citronellal cyclisation prepares isopulegol is -10-50 DEG C, preferably -
10-20 DEG C, more preferably 5-15 DEG C；Reaction time 3-24h, preferably 4-12h.
In the present invention, as one of them preferred scheme, the citronellal prepares isopulegol cyclization in 8-
10 DEG C of reaction 4-5h, then it is warming up to 15-20 DEG C of reaction 1-2h.
In the present invention, be additionally added solvent in the cyclization, the solvent with used in catalyst preparation process it is molten
Agent is identical or different, and selected solvent is to show inert solvent, preferably alkane, aromatic hydrocarbons, halogenated hydrocarbons, ether in cyclization process
One or more in class and esters solvent, more preferably n-hexane, normal heptane, toluene, dimethylbenzene, tetrahydrofuran and dichloromethane
One or more in one or more in alkane, further preferred toluene, n-hexane and dimethylbenzene.
In the present invention, substrate citronellal is generally first diluted using solvent, and used solvent can be catalyzed with preparing
The solvent used during agent is identical or different, preferably identical with preparing the solvent that is used in catalyst process, selected from alkane, virtue
Hydrocarbon, halogenated hydrocarbons, the preferably one or more of ethers and esters solvent, n-hexane, normal heptane, toluene, dimethylbenzene, tetrahydrofuran
With the one or more in dichloromethane, more preferably toluene and/or dimethylbenzene.
In the present invention, the quality of solvent and the mass ratio of citronellal for diluting citronellal are 10:1 to 1:5, preferably 2:
1 to 1:2.
In the present invention, the selectivity of cyclization product isopulegol is 90%-99%, and raw material citronellal conversion ratio can
Reach 80-99.0%.
In the present invention, as a preferred scheme, R- (+)-citronellal formula (IV-a) ring in the presence of a catalyst is used
Change and prepare L- (-)-n- isopulegol formula (V-a), wherein, the ee values scope of raw material R- (+)-citronellal is 95-100%, excellent
Select more than 98%；Raw material R- citronellal conversion ratios can reach 80-99.0%, the reaction pair of product L- (-)-n- isopulegol
It is 95%-99% to reflect selectivity.
In the present invention, cyclization also include be optionally added into auxiliary agent, selected from organic acid, carboxylic acid anhydrides, aldehyde, ketone, ester and
One or more in the compound of vinyl ethers, preferably are selected from acetaldehyde, propionic aldehyde, chloral, TFK, 1,1,1- trifluoro
One kind in acetophenone, methyl pyruvate, ethyl pyruvate, Hexafluoro acetone, acetic anhydride, propionic aldehyde, neopentanoic acid acid anhydride and benzoyl oxide
Or a variety of, more preferably methyl pyruvate, acetic anhydride, consumption is 0.01-5mol%, the consumption based on citronellal.The addition of auxiliary agent
Can be with the selectivity and final conversion ratio of larger raising citronellal cyclization, and the condition of reaction can be made gentleer
It is controllable.
In the present invention, the method that isopulegol is prepared by citronellal also comprises the following steps：
A) solvent is distilled off and optional auxiliary agent from cyclization mixture；
B) 1-4wt%, preferably 1.5-2wt% sodium hydroxide solutions are added into the residue obtained in step a),
Be sufficiently stirred for 3-6h at 60-80 DEG C, aryl benzene sulfonic acid sodium salt in aqueous phase fully after dissolving, by phase separator carry out aqueous phase,
Organic phase separation, respectively obtains aqueous phase, organic phase；
C) separated goes out isopulegol in the organic phase obtained from step b).
D) catalyst is reclaimed：The aqueous phase obtained in step b) is carried out to be neutralized to pH=1-3, aryl benzene sulfonic acid part is with solid
Body form is separated out, and obtained aryl benzene sulfonic acid solid ligand is washed, purification process.
Inventive process have the advantage that：
Catalyst is used as using aryl benzene sulfonic acid base aluminium compound, it is possible to achieve prepared by the cyclisation citronellal of high enantioselectivity
Isopulegol；The solubility of its part aryl benzene sulfonic acid base, can greatly simplification of flowsheet experiment condition it is gentleer,
It can just reach that preferable catalytic effect, i.e. feed stock conversion are high (without requiring low temperature) close under conditions of room temperature, product
Selectivity is high；More facilitate with cooling system, reduce energy expenditure and saved energy consumption, be adapted to plant-scale production.
Isopulegol separation process is simplified, part removal process, catalyst aryl benzene sulfonic acid base aluminium has been improved and optimizated
Compound after cyclization terminates can by conversion to aryl benzene sulfonic acid sodium salt form, be soluble in using sulfonic group sodium salt
The property of water, can realize the separation of catalyst and product in organic phase, then separating catalyst can be obtained from aqueous phase and matched somebody with somebody
Body, realizes the recycling of aryl benzene sulfonic acid part.Plant-scale production that operating procedure is easy, economy is particularly suitable for use in.
Embodiment
Following examples are used to illustrate the present invention, but without any limitation property.
Gas chromatograph：Agilent 7890, chromatographic column INNO-WAX, injector temperature：300℃；Split ratio 50:1；Carry
Throughput：30ml/min；Heating schedule：80-230 DEG C, 3 DEG C/min, fid detector temperature：280℃.
Toluene 99.5%, lark prestige Science and Technology Ltd.；
Tert-butyl lithium 1.3M pentane solutions, lark prestige Science and Technology Ltd.；
Triethyl aluminum, trimethyl aluminium, 98wt%, lark prestige Science and Technology Ltd.；
Lithium aluminium hydride reduction, 98wt%, lark prestige Science and Technology Ltd.；
Methyl pyruvate 98wt%, Sa En chemical technology (Shanghai) Co., Ltd.；
Acetic anhydride 98wt%, Sa En chemical technology (Shanghai) Co., Ltd.；
Citronellal 98wt%, Aladdin reagent Co., Ltd；
2,6- diphenyl benzene sulfonic acid 99wt%, Aladdin reagent Co., Ltd；
2,6- bis- (betanaphthyl) benzene sulfonic acid 99wt%, Aladdin reagent Co., Ltd；
2,6- bis- (3- trifluoromethyls) benzene sulfonic acid 99wt%, Aladdin reagent Co., Ltd；
2,6- bis- (chlorphenyl) benzene sulfonic acid 99wt%, Aladdin reagent Co., Ltd；
2,6- bis- (3- isopropyl phenyls) benzene sulfonic acid 99wt%, Aladdin reagent Co., Ltd；
Embodiment 1
Citronellal, is cyclized by the catalyst prepared using ligand i -1 in the presence of acetic anhydride
1.5519g (5mmol) ligand i -1 and 30.9g dry toluene are added in the flask of heated drying, at room temperature,
1M solution of 0.5ml (1mmol, relative to the 0.5mol% of the citronellal) triethyl aluminum in toluene is added thereto, then
Stirred in 25 DEG C 1 hour, the gel-like suspension of catalyst is obtained after several minutes, the catalyst suspension is cooled to 5
DEG C, and in 6h by 15.45g (100mmol) citronellal for being previously cooled to 5 DEG C and 514.5mg (relative to citronellal
5mol%) the mixture of acetic anhydride be added thereto in 5 DEG C of stirring reactions 4 hours, extract the reaction of differential responses period
Liquid sample.
Reaction solution sample is hydrolyzed with 1g 8wt% NaOH respectively, and in the process, existing aluminium is used as sodium metaaluminate
It is dissolved in aqueous phase, and obtains suspension first.After some times, two transparent phases are formed, organic phase passes through respectively
Gas chromatographic analysis, the retention time 16.115min of new-isopulegol, the retention time of new iso- isopulegol
The retention time of 17.393min, the retention time 18.156min, L- (-) of iso- isopulegol-n- isopulegol is
16.443min, reaction conversion ratio and isopulegol product selectivity, are as a result listed in Table 1.
The reaction solution sample organic phase analysis result of 1 embodiment of table 1
After reaction 4 hours, citronellal conversion ratio 90.02%, isopulegol selectivity 98.89%.
The content of new-isopulegol is 0.22wt% in product isopulegol, and the content of new iso- isopulegol is
0.05wt%, is not detected by iso- isopulegol.Based on all enantiomer meters of product isopulegol, wherein L- (-)-n- different
The ratio of pulegol enantio-selectivity and other enantio-selectivities is 99.73:0.27 (other enantiomers include new-different
Pulegol, new iso- isopulegol and iso- isopulegol).
Embodiment 2
Citronellal, is cyclized by the catalyst prepared using ligand i -2 in the presence of pyruvic acid
3588.375mg (8.75mmol) ligand i -2 and 154.5g dry toluene are added in the flask of heated drying,
At room temperature, 2.5ml (2.5mmol, relative to the 2.5mol% of citronellal) lithium aluminium hydride reduction is added thereto in tetrahydrofuran
In 1M solution.The solution is stirred 1 hour in 25 DEG C, the gel-like suspension of catalyst is obtained after several minutes.Should
Catalyst suspension is cooled to 10 DEG C, and by 15.45g (100mmol) citronellal for being previously cooled to 10 DEG C in 6h
It is added thereto with the mixture of 308.7mg (relative to the 3mol% of citronellal) methyl pyruvate and is stirred for the reaction in 10 DEG C
Mixture 8 hours, extracts the reaction solution sample of differential responses period.
Reaction solution sample is hydrolyzed with 5g 2% NaOH respectively.In the process, existing aluminium is molten as sodium metaaluminate
Solution obtains suspension first in aqueous phase.After some time, two transparent phases are formed, organic phase passes through gas-chromatography
Analysis, is as a result listed in Table 2.
The reaction solution sample organic phase analysis result of 2 embodiment of table 2
After reaction 8 hours, citronellal conversion ratio 95.11%, isopulegol selectivity 97.94%.
The content of new-isopulegol is 0.2wt% in isopulegol, and the content of new iso- isopulegol is
0.3wt%, the content of iso- isopulegol is 0.1wt%.L- (-)-n- isopulegol enantio-selectivity is right with other
The ratio for reflecting body selectivity is 99.4:0.6.
Embodiment 3
Citronellal is cyclized in the presence of the catalyst prepared using ligand i -3, acetic anhydride
15.623g (35mmol) ligand i -3 and 7.725g dry toluene are added in the flask of heated drying.In room temperature
Under, 1M solution of 5ml (5mmol, relative to the 5mol% of the citronellal) triethyl aluminum in toluene is added into clear solution.
The solution is stirred 1 hour in 25 DEG C, the gel-like suspension of catalyst is obtained after several minutes.By the catalyst suspension
15 DEG C are cooled to, and by 15.45g (100mmol) citronellal for being previously cooled to 15 DEG C and 257.25mg (phases in 6h
For the 2.5mol% of citronellal) the mixture of acetic anhydride be added thereto and the reactant mixture be stirred in 15 DEG C 12 hours,
Sample is extracted according to regular interval, and is hydrolyzed with 10g 8wt% NaOH.In the process, existing aluminium is as inclined
Sodium aluminate is dissolved in aqueous phase, and obtains suspension first.After some time, two transparent phases are formed.Organic phase passes through
Gas chromatographic analysis, is as a result listed in Table 3.
The reaction solution sample organic phase analysis result of 3 embodiment of table 3
After reaction 12 hours, citronellal conversion ratio 99.46%, isopulegol selectivity 94.89%.
The content of new-isopulegol is 0.3wt% in isopulegol, and the content of new iso- isopulegol is
0.4wt%, the content of iso- isopulegol is 0.1wt%.L- (-)-n- isopulegol enantio-selectivity is right with other
The ratio for reflecting body selectivity is 99.2:0.8.
Embodiment 4
Citronellal, is cyclized by the catalyst prepared using ligand i -1 in the presence of methyl pyruvate
9.3111g (1.5mmol) ligand i -1 and 309g anhydrous n-hexane, room temperature are added in the flask of heated drying
Under, 1M solution of 10ml (10mmol, relative to the 1mol% of the citronellal) triethyl aluminum in n-hexane is added thereto, so
Stirred after 25 DEG C 1 hour, the gel-like suspension of catalyst is obtained after several minutes, the catalyst suspension is cooled to
5 DEG C, and in 6h by 154.5g (1000mmol) citronellal for being previously cooled to 10 DEG C and 1.029g (relative to lemongrass
The 1mol% of aldehyde) the mixture of acetic anhydride be added thereto in 10 DEG C of stirring reactions 4 hours, then raise temperature to 20 DEG C, stirring is anti-
Answer 2 hours, extract the reaction solution sample of differential responses period.
Reaction solution sample is hydrolyzed with 2g 8wt% NaOH respectively, and in the process, existing aluminium is used as sodium metaaluminate
It is dissolved in aqueous phase, and obtains suspension first.After some times, two transparent phases are formed, organic phase passes through respectively
Gas chromatographic analysis, is as a result listed in Table 4.
The reaction solution sample organic phase analysis result of 4 embodiment of table 4
After reaction 6 hours, citronellal conversion ratio 99.05%, isopulegol selectivity 98.55%.
The content of new-isopulegol is 0.4wt% in isopulegol, and the content of new iso- isopulegol is
0.5wt%.The ratio of L- (-)-n- isopulegol enantio-selectivity and other enantio-selectivities is 99.1:0.9.
Embodiment 5
The catalyst prepared using ligand i -4, is added citronellal cyclisation in the presence of acetic anhydride in the flask of heated drying
Enter 33.185g (87.5mmol) ligand i -4 and 154.5g anhydrous dimethyl benzene.At room temperature, added into clear solution
1M solution of 25ml (25mmol, relative to the 2.5mol% of the citronellal) trimethyl aluminium in dimethylbenzene.By the solution in 25
DEG C stirring 1 hour, after several minutes obtain catalyst gel-like suspension.The catalyst suspension is cooled to 5 DEG C, and
By 154.5g (1mol) citronellal for being previously cooled to 5 DEG C and 514.5mg (relative to citronellal in 6h
The mixture of acetic anhydride 0.5mol%), which is added thereto, is stirred for the reactant mixture in 5 DEG C 8 hours, according to regular
Hydrolyzed every extraction sample, and with 50g 8wt% NaOH.In the process, existing aluminium is dissolved in water as sodium metaaluminate
Xiang Zhong, and suspension is obtained first.After some time, two transparent phases are formed.Organic phase passes through gas chromatographic analysis, knot
Fruit is listed in Table 5.
The reaction solution sample organic phase analysis result of 5 embodiment of table 5
After reaction 8 hours, citronellal conversion ratio 96.66%, isopulegol selectivity 97.11%.
The mass content of new-isopulegol is 0.3% in isopulegol, the mass content of new iso- isopulegol
For 0.3%, the mass content of iso- isopulegol is 0.2%.L- (-)-n- isopulegol enantio-selectivity and other
The ratio of enantio-selectivity is 99.2:0.8.
Embodiment 6
Citronellal, is cyclized by the catalyst prepared using ligand i -5 in the presence of methyl pyruvate, and is post-processed,
Reclaim part
78.906g (200mmol) ligand i -5 and 77.25g dry toluene are added in the flask of heated drying.In room
Under temperature, 1M of 50ml (50mmol, relative to the 5mol% of the citronellal) triethyl aluminum in toluene is added into clear solution
Solution.The solution is stirred 1 hour in 25 DEG C, the gel-like suspension of catalyst is obtained after several minutes.
The catalyst suspension is cooled to 10 DEG C, and being previously cooled to 154.5g (1000mmol) in 6h
The mixture of 10 DEG C of citronellal and 1.029g (relative to the 1mol% of citronellal) methyl pyruvate is added thereto and in 10
DEG C it is stirred for the reactant mixture 12 hours, sample is extracted according to regular interval, and with 100g 8% NaOH hydrolysis.
In the process, existing aluminium is dissolved in aqueous phase as sodium metaaluminate, and obtains suspension first.Some times it
Afterwards, two transparent phases are formed, as a result organic phase is listed in Table 6 by gas chromatographic analysis.
The reaction solution sample organic phase analysis result of 6 embodiment of table 6
After reaction 24 hours, citronellal conversion ratio 98.08%, isopulegol selectivity 95.23%.
The mass content of new-isopulegol is 0.7% in isopulegol, the mass content of new iso- isopulegol
For 0.1%, the mass content of iso- isopulegol is 0.2%.L- (-)-n- isopulegol enantio-selectivity and other
The ratio of enantio-selectivity is 99:1.
Reaction solution obtains organic phase and aqueous phase by phase separator, and then organic phase is handled.Solvent toluene via
Tower (diameter：30mm, filler 400mm, filler 3.5mm triangle spiral Sita rings, 100 millibars, 45-48 DEG C of head temperature, bottom temperature
48-90 DEG C of degree) removed by distilling.Distilled out under decompression (6 millibars, 55 DEG C of head temperature, 75 DEG C of bottom temp) as steaming
Evaporate the isopulegol of residue acquisition.First cut includes the isopulegol (142.86g) that purity is 98%.Bottom mother liquor
(14.85g) wherein isopulegol content is that 77.08%, I-5 ligand contents are 6.36%, remaining heavy constituent impurity (lemongrass
Alcohol, isopulegol ester, different pennyroyal mint lemongrass acid esters etc.) content be 16.56%.
Aqueous phase solution is added in 500ml round-bottomed flasks, adds 80g 2% concentration hydrochloric acid, is neutralized pH value to 7, is fully stirred
2h is mixed, until part is no longer separated out.It is filtered under diminished pressure molten in the I-5 parts for reclaiming and obtaining that 10.9g purity is 99.08%, detection water
Solution ligand concentration is 56.3ppm.
Embodiment 7
The catalyst prepared using ligand i -1, will in the presence of 0.05% (being based on citronellal mole) strength acetic acid acid anhydride
Citronellal is cyclized
93.111g (300mmol) ligand i -1 and 1545g anhydrous n-hexane, room temperature are added in the flask of heated drying
Under, 1M solution of 100ml (100mmol, relative to the 1mol% of the citronellal) triethyl aluminum in n-hexane is added thereto,
Then stirred 1 hour in 25 DEG C, the gel-like suspension of catalyst is obtained after several minutes, the catalyst suspension is cooled down
To 5 DEG C, and in 6h by 1545g (10mol) citronellal for being previously cooled to 5 DEG C and 514.5mg (relative to citronellal
0.05mol%) the mixture of acetic anhydride be added thereto in 5 DEG C of stirring reactions 16 hours, extract the differential responses period
Reaction solution sample.
Reaction solution sample is hydrolyzed with 200g 8wt% NaOH respectively, and in the process, existing aluminium is used as meta-aluminic acid
Sodium is dissolved in aqueous phase, and obtains suspension first.After some times, two transparent phases are formed, organic phase is led to respectively
Gas chromatographic analysis is crossed, is as a result listed in Table 7.
The reaction solution sample organic phase analysis result of 7 embodiment of table 7
After reaction 16 hours, citronellal conversion ratio 94.08%, isopulegol selectivity 91.98%.
The mass content of new-isopulegol is 0.8% in isopulegol, the mass content of new iso- isopulegol
For 0.2%, the mass content of iso- isopulegol is 0.2%.L- (-)-n- isopulegol enantio-selectivity and other
The ratio of enantio-selectivity is 98.9:1.1.
Embodiment 8
The catalyst prepared using ligand i -3, will in the presence of 0.01% (being based on citronellal mole) methyl pyruvate
Citronellal is cyclized
89.272g (200mmol) ligand i -3 and 1545g dry toluene are added in the flask of heated drying.In room temperature
Under, 1M of 50ml (50mmol, relative to the 0.5mol% of the citronellal) trimethyl aluminium in toluene is added into clear solution
Solution.The solution is stirred 1 hour in 25 DEG C, the gel-like suspension of catalyst is obtained after several minutes.By the catalyst
Suspension is cooled to 10 DEG C, and 1545g (10mol) is previously cooled into 10 DEG C of citronellal and 102.9mg in 6h
The mixture of the acetic anhydride of (relative to the 0.01mol% of citronellal) is added thereto that the reactant mixture 24 is stirred in 10 DEG C is small
When, sample is extracted according to regular interval, and hydrolyzed with 100g 8wt% NaOH.In the process, existing aluminium is made
It is dissolved in for sodium metaaluminate in aqueous phase, and obtains suspension first.After some time, two transparent phases are formed.Organic phase
By gas chromatographic analysis, as a result it is listed in Table 8.
The reaction solution sample organic phase analysis result of 8 embodiment of table 8
After reaction 24 hours, citronellal conversion ratio 96.01%, isopulegol selectivity 90.11%.
The mass content of new-isopulegol is 0.2% in isopulegol, the mass content of new iso- isopulegol
For 0.3%, the mass content of iso- isopulegol is 0.2%.L- (-)-n- isopulegol enantio-selectivity and other
The ratio of enantio-selectivity is 99.3:0.7.
Embodiment 9
Citronellal, is cyclized by the catalyst prepared using ligand i -4 in the presence of acetic anhydride
11.378g (30mmol) ligand i -4 and 154.5g dry toluene are added in the flask of heated drying.In room temperature
Under, 1M of 10ml (10mmol, relative to the 1mol% of the citronellal) triethyl aluminum in toluene is added into clear solution molten
Liquid.The solution is stirred 1 hour in 25 DEG C, the gel-like suspension of catalyst is obtained after several minutes.The catalyst is hanged
Supernatant liquid is cooled to 10 DEG C, and by 154.5g (1mol) citronellal for being previously cooled to 10 DEG C and 2.058g (phases in 6h
For the 2mol% of citronellal) the mixture of acetic anhydride be added thereto and the reactant mixture be stirred in 10 DEG C 4 hours, then rise
Temperature stirs the mixture 2 hours to 20 DEG C.Sample is extracted according to regular interval, and is hydrolyzed with 20g 8wt% NaOH.
In the process, existing aluminium is dissolved in aqueous phase as sodium metaaluminate, and obtains suspension first.Some times it
Afterwards, two transparent phases are formed.As a result organic phase is listed in Table 9 by gas chromatographic analysis.
The reaction solution sample organic phase analysis result of 9 embodiment of table 9
After reaction 6 hours, citronellal conversion ratio 99.52%, isopulegol selectivity 99.29%.
The mass content of new-isopulegol is 0.25% in isopulegol, the mass content of new iso- isopulegol
For 0.13%, the mass content of iso- isopulegol is 0.05%.L- (-)-n- isopulegol enantio-selectivity and its
The ratio of his enantio-selectivity is 99.57:0.43.
Comparative example
It is cyclized using part VI (structure is as follows) with acetic anhydride
1.05mmol part VI and 1 0ml dry toluene are added in the flask of heated drying.At room temperature, to transparent
0.66M solution of 350 μ l (0.65mmol, relative to the 1mol% of the citronellal) triethyl aluminum in toluene is added in solution.
The solution is stirred 1 hour in 25 DEG C, the gel-like suspension of catalyst is obtained after several minutes.By the catalyst suspension
Be cooled to 0 DEG C, and be added portionwise in 6 hours 10.15g (65.8mmol) citronellal for being previously cooled to 0 DEG C with
In 0 DEG C in the mixture of 0.1g (relative to the 1wt% of citronellal) acetic anhydride.
Stir the reactant mixture and extract sample according to regular interval, and hydrolyzed with 8wt% NaOH.In this process
In, existing aluminium is precipitated out as hydroxide, and obtains suspension first.After some time, two are formed thoroughly
As a result bright phase, organic phase is listed in Table 10 by gas chromatographic analysis.
The comparative example reaction solution sample organic phase analysis result of table 10
After reaction 72 hours, citronellal conversion ratio 99.70%, isopulegol selectivity 89.82%.Enantiomeric ratio
(new-isopulegol: isopulegol: new iso- isopulegol: iso- isopulegol) is 0.8: 98.5: 0.4: 0.3.
The mass content of new-isopulegol is 0.8% in isopulegol, the mass content of new iso- isopulegol
For 0.4%, the mass content of iso- isopulegol is 0.3%.L- (-)-n- isopulegol enantio-selectivity and other
The ratio of enantio-selectivity is 98.5:1.5.
Contrasted by embodiment and comparative example it can be found that reaction temperature when being reacted in the present invention is gentleer,
Faster, reaction conversion ratio, selectivity are higher, and the final ee values of L- (-)-n- isopulegol are more advantageous for reaction rate.
Claims (9)
1. a kind of method that isopulegol is prepared by citronellal, comprises the following steps：In catalyst aryl benzene sulfonic acid base calorize
In the presence of compound, citronellal occurs cyclization and prepares isopulegol；
The aryl benzene sulfonic acid base aluminium compound by the aryl benzene sulfonic acid part including formula (I) and formula (II) aluminium compound and/
Or the aluminium compound of formula (III) is prepared from；
(R1)3-pAIHp
(II)
MAIH4
(III)
Wherein Ar1、Ar2Can with it is identical or different and separately be selected from C6-C12Heteroaryl or C6-Cl5Aryl and virtue
Optionally containing 1-3 substituent on base, the substituent is selected from halogeno-group, trihalomethyl group, methoxyl group, acetyl group, diformazan
Base amino, diethylamino, trimethyl silicon substrate, triethyl group silicon substrate, cyano group, nitro；Preferably, the Ar1With Ar2Independently
Ground is selected from phenyl, betanaphthyl, 3- trifluoromethyls, chlorphenyl, 3- isopropyl phenyls；
R1It is C1-C5Alkyl；P is 0-3 integer；
M is lithium, sodium or potassium.
2. according to the method described in claim 1, it is characterised in that the aryl benzene sulfonic acid part of formula (I) may be selected from following part
In one or more：
The aluminium compound of described formula (II) is trimethyl aluminium and/or triethyl aluminum；
The aluminium compound of described formula (III) is lithium aluminium hydride reduction.
3. method according to claim 1 or 2, it is characterised in that the aryl benzene sulfonic acid part of the formula (I) and formula (II)
Aluminium compound and/or the mol ratio of aluminium compound of formula (III) be 3:1 to 10:1, preferably 3:1 to 4:1.
4. the method according to any one of claim 1-3, it is characterised in that with aluminium in aryl benzene sulfonic acid base aluminium compound
The molar amount of atom, the consumption of the catalyst is 0.5mo1% to 5mo1%, the mole based on citronellal.
5. the method according to any one of claim 1-4, it is characterised in that the preparation method of the catalyst include with
Lower step：
Under inert gas shielding, the aryl benzene sulfonic acid part of formula (I) is dissolved in solvent, the aryl benzene sulfonic acid part of formula (I) is obtained
Solution；
The aluminium compound of formula (II) and/or the aluminium compound of formula (III) are diluted using solvent, the calorize containing formula (II) is obtained and closes
The aluminum compound solution of thing and/or formula (III)；
Proportionally, the aluminum compound solution of the aluminium compound containing formula (II) and/or formula (III) is slowly added dropwise to formula (I)
Aryl benzene sulfonic acid ligand solution in, form catalyst solution or catalyst suspension.
6. the method according to any one of claim 1-5, it is characterised in that the catalysis citronellal cyclisation prepares different Hu
The reaction temperature of menthol is -10-50 DEG C, more preferably preferably -10-20 DEG C, 5-15 DEG C；Reaction time 4-24h, preferably 4-12h；
Preferably, the citronellal prepares isopulegol cyclization in 8-10 DEG C of reaction 4-5h, then is warming up to 15-20 DEG C of reaction 1-
2h。
7. the method according to any one of claim 1-6, it is characterised in that also include addition in the cyclization molten
Agent, selected solvent is shows inert solvent in cyclization process, and preferably alkane, aromatic hydrocarbons, halogenated hydrocarbons, ethers and esters are molten
One kind in one or more in agent, more preferably n-hexane, normal heptane, toluene, dimethylbenzene, tetrahydrofuran and dichloromethane
Or a variety of, the one or more in further preferred toluene, n-hexane and dimethylbenzene；The mass ratio of solvent load and citronellal is
1:5 to 10:1, preferably 1:2 to 2:1.
8. the method according to any one of claim 1-7, it is characterised in that also include being optionally added into cyclization
Auxiliary agent, the auxiliary agent is selected from the compound of organic acid, carboxylic acid anhydrides, aldehyde, ketone, ester and vinyl ethers, preferably is selected from acetaldehyde, propionic aldehyde, chlorine
Aldehyde, 1,1,1- trifluoroacetones, 1,1,1- trifluoroacetophenones, methyl pyruvate, ethyl pyruvate, Hexafluoro acetone, acetic anhydride, third
One or more in aldehyde, neopentanoic acid acid anhydride and benzoyl oxide, more preferably methyl pyruvate, consumption is 0.01-5mol%, based on perfume (or spice)
The consumption of thatch aldehyde.
9. method according to claim 8, it is characterised in that the method that isopulegol is prepared by citronellal, in addition to
Following steps：
A) solvent is distilled off and optional auxiliary agent from cyclization mixture；
B) 1-4wt% is added into the residue obtained in the step a), preferably 1.5-2wt% sodium hydroxide solutions, in 60-80
3-6h is sufficiently stirred at DEG C, after aryl benzene sulfonic acid sodium salt fully dissolves in aqueous phase, passes through phase separator and carries out aqueous phase, organic phase
Separation, respectively obtains aqueous phase, organic phase；
C) separated goes out isopulegol in the organic phase obtained from step b)；
D) catalyst is reclaimed：The aqueous phase obtained in step b) is carried out being neutralized to pH=1-3, aryl benzene sulfonic acid part is with solid shape
Formula is separated out, and obtained aryl benzene sulfonic acid solid ligand is washed, purification process.
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| CN108329194A (en) * | 2018-04-11 | 2018-07-27 | 万华化学集团股份有限公司 | A kind of citronellal prepares the method for isopulegol and its recovery method of catalyst |
| CN109456157A (en) * | 2018-12-10 | 2019-03-12 | 万华化学集团股份有限公司 | A method of L- menthones is prepared by R- citronellal |
| CN110845305A (en) * | 2019-11-25 | 2020-02-28 | 安徽一帆香料有限公司 | Method for preparing L-menthol by adopting modified homogeneous catalyst |
| CN110903173A (en) * | 2019-12-04 | 2020-03-24 | 万华化学集团股份有限公司 | Method for preparing L-menthone from R-citronellal |
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| CN114292160A (en) * | 2022-01-10 | 2022-04-08 | 万华化学集团股份有限公司 | Method for preparing isopulegol from citronellal |
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| CN108329194A (en) * | 2018-04-11 | 2018-07-27 | 万华化学集团股份有限公司 | A kind of citronellal prepares the method for isopulegol and its recovery method of catalyst |
| CN108329194B (en) * | 2018-04-11 | 2021-06-25 | 万华化学集团股份有限公司 | Method for preparing isopulegol from citronellal and recovery method of catalyst of isopulegol |
| US20210165325A1 (en) * | 2018-08-31 | 2021-06-03 | Fujifilm Corporation | Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern forming method, method for manufacturing electronic device, and compound |
| CN109456157A (en) * | 2018-12-10 | 2019-03-12 | 万华化学集团股份有限公司 | A method of L- menthones is prepared by R- citronellal |
| CN109456157B (en) * | 2018-12-10 | 2021-09-07 | 万华化学集团股份有限公司 | Method for preparing L-menthone from R-citronellal |
| CN110845305A (en) * | 2019-11-25 | 2020-02-28 | 安徽一帆香料有限公司 | Method for preparing L-menthol by adopting modified homogeneous catalyst |
| CN110845305B (en) * | 2019-11-25 | 2022-06-28 | 安徽一帆香料有限公司 | Method for preparing L-menthol by adopting modified homogeneous catalyst |
| CN110903173A (en) * | 2019-12-04 | 2020-03-24 | 万华化学集团股份有限公司 | Method for preparing L-menthone from R-citronellal |
| CN114292160A (en) * | 2022-01-10 | 2022-04-08 | 万华化学集团股份有限公司 | Method for preparing isopulegol from citronellal |
| CN114292160B (en) * | 2022-01-10 | 2023-12-19 | 万华化学集团股份有限公司 | Method for preparing isopulegol from citronellal |
| CN115974669A (en) * | 2023-02-10 | 2023-04-18 | 广西壮族自治区林业科学研究院 | Method for efficiently separating high-purity citronellal from eucalyptus citriodora essential oil |
| CN115974669B (en) * | 2023-02-10 | 2024-03-01 | 广西壮族自治区林业科学研究院 | Method for efficiently separating high-purity citronellal from eucalyptus citriodora essential oil |
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