CN112424154B - 酮类混合物的制造方法 - Google Patents
酮类混合物的制造方法 Download PDFInfo
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- CN112424154B CN112424154B CN201980046836.6A CN201980046836A CN112424154B CN 112424154 B CN112424154 B CN 112424154B CN 201980046836 A CN201980046836 A CN 201980046836A CN 112424154 B CN112424154 B CN 112424154B
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- bis
- heptanone
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- 150000002576 ketones Chemical class 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 10
- -1 ketone compound Chemical class 0.000 claims abstract description 41
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 12
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 10
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002168 alkylating agent Substances 0.000 claims abstract description 6
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 6
- 150000004808 allyl alcohols Chemical class 0.000 claims abstract description 6
- 239000007818 Grignard reagent Substances 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 25
- GSNKRSKIWFBWEG-UHFFFAOYSA-N 3-ethylpentan-2-one Chemical compound CCC(CC)C(C)=O GSNKRSKIWFBWEG-UHFFFAOYSA-N 0.000 claims description 20
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 20
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 19
- MBDOYVRWFFCFHM-UHFFFAOYSA-N 2-hexenal Chemical compound CCCC=CC=O MBDOYVRWFFCFHM-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 claims description 16
- 239000010948 rhodium Substances 0.000 claims description 16
- TYBCSQFBSWACAA-UHFFFAOYSA-N Nonan-4-one Chemical compound CCCCCC(=O)CCC TYBCSQFBSWACAA-UHFFFAOYSA-N 0.000 claims description 14
- PPKSOKLRYCVQPM-UHFFFAOYSA-N 3-ethylheptan-2-one Chemical compound CCCCC(CC)C(C)=O PPKSOKLRYCVQPM-UHFFFAOYSA-N 0.000 claims description 10
- PVCQESFACCIIOU-UHFFFAOYSA-N 3-ethylpent-3-en-2-ol Chemical compound CCC(=CC)C(C)O PVCQESFACCIIOU-UHFFFAOYSA-N 0.000 claims description 10
- SSOMPMJXZBMODL-UHFFFAOYSA-N 5-ethylnonan-4-one Chemical compound CCCCC(CC)C(=O)CCC SSOMPMJXZBMODL-UHFFFAOYSA-N 0.000 claims description 10
- MBDOYVRWFFCFHM-SNAWJCMRSA-N 2-Hexenal Natural products CCC\C=C\C=O MBDOYVRWFFCFHM-SNAWJCMRSA-N 0.000 claims description 9
- VXFNAXCUQUMXBB-UHFFFAOYSA-N 3-ethylhept-3-en-2-ol Chemical compound CCCC=C(CC)C(C)O VXFNAXCUQUMXBB-UHFFFAOYSA-N 0.000 claims description 9
- QMQBUTKELHAKRH-UHFFFAOYSA-N 3-ethylheptan-4-one Chemical compound CCCC(=O)C(CC)CC QMQBUTKELHAKRH-UHFFFAOYSA-N 0.000 claims description 9
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 9
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims description 9
- BOEWENCXVIMZRU-UHFFFAOYSA-N hept-3-en-2-ol Chemical compound CCCC=CC(C)O BOEWENCXVIMZRU-UHFFFAOYSA-N 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- IQGZCSXWIRBTRW-ZZXKWVIFSA-N (2E)-2-ethyl-2-butenal Chemical compound CC\C(=C/C)C=O IQGZCSXWIRBTRW-ZZXKWVIFSA-N 0.000 claims description 8
- DODCYMXUZOEOQF-HWKANZROSA-N (e)-hept-2-en-4-ol Chemical compound CCCC(O)\C=C\C DODCYMXUZOEOQF-HWKANZROSA-N 0.000 claims description 7
- AGJGJUGBPXOLEG-SOFGYWHQSA-N (e)-non-5-en-4-ol Chemical compound CCC\C=C\C(O)CCC AGJGJUGBPXOLEG-SOFGYWHQSA-N 0.000 claims description 6
- 238000006317 isomerization reaction Methods 0.000 claims description 5
- GJYMQFMQRRNLCY-ONEGZZNKSA-N (e)-pent-3-en-2-ol Chemical compound C\C=C\C(C)O GJYMQFMQRRNLCY-ONEGZZNKSA-N 0.000 claims description 4
- NKRNXXOIDPGFCL-UHFFFAOYSA-N 3-ethylhept-2-en-4-ol Chemical compound CCCC(C(=CC)CC)O NKRNXXOIDPGFCL-UHFFFAOYSA-N 0.000 claims description 4
- CDLYQPJYQNNBFV-UHFFFAOYSA-N 5-ethylnon-5-en-4-ol Chemical compound CCCC=C(CC)C(CCC)O CDLYQPJYQNNBFV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- PYLMCYQHBRSDND-SOFGYWHQSA-N (E)-2-ethyl-2-hexenal Chemical compound CCC\C=C(/CC)C=O PYLMCYQHBRSDND-SOFGYWHQSA-N 0.000 claims 2
- 150000001299 aldehydes Chemical class 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000000877 Sex Attractant Substances 0.000 abstract description 16
- 241000700157 Rattus norvegicus Species 0.000 abstract description 15
- 241000700159 Rattus Species 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 37
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 150000004795 grignard reagents Chemical class 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- PYLMCYQHBRSDND-VURMDHGXSA-N (Z)-2-ethyl-2-hexenal Chemical compound CCC\C=C(\CC)C=O PYLMCYQHBRSDND-VURMDHGXSA-N 0.000 description 8
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229910020366 ClO 4 Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003016 pheromone Substances 0.000 description 4
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RABYCESNCPESGM-UHFFFAOYSA-N 2-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound C1(=CC=CC=C1)P(CCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(CCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 RABYCESNCPESGM-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- JHOGQJHPYMBQKC-UHFFFAOYSA-N C1(=CC=CC=C1)P(CCCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(CCCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)P(CCCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(CCCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 JHOGQJHPYMBQKC-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000005667 attractant Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 230000031902 chemoattractant activity Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- UGVPKMAWLOMPRS-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].CC[CH2-] UGVPKMAWLOMPRS-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 3
- NFRYVRNCDXULEX-UHFFFAOYSA-N (2-diphenylphosphanylphenyl)-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C(=CC=CC=1)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 NFRYVRNCDXULEX-UHFFFAOYSA-N 0.000 description 2
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- XMYFZAWUNVHVGI-UHFFFAOYSA-N 3-ethylpent-2-ene Chemical compound CCC(CC)=CC XMYFZAWUNVHVGI-UHFFFAOYSA-N 0.000 description 2
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CWKDXHTYRIQWHR-UHFFFAOYSA-N C1(=CC=CC=C1)P(C1=CC=CC=C1)CP(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)CP(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)P(C1=CC=CC=C1)CP(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)CP(C1=CC=CC=C1)C1=CC=CC=C1 CWKDXHTYRIQWHR-UHFFFAOYSA-N 0.000 description 2
- XGQSPRHSHJJXGN-UHFFFAOYSA-N C1(=CC=CC=C1)P(CCCCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(CCCCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)P(CCCCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(CCCCP(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 XGQSPRHSHJJXGN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000003434 Sesamum indicum Nutrition 0.000 description 2
- 244000000231 Sesamum indicum Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000005575 aldol reaction Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ONDSBJMLAHVLMI-UHFFFAOYSA-N trimethylsilyldiazomethane Chemical compound C[Si](C)(C)[CH-][N+]#N ONDSBJMLAHVLMI-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
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- ZIWXVGHUDKNNSH-QPJJXVBHSA-N (e)-non-2-en-4-ol Chemical compound CCCCCC(O)\C=C\C ZIWXVGHUDKNNSH-QPJJXVBHSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 238000011925 1,2-addition Methods 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- NWBYLRTXCRACKB-UHFFFAOYSA-N 2-ethyl-N-methoxy-N-methylhexanamide Chemical compound CCCCC(CC)C(=O)N(C)OC NWBYLRTXCRACKB-UHFFFAOYSA-N 0.000 description 1
- HCUMFFMWWXUKIF-UHFFFAOYSA-N 2-ethyl-n-methoxy-n-methylbutanamide Chemical compound CCC(CC)C(=O)N(C)OC HCUMFFMWWXUKIF-UHFFFAOYSA-N 0.000 description 1
- QARLTYSAFQGMMB-UHFFFAOYSA-N 2-ethylbutanenitrile Chemical compound CCC(CC)C#N QARLTYSAFQGMMB-UHFFFAOYSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- JHHZQADGLDKIPM-AATRIKPKSA-N 3-Hepten-2-one Chemical compound CCC\C=C\C(C)=O JHHZQADGLDKIPM-AATRIKPKSA-N 0.000 description 1
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- CHZAMJVESILJGH-UHFFFAOYSA-N 3-[bis(2-cyanoethyl)phosphanyl]propanenitrile Chemical compound N#CCCP(CCC#N)CCC#N CHZAMJVESILJGH-UHFFFAOYSA-N 0.000 description 1
- ZBMZOFSLQIPSPW-UHFFFAOYSA-N 3-bis(3-sulfophenyl)phosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S(O)(=O)=O)C=2C=C(C=CC=2)S(O)(=O)=O)=C1 ZBMZOFSLQIPSPW-UHFFFAOYSA-N 0.000 description 1
- MMQDVLWWGWJSFS-UHFFFAOYSA-N 3-ethylheptan-2-ol Chemical compound CCCCC(CC)C(C)O MMQDVLWWGWJSFS-UHFFFAOYSA-N 0.000 description 1
- NEHRITNOSGFGGS-UHFFFAOYSA-N 3-ethylpentan-2-ol Chemical compound CCC(CC)C(C)O NEHRITNOSGFGGS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OQNKQWNDMBCKNI-UHFFFAOYSA-N 4-methylnon-1-en-4-ol Chemical compound CCCCCC(C)(O)CC=C OQNKQWNDMBCKNI-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- CTYPJIUQROQJBG-DQEYMECFSA-N [(2s,4s)-4-diphenylphosphanylpentan-2-yl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P([C@@H](C)C[C@H](C)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 CTYPJIUQROQJBG-DQEYMECFSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-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
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- FMJNZRCLIZWWJP-UHFFFAOYSA-N carbon monoxide;ruthenium;triphenylphosphane Chemical compound [Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FMJNZRCLIZWWJP-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- SAMCXPGNUAXAOO-UHFFFAOYSA-N diphenylphosphane;pentane Chemical compound CCCCC.C=1C=CC=CC=1PC1=CC=CC=C1 SAMCXPGNUAXAOO-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910021476 group 6 element Inorganic materials 0.000 description 1
- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical compound CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- BNHFWQQYLUPDOG-UHFFFAOYSA-N lithium;1,2,2,3-tetramethylpiperidine Chemical compound [Li].CC1CCCN(C)C1(C)C BNHFWQQYLUPDOG-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- ZUVAACFIEPYYOP-UHFFFAOYSA-N methoxycyclopropane Chemical compound COC1CC1 ZUVAACFIEPYYOP-UHFFFAOYSA-N 0.000 description 1
- PLFLRQISROSEIJ-UHFFFAOYSA-N methylborane Chemical compound CB PLFLRQISROSEIJ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WHWRXFLOPJUZDK-UHFFFAOYSA-N n-methoxy-n-methylformamide Chemical compound CON(C)C=O WHWRXFLOPJUZDK-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007833 oxidative deamination reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 238000012552 review Methods 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JHHZQADGLDKIPM-UHFFFAOYSA-N trans-hept-3-en-2-one Natural products CCCC=CC(C)=O JHHZQADGLDKIPM-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
- A01M23/00—Traps for animals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/02—Acyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- 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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
- C07C33/03—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond in beta-position, e.g. allyl alcohol, methallyl alcohol
-
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Abstract
提供一种酮类混合物的制造方法,所述酮为雄性褐家鼠(Rattus norvegicus)的性信息素的成分。一种酮的制造方法,包含以下三个阶段。(1)通过乙醛与丁醛的羟醛缩合而获得α,β‑不饱和醛的第一阶段;(2)使第一阶段中获得的α,β‑不饱和醛的一种以上与烷基化剂反应而获得烯丙基醇类的第二阶段;(3)使第二阶段中获得的烯丙基醇类异构化为酮的第三阶段。
Description
技术领域
本发明为一种酮类混合物的制造方法,所述酮为雄性褐家鼠(Rattusnorvegicus)的性信息素的成分。
背景技术
作为雄性褐家鼠(Rattus norvegicus)的性信息素,除了报告有两种哌嗪类以外,还报告有3-乙基-2-戊酮、3-乙基-2-庚酮、2-庚酮、4-庚酮、2-辛酮、4-壬酮、及2-十一酮此七种酮(非专利文献1)。作为这些酮的合成法,3-乙基-2-庚酮可通过3-乙基-2-庚醇的铬酸氧化(非专利文献2)、N-甲氧基-N-甲基-2-乙基己酸酰胺与甲基格氏试剂(MethylGrignard Reagent)的反应(非专利文献1、非专利文献3)、2-乙基己醛与甲基硼化合物的反应(非专利文献4)或三甲基硅烷基重氮甲烷的反应(非专利文献5)来合成。作为3-乙基-2-戊酮的合成法,报告有N-甲氧基-N-甲基-2-乙基丁酸酰胺与甲基格氏试剂的反应(非专利文献1、非专利文献6)、3-乙基-2-戊醇的氯铬酸吡啶鎓(Pyridinium Chlorochromate,PCC)氧化(非专利文献7)、2-乙基丁腈与甲基锂的反应(非专利文献8)、3-乙基-2-戊烯的利用硫酸铁进行的水合反应(非专利文献9)等。作为2-庚酮的合成法,报告有:2-庚醇的氧化反应(非专利文献10、非专利文献11、非专利文献12、非专利文献13)、1-庚炔的水合反应(非专利文献13、非专利文献14)、3-庚烯-2-酮的氢化反应(非专利文献15)、1-庚烯的氧化反应(非专利文献16)、2-氨基庚烷的氧化性脱氨基化反应(非专利文献17)、己酸氯化物与甲基格氏试剂的铁催化剂反应(非专利文献18)、4-羟基-4-甲基-1-壬烯的热分解反应(非专利文献19)等方法。关于4-壬酮,报告有利用如下反应的方法:2-壬烯-4-醇的利用铁催化剂进行的异构化反应(非专利文献20)或利用铑催化剂或钌催化剂进行的异构化反应(非专利文献20)。
现有技术文献
非专利文献
非专利文献1:《德国应用化学(Angew.Chem.Int.Ed.)》,(55,6062(2016))。
非专利文献2:《臭氧层(Chemosphere)》,(80,813(2010))。
非专利文献3:《天然产物期刊(J.Natural Products)》,(69,863(2006))。
非专利文献4:《四面体快报(Tetrahedron Lett.)》,(30 5643(1989))。
非专利文献5:《综合体(Synthesis)》,(228(1988))。
非专利文献6:《德国应用化学(Angew.Chem.Int.Ed.)》,(56,6646(2017))。
非专利文献7:《有机反应(Organic Reactions)》,(53,未给出页码(1998))。
非专利文献8:《四面体快报(Tetrahedron Lett.)》,(31,353(1990))。
非专利文献9:《四面体(Tetrahedron)》,(40,1469(1984))。
非专利文献10:《有机金属化合物(Organometallics)》,(37,584(2018))
非专利文献11:《英国皇家化学学会进展(RSC Advances)》,(6,63717(2016))。
非专利文献12:《有机合成试剂百科全书(e-EROS Encyclopedia of Reagentsfor Organic Synthesis)》,(1(2001))。
非专利文献13:《有机合成试剂百科全书(e-EROS Encyclopedia of Reagentsfor Organic Synthesis)》,(1(2011))。
非专利文献14:《分子催化A:化学品(J.Mol.Catal.A:Chemical)》,(425,283(2016))。
非专利文献15:《催化科学与技术(Catalysis Science&Technology)》,(6,1921(2016))。
非专利文献16:《欧洲化学期刊(Chem.-Eur.J.)》,(22,4738(2016))。
非专利文献17:《拉撒彦化学期刊(Rasayan J.of Chemistry)》,(3,16(2010))。
非专利文献18:《合成快报(Synlett)》,(383(2010))。
非专利文献19:《分子催化A:化学品(J.Mol.Catal.A:Chemical)》,(161,239(2000))。
非专利文献20:《化学技术与生物技术期刊(J.Chem.Technol.Biotechnol.)》,(48,483(1990))。
非专利文献21:《四面体(Tetrahedron)》,(57,2379(2001))
非专利文献22:《欧洲有机化学(Eur.J.Org.Chem.)》,(3141(2001))
发明内容
发明所要解决的问题
为了使用现有技术制造雄性褐家鼠(Rattus norvegicus)的性信息素的放散量多的五种酮(3-乙基-2-戊酮、3-乙基-2-庚酮、2-庚酮、4-庚酮、4-壬酮),例如,自羧酸向N-甲氧基-N-甲基羧酸酰胺转换、并与甲基格氏试剂或丙基格氏试剂进行反应,在所述二阶段的反应中,即便假设为容易获得对应的四种羧酸,也为需要合计九种反应的繁杂方法,在工业性实施方面有大的问题。
解决问题的技术手段
因此,仅通过使甲基格氏试剂和通过丁醛与乙醛的羟醛缩合而生成的四种α,β-不饱和醛反应,并使所获得的四种烯丙基醇类异构化,便可获得包含构成雄性褐家鼠(Rattusnorvegicus)的性信息素的放散量多的五种酮中的三种(3-乙基-2-戊酮、3-乙基-2-庚酮、2-庚酮)的酮的混合物。另外,仅通过代替甲基格氏试剂而使丙基格氏试剂与相同的四种醛反应并同样地进行异构化,便可获得包含剩余的两种性信息素(4-庚酮、4-壬酮)的酮的混合物,即,发现仅通过使甲基格氏试剂与丙基格氏试剂的混合物和通过丁醛与乙醛的羟醛缩合而生成的四种α,β-不饱和醛反应,并使所获得的烯丙基醇类异构化,便可获得包含构成性信息素的放散量多的全部五种酮的酮的混合物,从而完成了本发明。
发明的效果
根据本发明,仅通过使甲基格氏试剂及丙基格氏试剂和通过丁醛与乙醛的羟醛缩合而生成的四种α,β-不饱和醛反应,并使所获得的烯丙基醇类异构化,便可由廉价且容易获得的醛,通过仅三个阶段来简便地制造并提供构成雄性褐家鼠的性信息素的放散量多的主要的五种酮。作为副产物的三种酮作为稀释剂发挥功能,因此为不会产生废弃物、环保的制造方法。
具体实施方式
本发明由以下的[1]~[6]等构成。
[1]
一种酮的制造方法,所述酮由式(3)表示,所述制造方法包含以下三个阶段,
(1)通过乙醛与丁醛的羟醛缩合而获得式(1)所表示的α,β-不饱和醛的第一阶段;
(2)使第一阶段中获得的式(1)所表示的α,β-不饱和醛的一种以上与烷基化剂反应而获得式(2)所表示的烯丙基醇类的第二阶段;
(3)使第二阶段中获得的式(2)所表示的烯丙基醇类异构化为式(3)所表示的酮的第三阶段,
第一阶段:
第二阶段:
第三阶段:
式(1)~式(3)中,R1为甲基或丙基,R2为氢或乙基,R3为甲基、丙基、或戊基。
[2]
根据项[1]所述的酮的制造方法,其中,第三阶段中使用的金属催化剂的金属为钌、铑、铱、钯、及铁中的任一种以上。
[3]
根据项[1]或[2]所述的酮的制造方法,其中,第二阶段中使用的烷基化剂为R3MgX所表示的格氏试剂,
此处,R3为甲基、丙基、或戊基,X为卤素。
[4]
根据项[3]所述的酮的制造方法,其中,作为格氏试剂的R3MgX的R3为甲基或丙基。
[5]
根据项[1]至[4]中任一项所述的酮的制造方法,其中,第三阶段中使用的金属催化剂的金属为钌或铑。
[6]
根据项[1]至[5]中任一项所述的酮的制造方法,其中,并不将2-戊酮、3-乙基-4-庚酮、及5-乙基-4-壬酮中的任一种以上分离去除。
[7]一种引诱剂组合物,含有利用根据项[1]至[6]中任一项所述的酮的制造方法制造的褐家鼠(Rattus norvegicus)的性信息素,所述褐家鼠的性信息素含有2-戊酮、3-乙基-4-庚酮、及5-乙基-4-壬酮中的任一种以上。
[8]一种捕捉器,其利用根据项[7]所述的含有褐家鼠(Rattus norvegicus)的性信息素的引诱剂组合物。
对成为本发明的酮制造方法的三个阶段进行说明,所述酮为雄性褐家鼠(Rattusnorvegicus)的性信息素的成分。
<第一阶段>
由第一阶段的乙醛与丁醛、并通过羟醛缩合来获得四种α,β-不饱和醛(2-丁烯醛、2-乙基-2-丁烯醛、2-己烯醛、及2-乙基-2-己烯醛)。例如,可依照已知的方法(日本专利特开平9-59201、日本专利特开平9-57108、国际公开2012/116775号、日本专利特开2011-219395等)来获得。
R1为甲基或丙基,R2为氢或乙基。
第一阶段包含:作为碱催化剂羟醛反应的第一工序、以及作为羟醛反应产物的β-羟基醛的酸催化剂脱水反应的第二工序。
[第一工序]
作为第一工序中所使用的碱催化剂,可优选地使用:氢氧化钠、氢氧化钾、氢氧化锂、氢氧化钡等碱金属或碱土金属的氢氧化物,氧化钡、氧化钙、氧化镁等碱土金属的氧化物,碳酸钠、碳酸钾、碳酸钙等碱金属或碱土金属的碳酸盐,甲醇钠、乙醇钠、叔丁醇钠、叔丁醇钾等醇盐,1,8-二氮杂双环[5.4.0]-7-十一烯、1,5-二氮杂双环[4.3.0]-5-壬烯等缩合杂环式化合物,吡啶、脯氨酸、哌啶、吡咯烷、吗啉、N-甲基哌嗪、二甲基胺、二乙基胺、二异丙基胺、二环己基胺等有机碱,及这些的有机碱与乙酸、苯酚、儿茶酚等布朗斯台德酸(Bronsted acid)的混合物等。优选为-30℃~100℃,更优选为0℃~50℃。原料的添加形态并无特别限制。根据第一工序中选择的反应的种类或反应条件,生成的四种α,β-不饱和醛的生成比不同,可选择最终的雄性褐家鼠的性信息素的构成酮的比。
[第二工序]
第二工序为β-羟基醛的酸催化剂脱水反应,作为酸催化剂,可使用:盐酸、硫酸、高氯酸、磷酸等无机酸,甲酸、乙酸、丙酸、丁酸、异丁酸、戊酸、异戊酸、特戊酸、己酸、辛酸、苯甲酸、草酸、三氯乙酸等羧酸,对甲苯磺酸、甲磺酸等磺酸等。优选为饱和脂肪族羧酸。通过加热来促进反应,优选为加热到100℃,通过与水的共沸而自反应液分离作为目标物的α,β-不饱和醛,并利用蒸馏进行精制。
在接下来的第二阶段中,仅使用甲基格氏试剂作为格氏试剂,于在α,β-不饱和醛中不需要包含2-丁烯醛的情况下,可在第一阶段的第二工序中,通过蒸馏仅将沸点最低的2-丁烯醛分离去除。另外,在所述第二阶段中,仅使用丙基格氏试剂作为格氏试剂,于在α,β-不饱和醛中不需要包含2-乙基-2-己烯醛的情况下,可在第一阶段的第二工序中,通过蒸馏仅将沸点最高的2-乙基-2-己烯醛分离去除。另外,在使用甲基格氏试剂与丙基格氏试剂两者作为格氏试剂的情况下,由于需要四种α,β-不饱和醛的全部,因此,可在第一阶段的第二工序中只进行用于进行水分去除的蒸馏,或者,为了调整第三阶段的作为最终目标物的酮的构成比,也可进行用于调整α,β-不饱和醛的构成比的精馏。另外,视需要,也可将四种α,β-不饱和醛全部分馏,个别地进行第二阶段以后的反应,并在作为最终目标物的酮的阶段以信息素用途来调整构成比。
在下述表1中示出由α,β-不饱和醛与格氏试剂生成的酮。A-1、B-2、D-2的框中所示的分别为2-戊酮、3-乙基-3-庚酮、5-乙基-4-壬酮的酮迄今为止还没有作为褐家鼠(Rattusnorvegicus)的信息素的报告。2-戊酮(A-1)与所述性信息素的其他酮结构相似,但分子更小,3-乙基-4-庚酮(B-2)及5-乙基-4-壬酮(D-2)与所述信息素的酮也是结构相似,但分子更大。在与信息素的结构活性相关性有关的研究(《化学与教育》,(50,194-197(2002));《分子(Molecules)》,(10,1023-1047(2005)))等中明了的是:为了具有弱的活性、或阻碍活性,通常至少需要碳数相同且取代基或官能基的分子内配置相似,并呈现非对映体或镜像体的关系。因此,不仅不需要使用通过蒸馏等将2-戊酮、3-乙基-4-庚酮、5-乙基-4-壬酮分离所需的能量,而且这些酮在结构上与所述信息素的酮的相容性高,具备作为稀释剂的功能,因此不需要重新另行添加稀释剂。
表1.生成的酮
<第二阶段>
作为第二阶段的目标物的烯丙基醇类可通过如下方式获得:依据已知的方法(《四面体(Tetrahedron)》,(57,2379(2001))等),使烷基化试剂与第一阶段中获得的α,β-不饱和醛反应。作为烷基化试剂,优选为格氏试剂、烷基锂等亲核性强、容易引起1,2-加成的试剂,就经济方面而言,更优选为格氏试剂,可使甲基格氏试剂或丙基格氏试剂进行反应而获得。
甲基格氏试剂或丙基格氏试剂的卤素可为氯、溴、碘中的任一种,作为格氏试剂的溶媒,可为四氢呋喃、二乙基醚、2-甲基四氢呋喃、环丙基甲基醚、甲基叔丁基醚等的任一种,其浓度优选为1mol/L~3mol/L。除了格氏试剂的溶液中所使用的溶媒以外,无需使用反应溶媒,但就温度控制或搅拌控制的方面而言,也可使用有机溶媒,除了格氏试剂中所使用的溶媒以外,还可使用甲苯等不与格氏试剂反应的溶媒。原料的添加顺序并无限制。
反应温度通常为-80℃到溶媒沸点,在滴加格氏试剂或α,β-不饱和醛时,优选为-30℃~10℃,为了滴加后的熟化,也可自室温加热到溶媒沸点。
转化率、选择率均大致为100%,因此,反应结束后,可利用常规方法进行分离,无需精制而直接在第三阶段的反应中使用。
<第三阶段>
第三阶段的自烯丙基醇类向酮的异构化反应可依据已知的方法(《欧洲有机化学(Eur.J.Org.Chem.)》,(3141(2001));《四面体(Tetrahedron)》,(57,2379(2001));《美国化学学会期刊(J.Am.Chem.Soc.),(128,1360(2006));《化学通讯(Chem.Commun.),(232(2004));《有机金属化合物(Organometallics)》,(18,4230(1999));《有机金属化学期刊(J.Organomet.Chem.),(650,1(2002));《有机金属化合物(Organometallics)》,(29,2166(2010));《化学综述(Chem.Rev.),(103,27(2003))等)进行。
作为催化剂,可使用第6族元素至第10族元素的金属或金属化合物,具体而言,可列举:Cr、Mo、W、Mn、Re、Fe、Ru、Os、Rh、Ir、Ni、Pd等的金属或金属化合物。进而优选为以Fe、Ru、Rh、Ir、Pd的金属或金属化合物为宜,具体可列举以下催化剂,但并不限定于这些。
作为Ru催化剂,可列举:RuCl3、Ru(乙酰丙酮)3、Ru(η5-C5H5)2Cl、RuCl2(PPh3)2、RuClH(PPh3)3、RuClMe(PPh3)3、RuClPh(PPh3)3、RuH2(PPh3)3、RuMe2(PPh3)3、RuPh2(PPh3)3、RuH2(Pn-Bu3)4、[RuCl(PPh3)3]PF6、RuH2(PPh3)4、RuH4(PPh3)3、[HRu3(CO)11]K、Pr4NRuO4、以及这些与双(二苯基膦基)甲烷(Bis(diphenylphosphino)methane)、1,2-双(二苯基膦基)乙烷(1,2-Bis(diphenylphosphino)ethane)、1,2-双(二环己基膦基)乙烷(1,2-Bis(dicyclohexylphosphino)ethane)、1,3-双(二苯基膦基)丙烷(1,3-Bis(diphenylphosphino)propane)、1,4-双(二苯基膦基)丁烷(1,4-Bis(diphenylphosphino)butane)、1,4-双(二异丙基膦基)丁烷(1,4-Bis(diisopropylphosphino)butane)、2,2′-双(二苯基膦基)-1,1′-联萘(2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl)、1,2-双(二苯基膦基)苯(1,2-Bis(diphenylphosphino)benzene)、顺式-1,2-双(二苯基膦基)乙烷(cis-1,2-Bis(diphenylphosphino)ethene)、Ph3P、1,10-菲咯啉(1,10-phenanthroline)等配体的络合物、以及这些与对甲苯磺酸(p-toluenesulfonic acid)等布朗斯台德酸的组合、Ru3O(OCOCH3)7、Ru(H2O)6(O3SCF3)2、Ru(H2O)6(O3S甲苯基)2、Ru(η5-C5H5)(PPh3)2Cl、Ru(茚基)(PPh3)2Cl、[Ru(η5-C5H5)(对异丙甲苯)]PF6、[{Ru(η3:η3-2,7-二甲基辛-2,6-二烯-1,8-二基)(μ-Cl)Cl}2]、[{Ru(η6-对异丙甲苯)(μ-Cl)Cl}2]、[Ru(η5-C9H7)Cl(PPh3)2]2、[Ru(η5-C5H5)Cl(PPh3)2]2、[Ru(η3:η3-2,7-二甲基辛-2,6-二烯-1,8-二基)Cl2(CO)]、[Ru(η3:η3-2,7-二甲基辛-2,6-二烯-1,8-二基)Cl2(PPh3)]、[Ru(η3:η3-2,7-二甲基辛-2,6-二烯-1,8-二基)Cl2(Pi-Pr3)]、[Ru(η3:η3-2,7-二甲基辛-2,6-二烯-1,8-二基)Cl2(P(OMe)3)]、[Ru(η3:η3-2,7-二甲基辛-2,6-二烯-1,8-二基)Cl2(CNt-Bu)]、[Ru(η3:η3-2,7-二甲基辛-2,6-二烯-1,8-二基)Cl2(NH2Ph)]、[Ru(η3:η3-2,7-二甲基辛-2,6-二烯-1,8-二基)Cl2(NCMe)]、[Ru(η3:η3-2,7-二甲基辛-2,6-二烯-1,8-二基)Cl(NCMe)2]SbF6、RuCl(PPh3)3 +PF6 -、Ru(CO)3(PPh3)2等。
作为Rh催化剂,可列举:RhCl3、Rh2(SO4)3、[Rh(η2:η2-1,5-环辛二烯)2]Cl、[Rh(η2:η2-1,5-环辛二烯)2]ClO4、[Rh(η2:η2-1,5-环辛二烯)2]BF4、及这些与三(间磺苯基)磷烷(Tris(m-sulfophenyl)phosphane)、二(磺苯基磷烷基)丁烷(Di(sulfophenylphosphanyl)butane)、磺化(2S,4S)-(-)-2,4-双(二苯基磷烷基)戊烷(Sulfonated(2S,4S)-(-)-2,4-bis(diphenylphosphanyl)pentane)、磺化(S,S)-1,2-双(二苯基磷烷基甲基)环丁烷(Sulfonated(S,S)-1,2-bis(diphenylphosphanylmethyl)cyclobutane)、1,2-双(二苯基膦基)乙烷(1,2-Bis(diphenylphosphino)ethane)、1,2-双(二环己基膦基)乙烷(1,2-Bis(dicyclohexylphosphino)ethane)、1,3-双(二苯基膦基)丙烷(1,3-Bis(diphenylphosphino)propane)、1,4-双(二苯基膦基)丁烷(1,4-Bis(diphenylphosphino)butane)、1,4-双(二异丙基膦基)丁烷(1,4-Bis(diisopropylphosphino)butane)、2,2′-双(二苯基膦基)-1,1′-联萘(2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl)等配体的络合物、Rh(CO)Cl2、RhH[P(OPh)3]4、[Rh[P(OPh)3]4]ClO4、Rh[P(OPh)3]3[P(OPh)2(OC6H4))、Rh(乙酰基丙酮)(CO)(三(2-氰乙基)膦、RhH(PPh3)3、RhMe(PPh3)3、RhPh(PPh3)3、RhPhCO(PPh3)2、RhHCO(PPh3)2、RhHCO(PPh3)3、Rh(PPh3)3 +PF6 -、Rh(-O3S(C6H4)CH2C(CH2PPh2)3)(η2:η2-1,5-环辛二烯)、RhH(PPh3)4、[Rh(η2:η2-1,5-环辛二烯)2]BF4、RhCl(PPh3)3、RhClCO(PPh3)2、Rh(2,2,6,6-四甲基哌啶)等。
作为Pd催化剂,可列举:PdCl2、Pd/C、Pd/聚合物、Pd2(dba)3、Pd(dba)2、以及这些与双(二苯基膦基)甲烷(Bis(diphenylphosphino)methane)、1,2-双(二苯基膦基)乙烷(1,2-Bis(diphenylphosphino)ethane)、1,2-双(二环己基膦基)乙烷(1,2-Bis(dicyclohexylphosphino)ethane)、1,3-双(二苯基膦基)丙烷(1,3-Bis(diphenylphosphino)propane)、1,4-双(二苯基膦基)丁烷(1,4-Bis(diphenylphosphino)butane)、1,4-双(二异丙基膦基)丁烷(1,4-Bis(diisopropylphosphino)butane)、2,2′-双(二苯基膦基)-1,1′-联萘(2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl)、1,2-双(二苯基膦基)苯(1,2-Bis(diphenylphosphino)benzene)、顺式-1,2-双(二苯基膦基)乙烷(cis-1,2-Bis(diphenylphosphino)ethene)、Ph3P、n-Bu3P、t-Bu3P、三环己基膦(Tricyclohexylphosphine)、1,10-菲咯啉(1,10-phenanthroline)等配体的络合物等。
作为Fe催化剂,可列举:Fe(CO)5、Fe2(CO)9、Fe3(CO)12、Fe2(CO)9等。
作为Ni催化剂,可列举:Ni(C2H4)(PO甲苯基3)2、Ni(η2:η2-1,5-环辛二烯)2等。
作为Ir催化剂,可列举:IrCl3、[(η2:η2-1,5-环辛二烯)Ir(PMePh2)2]PF6、[Ir(CO)(PPh3)2]ClO4、[Ir(η2:η2-1,5-环辛二烯)(PhCN)(PPh3)]ClO4等。
作为Co催化剂,可列举:HCo(CO)4等。
作为Os催化剂,可列举:H2Os3(CO)12、[P(CH2CH2PPh2)3OsH(N2)][BPh4]、[P(CH2CH2PPh2)3OsH(η-OCMe2)][BPh4]等。
作为Pt催化剂,可列举:反式-[PtH(PR3)2(Me2CO)]X等。
作为Mo催化剂,可列举:反式-[Mo(N2)2(1,2-双(二苯基膦基)乙烷)2]、MoH4(1,2-双(二苯基膦基)乙烷)2等。
作为Cr催化剂,可列举:Cr(CO)3(萘)等。
作为添加到这些催化剂中并用于在系统内生成活性催化剂的添加物,可列举:正丁基锂、锂二异丙基酰胺、甲基溴化镁、苯基溴化镁、甲基锂、苯基锂、四甲基哌啶锂、叔丁醇钾、叔丁醇钠、碳酸钾、碳酸铯、氢氧化钠、氢氧化钾、六氟磷酸铵、六氟磷酸三乙基铵、六氟磷酸银、三乙基胺、三异丙基膦、三环己基膦、三苯基膦、1,10-菲咯啉、对甲苯磺酸等。
反应溶媒可使用四氢呋喃、二乙基醚、1,4-二噁烷、甲醇、乙醇、甲苯、二甲苯、均三甲苯、水、二氯乙烷、二氯甲烷、丙酮、戊烷、己烷、庚烷等,此外,也可在无溶媒下进行。反应温度优选为自室温到反应溶媒回流温度。反应时间通常为数十分钟~数十小时,且大程度依存于作为原料的烯丙基醇类的体积大小,体积越大,时间越长。具体而言,在羰基的位置的比较中,2-庚酮的生成速度比4-庚酮快,在碳数的比较中,4-庚酮的生成速度比4-壬酮快,在有无取代基的比较中,2-庚酮的生成速度比3-乙基-2-庚酮快,另外,在碳数相同的情况下结构的差异的比较中,2-庚酮的生成速度比3-乙基-2-戊酮快。另外,催化剂的活性越高,反应时间越短。
实施例
其次,通过实施例对本发明更详细地进行说明,但本发明不受这些例子的任何限定。
关于产物,利用气相色谱法进行分析,并通过面积百分率算出组成比。测定条件为如下所述。
气相色谱(Gas Chromatography,GC)装置:岛津制作所GC-2014
管柱:安捷伦(Agilent)J&W GC管柱DB-1ms(L60m×φ0.250mm,D:0.25μm)
管柱温度:50℃(保持5分钟)→10℃/min→250℃(保持5分钟)
注射温度:280℃
载气:纯氦G1
检测器:氢火焰离子化检测器(Flame Ionization Detector,FID)
气相色谱-质谱(Gas Chromatography-Mass Spectrometry,GC-MS)装置:岛津制作所GC-2010、GCMS-TQ8040
管柱:安捷伦(Agilent)J&W GC管柱DB-5ms(L30m×φ0.250mm,D:0.25μm)
管柱温度:50℃→10℃/min→250℃(保持10分钟)
注射温度:250℃
载气:纯氦G1
GC检测器:氢火焰离子化检测器(FID)
GC检测器温度:320℃
离子源:EI
离子源温度:200℃
介面温度:230℃
测定模式:Q3扫描
m/e=30~500
<实施例1>(第一阶段)
在氮气环境下,依照日本专利特开平9-59201的实施例1,进行丁醛与乙醛的羟醛缩合,获得所生成的四种α,β-不饱和醛(2-丁烯醛、2-乙基-2-丁烯醛、2-己烯醛、2-乙基-2-己烯醛)的混合物,利用蒸馏仅去除2-丁烯醛,以35.5:44.7:19.7的比率获得2-乙基-2-丁烯醛、2-己烯醛、2-乙基-2-己烯醛的混合物。
<实施例2>(第二阶段)
在氮气环境下,在烧瓶中放入1mol/L的甲基溴化镁的四氢呋喃溶液(60ml),冷却到-15℃。历时20分钟向其中以不超过0℃的方式滴加实施例1中所获得的2-乙基-2-丁烯醛、2-己烯醛、2-乙基-2-己烯醛的混合物(5.95g,35:45:20),之后,一边升温到室温一边搅拌1小时。利用冰浴进行冷却,并利用饱和氯化铵水溶液使反应停止。利用叔丁基甲醚进行提取,并利用饱和食盐水对有机层进行清洗,之后,利用无水硫酸钠进行干燥、过滤,在25℃下、减压下利用蒸发器对滤液进行浓缩,以45:37:18的比率获得3-乙基-3-戊烯-2-醇、3-庚烯-2-醇、3-乙基-3-庚烯-2-醇的混合物(6.11g)。
<实施例3>(第三阶段)
在氮气环境下,在烧瓶中放入实施例2中获得的3-乙基-3-戊烯-2-醇、3-庚烯-2-醇、3-乙基-3-庚烯-2-醇的混合物(1.0g,45:37:18),放入四氢呋喃(8.7ml)、碳酸铯(57mg)、三(三苯基膦)钌(II)二氯化物(84mg),加热回流21小时,确认到由3-乙基-3-戊烯-2-醇生成52%的3-乙基-2-戊酮,由3-庚烯-2-醇生成95%的2-庚酮,由3-乙基-3-庚烯-2-醇生成41%的3-乙基-2-庚酮。
<实施例4>(第二阶段)
在氮气环境下,在烧瓶中放入1mol/L的甲基溴化镁的四氢呋喃溶液(53ml),冷却到-15℃。历时20分钟向其中以不超过0℃的方式滴加2-乙基-2-丁烯醛(5.0g)。在冰浴下,搅拌30分钟后,加入饱和氯化铵水溶液,利用叔丁基甲醚进行提取。利用饱和食盐水对有机层进行清洗,利用硫酸钠进行干燥、过滤,在减压下、25℃下对滤液进行浓缩,获得3-乙基-3-戊烯-2-醇(5.7g)。
<实施例5>(第三阶段)
在氮气环境下,在烧瓶中放入实施例4中获得的3-乙基-3-戊烯-2-醇(1.0g)、四氢呋喃(8.8ml)、碳酸钾(12mg)、三(三苯基膦)钌(II)二氯化物(84mg),进行32小时加热回流。确认到以转化率82%、选择率70%生成3-乙基-2-戊酮。
<实施例6>(第二阶段)
在氮气环境下,在烧瓶中放入1mol/L的甲基溴化镁的四氢呋喃溶液(64ml),冷却到-15℃。历时20分钟向其中以不超过0℃的方式滴加2-己烯醛(6.0g)。拆除冷却浴,一边升温到室温一边搅拌1小时。再次进行冰浴冷却后,加入饱和氯化铵水溶液,利用叔丁基甲醚进行提取。利用饱和食盐水对有机层进行清洗,利用硫酸钠进行干燥、过滤,在减压下、25℃下对滤液进行浓缩,获得3-庚烯-2-醇(7.0g)。
<实施例7>(第三阶段)
在氮气环境下,在烧瓶中放入实施例6中获得的3-庚烯-2-醇(1.0g)、四氢呋喃(8.8ml)、碳酸钾(48mg)、三(三苯基膦)钌(II)二氯化物(168mg),进行11小时加热回流。确认到以转化率100%、选择率100%生成2-庚酮。
<实施例8>(第二阶段)
在氮气环境下,在烧瓶中放入1mol/L的甲基溴化镁的四氢呋喃溶液(50ml),冷却到-15℃。历时20分钟向其中以不超过0℃的方式滴加2-乙基-2-己烯醛(6.0g)。拆除冷却浴,一边升温到室温一边搅拌1小时。再次进行冰浴冷却后,加入饱和氯化铵水溶液,利用叔丁基甲醚进行提取。利用饱和食盐水对有机层进行清洗,利用硫酸钠进行干燥、过滤,在减压下、25℃下对滤液进行浓缩,获得3-乙基-3-庚烯-2-醇(6.8g)。
<实施例9>(第三阶段)
在氮气环境下,在烧瓶中放入3-乙基-3-庚烯-2-醇(1.0g)、四氢呋喃(3.5ml)、水(3.5ml)、碳酸钾(19mg)、三(三苯基膦)钌(II)二氯化物(67mg),进行23小时加热回流。确认到以转化率99%、选择率96%生成3-乙基-2-庚酮。
<实施例10>(第二阶段)
在氮气环境下,在烧瓶中放入1mol/L的丙基溴化镁的四氢呋喃溶液(78ml),冷却到-10℃。历时20分钟向其中以不超过5℃的方式滴加2-丁烯醛(5.0g)。拆除冷却浴,一边升温到室温一边搅拌1小时。再次进行冰浴冷却后,加入饱和氯化铵水溶液,利用叔丁基甲醚进行提取。利用饱和食盐水对有机层进行清洗,利用硫酸钠进行干燥、过滤,在减压下、25℃下对滤液进行浓缩,获得2-庚烯-4-醇(8.1g)。
<实施例11>(第三阶段)
在氮气环境下,在烧瓶中放入2-庚烯-4-醇(1.0g)、四氢呋喃(8ml)、碳酸钾(25mg)、三(三苯基膦)钌(II)二氯化物(84mg),进行40小时加热回流。确认到以转化率77%、选择率80%生成4-庚酮。
<实施例12>(第二阶段)
在氮气环境下,在烧瓶中放入1mol/L的丙基溴化镁的四氢呋喃溶液(56ml),冷却到-10℃。历时20分钟向其中以不超过5℃的方式滴加2-己烯醛(5.0g)。拆除冷却浴,一边升温到室温一边搅拌1小时。再次进行冰浴冷却后,加入饱和氯化铵水溶液,利用叔丁基甲醚进行提取。利用饱和食盐水对有机层进行清洗,利用硫酸钠进行干燥、过滤,在减压下、25℃下对滤液进行浓缩,获得5-壬烯-4-醇(7.1g)。
<实施例13>(第三阶段)
在氮气环境下,在烧瓶中放入5-壬烯-4-醇(1.0g)、四氢呋喃(7ml)、碳酸钾(19mg)、三(三苯基膦)钌(II)二氯化物(67mg),进行40小时加热回流。确认到以转化率80%、选择率64%生成4-壬酮。
<实施例14>(第二阶段)
在氮气环境下,在烧瓶中放入1mol/L的甲基溴化镁的四氢呋喃溶液(25ml)及1mol/L的丙基溴化镁的四氢呋喃溶液(25ml),冷却到-15℃。历时20分钟向其中以不超过5℃的方式滴加依照日本专利特开平9-59201的实施例1并由丁醛与乙醛的羟醛缩合而获得的四种α,β-不饱和醛(2-丁烯醛、2-乙基-2-丁烯醛、2-己烯醛、2-乙基-2-己烯醛)的混合物(32:22:30:15)。拆除冷却浴,一边升温到室温一边搅拌1小时。再次进行冰浴冷却后,加入饱和氯化铵水溶液,利用叔丁基甲醚进行提取。利用饱和食盐水对有机层进行清洗,利用硫酸钠进行干燥、过滤,在减压下、25℃下对滤液进行浓缩,通过GC-MS确认到获得3-戊烯-2-醇、3-庚烯-2-醇、2-庚烯-4-醇、3-乙基-3-戊烯-2-醇、3-乙基-3-庚烯-2-醇、3-乙基-2-庚烯-4-醇、5-壬烯-4-醇、5-乙基-5-壬烯-4-醇的混合物(GC保持时间顺序,12:13:24:6.5:5.5:13:17:9,其中,2-庚烯-4-醇与3-乙基-3-戊烯-2-醇的波峰没有完全分离,因此使用计算值)。
<实施例15>(第三阶段)
在氮气环境下,在烧瓶中放入实施例14中获得的3-戊烯-2-醇、3-庚烯-2-醇、2-庚烯-4-醇、3-乙基-3-戊烯-2-醇、3-乙基-3-庚烯-2-醇、3-乙基-2-庚烯-4-醇、5-壬烯-4-醇、5-乙基-5-壬烯-4-醇的混合物(1.0g)、四氢呋喃(8ml)、碳酸铯(104mg)、(2,6,10-十二碳三烯-1,12-二基)钌(II)二氯化物(53mg),进行20小时加热回流。通过GC-MS确认到以转化率84%、选择率94%生成目标酮。将各者的转化率示于括号内。
2-戊酮(转化率93%)、3-乙基-2-戊酮(转化率97%)、4-庚酮(转化率99%)、2-庚酮(转化率91%)、3-乙基-4-庚酮(转化率58%)、3-乙基-2-庚酮(转化率89%)、4-壬酮(转化率97%)、5-乙基-4-壬酮(转化率46%)。
<实施例16>(第三阶段)
在氮气环境下,在烧瓶中放入实施例14中获得的3-戊烯-2-醇、3-庚烯-2-醇、2-庚烯-4-醇、3-乙基-3-戊烯-2-醇、3-乙基-3-庚烯-2-醇、3-乙基-2-庚烯-4-醇、5-壬烯-4-醇、5-乙基-5-壬烯-4-醇的混合物(1.0g)、四氢呋喃(8ml)、碳酸钾(73mg)、三(三苯基膦)铑(I)氯化物(243mg),进行3小时加热回流。
通过GC-MS确认到以转化率100%、选择率94%生成2-戊酮、3-乙基-2-戊酮、4-庚酮、2-庚酮、3-乙基-4-庚酮、3-乙基-2-庚酮、4-壬酮、5-乙基-4-壬酮的混合物(GC保持时间顺序,10:9:22:12:14:6:18:9)。
产业上的可利用性
根据本发明的制造方法,通过在丁醛与乙醛的羟醛缩合之后进行烷基化与异构化,可简便地制造构成雄性褐家鼠(Rattus norvegicus)的性信息素的主要成分的五种酮,并可作为引诱剂组合物来提供。
Claims (1)
1.一种酮类混合物的制造方法,所述制造方法包含以下三个阶段,
(1)通过乙醛与丁醛的羟醛缩合而获得2-丁烯醛、2-乙基-2-丁烯醛、2-己烯醛、2-乙基-2-己烯醛的混合物的第一阶段;
(2)使第一阶段中获得的2-丁烯醛、2-乙基-2-丁烯醛、2-己烯醛、2-乙基-2-己烯醛的混合物与烷基化剂反应而获得烯丙基醇类混合物的第二阶段,所述烯丙基醇类混合物为3-戊烯-2-醇、3-庚烯-2-醇、2-庚烯-4-醇、3-乙基-3-戊烯-2-醇、3-乙基-3-庚烯-2-醇、3-乙基-2-庚烯-4-醇、5-壬烯-4-醇及5-乙基-5-壬烯-4-醇的混合物;
(3)使第二阶段中获得的所述烯丙基醇类的混合物异构化而获得酮类混合物的第三阶段,所述酮类混合物为2-戊酮、3-乙基-2-戊酮、4-庚酮、2-庚酮、3-乙基-4-庚酮、3-乙基-2-庚酮、4-壬酮及5-乙基-4-壬酮的混合物,
其中,
所述第二阶段中使用的烷基化剂为甲基格氏试剂与丙基格氏试剂的混合物,
在所述第三阶段的异构化中使用铑催化剂与碳酸钾,并且
并不将2-戊酮、3-乙基-4-庚酮、及5-乙基-4-壬酮中的任一种以上分离去除。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0957108A (ja) * | 1995-08-28 | 1997-03-04 | Chisso Corp | 新規ゼオライト担持塩基触媒を用いるエナールの製造方法 |
JPH0959201A (ja) * | 1995-08-28 | 1997-03-04 | Chisso Corp | アルカリ土類金属酸化物を用いるエナールの製造方法 |
CN101125797A (zh) * | 2007-09-14 | 2008-02-20 | 杭州格林香料化学有限公司 | 2,6-二甲基-2-庚醇的制备方法 |
JP2011219395A (ja) * | 2010-04-07 | 2011-11-04 | Kuraray Co Ltd | α,β−不飽和アルデヒドの製造方法 |
JP2014514252A (ja) * | 2011-03-03 | 2014-06-19 | オクセア・ゲゼルシャフト・ミト・べシュレンクテル・ハフツング | 混合α,β−不飽和アルデヒドへの多相アルドール縮合反応を実施する方法 |
-
2019
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- 2019-05-15 CN CN201980046836.6A patent/CN112424154B/zh active Active
- 2019-05-15 WO PCT/JP2019/019245 patent/WO2020017135A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0957108A (ja) * | 1995-08-28 | 1997-03-04 | Chisso Corp | 新規ゼオライト担持塩基触媒を用いるエナールの製造方法 |
JPH0959201A (ja) * | 1995-08-28 | 1997-03-04 | Chisso Corp | アルカリ土類金属酸化物を用いるエナールの製造方法 |
CN101125797A (zh) * | 2007-09-14 | 2008-02-20 | 杭州格林香料化学有限公司 | 2,6-二甲基-2-庚醇的制备方法 |
JP2011219395A (ja) * | 2010-04-07 | 2011-11-04 | Kuraray Co Ltd | α,β−不飽和アルデヒドの製造方法 |
JP2014514252A (ja) * | 2011-03-03 | 2014-06-19 | オクセア・ゲゼルシャフト・ミト・べシュレンクテル・ハフツング | 混合α,β−不飽和アルデヒドへの多相アルドール縮合反応を実施する方法 |
Non-Patent Citations (4)
Title |
---|
Catalyst versus Substrate Induced Selectivity: Kinetic Resolution by Palladacycle Catalyzed Allylic Imidate Rearrangements;Frank Maier 等;《Chem. Asian J.》;20101231;第5卷;Supporting Information第6,16页 * |
From allylic alcohols to saturated carbonyls using Fe(CO)5 as catalyst: scope and limitation studiesand preparation of two perfume components;Hassan Cherkaoui 等;《Tetrahedron》;20011231;第57卷;全文 * |
Homogeneously catalysed isomerisation of allylic alcohols to carbonyl compounds;Eite Drent 等;《Journal of Organometallic Chemistry》;20021231;第650卷;第8页 * |
The Sex Attractant PheromoneofMale Brown Rats :Identification and Field Experiment;Gerhard Gries 等;《Angew.Chem.Int. Ed.》;20161231;第55卷;Figure1-2 * |
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