CN101133067B - Diarylphenoxy aluminum compounds - Google Patents
Diarylphenoxy aluminum compounds Download PDFInfo
- Publication number
- CN101133067B CN101133067B CN2006800068756A CN200680006875A CN101133067B CN 101133067 B CN101133067 B CN 101133067B CN 2006800068756 A CN2006800068756 A CN 2006800068756A CN 200680006875 A CN200680006875 A CN 200680006875A CN 101133067 B CN101133067 B CN 101133067B
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- Prior art keywords
- formula
- isopulegol
- different
- aryl
- alkyl
- Prior art date
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims description 40
- -1 aluminum compound Chemical class 0.000 claims abstract description 137
- ZYTMANIQRDEHIO-KXUCPTDWSA-N isopulegol Chemical compound C[C@@H]1CC[C@@H](C(C)=C)[C@H](O)C1 ZYTMANIQRDEHIO-KXUCPTDWSA-N 0.000 claims abstract description 136
- 239000001871 (1R,2R,5S)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Substances 0.000 claims abstract description 120
- 229940095045 isopulegol Drugs 0.000 claims abstract description 120
- 238000000034 method Methods 0.000 claims abstract description 78
- ZYTMANIQRDEHIO-UHFFFAOYSA-N neo-Isopulegol Natural products CC1CCC(C(C)=C)C(O)C1 ZYTMANIQRDEHIO-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 46
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 33
- 125000003118 aryl group Chemical group 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 178
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 89
- 241000134874 Geraniales Species 0.000 claims description 89
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 28
- 229910052736 halogen Inorganic materials 0.000 claims description 26
- 150000002367 halogens Chemical class 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 150000001299 aldehydes Chemical class 0.000 claims description 18
- 150000002576 ketones Chemical class 0.000 claims description 18
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 15
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 12
- NOOLISFMXDJSKH-AEJSXWLSSA-N (+)-menthol Chemical compound CC(C)[C@H]1CC[C@H](C)C[C@@H]1O NOOLISFMXDJSKH-AEJSXWLSSA-N 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000011591 potassium Chemical group 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000011734 sodium Chemical group 0.000 claims description 4
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 claims description 4
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 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
- 238000005194 fractionation Methods 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
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 32
- 239000003446 ligand Substances 0.000 abstract description 28
- 238000006467 substitution reaction Methods 0.000 abstract 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 abstract 1
- NEHNMFOYXAPHSD-UHFFFAOYSA-N beta-citronellal Natural products O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 abstract 1
- 229930003633 citronellal Natural products 0.000 abstract 1
- 235000000983 citronellal Nutrition 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 229940041616 menthol Drugs 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 93
- 239000000243 solution Substances 0.000 description 52
- 239000002585 base Substances 0.000 description 35
- GJWSUKYXUMVMGX-UHFFFAOYSA-N citronellic acid Chemical compound OC(=O)CC(C)CCC=C(C)C GJWSUKYXUMVMGX-UHFFFAOYSA-N 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 21
- 239000011541 reaction mixture Substances 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- QPBVYDIIQIYFQO-UHFFFAOYSA-N 3,7-dimethyloct-6-enyl prop-2-enoate Chemical compound CC(C)=CCCC(C)CCOC(=O)C=C QPBVYDIIQIYFQO-UHFFFAOYSA-N 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 150000003851 azoles Chemical class 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 3
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical group [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 description 2
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000005792 Geraniol Substances 0.000 description 2
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 229940113087 geraniol Drugs 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 2
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 2
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 2
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical group Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- AFINGIXRSWIXIG-UHFFFAOYSA-N CC(C(F)(F)F)(c(cc1-c2ccccc2)cc(-c2ccccc2)c1O)c(cc1-c2ccccc2)cc(-c2ccccc2)c1O Chemical compound CC(C(F)(F)F)(c(cc1-c2ccccc2)cc(-c2ccccc2)c1O)c(cc1-c2ccccc2)cc(-c2ccccc2)c1O AFINGIXRSWIXIG-UHFFFAOYSA-N 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000006423 Tishchenko reaction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZXRRHFSTAFVGOC-UHFFFAOYSA-N [AlH3].[K] Chemical compound [AlH3].[K] ZXRRHFSTAFVGOC-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 125000006202 diisopropylaminoethyl group Chemical group [H]C([H])([H])C([H])(N(C([H])([H])C([H])([H])*)C([H])(C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical group O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 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
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- 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
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Diarylphenoxy-aluminum compound (A), obtained by a reaction of bis(diarylphenol) ligand (I) with aluminum compound (II) and/or aluminum compound (III), is new. Diarylphenoxy-aluminum compound, obtained by a reaction of bis(diarylphenol) ligand of formula (I) with aluminum compound (II) of formula ((R1>4>)3-pAlHp) and/or aluminum compound (III) of formula (MAlH4), is new. T : 1-6C-alkyl, 1-6C-perfluoroalkyl, 1-6C-alkoxy, 7-12C-aralkyl, halo, optionally substituted 6-10C-aryl or NO2; Ar1>-Ar4>6-15C aryl or 2-15C heteroaryl (optionally substituted by 1-7 substitutions of T SiR5>aR6>aR7>a, NR8>aR9>a or SR1>0a); either R1>-R4>H, T, SiR5>bR6>bR7>b, NR8>bR9>b or SR1>0b; or A+R1>-R4 : aromatic or non-aromatic cycle; D : O, S, NR1>1>, C(O), S(O) and/or S(O)2; A : 1-25C-hydrocarbon, heteroatom of D, T, 1-10C-acyloxy, SiR5>cR6>cR7>c, 2-10C-heteroaryl, NR8>cR9>c, SR1>0c, 1-12-acyl, 1-10C-carboxyl, 6-15C-aryl or 2-15C-hereroaryl optionally substituted by 1-5 substitutions of T, SiR5>dR6>dR7>d, NR8>dR9>d, SR1>0d, heteroatom of D, P(R1>1>), (R1>1>)P(O) or Si(R1>2>R1>3>); R5>a-R5>d, R6>a-R6>d, R7>a-R7>d, R1>0>a-R1>0>d, R1>1>-R1>3>, R1>1>a : 1-6C-alkyl, 7-12C-aralkyl and/or optionally substituted 6-10C-aryl; either R8>a-R8>d, R9>a-R9>d : 1-6C-alkyl, 7-12C-aralkyl and/or optionally substituted 6-10C-aryl; or R8>aR9>a, R8>bR9>b, R8>cR9>c, R8>dR9>d : 2-8C cyclic hydrocarbon containing one or morehetero atoms of O, S or NR1>1>a; Al : aluminum; R1>4>1-5C-alkyl; p : 0-3; and M : Li, Na or K. Independent claims are included for: (1) a method for preparation of isopulegol of the formula (IV) comprising cyclization of citronellal compound of formula (V) in the presence of (I) as a catalyst; and (2) a method for preparing menthol comprising preparing (IV) and hydrogenating the ethylenic double bonds in the (IV).
Description
Invention field
The present invention relates to Diarylphenoxy aluminum compounds, two (diaryl phenol) parts of its through type (I) and alkylaluminium cpd and/or the reaction of title complex aluminum hydride obtain:
The invention still further relates to the purposes of these Diarylphenoxy aluminum compounds as catalyzer.
In addition, the present invention relates to a kind of method for preparing the non-enantiomer mixture of isopulegol and isopulegol, wherein make geranial in the presence of as the Diarylphenoxy aluminum compounds of catalyzer, carry out cyclization.
Aspect consumption, Therapeutic Mineral Ice is most important in the world aromachemicals.Demand for Therapeutic Mineral Ice still mainly is the separation from natural origin.But, in addition, the method for synthetic Therapeutic Mineral Ice is arranged also, be the form of racemic modification sometimes, be the form of natural enantiomorph L-Therapeutic Mineral Ice sometimes.
The important intermediate that is used to prepare racemize and optically-active Therapeutic Mineral Ice is an isopulegol; It carries out cyclisation oxygen base-alkene formula through geranial usually and reacts and prepare in the presence of lewis acid catalyst; And the form of mixtures of four kinds of enantiomorphs normally, i.e. isopulegol, different-isopulegol, new-isopulegol and strange-isopulegol.
Prior art:
Disclosed to be used to carry out above-mentioned geranial be heterogeneous catalyst to the suitable catalyst of the cyclization of isopulegol, for example SiO
2, Al
2O
3/ SiO
2, SiO
2/ ZrO
2, SiO
2/ TiO
2Mixed catalyst, mordenite, faujusite, smectite and zeolite; And homogeneous catalyst, for example sulfonic acid or Lewis acid, for example SnCl
4, ZnCl
2Or ZnBr
2
The catalyzer that is used for the geranial cyclization in the industry is a zinc bromide.But, when using this catalyzer, only obtain about 87% productive rate and 91: 9 enantioselectivity (ratio of isopulegol and other isopulegol isomer).
EP-A 1 225 163 has described under three (2,6-phenylbenzene phenol) Al catalysts exists geranial has been cyclized into isopulegol.Three (2,6-phenylbenzene phenol) aluminium is disclosed in document, and as being used for α; The selectivity 1 of beta-unsaturated carbonyl compound, the catalyzer of 4-functionalization and conduct are used for the catalyzer of special Claisen rearrangement reaction; Angew.Chem.Iht.Ed.2004 for example, 43,994 is said.
People such as S.Saito are at Synlett, and 1, described the triple phenoxyl aluminium polymer among the 57-58 and be used to carry out α as the lewis acidity catalyzer, the purposes of the Diels-Alder reaction between beta-unsaturated aldehyde and the diene as dienophile with it.Described triple phenoxyl aluminium polymer is through 4, and reaction obtains under ultrasonication in toluene for 4 '-(2,6,2 ', 6 '-tetraphenyl) bis-phenol and trimethylaluminium.The by product of required Diels-Alder reaction adducts is two polyester, and this is because the Tishchenko reaction in downstream.
JP 9-278817A relates to the catalyzer that is used for olefinic polyreaction, and it is suitable for replacing aikyiaiurnirsoxan beta.This catalyzer contains the transition metal of (a) periodic table of elements 4-6 family, the cyclopentadienyl system bonding of itself and cyclopentadienyl system or two bridge joints, (b) alkylaluminium cpd with (c) have at least two aromatic substance with the hydroxyl of aromatic ring keyed jointing.
The object of the invention:
Said three (2 according to EP-A 1 225 163 (as immediate prior art); 6-phenylbenzene phenol) Al catalysts is cyclized into geranial in the method for isopulegol under existing; Used catalyst complexes is expensive, and only can produce with the title complex mode.The recovery that a shortcoming of said method of in homogeneous phase, carrying out is the catalyst system therefor title complex is impossible, and this is because catalyst complexes is hydrolyzed after reaction is accomplished.And, there are not to describe the recovery possibility of the part that discharges in the method and usability again.
Therefore; The purpose of this invention is to provide a kind of catalyst system; It can be at least with known catalyst system equally well the catalysis geranial to the cyclization of isopulegol; And when reaction is accomplished, can also can utilize again with high purity and recovered in high yields, or its part can also can utilize with high purity and recovered in high yields with the simple mode of technology after reacting again with the simple mode of technology.
The description of the present invention and preferred embodiment:
The object of the invention realizes through Diarylphenoxy aluminum compounds is provided, two (diaryl phenol) parts of said Diarylphenoxy aluminum compounds through type (I) and the aluminum compound of formula (II) and/or obtain with the aluminum compound reaction of formula (III):
Wherein,
Ar
1, Ar
2, Ar
3, Ar
4Be identical or different, and be the heteroaryl that has the aryl of 6-15 carbon atom or have 2-15 carbon atom in each case independently of one another, its when suitable, can carry in each case 1-7 identical or different be selected from following substituting group: C
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen ,-SiR
5aR
6aR
7a, replace or unsubstituted C
6-C
10Aryl ,-NR
8aR
9a,-SR
10aAnd-NO
2,
R
1, R
2, R
3, R
4Be identical or different, and be hydrogen independently of one another in each case, C
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen ,-SiR
5bR
6bR
7b, replace or unsubstituted C
6-C
10Aryl ,-NR
8bR
9b,-SR
10b, and/or-NO
2, and R
1Or R
2And/or R
3Or R
4Can with A form aromatics or non-aromatics ring and
A (1) is the alkyl that straight chain or branching and/or cyclic have 1-25 carbon atom; It can be saturated or single unsaturated or polyunsaturated; And/or be partially aromatic and when suitable, can have one or more identical or different heteroatoms O, S and NR of being selected from
11In heteroatoms and/or the one or more identical or different C of functional group (O), S (O) and S (O) of being selected from
2In functional group and when suitable, can carry one or more identical or different following substituting group: C that are selected from
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
1-C
10Acyloxy, C
7-C
12Aralkyl, halogen ,-SiR
5cR
6cR
7c, replace or unsubstituted C
6-C
10Aryl replaces or unsubstituted C
2-C
10Heteroaryl ,-NR
8cR
9c,-SR
10c,-NO
2, C
1-C
12Acyl group, and C
1-C
10Carboxyl, or
(2) be the heteroaryl that has the aryl of 6-15 carbon atom or have 2-15 carbon atom, it can carry 1-5 in each case and be selected from following substituting group: C when suitable
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen ,-SiR
5dR
6dR
7d, replace or unsubstituted C
6-C
10Aryl ,-NR
8dR
9d,-SR
10dAnd-NO
2, or
(3) be selected from following functional group or heteroatoms :-O-,-S-,-N (R
11)-,-S (O)-,-C (O)-,-S (O)
2-,-P (R
11)-,-(R
11) P (O)-with-Si (R
12R
13),
Radicals R wherein
5a, R
6a, R
7a, R
8a, R
9a, R
10aTo R
5d, R
6d, R
7d, R
8d, R
9d, R
10dAnd R
11To R
13Be C in each case independently
1-C
6Alkyl, C
7-C
12Aralkyl and/or replacement or unsubstituted C
6-C
10Aryl, radicals R
8aAnd R
9a, R
8bAnd R
9b, R
8cAnd R
9c, R
8dAnd R
9dIndependently of one another can be in each case also form together and have the cyclic hydrocarbon group of 2-8 carbon atom, it can have one or more identical or different O, S and NR of being selected from
11aIn heteroatoms, and R
11aCan have for R
11Given definition,
(R
14)
3-pAlH
p (II)，
Wherein
Al is an aluminium,
R
14Be a branching or the nonbranched 1-5 of a having carbon atom alkyl and
P is 0 or the integer of 1-3,
MAlH
4 (III)，
Wherein
Al be aluminium and
M is lithium, sodium or potassium.
Formula (I) two (diaryl phenol) part that is used to prepare Diarylphenoxy aluminum compounds of the present invention has two phenol systems, this two individual system in each case all at the ortho position of phenolic hydroxyl group by aryl or heteroaryl (Ar
1To Ar
4) replace, and be bonded together via structural unit A, and when suitable, also can carry other substituting group (R
1To R
4).
Aromatics or heteroaromatic substituent A r
1To Ar
4Can be identical or different independently of one another.Preferably, in each case with two substituting group (Ar of phenol system bonding
1And Ar
2, perhaps Ar
3And Ar
4) be identical in pairs.Particularly preferably be all four substituent A r
1To Ar
4Be identical.
Described substituent A r
1To Ar
4Be aryl, or in aromatic ring system, have the heteroaryl of individual, preferred 3-10 the carbon atom of 2-15 with individual, preferred 6-10 the carbon atom of 6-15.
The aryl with 6-15 carbon atom that can mention for example is: phenyl, naphthyl, anthryl, preferred phenyl and naphthyl.
The heteroaryl of the described 2-15 of a having carbon atom have 1 to about 6, usually 1-3 identical or different be selected from the heteroatoms among O, S and the N.The example that can mention is following heteroaryl: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrryl, 3-pyrryl, 3-different
azoles base, 4-different
azoles base; 5-different
azoles base, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-
azoles base; 4-
azoles base, 5-
azoles base, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1; 2,4-
diazole-3-base, 1,2,4-
diazole-5-base, 1,2; 4-thiadiazoles-3-base, 1,2,4-thiadiazoles-5-base, 1,2,4-triazole-3-base; 1,3,4-
diazole-2-base, 1,3,4-thiadiazoles-2-base and 1,3; 4-triazole-2-base, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidyl; The 4-pyrimidyl, 5-pyrimidyl, 2-pyrazinyl, 1,3,5-triazines-2-base and 1,2; 4-triazine-3-base, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrryl, 3-pyrryl; 3-different
azoles base, 4-different
azoles base, 5-different
azoles base, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl; The 4-pyrazolyl, 5-pyrazolyl, 2-
azoles base, 4-
azoles base, 5-
azoles base, 2-thiazolyl, 4-thiazolyl; The 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-
diazole-3-base, 1; 2,4-
diazole-5-base, 1,2,4-thiadiazoles-3-base, 1,2; 4-thiadiazoles-5-base, 1,2,4-triazole-3-base, 1,3,4-
diazole-2-base; 1,3,4-thiadiazoles-2-base and 1,3,4-triazole-2-base, 2-pyridyl, 3-pyridyl; The 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 2-pyrazinyl; 1,3,5-triazines-2-base and 1,2,4-triazine-3-base, benzofuryl, isobenzofuran-base; Benzothienyl, indyl, pseudoindoyl, carbazyl, pyridyl, quinolyl, isoquinolyl and pyrazolyl.Preferred heteroaryl is for example 2-furyl, 2-pyridyl, 2-imidazolyl.
For Ar
1To Ar
4Described aryl or heteroaryl can be unsubstituted in each case independently of one another, or carry 1 to about 7, preferred 1-3, particularly 1 or 2 identical or different following substituting group: C that is selected from
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen ,-SiR
5aR
6aR
7a, replace or unsubstituted C
6-C
10Aryl ,-NR
8aR
9a,-SR
10aAnd-NO
2, radicals R wherein
5a, R
6a, R
7a, R
8a, R
9a, R
10aAnd R
11To R
13Be C in each case independently
1-C
6Alkyl, C
7-C
12Aralkyl and/or replacement or unsubstituted C
6-C
10Aryl, radicals R
8aAnd R
9aIndependently of one another can be in each case also form together and have the cyclic hydrocarbon group of 2-8 carbon atom, it can have one or more identical or different O, S and NR of being selected from
11aIn heteroatoms, and R
11aCan have for R
11Given definition.
In this respect, the concrete substituting group in the present invention's full text scope can have the following implication that provides for example:
C
1-C
6Alkyl is a methyl for example, ethyl, propyl group, 1-methylethyl, butyl, 1-methyl-propyl group, 2-methyl-propyl, 1; The 1-dimethyl ethyl, amyl group, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl propyl; The 1-ethyl propyl, hexyl, cyclohexyl, 1,1-dimethyl propyl, 1,2-dimethyl propyl, 1-methyl amyl; The 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1; The 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-butyl; The 2-ethyl-butyl, 1,1,2-trimethylammonium propyl group, 1,2,2-trimethylammonium propyl group, 1-ethyl-1-methyl-propyl and 1-ethyl-2-methyl-propyl;
C
1-C
6Perfluoroalkyl is a trifluoromethyl for example, pentafluoroethyl group, seven fluoropropyls, seven fluorine sec.-propyls, nine fluorine butyl;
C
1-C
6Alkoxyl group is a methoxyl group for example, oxyethyl group, propoxy-, 1-methyl ethoxy, butoxy, 1-methyl propoxy-, 2-methyl propoxy-and 1,1-dimethyl-oxyethyl group; Pentyloxy, 1-methyl butoxy, 2-methyl butoxy, 3-methyl butoxy, 1,1-dimethyl-propoxy-, 1,2-dimethyl-propoxy-; 2,2-dimethyl-propoxy-, 1-ethyl propoxy-, hexyloxy, 1-methyl pentyloxy, 2-methyl pentyloxy, 3-methyl pentyloxy, 4-methyl pentyloxy; 1,1-dimethyl-butoxy, 1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy, 2; 2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1-ethyl butoxy, 2-ethyl butoxy; 1,1,2-trimethylammonium propoxy-, 1,2,2-trimethylammonium propoxy-, 1-ethyl-1-methyl propoxy-and 1-ethyl-2-methyl propoxy-;
C
7-C
12Aralkyl is a benzyl for example, 1-styroyl, 2-styroyl;
C
1-C
10Acyloxy is an acetoxyl group for example, propionyloxy;
C
1-C
10Carboxyl is a methoxycarbonyl for example, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl;
C
1-C
10Acyl group is a formyl radical for example, ethanoyl, propionyl group.
Term " replaces or unsubstituted C
6-C
10Aryl " be construed as the above-mentioned aryl of expression, it has one or more, common 1 to about 3 identical or different substituting groups, and wherein substituting group for example is selected from the C of above-mentioned and following definition
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen, silyl, dialkyl amido and nitro.
Within the scope of the present invention, term " halogen " is interpreted as expression fluorine, chlorine, bromine and iodine, preferred fluorine and chlorine.
Within the scope of the present invention, substituting group-SiR
5aR
6aR
7aTo-SiR
5dR
6dR
7dBe to have independently of one another three identical or different C that are selected from separately in each case
1-C
6Alkyl, C
7-C
12Aralkyl and replacement or unsubstituted C
6-C
10The silyl substituting group of the group in the aryl.For example, the silyl substituting group that can mention is trimethyl silyl, triethylsilyl, t-butyldimethylsilyl and t-butyldiphenylsilyl.
Within the scope of the present invention, substituting group-NR
8aR
9aTo-NR
8dR
9dBe amino substituting group in each case, it carries two identical or different, preferred two separately independently of one another and identical is selected from above-mentioned C
1-C
6Alkyl, C
7-C
12Aralkyl and/or replacement or unsubstituted C
6-C
10Group in the aryl.For example, the amino substituting group that can mention is: dimethylamino, diethylamino, dibenzyl amino, amino, the diisopropylaminoethyl of diallyl.Within the scope of the present invention, radicals R
8aAnd R
9aTo R
8dAnd R
9dCan be independently of one another also form together in each case and have the cyclic hydrocarbon group of 2-8 carbon atom, it can have one or more identical or different O, S and NR of being selected from
11aIn heteroatoms.Radicals R
11aHere can be above-mentioned C
1-C
6Alkyl, C
7-C
12Aralkyl and/or replacement or unsubstituted C
6-C
10Aryl.These cyclic substituents R
8aAnd R
9aTo R
8dAnd R
9dCan be for example piperidyl, morpholinyl, N methyl piperazine base, N-benzyl-piperazinyl.
At substituting group-SR
10aIn, radicals R
10aBe above-mentioned C
1-C
6Alkyl, C
7-C
12Aralkyl and/or replacement or unsubstituted C
6-C
10Aryl, preferably methyl, ethyl, sec.-propyl, phenyl, benzyl.
The preferred within the scope of the present invention aromatics or the heteroaromatic substituent A r that can mention
1, Ar
2, Ar
3, Ar
4Example be phenyl, 4-aminomethyl phenyl, 2,4,6-trimethylphenyl, naphthyl, 2-fluorophenyl, 4-fluorophenyl; The 4-chloro-phenyl-, 4-bromophenyl, 3-fluorophenyl, 3-chloro-phenyl-, 3,5-difluorophenyl, 3,5-dichlorophenyl; 2,3,6-trichlorophenyl, 2,4,6-trichlorophenyl, 2-aminomethyl phenyl, 4-aminomethyl phenyl; 2,2,4,6-trimethylphenyl, 2-isopropyl phenyl, 4-isopropyl phenyl; The 4-tert-butyl-phenyl, 4-n-butylphenyl, 3-trifluoromethyl, 4-trifluoromethyl, 3,5-two (trifluoromethyl) phenyl, 4-aryl phenyl, 3-nitrophenyl; Preferred 4-fluorophenyl, 4-chloro-phenyl-, 3-chloro-phenyl-, 3,5-dichlorophenyl, 3-trifluoromethyl, 4-trifluoromethyl.In the scope of preferred embodiment, group Ar
1, Ar
2, Ar
3, Ar
4Be identical, and preferably 4-fluorophenyl, 4-chloro-phenyl-, 3-chloro-phenyl-, 3,5-dichlorophenyl, 3-trifluoromethyl, 4-trifluoromethyl, especially preferably phenyl.
According to the present invention, be positioned at corresponding phenolic hydroxyl group between the position or contraposition on substituent R
1, R
2, R
3, R
4Can be identical or different, preferably identical, and be hydrogen and/or above-mentioned C in each case independently of one another
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen ,-SiR
5aR
6aR
7a, replacement or unsubstituted C
6-C
10Aryl ,-NR
8aR
9a,-SR
10aAnd/or-NO
2
The preferred radicals R that can mention
1, R
2, R
3, R
4Be: methyl, ethyl, sec.-propyl, halogen (particularly fluorine and/or chlorine), trifluoromethyl, phenyl, methoxyl group, nitro.Preferably, radicals R
1, R
2, R
3, R
4Be identical, hydrogen especially preferably.
Radicals R
1Or R
2And/or R
3Or R
4Can also form cyclic aromatics or non-aromatic ring with structural unit A.In these cases, formula used according to the invention (I) two (diaryl phenol) part has three these structures of cyclic group, for example the substruction of this structure of anthryl of formula (X) or formula (XI):
Other texture improvement of these these structures of three cyclic groups, when suitable, be included in have in the substruction heteroatomic those, be well known to a person skilled in the art, and belong to and can be used for two (diaryl phenol) of the present invention part.
Structural unit A in formula (I) can be straight chain or branching and/or cyclic have the alkyl of 1-25 carbon atom, it can be saturated or single unsaturated or polyunsaturated, normally 1 to about 6 times undersaturated, and/or can be partially aromatic.Described alkyl can when suitable, have one or more, common 1-3 identical or different be selected from O, S and NR
11Heteroatoms and/or the one or more identical or different C of functional group (O), S (O) and S (O) of being selected from
2In functional group and when suitable, can carry one or more identical or different following substituting group: C that are selected from
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
1-C
10Acyloxy, C
7-C
12Aralkyl, halogen ,-SiR
5cR
6cR
7c, replace or unsubstituted C
6-C
10Aryl replaces or unsubstituted C
2-C
10Heteroaryl ,-NR
8cR
9c,-SR
10c,-NO
2, C
1-C
12Acyl group, and C
1-C
10Carboxyl.
Preferably; Structural unit A in the formula (I) be straight chain or branching and/or cyclic have 1-25, preferred 1-15, the alkyl of preferred especially 1-10 carbon atom; It can be saturated or single unsaturated or triunsaturated, and/or can be partially aromatic.Preferred alkyl can have one or more, common 1-3 identical or different O, S and the NR of being selected from when suitable
11Heteroatoms and/or one or more C (O) group and when suitable, can carry one or more identical or different following substituting group: C that are selected from
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
1-C
10Acyloxy, C
7-C
12Aralkyl, halogen replaces or unsubstituted C
6-C
10Aryl ,-NO
2, C
1-C
12Acyl group, and C
1-C
10Carboxyl.
The non-limitative example of structural unit A is following structural unit 1-44 in the formula that can mention (I), wherein within the scope of the present invention, wavy line in each case with the bonding position of remaining respective ligand structure of expression:
If the structural unit 1-44 that is shown also can carry in each case above-mentioned substituting group with suitable have other, common 1 or 2 olefinic double bond.
Structural unit A also can be aryl, particularly phenylene, naphthylidene or the anthrylene with individual, preferred 6-10 the carbon atom of 6-15, or the heteroaryl with individual, preferred 3-10 the carbon atom of 2-15 that as above defines.
Described aryl and heteroaryl can carry 1-5 in each case and be selected from following above-mentioned substituting group: C when suitable
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen ,-SiR
5dR
6dR
7d, replace or unsubstituted C
6-C
10Aryl ,-NR
8dR
9d,-SR
10dAnd-NO
2
In addition, structural unit A also can be selected from following functional group or heteroatoms :-O-,-S-,-N (R
11)-,-S (O)-,-C (O)-,-S (O)
2-,-P (R
11)-,-(R
11) P (O)-,-OP (O) O-,-OP (O
2) O-and-Si (R
12R
13)-, be radicals R wherein
11, R
12, R
13Be above-mentioned C in each case independently of one another
1-C
6Alkyl, C
7-C
12Aralkyl and/or replacement or unsubstituted C
6-C
10Aryl.In this scope, structural unit A preferably-O-,-S-,-S (O)-,-S (O)
2-or-Si (R
12R
13)-.
Those that two (diaryl phenol) parts that preferred within the scope of the present invention Diarylphenoxy aluminum compounds is a through type (Ia) and the aluminum compound reaction of formula (II) and/or formula (III) obtain:
The part of formula (Ia) has two phenol systems equally, this two individual system in each case on two ortho positions of phenolic hydroxyl group by aromatics or heteroaromatic (Ar
1To Ar
4) group replaces, and if be bonded together and suitable other substituting group (R that also can carry via structural unit A
1To R
4), wherein structural unit A links together two phenol systems in the contraposition of phenolic hydroxyl group in each case.Here, group Ar
1, Ar
2, Ar
3, Ar
4, radicals R
1, R
2, R
3, R
4With structural unit A can have with above-mentioned formula (I) in identical implication.
According to the present invention, special preferred ligands is aryl Ar wherein
1, Ar
2, Ar
3, Ar
4Be identical and have those of preferred meaning described in the above-mentioned formula (I).Special preferred aryl groups Ar
1To Ar
4Be phenyl, naphthyl, 4-fluorophenyl, 4-chloro-phenyl-, 3-chloro-phenyl-, 3,5-dichlorophenyl, 4-aminomethyl phenyl, 3-trifluoromethyl, 4-trifluoromethyl, preferred very especially phenyl.
In preferred formula (Ia) part according to the present invention, radicals R
1, R
2, R
3, R
4Be identical or different, preferably identical, and preferably: hydrogen, halogen (particularly fluorine or chlorine), methyl, trifluoromethyl, sec.-propyl, the tertiary butyl, phenyl, nitro.
Structural unit A in the formula (Ia) have with above-mentioned formula (I) in identical implication.Preferred structure unit A in the formula (Ia) is structural unit 1-44 particularly also, and they can be substituted in the manner described.
Special preferred ligands is formula (Ia
1) to (Ia
3) those, wherein said group Ar
1To Ar
4, R
1To R
4And R
15To R
18Preference is as having the implication that provides in the table:
Table 1
Table 2
Table 3:
Here, in table 1-3, Ph is a phenyl, and C (O) is a carbonyl in the whole scope of the invention.Usually, radicals R
15, R
16And R
17Can be the C of above-mentioned definition independently of one another
1-C
6Alkyl, C
1-C
10Acyl group, C
1-C
10Carboxyl or C
6-C
10Aryl, wherein said group can carry one or more identical or different halogens and/or NO
2Substituting group and radicals R wherein
16And R
17Can also form the ring texture unit together, preferred alkylidene bridge.
Can be used to prepare two (diaryl phenol) part known method preparation by one of skill in the art easily of the formula (I) or the formula (Ia) of Diarylphenoxy aluminum compounds of the present invention.(Ia
1) compound of type for example can be through corresponding two-neighbour-aryl phenol and aldehyde R
15CHO is at Lewis acid (AlCl for example
3) existence down reaction obtain, Z.Y.Wang for example, A.S.Hay be at Synthesis1989,471-472 or at US3, described in 739,035.(Ia
2) part of type for example can be through corresponding two-neighbour-aryl phenol and suitable formula R
16C (O) R
17Reactive ketone obtain, like US3,739,035 is said.(Ia
3) part of type for example can carry out the acquisition of Friedel-Crafts acylation reaction with the dicarboxylicacid acyl chlorides through the phenol of corresponding phenol or O-protection, for example people such as F.F.Blicke is at J.Am.Chem.Soc.1938, and 60,2283-2285; People such as CH 350461 or G.Maier are at Chem.Ber.1985, and 118, described in the 704-721..Preparation (Ia
3) the another kind of method of part of type also is that corresponding phenol and uncle's glycol carry out the Friedel-Crafts acylation reaction; For example be described among the DE-A 25 34 558; Or carry out the Friedel-Crafts acylation reaction with dihalide, and for example J.Zavada is at Collect.Czech.Chem.Commun, and 1976; 41, described in the 1777-1790.
Diarylphenoxy aluminum compounds of the present invention for example obtains through the aluminum compound reaction of above-mentioned formula (I) or two (diaryl phenol) parts (Ia) and formula (II):
(R
14)
3-pAlH
p (II)，
R wherein
14Be the alkyl of a branching or the nonbranched 1-5 of a having carbon atom, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or neo-pentyl.P is 0 or the integer of 1-3.Preferably, p is 1 or 0, especially preferably 0.Preferred formula (II) compound is for example trimethylaluminium, triethyl aluminum, diisobutyl aluminium hydride, preferred especially trimethylaluminium and triethyl aluminum.
Perhaps, Diarylphenoxy aluminum compounds of the present invention for example obtains through the aluminum compound reaction of above-mentioned formula (I) or two (diaryl phenol) parts (Ia) and formula (III):
MAlH
4 (III)，
Wherein M is lithium, sodium or potassium.As a result, lithium aluminum hydride, sodium aluminum hydride and aluminum hydride potassium and their mixture also be suitable for through with above-mentioned formula (I) or (Ia) two (diaryl phenol) part react and prepare Diarylphenoxy aluminum compounds of the present invention.In addition, said formula (II) and (III) mixture of compound also be suitable for through with above-mentioned formula (I) or (Ia) two (diaryl phenol) part react and prepare Diarylphenoxy aluminum compounds of the present invention.
This reaction is advantageously carried out, make above-mentioned formula (I) or two (diaryl phenol) part (Ia) and formula (II) or (III) compound contact.This reaction is advantageously carried out in inert organic solvents; For example toluene, hexanaphthene, methylene dichloride, YLENE, ethylbenzene, chlorobenzene, THF, ether, MTBE, ETHYLE ACETATE, pentane, hexane, ethylene dichloride, N (DMF), DMSO 99.8MIN. (DMSO) etc., wherein pre-dry or anhydrous solvent are preferred especially the uses.This reaction is carried out to about 100 ℃ temperature at about-100 ℃ usually, and preferred-50 ℃ to about 50 ℃ approximately, especially preferably about-30 ℃ to about 30 ℃.
In the process of preparation Diarylphenoxy aluminum compounds of the present invention, used formula (I) or (Ia) phenolic hydroxyl group in two (diaryl phenol) part react with formula (II) and one or more compounds (III).
In theory, each aluminium nuclear power and 1-3 phenolic hydroxyl group reaction.Consider three-dimensional performance or used formula (I) or (Ia) needs of two (diaryl phenol) part, this possibly cause forming high-molecular weight structure, for example linear structure or network.
, advantageously select used formula (I) or (Ia) two (diaryl phenol) parts and used formula (II) and/or (III) mol ratio of compound here, make unreacted formula (II) and/or (III) amount of compound is low as far as possible.Preferably, select said ratio, make at formula (I) or two (diaryl phenol) part (Ia), no longer have unreacted formula (II) and/or (III) compound with after one or more compounds of formula (II) and (III) contact.Consider cost, suggestion freeze mode (I) or (Ia) part excessive low.Preferred especially formula (I) or (Ia) two (diaryl phenol) parts and used formula (II) and/or (III) mol ratio of compound be about 4: 1 to 1: 1, very especially preferably about 3: 1 to 1.5: 1, most preferably from about 1.5: 1.
In the scope of the preferred embodiment of the invention; The preparation of Diarylphenoxy aluminum compounds of the present invention comprise earlier approximately-10 ℃ add selected formula (I) or (Ia) the about 0.001-1 molar solution of part in suitable organic solvent (for example toluene) to about 30 ℃ temperature according to solvability; Add formula (II) and/or aluminum compound (III) then; Preferably solution form, for example trimethylaluminium or the triethyl aluminum solution in toluene.
Used formula (I) or (Ia) reaction between part and formula (II) and/or the aluminum compound (III) take place fast usually, and great majority after about 10 minutes to about 2 hours, completion after about 1 hour usually, this depends on selected reaction conditions.When using the lower reactant of reactive behavior, can advantageously temporarily improve the temperature of reaction mixture.
According to selected reaction conditions; The formula that particularly will react (I) or (Ia) part and formula (II) and/or (III) solubleness, concentration and the temperature of reaction of aluminum compound in selected solvent, Diarylphenoxy aluminum compounds of the present invention are to obtain with solid, suspension-s or the solution form in solvent for use or solvent mixture.The Diarylphenoxy aluminum compounds of the present invention that obtains in this way can re-use with the form that makes in each case, or is separated and removes used solvent.
Here, separation can be through favourable carrying out with the method that well known to a person skilled in the art.Preferably, the separation of Diarylphenoxy aluminum compounds of the present invention, storage and further the processing are under the situation of getting rid of oxygen and moisture, to carry out.
Diarylphenoxy aluminum compounds of the present invention extremely is suitable as the reaction or the conversion of the catalyzer of chemical reaction, particularly organic cpds.Therefore, another aspect of the present invention relate to through type (I) or two (diaryl phenol) parts (Ia) and formula (II) and/or (III) the compound reaction obtain Diarylphenoxy aluminum compounds as the purposes of catalyzer.Diarylphenoxy aluminum compounds of the present invention is particularly suitable for as be used for can be by the catalyst for reaction of acid or Louis acid catalysis.Still nonrestrictive as an example, can mention following reaction type: reset, isomerizing, cyclisation is eliminated, aromatic carbonyl compounds to take off virtueization nucleophilic functionalized, at α, the conjugate addition on the beta-unsaturated carbonyl compound, Diels-Alder reacts.
Described reaction is advantageously being carried out under the non-proton condition of exsiccant as far as possible, and farthest gets rid of oxygen.
After reacting, used Diarylphenoxy aluminum compounds can use conventional separation method (for example filtration, centrifugal) from reaction mixture, to separate at least in part, and then uses.Select as another kind; Formula (I) or two (diaryl phenol) part (Ia) also can reclaim from rough or the reaction mixture handled; If suitablely also can after isolating reaction product and/or by product, carry out; Because they have favourable physical properties usually, for example good crystallizing power.
Diarylphenoxy aluminum compounds of the present invention is especially suitable for use as the catalyzer that carries out intramolecular reaction, is used in particular for carrying out cyclization.
According to the present invention, preferred especially Diarylphenoxy aluminum compounds of the present invention is used as catalyzer in the reaction that racemize or non-racemize geranial is cyclized into racemize or non-racemize isopulegol.In this respect, especially preferably through type (Ia) two (diaryl phenol) part and formula (II) and/or (III) Diarylphenoxy aluminum compounds of aluminum compound reaction acquisition according to the present invention.Very especially preferably use through type (Ia
1) to (Ia
3) Diarylphenoxy aluminum compounds that obtains of two (diaryl phenol) part reaction is as the catalyzer that geranial is cyclized into isopulegol.
Therefore the present invention also relates to the method for the isopulegol of a kind of preparation formula (IV),
Be included in the catalyzer existence and down the geranial of formula V carried out cyclisation:
Two (diaryl phenol) parts of wherein said catalyzer through type (I) and the aluminum compound of formula (II) and/or obtain with the reaction of the aluminum compound of formula (III):
Wherein, Ar
1, Ar
2, Ar
3, Ar
4, R
1, R
2, R
3, R
4With A have with above-mentioned formula (I) in identical implication,
(R
14)
3-pAlH
p (II)，
Wherein
Al is an aluminium,
R
14Be a branching or the nonbranched 1-5 of a having carbon atom alkyl and
P is 0 or the integer of 1-3,
MAlH
4 (III)，
Wherein
Al be aluminium and
M is lithium, sodium or potassium.
The inventive method also is applicable to the optically-active isopulegol of preparation formula (IVa):
Comprise that the optically-active geranial with formula (Va) carries out cyclisation:
Wherein (*) representes asymmetric c atom in each case.
Method of the present invention is specially adapted to prepare L-(-)-isopulegol through the cyclization of D-(+)-geranial.
Preferred within the scope of the present invention catalyzer is to react those that obtain through two (diaryl phenol) part that makes formula (Ia):
Wherein, Ar
1, Ar
2, Ar
3, Ar
4, R
1, R
2, R
3, R
4With A have with above-mentioned formula (Ia) in identical implication.In the middle of these, further preferred above-mentioned formula (Ia
1) to (Ia
3) part.Special preferred ligands is compound I a in the inventive method scope
1-1, Ia
1-4, Ia
1-5, Ia
2-1 and Ia
2-3.
Diarylphenoxy aluminum compounds of the present invention from above-mentioned part through with formula (II) and/or aluminum compound (III), preferably the aluminum compound reaction with formula (II) obtains.
In order to carry out the method for preparing isopulegol of the present invention, this technology advantageously comprises the solution of Diarylphenoxy aluminum compounds of the present invention in above-mentioned suitable solvent is provided earlier.According to the present invention, in this solution, add racemize or the non-racemize geranial of wanting cyclisation then.Here the geranial that adds can be itself or the form of solution, advantageously the solution form in one of above-mentioned suitable solvent.In the scope of the preferred embodiment of the inventive method; Earlier preparation selected formula (I) or (Ia) solution of part in toluene advantageously add selected formula (II) and/or (III) aluminum compound, preferred trimethylaluminium or the solution of triethyl aluminum in toluene then when stirring.
The suitable feedstock that is used to carry out cyclization method of the present invention is a geranial, and it can be through any method preparation.The preferred purity of using is about 90-99.9 weight %, the especially preferred geranial of about 95-99.9 weight %.
Add the operation of the geranial of wanting cyclisation and advantageously to about 40 ℃ temperature, carry out preferred-20 ℃ to about 20 ℃ approximately at about-40 ℃.For this reason, the solution of Diarylphenoxy aluminum compounds prepared in accordance with the present invention advantageously for example is cooled to-10 ℃ to 10 ℃ temperature under the temperature in this scope, and adds refrigerative geranial or refrigerative geranial solution in advance in advance.
Geranial or its solution can carry out as follows, and whole total amounts are added by a, and perhaps portioning adds in the catalyst solution of preparation, perhaps adds continuously.Suitable solvent and then be above-mentioned solvent, particularly toluene.Preferably, the geranial of cyclisation to use, promptly no longer add solvent as former state.If the use solvent, then the total amount of solvent (be used for Preparation of Catalyst and be used to carry out cyclization) is advantageously selected to make that the geranial of question response and the volume ratio between the solvent are about 2: 1 to about 1: 20, preferred about 1.5: 1 to about 1: 10.
Quantitative ratio between the geranial of question response and the consumption of Diarylphenoxy aluminum compounds of the present invention through being used to prepare it formula (I) or (Ia) compound and formula (II) and/or (III) amount of compound confirm, promptly through used part and used formula (II) and/or (III) aluminum compound quantitatively recently definite.
According to the present invention, the amount of the geranial that selection will be reacted makes that with respect to the used formula (II) and/or (III) amount of aluminum compound this mol ratio is about 5: 1 to about 1000: 1, preferred about 10: 1 to about 500: 1, and preferred about 50: 1 to about 200: 1 especially.
In this respect, used formula (I) or (Ia) part and used formula (II) and/or (III) ratio between the aluminum compound can be in the above for changing in the described limit of Diarylphenoxy aluminum compounds of the present invention.
Geranial according to the present invention takes place to the cyclization of isopulegol usually fast, and usually after about 0.5-10 hour, through the major part completion after about 5 hours of being everlasting, this depends on the selection of reactant and reaction conditions.Reaction process known method monitoring by one of skill in the art easily is for example through chromatography, particularly vapor-phase chromatography, perhaps HPLC method.
In through the reaction process that in the presence of above-mentioned Diarylphenoxy aluminum compounds, geranial is cyclized into isopulegol, (for example use described geranial rank; If geraniol impurity is present in the geranial) time; Sometimes observe especially under plant-scale response situation, unwanted side reaction can take place troublesomely: the rhodinic acid citronellyl ester that promptly forms formula (XII):
Or other high-boiling-point impurity, these materials are being unacceptable aspect the high request of the productive rate of plant-scale above-mentioned reaction, selectivity and stability.
In the scope of the preferred embodiment of the invention, geranial carries out in the presence of acid, preferred organic acid to the cyclization of isopulegol.Organic acid example that can favourable use is: acetate, propionic acid, phenylformic acid, toluenesulphonic acids, methylsulfonic acid, preferred acetate.The advantageously about 0.5-10 weight of the consumption of said acid % is based on the geranial meter that will react.Said acid advantageously adds in the reaction mixture with geranial, and for example the form with mixture adds.
In particularly preferred embodiments, the present invention's method of preparing isopulegol through the cyclisation geranial is carried out in the presence of at least a compound that is selected from carboxylic acid anhydride, aldehyde, ketone and vinyl ether.
The compound of said types of materials can use separately in each case or use with the form of the thing that is mixed with each other.Under the situation of mixture, preferred those that form by the compound that belongs to one type of material that use.The preferred especially list kind compound that uses.Use following compound, can suppress the formation of the unwanted by product of formula (XII) usually to a great extent.
In the scope of preferred embodiment, cyclization method of the present invention carries out in the presence of the carboxylic acid anhydride of formula (VI):
Wherein, radicals R
20And R
20' can be identical or different, preferably identical, and be branching or nonbranched C
1-C
12Alkyl or C
7-C
12Aralkyl or C
6-C
10Aryl, wherein said group can have one or more, common 1 in each case to about 3 identical or different OR that are selected from
10e, SR
10f, NR
8eR
9eWith substituting group in the halogen and R wherein
20And R
20' also can form 5-8 unit ring together, said ring can have one or more olefinic double bonds and one or more identical or different O, S and NR of being selected from
11bIn heteroatoms and R wherein
10e, R
10f, R
8e, R
9eAnd R
11bCan have and R
11Identical implication.
In the scope of another preferred embodiment, cyclization method of the present invention carries out in the presence of the aldehyde of formula (VII):
Radicals R wherein
21Be branching or nonbranched C
1-C
12Alkyl or C
7-C
12Aralkyl or C
6-C
10Aryl, wherein said group can have in each case one or more, preferred 1-3 identical or different be selected from OR
10e, SR
10f, NR
8eR
9eWith the substituting group in the halogen, wherein R
10e, R
10f, R
8eAnd R
9eCan have and R
11Identical implication.
In the scope of another preferred embodiment, cyclization method of the present invention carries out in the presence of the ketone of formula (VIII):
Radicals R wherein
22And R
23Can be identical or different, and be branching or nonbranched C
1-C
12Alkyl or C
7-C
12Aralkyl or C
6-C
10Aryl or C
1-C
6Alkoxy carbonyl, wherein said group can have one or more, preferred 1 to 3 identical or different OR that is selected from each case
10e, SR
10f, NR
8eR
9eWith substituting group in the halogen and R wherein
22And R
23Also can form 5-8 unit ring together, said ring can have one or more olefinic double bonds and one or more identical or different O, S and NR of being selected from
11bIn heteroatoms and R wherein
10e, R
10f, R
8e, R
9eAnd R
11bCan have and R
11Identical implication.
Except that said carbonyl compound, in the scope of the inventive method, also can use the vinyl ether of general formula (IX):
Radicals R wherein
24, R
25, R
26And R
27Can be identical or different independently of one another in each case, and be branching or nonbranched C
1-C
12Alkyl or C
7-C
12Aralkyl or C
6-C
10Aryl, wherein said group can have in each case one or more, preferred 1-3 identical or different be selected from oxygen base, OR
10e, SR
10f, NR
8eR
9eWith substituting group in the halogen and R wherein
25And R
26Also can form 5-8 unit ring together, said ring can have one or more olefinic double bonds and one or more, common 1 or 2 identical or different O, S and NR of being selected from
11bIn heteroatoms and R wherein
10e, R
10f, R
8e, R
9eAnd R
11bCan have and R
11Identical implication.
Here, C
1-C
12Alkyl is above-mentioned C
1-C
6Alkyl and for example be heptyl, octyl group, nonyl, decyl, undecyl or dodecyl in addition.Two alkyl form under the situation of ring together therein, and alkyl also is appreciated that and is thiazolinyl.C
7-C
12Aralkyl and C
6-C
10Aryl can for example have above-mentioned implication.The C that for example, can mention
1-C
6Alkoxy carbonyl is: methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl and isopropoxy carbonyl, preferred methoxycarbonyl and ethoxy carbonyl.
In the scope of preferred embodiment, cyclization method of the present invention carries out in the presence of the carboxylic acid anhydride of formula (VI), wherein radicals R
20And R
20' be identical, and be branching or nonbranched C
1-C
12Alkyl or C
7-C
12Aralkyl or C
6-C
10Aryl and R wherein
20And R
20' also can form 5-8 unit ring together, said ring can have one or more olefinic double bonds and one or more identical or different OR that is selected from
10e, SR
10fAnd NR
11bIn heteroatoms and R wherein
10e, R
10fAnd R
11bCan have independently of one another and R
11Identical implication.
Especially preferably use wherein radicals R
20And R
20' be identical and be branching or nonbranched C
1-C
12Alkyl or C
6-C
10Those carboxylic acid anhydride of aryl.For example, the carboxylic acid anhydride that especially preferably uses according to the present invention is: diacetyl oxide, propionic anhydride, PIVALIC ACID CRUDE (25) acid anhydride and benzoyl oxide.
Same formula (VII) aldehyde preferably used according to the invention is for example acetaldehyde, propionic aldehyde and chloral (trichoro-aldehyde).
In another preferred embodiment of the present invention,, then advantageously use those in the presence of the ketone of formula (VIII) with activatory (promptly hanging down electronics) carbonyl functional group if cyclization method of the present invention carries out.For example, the ketone that uses in the inventive method scope that is highly suitable for that can mention is: 1,1, and 1-trifluoroacetone, 1,1,1-trifluoroacetophenone, Perfluoroacetone, Pyruvic Acid Methyl ester and Pyruvic Acid Ethyl ester.
Same formula (IX) vinyl ether preferably used according to the invention for example is: methylvinylether, ethyl vinyl ether, IVE and 3,4-dihydro-2H-pyrans.
The compound of said these types can equally successfully use in the scope of this preferred embodiment of the present invention.About putting into practice the aspect, for example higher speed of reaction, verified aldehyde and/or the low electronics ketone of advantageously using.
Consumption according to carboxylic acid anhydride of the present invention, aldehyde, ketone and/or vinyl ether can change in wide region, and the existence of the type through used material and purity or the impurity accurately do not confirmed is as yet controlled.Usually, the consumption of said compound and their mixture is about 0.01-5mol%, and preferably about 0.1-2mol% is based on the consumption meter of geranial.
The type of reaction process and mode, for example the interpolation of the structure of reactor drum or each reactant order is not limited to special requirement, and prerequisite is to guarantee oxygen-free and water in the reaction process.
In order in this preferred embodiment scope, to carry out method of the present invention, technology advantageously comprises the solution of Diarylphenoxy aluminum compounds in above-mentioned suitable solvent that at first provides the present invention to use.Then, according to the present invention, preferably in this solution, add and to use the racemize of selected carboxylic acid anhydride, aldehyde, activation ketone and/or vinyl ether cyclisation or the mixture of non-racemize geranial.Perhaps, if suitable, in each case, the solution of the Diarylphenoxy aluminum compounds that can for example also will will use according to the present invention mixes with selected carboxylic acid anhydride, aldehyde, activation ketone and/or vinyl ether earlier, adds the geranial of wanting cyclisation then.
Verified advantageously about 30 minutes to about 6 hours, preferably geranial or geranial mixture and selected compound are metered in catalyst solution or the reaction mixture in time of about 2-4 hour.Here, geranial can perhaps add with the form of solution in the former state adding, preferably the solution in one of above-mentioned suitable solvent.In another embodiment preferred of the present invention; Earlier preparation selected formula (I) or (Ia) solution of part in toluene under agitation add the toluene solution of selected formula (II) and/or aluminum compound (III), preferred trimethylaluminium or triethyl aluminum then easily.
In this embodiment, the geranial of cyclisation or the interpolation of geranial mixture and selected carboxylic acid anhydride, aldehyde, activation ketone and/or vinyl ether advantageously to about 40 ℃ temperature, to carry out preferred-20 ℃ to about 20 ℃ approximately at about-40 ℃.For this reason, the solution of prepared Diarylphenoxy aluminum compounds or suspension-s advantageously are cooled to the temperature in this scope according to the present invention, for example are cooled to-10 ℃ to 10 ℃ temperature, and with other reactant of refrigerative form adding in advance.
The interpolation of geranial mixture and selected other compound can make geranial once all add, and perhaps portioning adds in the prepared catalyst solution, perhaps adds continuously.Suitable solvent further preferably above-mentioned solvent, particularly toluene.The preferred geranial of wanting cyclisation that uses conduct and the form of mixtures of selected carboxylic acid anhydride, aldehyde, activation ketone and/or vinyl ether, and no longer add solvent.When using solvent, the total amount of selective solvent advantageously, making geranial and the volume ratio between the solvent that must react is about 1: 1 to about 1: 20, preferred about 1: 1 to about 1: 10.
Have been found that some catalyst complexes inactivation during reaction usually.This is particularly because the ligand exchange process between every kind of isopulegol that uses two used under the situation of Diarylphenoxy aluminum compounds (diaryl phenol) parts and formed by cyclization.Compare with the reactive polymer catalyzer, the inactivation form of catalyzer is dissolved in the reaction mixture usually, and this depends on selected solvent.
In preferred embodiments, simple physics separation method (the for example still filtration of activated catalyzer or centrifugal) can be used to isolate inactivation part and remaining reaction mixture of catalyzer.The still activated catalyzer that is kept can be when needed replenishes with live catalyst, and reuses ignoring under the situation of loss of activity, preferably at geranial according to the present invention in the further cyclization process of isopulegol.
Perhaps, consumption that can selecting catalyst makes used whole catalyst complexes inactivation in cyclization process of the present invention or after said reaction finishes, and and then dissolving, this can observe through the transparent reaction mixture.In this respect, advantageously in this case, consider above-mentioned ligand exchange process, the formula of in every kind of situation, using (I) two (diaryl phenol) part discharges under the situation of not carrying out independent hydrolysis.
In addition; Have been found that; The solvent that uses in each case (preferred toluene) and if other suitable compound used therefor be distilled remove after; The cyclisation product isopulegol can distill away with high purity from reaction mixture, the hydrolysis formerly of the Diarylphenoxy aluminum compounds that does not need to use in each case.In this respect, usually do not form the by product of discernible unwanted or trouble in the distillation tower bottom yet.Between distillation, add suitable inertia high boiling solvent; It is the solvent that preferred boiling point is higher than isopulegol; For example 1-methylnaphthalene, 1-decanol, tridecane, carbonic acid 1; 2-propylidene ester, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether and dibenzyl ether have obtained the solution of free ligand in the high boiling component of used heat in each case in distillation tower.Said part can crystallize out through simple cooling from this hot soln, and reclaims with high purity through filtering.Two (diaryl phenol) part that reclaims in this way can (usually under the situation that does not need further purification step) in new batch of material with corresponding formula (II) or (III) aluminum compound reaction; Obtain the active catalyst title complex; Wherein under the situation of the catalyst complexes that reclaims in this way; Reactive behavior does not reduce, and perhaps the reduction of reactive behavior can be ignored.In addition, after hydrolysis, can from the mother liquor that obtains as above-mentioned resistates, obtain isopulegol and two (diaryl phenol) part of other amount of use in each case.In the scope of this preferred embodiment, geranial of the present invention correspondingly may further comprise the steps to the cyclization of isopulegol:
A) the optional solvent that uses and optional other compound (being carboxylic acid anhydride, aldehyde, activation ketone and/or vinyl ether) that uses are removed in distillation from the product mixtures that obtains according to aforesaid method,
B) in the resistates that in step a), obtains, add high boiling solvent,
C) from the mixture that step b), obtains fractionation by distillation go out isopulegol and
D) cool off the distillation tower bed material that in step c), obtains, crystallization simultaneously goes out two (diaryl phenol) part of used formula (I).
After realizing required reaction process, cyclization of the present invention also can stop in a conventional manner, and this for example carries out through adding aqueous reagent, alkali aqueous solution for example, and for example sodium hydroxide or potassium hydroxide solution, or for example carry out through adding entry.Aftertreatment can be carried out according to the method for well known to a person skilled in the art with separating then.
The optional additive that uses, promptly used carboxylic acid anhydride, ketone, aldehyde or vinyl ether can reclaim according to its physicals (for example boiling point), for example through from the mixture of total overall reaction, distilling, and reach its unreacted degree.
In the process of the inventive method, isopulegol obtains as the mixture of the enantiomeric form of isopulegol usually: new-isopulegol of the isopulegol of formula (XIII), formula (XIV), the strange-isopulegol of formula (XV) and the different-isopulegol of formula (XVI).
According to the present invention; The embodiment of preferred such the inventive method; Wherein in the isopulegol mixture of enantiomers that obtains, itself contain at least about 85%, preferably at least about 90%, especially preferably at least about 95%, very especially preferably at least about 98% the formula (XII) or the main isopulegol enantiomorph of formula (IVa).
As stated, method of the present invention is suitable for obtaining racemize and non-racemic isopulegol from racemize and non-racemize (being optically-active) geranial cyclisation equally.In preferred embodiments, the inventive method is used for preparing L-(-) isopulegol through the cyclization of D-(+)-geranial.
The racemize and the non-racemic isopulegol of preparation are the valuable midbodys that is used to prepare racemize and non-racemic Therapeutic Mineral Ice in this way, and the latter is one of most important in the world spices or aromatic substance.Therapeutic Mineral Ice can obtain from the known by one of skill in the art method for hydrogenation of isopulegol, particularly on suitable transition-metal catalyst, carries out catalytic hydrogenation, as people such as Pickard, and J.Chem.Soc.1920,1253; People such as Ohloff, Chem.Ber.1962,95,1400; People such as Pavia, Bull.Soc.Chim.Fr.1981,24, people such as Otsuka, Synthesis 1991,665 or described in EP 1 053 974 A.Here, if the reaction conditions of selecting is suitable, then relative the or absolute configuration of used isopulegol is maintained to a great extent, and is kept fully in many cases.
So, the invention still further relates to a kind of through by method for preparing racemize or non-racemic isopulegol, and subsequently its olefinic double bond hydrogenation is prepared the method for racemize or non-racemic menthol.Particularly, the present invention relates to a kind ofly prepare the method for L-(-) Therapeutic Mineral Ice from L-(-) isopulegol, wherein said L-(-) isopulegol is through the cyclization preparation of aforesaid method through D-(+)-geranial.
Following examples are used for explaining without limitation the present invention:
Gas chromatographic analysis is carried out according to following method: 30m DB-WAX, ID.:0.32mm, FD.:0.25 μ m; 80-230 ℃, 3 ℃/min; Rf (geranial): 10.5; Rf (new-isopulegol): 13.24; Rf (isopulegol): 13.58; Rf (strange-isopulegol): 14.64; Rf (different-isopulegol) 15.28; Rf (rhodinic acid citronellyl acrylate): 39.80.The concentration (in each case unit be weight %) of gained reaction product in reaction soln is to analyze to mark in the use through GC to confirm.The corresponding data (unit in each case is g) of report departs from so can have slightly through calculating from its extrapolation in addition.Enantioselectivity is definite through the corresponding GC area % of four kinds of enantiomorphs.
Embodiment 1: from ligand i a
1The catalyzer of-1 preparation exists down and in the presence of diacetyl oxide, geranial is cyclized into isopulegol
In the flask of heated drying, add the ligand i a1-1 of 1.05mmol and the dry toluene of 10ml.At room temperature, in clear solution, add 350 μ l (0.66mmol, triethyl aluminum 1mol%) 25% concentration solution in toluene.This solution was stirred 1 hour in 25 ℃.After several minutes, obtain the gel suspension-s of catalyzer.This catalyst suspension is cooled to 0 ℃, and in 6 hour time, added the mixture of diacetyl oxide that is cooled to 0 ℃ geranial and 1 weight % (based on geranial) in advance of 10.15g (65.8mmol).Stir this reaction mixture, according to clocklike extracting at interval sample, and with 8% NaOH hydrolysis.In this process, existing aluminium comes out as precipitation of hydroxide, and at first obtains suspension-s.After some times, form two transparent phases.Organic phase is through gas chromatographic analysis.The result is listed in the table 4.
Table 4:
*The rhodinic acid citronellyl acrylate
Said cyclization makes isopulegol in 90% selectivity based on all isopulegol isomer.Enantioselectivity is (new-isopulegol: as to be 0.4: 99.4: 0.2 isopulegol: strange-isopulegol: different-isopulegol): 0.0.
Embodiment 2: use ligand i a
1-4 (with diacetyl oxide) are carried out cyclization
Repeat embodiment 1, under other identical condition, use ligand i a
1-4 (fairly large).The result is listed in the table 5.
Table 5:
After reaction 24 hours, accomplished the conversion of geranial, be 90% with respect to the selectivity of whole isopulegol isomer.Enantioselectivity is (new-isopulegol: as to be 0.6: 99.0: 0.3 isopulegol: strange-isopulegol: different-isopulegol): 0.1.
Embodiment 3: use ligand i a
2-1 (additive-free) carries out cyclisation
The ligand i a that in the flask of heated drying, adds 640mg (1.0mmol)
2-1 with the dry toluene of 10ml.At room temperature, the 0.66M solution of triethyl aluminum in toluene that in clear solution, adds 350 μ l (0.65mmol is with respect to the 1mol% of geranial).This solution in 25 ℃ of stirrings 1 hour, was obtained the gel suspension-s of catalyzer after several minutes.This catalyst suspension is cooled to 0 ℃, and in 6 hours, add 10.2g (65.8mmol) be cooled to-15 ℃ geranial in advance.In this reaction mixture of 0 ℃ of restir 18 hours, according to clocklike extracting sample at interval, and with 8% NaOH hydrolysis.In this process, existing aluminium comes out as precipitation of hydroxide, and at first obtains suspension-s.After some times, form two transparent phases.Organic phase is through gas chromatographic analysis.The result is listed in the table 6.
Table 6:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 1.6: 96.7: 1.2 isopulegol: strange-isopulegol: different-isopulegol): 0.4.
Embodiment 4: use ligand i a
2-1 (with diacetyl oxide) carried out cyclisation
The ligand i a that in the flask of heated drying, adds 640mg (1.0mmol)
2-1 with the dry toluene of 10ml.At room temperature, the 0.66M solution of triethyl aluminum in toluene that in clear solution, adds 350 μ l (0.65mmol is with respect to the 1mol% of geranial).This solution in 25 ℃ of stirrings 1 hour, was obtained the gel suspension-s of catalyzer after several minutes.This catalyst suspension is cooled to 0 ℃, and in 6 hours, adds the mixture of diacetyl oxide that is cooled to-15 ℃ geranial and 0.1g (with respect to the 1mol% of geranial) in advance of 10.2g (65.8mmol).In this reaction mixture of 0 ℃ of restir 18 hours, according to clocklike extracting sample at interval, and with 8% NaOH hydrolysis.In this process, existing aluminium comes out as precipitation of hydroxide, and at first obtains suspension-s.After some times, form two transparent phases.Organic phase is through gas chromatographic analysis.The result is listed in the table 7.
Table 7:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 0.8: 98.5: 0.4 isopulegol: strange-isopulegol: different-isopulegol): 0.3.
Embodiment 5: from ligand i a
1The catalyzer of-3 preparations exist down and under diacetyl oxide with the geranial cyclisation and with aftertreatment and the said part of recovery
Ligand i a with 8.0g (13.6mmol)
2-3 are dissolved in argon gas atmosphere in the 140ml toluene in room temperature.25% solution of triethyl aluminum in toluene that adds 4.78mol (9.09mmol) stirs this mixture 1 hour then.The catalyst solution of gained is cooled to 0 ℃, and in 5 hours, adds the geranial of 70.0g (0.45mol) and the mixture of 0.7g (6.86mmol is with respect to the 1mol% of geranial) diacetyl oxide.With this reaction mixture in 0 ℃ of restir 1 hour with in room temperature restir 12 hours.When experiment finishes, add the 8%NaOH solution of 100ml, and separate each phase.Organic phase is used dried over sodium sulfate, and under reduced pressure removes and desolvate.Crude product distills down at 1 millibar on short column.Under 58 ℃ of tower top temperatures, obtain to have the 68.4g isopulegol (being GC area %) of following composition under various situation: isopulegol=98.4%, new-isopulegol=0.6%, strange-isopulegol=0.4%.This is corresponding to 97% chemical yield, and based on all enantiomorph meters, enantioselectivity is 99: 1 (isopulegols: other enantiomorph).
The distillation bed material that when distillation is accomplished, remains is the light yellow solid of 7.7g, and it is by the formula Ia of 95 weight %
2The isopulegol of-3 part and 5 weight % is formed.
Embodiment 6-13: using ligand i a
2Use various carbonyl compound to come the cyclisation geranial in-3 the cyclization as additive
Embodiment 6: under non-additive situation, carry out cyclisation
The ligand i a that in the flask of heated drying, adds 580mg (1.0mmol)
2-3 with the dry toluene of 20ml.At room temperature, the 0.66M solution of triethyl aluminum in toluene that in clear solution, adds 350 μ l (0.65mmol is with respect to the 1mol% of geranial).This solution in 25 ℃ of stirrings 1 hour, was obtained the gel suspension-s of catalyzer after several minutes.This catalyst suspension is cooled to 0 ℃, and in 3 hours, add 10.2g (65.8mmol) be cooled to-15 ℃ geranial.In this reaction mixture of 0 ℃ of restir 4 hours, according to clocklike extracting sample at interval, and with 8% NaOH hydrolysis.In this process, existing aluminium comes out as precipitation of hydroxide, and at first obtains suspension-s.After some times, form two transparent phases.Organic phase is through gas chromatographic analysis.The result is listed in the table 8.
Table 8:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 0.4: 99.0: 0.5 isopulegol: strange-isopulegol: different-isopulegol): 0.1.
Embodiment 7: add acetaldehyde
Mode according to embodiment 6 repeats experiment, and different is the acetaldehyde that before adding geranial, in geranial, adds 0.4 weight %.The result is listed in the table 9.
Table 9:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 0.4: 99.1: 0.5 isopulegol: strange-isopulegol: different-isopulegol): 0.0.
Embodiment 8: add nitrobenzaldehyde
Mode according to embodiment 6 repeats experiment, and different is the nitrobenzaldehyde that before adding geranial, in geranial, adds 1.3 weight %.The result is listed in the table 10.
Table 10:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 0.4: 99.2: 0.4 isopulegol: strange-isopulegol: different-isopulegol): 0.0.
Embodiment 9: add chloral
Mode according to embodiment 6 repeats experiment, and different is the chloral that before adding geranial, in geranial, adds 1.3 weight %.The result is listed in the table 11.
Table 11:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 0.5: 99.3: 0.2 isopulegol: strange-isopulegol: different-isopulegol): 0.0.
Embodiment 10: add Pyruvic Acid Ethyl ester
Mode according to embodiment 6 repeats experiment, and different is the Pyruvic Acid Ethyl ester that before adding geranial, in geranial, adds 1.0 weight %.The result is listed in the table 12.
Table 12:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 0.5: 99.5: 0.0 isopulegol: strange-isopulegol: different-isopulegol): 0.0.
Embodiment 11: add trifluoroacetone
Mode according to embodiment 6 repeats experiment, and different is before adding geranial, in geranial, to add 1,1 of 1.0 weight %, 1-trifluoroacetone.The result is listed in the table 13.
Table 13:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 0.8: 98.9: 0.3 isopulegol: strange-isopulegol: different-isopulegol): 0.0.
Embodiment 12:
Adopt the thick geranial sample (increase of geraniol content) through the hydrogenation preparation to repeat to test according to the mode of embodiment 6.The result is listed in the table 14.
Table 14:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 0.5: 99.5: 0.0 isopulegol: strange-isopulegol: different-isopulegol): 0.0.
Embodiment 13:
Mode according to embodiment 12 repeats experiment, and different is before adding geranial, in geranial, to add 1,1 of 1.0 weight %, 1-trifluoroacetone.The result is listed in the table 15.
Table 15:
* rhodinic acid citronellyl acrylate
Enantiomeric ratio is (new-isopulegol: as to be 0.5: 99.0: 0.3 isopulegol: strange-isopulegol: different-isopulegol): 0.2.
Embodiment 14: recovery has ligand i a
2-3 catalyst complexes
The ligand i a that in the flask of heated drying, adds 2.93g (4.99mmol)
2-3 with the dry toluene of 100ml.At room temperature, the 0.66M solution of triethyl aluminum in toluene that in clear solution, adds 1.75ml (3.33mmol is with respect to the 5mol% of geranial).This solution in 25 ℃ of stirrings 1 hour, was obtained the gel suspension-s of catalyzer after several minutes.This catalyst suspension is cooled to 0 ℃, and in 1 hour, add 10.2g (65.8mmol) be cooled to-15 ℃ geranial.In this reaction mixture of 0 ℃ of restir 1 hour.From solid catalyst, isolate reaction mixture through filtering.Filtrating is carried out conventional aftertreatment, and removes toluene through distillation, and the crude product of gained is analyzed.The result is listed in the table 16.
Table 16:
The catalyzer that filters out is suspended in the other 100ml toluene.The catalyst suspension of preparation in this way is cooled to 0 ℃, and in 6 hours, add 10.2g (65.8mmol) be cooled to-15 ℃ geranial.In this reaction mixture of 0 ℃ of restir 18 hours, and carry out aftertreatment and analysis according to routine.The result is listed in the table 17.
Table 17:
Embodiment 15: reclaim ligand i a
2-3 method
At room temperature, the 0.66M solution of triethyl aluminum in toluene with 14ml (26.4mmol is with respect to the 1mol% of geranial) adds 23.44g (40mmol) ligand i a
2In-3 the solution in the 800ml dry toluene.This solution in 25 ℃ of stirrings 1 hour, was obtained the gel suspension-s of catalyzer after several minutes.This catalyst suspension is cooled to 0 ℃, the mixture of 406g (2.64mol) geranial and 4.06g (with respect to the 1mol% of geranial) trifluoroacetone is cooled to-15 ℃ and in 3 hours, add.In this reaction mixture of 0 ℃ of restir 4 hours, obtain clear solution.Under atmospheric pressure in 15cm Vigreux tower, distill out toluene.The 1-methylnaphthalene of 80g is added in the said clear solution as high boiling component, under 10 millibars, distill out 364g isopulegol altogether.This is corresponding to 87% productive rate.Under cooling, go out white crystal from tower bear building-up crystalline substance.Filtration obtains the white solid of 20.0g altogether, through analyzing the ligand i a that confirms by about 5%1-methylnaphthalene pollution
2-3.Therefore, can reclaim 81% ligand i a through simple crystallization
2-3.The ligand i a of 3.1g in addition
2-3 can obtain with pure form through distilling out the 1-methylnaphthalene.
Embodiment 16 (not according to the present invention): with part 45 catalyzer with triethyl aluminum in the presence of acetate through the part cyclisation geranial that is converted
The part 36 (purity 98.8%) of 618mg (1.2mmol) is dissolved in the 30g toluene.Slowly add 25% solution of 0.342g (0.74mmol) triethyl aluminum in toluene.Form the gel product, and with this mixture subsequently in 20 ℃ of restir 40 minutes.Catalyst solution with gained is cooled to 0 ℃ then, and divides 6 parts of racemize geranial and 61mg acetate solution in 24g toluene that add 11.7g (74.4mmol).After each time added, with mixture stir about 50 minutes subsequently.Then the 8%NaOH solution of mixture with 10ml is stirred, isolate organic phase, and through gas chromatographic analysis.Obtained following result: geranial=63.9%, new-isopulegol=0.2%, isopulegol=24.9%, strange-isopulegol=0.1%, different-isopulegol=0.07%, rhodinic acid citronellyl acrylate=7.3%.
Under 34.1% transformation efficiency, be 74.2% for the selectivity of isopulegol.It is (new-isopulegol: product isopulegol: strange-isopulegol: different-isopulegol): 0.8: 98.5: 0.4: 0.3 to have obtained to have following isomeric distribution.
Claims (23)
1. method for preparing the isopulegol of formula (IV),
Be included in the catalyzer existence and down the geranial of formula V carried out cyclisation:
Two (diaryl phenol) parts of wherein said catalyzer through type (I) and the aluminum compound of formula (II) and/or obtain with the reaction of the aluminum compound of formula (III):
Wherein, Ar
1, Ar
2, Ar
3, Ar
4Be identical or different, and be the heteroaryl that has the aryl of 6-15 carbon atom or have 2-15 carbon atom in each case independently of one another, its when suitable, can carry in each case 1-7 identical or different be selected from following substituting group: C
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen ,-SiR
5aR
6aR
7a, replace or unsubstituted C
6-C
10Aryl ,-NR
8aR
9a,-SR
10a,-NO
2,
R
1, R
2, R
3, R
4Be identical or different, and be hydrogen independently of one another in each case, C
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen ,-SiR
5bR
6bR
7b, replace or unsubstituted C
6-C
10Aryl ,-NR
8bR
9b,-SR
10b,-NO
2, and R
1Or R
2And/or R
3Or R
4Can with A form aromatics or non-aromatics ring and
A (1) is the alkyl that straight chain or branching and/or cyclic have 1-25 carbon atom; It can be saturated or single unsaturated or polyunsaturated; And/or be partially aromatic and when suitable, can have one or more identical or different heteroatoms O, S and NR of being selected from
11In heteroatoms and/or the one or more identical or different C of functional group (O), S (O) and S (O) of being selected from
2In functional group and when suitable, can carry one or more identical or different following substituting group: C that are selected from
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
1-C
10Acyloxy, C
7-C
12Aralkyl, halogen ,-SiR
5cR
6cR
7c, replace or unsubstituted C
6-C
10Aryl replaces or unsubstituted C
2-C
10Heteroaryl ,-NR
8cR
9c,-SR
10c,-NO
2, C
1-C
12Acyl group, C
1-C
10Carboxyl, or
(2) be the heteroaryl that has the aryl of 6-15 carbon atom or have 2-15 carbon atom, it can carry 1-5 in each case and be selected from following substituting group: C when suitable
1-C
6Alkyl, C
1-C
6Perfluoroalkyl, C
1-C
6Alkoxyl group, C
7-C
12Aralkyl, halogen ,-SiR
5dR
6dR
7d, replace or unsubstituted C
6-C
10Aryl ,-NR
8dR
9d,-SR
10d,-NO
2, or
(3) be selected from following functional group or heteroatoms :-O-,-S-,-N (R
11)-,-S (O)-,-C (O)-,-S (O)
2-,-P (R
11)-,-(R
11) P (O)-with-Si (R
12R
13),
Radicals R wherein
5a, R
6a, R
7a, R
8a, R
9a, R
10aTo R
5d, R
6d, R
7d, R
8d, R
9d, R
10dAnd R
11To R
13Be C in each case independently
1-C
6Alkyl, C
7-C
12Aralkyl and/or replacement or unsubstituted C
6-C
10Aryl, radicals R
8aAnd R
9a, R
8bAnd R
9b, R
8cAnd R
9c, R
8dIndependently of one another can be in each case also form together with R9d and to have the cyclic hydrocarbon group of 2-8 carbon atom, it can have one or more identical or different O, S and NR of being selected from
11aIn heteroatoms, and R
11aCan have for R
11Given definition,
(R
14)
3-pAlH
p (II)，
Wherein
Al is an aluminium,
R
14Be a branching or the nonbranched 1-5 of a having carbon atom alkyl and
P is 0 or the integer of 1-3,
MAlH
4 (III)，
Wherein
Al be aluminium and
M is lithium, sodium or potassium.
2. according to the process of claim 1 wherein that said cyclization carries out in the presence of catalyzer, this catalyzer obtains through two (diaryl phenol) part reaction that makes formula (Ia):
Wherein, Ar
1, Ar
2, Ar
3, Ar
4, R
1, R
2, R
3, R
4Has identical implication in the formula (I) with claim 1 with A.
3. according to the method for claim 1, be used for the optically-active isopulegol of preparation formula (IVa):
Comprise that the optically-active geranial with formula (Va) carries out cyclisation:
Wherein (*) representes asymmetric c atom in each case.
4. according to the method for claim 3, be used to prepare L-(-)-isopulegol, comprise D-(+)-geranial is carried out cyclization.
5. according to the process of claim 1 wherein that used aluminum compound is the compound of formula (II).
6. according to the method for claim 5, wherein used aluminum compound is trimethylaluminium or triethyl aluminum.
7. it is 10: 1 to 1: 1 according to two (diaryl phenol) parts of the formula of the process of claim 1 wherein (I) and the mol ratio between formula (II) and/or the aluminum compound (III).
8. according to the method for claim 7, two (diaryl phenol) parts of its Chinese style (I) and the mol ratio between formula (II) and/or the aluminum compound (III) are 1.5: 1.
9. according to the process of claim 1 wherein that said cyclization carries out in the presence of organic acid.
10. according to the method for claim 9, wherein said organic acid is an acetate.
11. according to the process of claim 1 wherein that cyclization carries out in the presence of at least a compound that is selected from carboxylic acid anhydride, aldehyde, ketone and vinyl ether.
12. according to the method for claim 11, wherein said cyclization carries out in the presence of the carboxylic acid anhydride of formula (VI),
Wherein,
R
20, R
20' be identical or different, and be branching or nonbranched C
1-C
12Alkyl or C
7-C
12Aralkyl or C
6-C
10Aryl, wherein said group can have one or more identical or different OR that are selected from each case
10e, SR
10f, NR
8eR
9eWith substituting group in the halogen and R wherein
20And R
20' also can form 5-8 unit ring together, said ring can have one or more olefinic double bonds and one or more identical or different O, S and NR of being selected from
11bIn heteroatoms and R wherein
10e, R
10f, R
8e, R
9eAnd R
11bCan be C independently of one another in each case
1-C
6Alkyl, C
7-C
12Aralkyl and/or replacement or unsubstituted C
6-C
10Aryl,
Or in the presence of the aldehyde of formula (VII), carry out:
Wherein
R
21Be branching or nonbranched C
1-C
12Alkyl or C
7-C
12Aralkyl or C
6-C
10Aryl, wherein said group can have one or more identical or different OR that are selected from each case
10e, SR
10f, NR
8eR
9eWith the substituting group in the halogen, wherein R
10e, R
10f, R
8eAnd R
9eCan have independently of one another and R
11Identical implication,
Or in the presence of the ketone of formula (VIII), carry out:
Wherein
R
22, R
23Be identical or different, and each branching or nonbranched C naturally
1-C
12Alkyl or C
7-C
12Aralkyl or C
6-C
10Aryl or C
1-C
6Alkoxy carbonyl, wherein said group can have one or more identical or different OR that are selected from each case
10e, SR
10f, NR
8eR
9eWith substituting group in the halogen and R wherein
22And R
23Also can form 5-8 unit ring together, said ring has one or more olefinic double bonds and one or more identical or different O, S and NR of being selected from
11bIn heteroatoms and R wherein
10e, R
10f, R
8e, R
9eAnd R
11bCan have independently of one another and R
11Identical implication,
Or in the presence of the vinyl ether of general formula (IX), carry out:
Wherein
R
24, R
25, R
26And R
27Being identical or different, is branching or nonbranched C independently of one another in each case
1-C
12Alkyl or C
7-C
12Aralkyl or C
6-C
10Aryl, wherein said group can have one or more identical or different oxygen base, OR of being selected from each case
10e, SR
10f, NR
8eR
9eWith substituting group in the halogen and R wherein
25And R
26Also can form 5-8 unit ring together, said ring can have one or more olefinic double bonds and one or more identical or different O, S and NR of being selected from
11bIn heteroatoms and R wherein
10e, R
10f, R
8e, R
9eAnd R
11bCan have independently of one another and R
11Identical implication.
13. according to the method for claim 12, wherein said cyclization carries out in the presence of diacetyl oxide, propionic aldehyde, PIVALIC ACID CRUDE (25) acid anhydride and/or benzoyl oxide.
14. according to the method for claim 12, wherein said cyclization is at acetaldehyde, propionic aldehyde, chloral, 1,1,1-trifluoroacetone, 1,1 carries out under the existence of 1-trifluoroacetophenone, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester or Perfluoroacetone.
15. according to the method for claim 11, the consumption of wherein said carboxylic acid anhydride, aldehyde, ketone and/or vinyl ether is 0.01-5mol%, based on the consumption meter of geranial.
16. according to the method for claim 11, wherein add earlier the solution or the suspension-s of said catalyzer, add the geranial that will react and the mixture of carboxylic acid anhydride, aldehyde, ketone and/or vinyl ether again.
17. according to the method for claim 11, the geranial that wherein adding will be reacted in 30 minutes to 6 hours time and the mixture of carboxylic acid anhydride, aldehyde, ketone and/or vinyl ether.
18. according to the process of claim 1 wherein at two (diaryl phenol) part of recovery type (I) afterwards that reacts.
19. the method according to claim 18 may further comprise the steps:
A) the optional solvent that uses and optional other compound that uses are removed in distillation from product mixtures,
B) in the resistates that in step a), obtains, add the solvent that boiling point is higher than isopulegol,
C) from the mixture that step b), obtains fractionation by distillation go out isopulegol and
D) cool off the distillation tower bed material that in step c), obtains, crystallization simultaneously goes out two (diaryl phenol) part of used formula (I).
20., wherein after reacting, reclaim Diarylphenoxy aluminum compounds as catalyzer according to each method among the claim 1-17.
21. a method for preparing Therapeutic Mineral Ice comprises the isopulegol for preparing formula (IV) according to each method among the claim 1-20, the olefinic double bond hydrogenation of the isopulegol that will obtain in this way subsequently.
22. according to the method for claim 21, wherein prepare the optically-active Therapeutic Mineral Ice, may further comprise the steps:
A) according to each method among the claim 1-21 prepare formula (IVa) the optically-active isopulegol and
The olefinic double bond hydrogenation of the optically-active isopulegol that b) will obtain in this way.
23. according to the method for claim 22, wherein prepare L-(-)-Therapeutic Mineral Ice, may further comprise the steps:
A) according to each method among the claim 1-22 prepare L-(-)-isopulegol and
The olefinic double bond hydrogenation of optically-active L-(-)-isopulegol that b) will obtain in this way.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005010329.4 | 2005-03-03 | ||
| DE102005010329A DE102005010329A1 (en) | 2005-03-03 | 2005-03-03 | New diarylphenoxy-aluminum compound, obtained by a reaction of bis(diarylphenol) ligand with aluminum compound and/or aluminum compound, useful as a catalyst |
| DE102005044518.7 | 2005-09-16 | ||
| DE102005044518A DE102005044518A1 (en) | 2005-09-16 | 2005-09-16 | New diarylphenoxy-aluminum compound, obtained by a reaction of bis(diarylphenol) ligand with aluminum compound and/or aluminum compound, useful as a catalyst |
| PCT/EP2006/060416 WO2006092433A1 (en) | 2005-03-03 | 2006-03-03 | Diarylphenoxy aluminum compounds |
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| CN2009102583278A Division CN101723809B (en) | 2005-03-03 | 2006-03-03 | Diaryl phenoxy aluminium compound |
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| CN101133067B true CN101133067B (en) | 2012-05-02 |
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| JP5648240B2 (en) * | 2010-05-25 | 2015-01-07 | 高砂香料工業株式会社 | Organoaluminum compound |
| CN107188781B (en) * | 2017-06-02 | 2020-07-24 | 万华化学集团股份有限公司 | Method for preparing isopulegol from citronellal |
| 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 |
| CN112142561B (en) * | 2020-10-26 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing isopulegol from citronellal |
| CN112142583B (en) * | 2020-10-26 | 2022-07-26 | 万华化学集团股份有限公司 | Method for preparing neral from geranial |
| CN114478889B (en) * | 2020-10-26 | 2024-06-04 | 中国石油化工股份有限公司 | Ethylene polymer and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1225163A2 (en) * | 2001-01-18 | 2002-07-24 | Takasago International Corporation | Process for producing isopulegol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1225163A2 (en) * | 2001-01-18 | 2002-07-24 | Takasago International Corporation | Process for producing isopulegol |
Non-Patent Citations (2)
| Title |
|---|
| Hirotsugu Ito et al..Chiral Molecular Recognition by Aluminum Tris(2,6-diphenylphenoxide) in an Asymmetric 1,4-Addition.Aggew.Chem.Int.Ed. 43.2004,(43),994-997. |
| Hirotsugu Ito et al..Chiral Molecular Recognition by Aluminum Tris(2,6-diphenylphenoxide) in an Asymmetric 1,4-Addition.Aggew.Chem.Int.Ed. 43.2004,(43),994-997. * |
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