JP5496366B2 - 酸素でアルコールを酸化する、アルデヒド或いはケトンの製造方法 - Google Patents
酸素でアルコールを酸化する、アルデヒド或いはケトンの製造方法 Download PDFInfo
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- JP5496366B2 JP5496366B2 JP2012550299A JP2012550299A JP5496366B2 JP 5496366 B2 JP5496366 B2 JP 5496366B2 JP 2012550299 A JP2012550299 A JP 2012550299A JP 2012550299 A JP2012550299 A JP 2012550299A JP 5496366 B2 JP5496366 B2 JP 5496366B2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 28
- 150000002576 ketones Chemical class 0.000 title claims description 22
- 150000001299 aldehydes Chemical class 0.000 title claims description 21
- 239000001301 oxygen Substances 0.000 title claims description 19
- 229910052760 oxygen Inorganic materials 0.000 title claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 18
- 230000001590 oxidative effect Effects 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 11
- -1 iron nitrate 2,2,6,6-tetramethylpiperidine nitrogen oxide Chemical compound 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910001504 inorganic chloride Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- AKKLAJYCGVIWBS-UHFFFAOYSA-N O=[N].CC1(C)CCCC(C)(C)N1 Chemical compound O=[N].CC1(C)CCCC(C)(C)N1 AKKLAJYCGVIWBS-UHFFFAOYSA-N 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 125000006501 nitrophenyl group Chemical group 0.000 claims description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 2
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 claims description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical group C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 2
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 claims description 2
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 claims description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229940102127 rubidium chloride Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 56
- 238000003786 synthesis reaction Methods 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 30
- 230000035484 reaction time Effects 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 21
- 239000002994 raw material Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- NIOYUNMRJMEDGI-UHFFFAOYSA-N hexadecanal Chemical compound CCCCCCCCCCCCCCCC=O NIOYUNMRJMEDGI-UHFFFAOYSA-N 0.000 description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 4
- CYIFVRUOHKNECG-UHFFFAOYSA-N tridecan-2-one Chemical compound CCCCCCCCCCCC(C)=O CYIFVRUOHKNECG-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CAXIQKXPSQYDIR-CMDGGOBGSA-N (e)-4-methyl-1-phenylpent-1-en-3-one Chemical compound CC(C)C(=O)\C=C\C1=CC=CC=C1 CAXIQKXPSQYDIR-CMDGGOBGSA-N 0.000 description 2
- LNLPUXCBDRLOKT-UHFFFAOYSA-N 2-ethenylidene-1-phenyloctan-1-ol Chemical compound CCCCCCC(=C=C)C(O)C1=CC=CC=C1 LNLPUXCBDRLOKT-UHFFFAOYSA-N 0.000 description 2
- QBKAQTWEICLWHV-UHFFFAOYSA-N 2-phenylcyclohex-2-en-1-one Chemical compound O=C1CCCC=C1C1=CC=CC=C1 QBKAQTWEICLWHV-UHFFFAOYSA-N 0.000 description 2
- IDASOVSVRKONFS-UHFFFAOYSA-N 3-phenylprop-2-ynal Chemical compound O=CC#CC1=CC=CC=C1 IDASOVSVRKONFS-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 2
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 2
- BTVGBPHQRMNHRN-UHFFFAOYSA-N 6-ethenylidenedodecan-5-one Chemical compound CCCCCCC(=C=C)C(=O)CCCC BTVGBPHQRMNHRN-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- LEVRLCQBCCQFHB-UHFFFAOYSA-N trideca-1,2-dien-4-one Chemical compound CCCCCCCCCC(=O)C=C=C LEVRLCQBCCQFHB-UHFFFAOYSA-N 0.000 description 2
- YCFZAKKEGLQUIK-UHFFFAOYSA-N trideca-2,3-dienal Chemical compound CCCCCCCCCC=C=CC=O YCFZAKKEGLQUIK-UHFFFAOYSA-N 0.000 description 2
- HKOLRKVMHVYNGG-UHFFFAOYSA-N tridecan-2-ol Natural products CCCCCCCCCCCC(C)O HKOLRKVMHVYNGG-UHFFFAOYSA-N 0.000 description 2
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N (E)-Geraniol Chemical compound CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- DBZFJCXQJLIGCS-CMDGGOBGSA-N (e)-4-methyl-1-phenylpent-1-en-3-ol Chemical compound CC(C)C(O)\C=C\C1=CC=CC=C1 DBZFJCXQJLIGCS-CMDGGOBGSA-N 0.000 description 1
- VRKAQRZHXIGEAQ-UHFFFAOYSA-N 1-(4-chlorophenyl)buta-2,3-dien-1-ol Chemical compound C=C=CC(O)C1=CC=C(Cl)C=C1 VRKAQRZHXIGEAQ-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- XAHDRXXKLCEOAC-UHFFFAOYSA-N 1-phenylhept-1-yn-3-ol Chemical compound CCCCC(O)C#CC1=CC=CC=C1 XAHDRXXKLCEOAC-UHFFFAOYSA-N 0.000 description 1
- RXZSWIQKCYTVBB-UHFFFAOYSA-N 1-phenylhept-1-yn-3-one Chemical compound CCCCC(=O)C#CC1=CC=CC=C1 RXZSWIQKCYTVBB-UHFFFAOYSA-N 0.000 description 1
- GZLATWWTNLJYDL-UHFFFAOYSA-N 2-benzylbuta-2,3-dien-1-ol Chemical compound OCC(=C=C)CC1=CC=CC=C1 GZLATWWTNLJYDL-UHFFFAOYSA-N 0.000 description 1
- ILOJNPDJWLYAMG-UHFFFAOYSA-N 2-benzylbuta-2,3-dienal Chemical compound C=C=C(C=O)CC1=CC=CC=C1 ILOJNPDJWLYAMG-UHFFFAOYSA-N 0.000 description 1
- SSZZWKMSCLLYGN-UHFFFAOYSA-N 2-phenylcyclohex-2-en-1-ol Chemical compound OC1CCCC=C1C1=CC=CC=C1 SSZZWKMSCLLYGN-UHFFFAOYSA-N 0.000 description 1
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 description 1
- HICDDWYCMJZFHD-UHFFFAOYSA-N 6-ethenylidenedodecan-5-ol Chemical compound CCCCCCC(=C=C)C(O)CCCC HICDDWYCMJZFHD-UHFFFAOYSA-N 0.000 description 1
- VOFGTOWWZACDOH-ARJAWSKDSA-N C/C(/N)=C(\C#[O])/N Chemical compound C/C(/N)=C(\C#[O])/N VOFGTOWWZACDOH-ARJAWSKDSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-UHFFFAOYSA-N KU0063794 Natural products CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- DXMAKTJNDNLDBX-UHFFFAOYSA-N [N].CC1(NC(CCC1)(C)C)C Chemical compound [N].CC1(NC(CCC1)(C)C)C DXMAKTJNDNLDBX-UHFFFAOYSA-N 0.000 description 1
- LSHFIWNMHGCYRS-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2] LSHFIWNMHGCYRS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229910052799 carbon Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- SMMBOGRIRFLHLF-UHFFFAOYSA-N dec-6-yn-5-ol Chemical compound CCCCC(O)C#CCCC SMMBOGRIRFLHLF-UHFFFAOYSA-N 0.000 description 1
- ABPBGEZLLMTNRL-UHFFFAOYSA-N dec-6-yn-5-one Chemical compound CCCCC(=O)C#CCCC ABPBGEZLLMTNRL-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 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
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XERDOEKKHDALKJ-UHFFFAOYSA-N non-2-yn-1-ol Chemical compound CCCCCCC#CCO XERDOEKKHDALKJ-UHFFFAOYSA-N 0.000 description 1
- ZQGZJHCODJQNCB-UHFFFAOYSA-N non-2-ynal Chemical compound CCCCCCC#CC=O ZQGZJHCODJQNCB-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FWLKYEAOOIPJRL-UHFFFAOYSA-N prop-1-yn-1-ol Chemical compound CC#CO FWLKYEAOOIPJRL-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SMQNJYWJIBTMTE-UHFFFAOYSA-N trideca-1,2-dien-4-ol Chemical compound CCCCCCCCCC(O)C=C=C SMQNJYWJIBTMTE-UHFFFAOYSA-N 0.000 description 1
- KMDXUZQXACRQHF-UHFFFAOYSA-N trideca-2,3-dien-1-ol Chemical compound CCCCCCCCCC=C=CCO KMDXUZQXACRQHF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/006—Catalysts comprising hydrides, coordination complexes or organic compounds comprising organic radicals, e.g. TEMPO
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
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Description
Claims (5)
- 室温で有機溶媒において酸素又は空気を酸化剤とし、硝酸鉄2,2,6,6-テトラメチルピペリジン窒素酸化物と無機塩化物とを触媒とし、1〜24時間の反応時間で、アルコールをアルデヒド或いはケトンに酸化させ、前記アルコールと2,2,6,6-テトラメチルピペリジン窒素酸化物と硝酸鉄と無機塩化物との比はモル比で100:1〜10:1〜10:1〜10であって、前記無機塩化物は、塩化ナトリウム、塩化カリウム、塩化リチウム、塩化ルビジウム又は塩化セシウムであることを特徴とする、アルコールを酸化してアルデヒド或いはケトンを製造する方法。
- 前記アルコールは、R1R2CHOH(ただし、前記R1は水素、炭素数1〜16のアルキル基、R3及び/又はR4で置換されたアルケニル基、R5及び/又はR6で置換されたアルケニル基、R7で置換されたアルキニル基、アリール基、トリフルオルメチルフェニル基、ニトロフェニル基、ハロゲン化フェニル基、或いは炭素数1〜4のアルコキシフェニル基であって、前記R2は水素、炭素数1〜16のアルキル基、アリール基、トリフルオルメチルフェニル基、ハロゲン化フェニル基或いはメトキシフェニル基であって、前記R3は炭素数1〜6のアルキル基又はアリール基であって、前記R4は水素、炭素数1〜6のアルキル基又はアリール基であって、前記R5は水素、炭素数1〜9のアルキル基、アリールフェニール基又はベンジル基であって、前記R6は水素、炭素数4〜9のアルキル基、アリール基又はベンジル基であって、前記R7は水素、炭素数1〜12のアルキル基、トリメチルシリコン基、アリール基、ハロゲン化フェニル基、ニトロフェニル基又はメトキシフェニル基である)或いはC5〜C8の環状アルコールであることを特徴とする、請求項1に記載のアルコールを酸化してアルデヒド或いはケトンを製造する方法。
- 前記アリール基は、フェニル基、ハロゲン化フェニル基、アルコキシフェニル又はナフチル基であることを特徴とする、請求項2に記載のアルコールを酸化してアルデヒド或いはケトンを製造する方法。
- 前記C5〜C8の環状アルコールは、シクロペンタノール、シクロヘキサノール、シクロヘプタノール又はシクロオクタノールであることを特徴とする、請求項2に記載のアルコールを酸化してアルデヒド或いはケトンを製造する方法。
- 前記有機溶媒は、ベンゼン、トルエン、ジクロロメタン、1、2−ジクロロエタン、1、1−ジクロロエタン、1、2−ジクロロプロパン、1、3−ジクロロプロパン、ニトロメタン、エチレングリコールジメチルエーテル、テトラヒドロフラン、アセトニトリル又は酢酸エチルから選ばれる一種或いは多種の混合物であることを特徴とする、請求項1に記載のアルコールを酸化してアルデヒド或いはケトンを製造する方法。
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ITMI20130183A1 (it) * | 2013-02-08 | 2014-08-09 | Ind Chimica Srl | Processo per la preparazione di drospirenone. |
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CN104119212B (zh) * | 2013-04-27 | 2016-03-02 | 中国科学院大连化学物理研究所 | 一种催化氧化3,3-二甲基-1-丁醇制备3,3-二甲基-1-丁醛的方法 |
CN104130112A (zh) * | 2014-08-05 | 2014-11-05 | 楚澜科技武汉有限公司 | 一种通过氧气连续氧化制备醛或酮的方法及其设备 |
CN105753821B (zh) * | 2014-12-17 | 2018-11-02 | 中国科学院宁波材料技术与工程研究所 | 一种2,5-呋喃二甲酸的制备方法 |
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CN104478835A (zh) * | 2014-12-26 | 2015-04-01 | 合肥利夫生物科技有限公司 | 一种2,5-呋喃二甲醛的制备方法 |
CN104529957B (zh) * | 2014-12-26 | 2016-04-13 | 中国科学技术大学先进技术研究院 | 一种2,5-呋喃二甲酸的制备方法 |
CN104649856B (zh) * | 2015-02-27 | 2016-08-24 | 中山大学惠州研究院 | 一种酮类化合物的制备方法 |
CN105148994B (zh) * | 2015-06-18 | 2018-08-24 | 中北大学 | 交联聚苯乙烯微球固载四甲基哌啶氮氧自由基催化剂及其制备和应用方法 |
ES2779460T3 (es) * | 2015-08-18 | 2020-08-17 | Basf Se | Proceso de preparación del alfa-damascona |
CN105294413B (zh) * | 2015-09-17 | 2017-04-12 | 浙江工业大学 | 一种铁盐催化醇氧化制备醛/酮的方法 |
CN106800492A (zh) * | 2015-11-26 | 2017-06-06 | 中国科学院大连化学物理研究所 | 一种铁催化醇氧化制备醛或铜的绿色方法 |
CN107176899B (zh) * | 2016-03-11 | 2021-04-13 | 中国科学院上海有机化学研究所 | 一种氧气氧化醇或醛制备酸的方法 |
CN117603025A (zh) * | 2017-03-20 | 2024-02-27 | 巴斯夫欧洲公司 | 通过在液相存在下氧化醇制备α,β不饱和醛的方法 |
CN109180418B (zh) * | 2018-10-09 | 2021-03-30 | 江苏扬农化工集团有限公司 | 一种环氧丙烷联产物资源化利用合成农药中间体2,4-二氯苯乙酮方法 |
CN111484404A (zh) * | 2019-01-29 | 2020-08-04 | 复旦大学 | 铜催化的以氧气为氧化剂氧化醇制备醛或酮类化合物的方法和应用 |
CN112409144B (zh) * | 2019-08-22 | 2022-10-28 | 浙江大学 | 一种以氧气或空气中的氧气作为氧化剂从醇或醛合成羧酸或酮类化合物的方法 |
CN112920028B (zh) * | 2021-02-05 | 2023-01-31 | 湖北滋兰生物医药科技有限公司 | 一种烯烃氧化制备醛类化合物的方法 |
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