JP4066679B2 - Process for producing aralkyl ketones and catalyst thereof - Google Patents
Process for producing aralkyl ketones and catalyst thereof Download PDFInfo
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- JP4066679B2 JP4066679B2 JP2002066610A JP2002066610A JP4066679B2 JP 4066679 B2 JP4066679 B2 JP 4066679B2 JP 2002066610 A JP2002066610 A JP 2002066610A JP 2002066610 A JP2002066610 A JP 2002066610A JP 4066679 B2 JP4066679 B2 JP 4066679B2
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- Prior art keywords
- tungsten
- group
- hydrogen peroxide
- metal
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims description 20
- -1 aralkyl ketones Chemical class 0.000 title claims description 19
- 238000000034 method Methods 0.000 title description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 89
- 150000001336 alkenes Chemical class 0.000 claims description 34
- 239000003960 organic solvent Substances 0.000 claims description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052721 tungsten Inorganic materials 0.000 claims description 17
- 239000010937 tungsten Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 9
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 9
- OFEAOSSMQHGXMM-UHFFFAOYSA-N 12007-10-2 Chemical compound [W].[W]=[B] OFEAOSSMQHGXMM-UHFFFAOYSA-N 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 7
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 6
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 27
- UMYZWICEDUEWIM-UHFFFAOYSA-N 1-(3,4-dimethoxyphenyl)propan-2-one Chemical compound COC1=CC=C(CC(C)=O)C=C1OC UMYZWICEDUEWIM-UHFFFAOYSA-N 0.000 description 16
- 150000002736 metal compounds Chemical class 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 12
- 150000002576 ketones Chemical class 0.000 description 11
- NNWHUJCUHAELCL-SNAWJCMRSA-N trans-isomethyleugenol Chemical compound COC1=CC=C(\C=C\C)C=C1OC NNWHUJCUHAELCL-SNAWJCMRSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NNWHUJCUHAELCL-UHFFFAOYSA-N cis-Methyl isoeugenol Natural products COC1=CC=C(C=CC)C=C1OC NNWHUJCUHAELCL-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XIYKRJLTYKUWAM-UHFFFAOYSA-N 3,4-methylenedioxyphenylpropan-2-one Chemical compound CC(=O)CC1=CC=C2OCOC2=C1 XIYKRJLTYKUWAM-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WFWKNGZODAOLEO-UHFFFAOYSA-N 1-(4-Methoxyphenyl)-2-propanone Chemical compound COC1=CC=C(CC(C)=O)C=C1 WFWKNGZODAOLEO-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VHVOLFRBFDOUSH-NSCUHMNNSA-N Isosafrole Chemical compound C\C=C\C1=CC=C2OCOC2=C1 VHVOLFRBFDOUSH-NSCUHMNNSA-N 0.000 description 2
- VHVOLFRBFDOUSH-UHFFFAOYSA-N Isosafrole Natural products CC=CC1=CC=C2OCOC2=C1 VHVOLFRBFDOUSH-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- BWDCJRUCCWZCIY-AATRIKPKSA-N 1,2,3-trimethoxy-4-[(e)-prop-1-enyl]benzene Chemical compound COC1=CC=C(\C=C\C)C(OC)=C1OC BWDCJRUCCWZCIY-AATRIKPKSA-N 0.000 description 1
- HSCYFBGYMUIJSE-UHFFFAOYSA-N 1-(2,3,4-trimethoxyphenyl)propan-2-one Chemical compound COC1=CC=C(CC(C)=O)C(OC)=C1OC HSCYFBGYMUIJSE-UHFFFAOYSA-N 0.000 description 1
- RRCBTNOKGAYRHH-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylphenyl)propan-2-one Chemical compound CC(C)C1=CC=C(C)C(CC(C)=O)=C1 RRCBTNOKGAYRHH-UHFFFAOYSA-N 0.000 description 1
- ADHCSWSBGUURFV-UHFFFAOYSA-N 1-(4-ethoxy-3-methoxyphenyl)propan-2-one Chemical compound CCOC1=CC=C(CC(C)=O)C=C1OC ADHCSWSBGUURFV-UHFFFAOYSA-N 0.000 description 1
- QFAYQKVAKVNBNG-UHFFFAOYSA-N 1-(4-ethoxyphenyl)propan-2-one Chemical compound CCOC1=CC=C(CC(C)=O)C=C1 QFAYQKVAKVNBNG-UHFFFAOYSA-N 0.000 description 1
- IRICXAFZMINCTB-UHFFFAOYSA-N 1-Methyl-4-(1-methyl-2-propenyl)-benzene Chemical compound CC=CC1=CC(C(C)C)=CC=C1C IRICXAFZMINCTB-UHFFFAOYSA-N 0.000 description 1
- JPHQCDCEBDRIOL-UHFFFAOYSA-N 1-[3-(trifluoromethyl)phenyl]propan-2-one Chemical compound CC(=O)CC1=CC=CC(C(F)(F)F)=C1 JPHQCDCEBDRIOL-UHFFFAOYSA-N 0.000 description 1
- AOSKXPFBGRLCEG-GQCTYLIASA-N 1-ethoxy-2-methoxy-4-[(e)-prop-1-enyl]benzene Chemical compound CCOC1=CC=C(\C=C\C)C=C1OC AOSKXPFBGRLCEG-GQCTYLIASA-N 0.000 description 1
- MKFWKDNSZLCLDV-UHFFFAOYSA-N 1-ethoxy-4-prop-1-enylbenzene Chemical compound CCOC1=CC=C(C=CC)C=C1 MKFWKDNSZLCLDV-UHFFFAOYSA-N 0.000 description 1
- RKSHYZZUJFUXEY-UHFFFAOYSA-N 1-prop-1-enyl-4-(trifluoromethyl)benzene Chemical compound CC=CC1=CC=C(C(F)(F)F)C=C1 RKSHYZZUJFUXEY-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229940011037 anethole Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000004651 chloromethoxy group Chemical group ClCO* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 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
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([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
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WKUHYPLZMSDBPZ-UHFFFAOYSA-N hydrogen peroxide tungsten Chemical compound [W].OO WKUHYPLZMSDBPZ-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JYJVVHFRSFVEJM-UHFFFAOYSA-N iodosobenzene Chemical class O=IC1=CC=CC=C1 JYJVVHFRSFVEJM-UHFFFAOYSA-N 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【０００１】
【発明の属する技術分野】
本発明は、アラルキルケトン類の製造方法とその触媒に関する。
【０００２】
【従来の技術】
一般式（２）
で示されるアラルキルケトン類は、医薬品の合成中間体や香料等として極めて重要な化合物である（例えば特開平２−１３１４５５号公報等）。かかる一般式（２）で示されるアラルキルケトン類の製造方法としては、例えばハロゲン化炭化水素を溶媒として、炭酸塩の存在下に、アリール置換オレフィン類を有機過酸で酸化した後、得られた中間体を鉱酸と加熱する方法（特開昭４９−１０００４４号公報）、アリール置換オレフィン類とＮ−ブロモスクシンイミド反応させた後、塩基で処理してエポキシ体を得、該エポキシ体に臭化水素酸水溶液を作用させる方法（Ｔｅｔｒａｈｅｄｒｏｎ，４３，５４３１（１９８７））等が報告されているが、いずれも二段階の反応であり、必ずしも効率的な方法とは言えなかった。
【０００３】
一方で、アリール置換オレフィン類から一段階でアラルキルケトン類を製造する方法として、ヨードシルベンゼン類を用いる方法（特開平２−１３１４３５号公報）も報告されているが、高価なヨードシルベンゼン類を用いており、必ずしも経済的に有利な方法とは言えなかった。
【０００４】
【発明が解決しようとする課題】
このような状況のもと、本発明者らは、一般式（１）で示されるアリール置換オレフィン類から一段階で、経済的に有利にアラルキルケトン類を製造する方法として、安価で、取扱いが容易で、クリーンな酸化剤である過酸化水素を用いる方法を開発すべく鋭意検討したところ、入手が容易なタングステン金属、ホウ化タングステン等のタングステン化合物と過酸化水素とを反応せしめてなる金属酸化物が、一般式（１）で示されるアリール置換オレフィン類と過酸化水素とを反応させて、アラルキルケトン類を製造する方法において、良好な触媒活性を示すことを見出し、本発明に至った。
【０００５】
【課題を解決するための手段】
すなわち本発明は、タングステン金属、ホウ化タングステン、硫化タングステン、炭化タングステン、酸化タングステンおよびタングステン酸からなる群から選ばれる少なくとも一つと過酸化水素とを反応せしめてなる金属酸化物触媒の存在下に、一般式（１）
で示されるアリール置換オレフィン類と過酸化水素とを反応させることを特徴とする一般式（２）
【０００６】
【発明の実施の形態】
まず最初に、本発明に用いられる金属酸化物触媒について説明する。触媒としては、タングステン金属、ホウ化タングステン、硫化タングステン、炭化タングステン、酸化タングステンおよびタングステン酸からなる群から選ばれる少なくとも一つ（以下、金属化合物と略記する。）と過酸化水素とを反応せしめてなる金属酸化物が用いられる。
【０００８】
タングステン酸を用いる場合は、例えばタングステン酸ナトリウム等のタングステン酸アルカリ金属塩を酸で中和処理したものを用いてもよい。
【００１１】
かかる金属化合物のなかでも、タングステン金属、ホウ化タングステン、硫化タングステン、酸化タングステン、タングステン酸が好ましい。
【００１２】
かかる金属化合物と反応せしめる過酸化水素としては、通常水溶液が用いられる。もちろん過酸化水素の有機溶媒溶液を用いてもよいが、取扱いが容易という点で、過酸化水素水を用いることが好ましい。過酸化水素水もしくは過酸化水素の有機溶媒溶液中の過酸化水素濃度は特に制限されないが、容積効率、安全面等を考慮すると、実用的には１〜６０重量％である。過酸化水素水を用いる場合は、通常市販のものをそのままもしくは必要に応じて希釈、濃縮等により濃度調整を行なったものを用いればよい。また過酸化水素の有機溶媒溶液を用いる場合は、例えば過酸化水素水を有機溶媒で抽出処理する、もしくは有機溶媒の存在下に過酸化水素水を蒸留処理する等の手段により、調製したものを用いればよい。
【００１３】
金属化合物と反応せしめる過酸化水素の使用量は、金属化合物に対して、通常３モル倍以上、好ましくは５モル倍以上であり、その上限は特にない。
【００１４】
金属化合物と過酸化水素との反応は、通常水溶液中で実施される。もちろん例えばジエチルエーテル、メチルｔｅｒｔ−ブチルエーテル、テトラヒドロフラン等のエーテル系溶媒、例えば酢酸エチル等のエステル系溶媒、例えばメタノール、エタノール、ｔｅｒｔ−ブタノール等アルコール系溶媒、例えばアセトニトリル、プロピオニトリル等のニトリル系溶媒等の有機溶媒中または該有機溶媒と水との混合溶媒中で実施してもよい。
【００１５】
金属化合物と過酸化水素との反応は、通常その両者を混合、接触させることにより行われ、金属化合物と過酸化水素との接触効率をより向上させるため、金属酸化物調製液中で、金属化合物が十分分散するよう攪拌しながら反応を行うことが好ましい。また、金属化合物と過酸化水素との接触効率を高め、金属酸化物調製時の制御をより容易にするという点で、例えば粉末状の金属化合物等粒径の小さな金属化合物を用いることが好ましい。
【００１６】
金属酸化物調製時の調製温度は、通常−１０〜１００℃である。
【００１７】
金属化合物と過酸化水素とを水中、有機溶媒中もしくは有機溶媒と水との混合溶媒中で反応させることにより、金属化合物の全部もしくは一部が溶解して、金属酸化物を含む均一溶液もしくは懸濁液を調製することができるが、該金属酸化物を、例えば濃縮処理等により調製液から取り出して、触媒として用いてもよいし、該調製液をそのまま触媒として用いてもよい。
【００１８】
次に、上記金属酸化物を触媒とする一般式（１）
で示されるアリール置換オレフィン類（以下、オレフィン類（１）と略記する。）と過酸化水素との反応について説明する。
【００１９】
オレフィン類（１）の式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4およびＲ5はそれぞれ同一または相異なって、水素原子、置換されていてもよいアルキル基または置換されていてもよいアルコキシ基を表わす。Ｒ6は低級アルキル基を表わす。
【００２０】
置換されていてもよいアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−デシル基、シクロプロピル基、２，２−ジメチルシクロプロピル基、シクロペンチル基、シクロヘキシル基、メンチル基等の直鎖状、分枝鎖状または環状の炭素数１〜２０のアルキル基およびこれらアルキル基が、後述するアルコキシ基、アリールオキシ基、アラルキルオキシ基、ハロゲン原子、アシル基、カルボアルコキシ基、カルボアリールオキシ基、カルボアラルキルオキシ基、カルボキシル基等の置換基で置換された、例えばクロロメチル基、フルオロメチル基、トリフルオロメチル基、メトキシメチル基、エトキシメチル基、メトキシエチル基、カルボメトキシメチル基、１−カルボエトキシ−２，２−ジメチル−３−シクロプロピル基等が挙げられる。
【００２１】
置換されていてもよいアルコキシ基としては、前記置換されていてもよいアルキル基と酸素原子とから構成されるものが挙げられ、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−デシルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、メンチルオキシ基等の直鎖状、分枝鎖状または環状の炭素数１〜２０のアルコキシ基およびこれらアルコキシ基が、例えばハロゲン原子、アルコキシ基等の置換基で置換された、例えばクロロメトキシ基、フルオロメトキシ基、トリフルオロメトキシ基、メトキシメトキシ基、エトキシメトキシ基、メトキシエトキシ基等が挙げられる。
【００２２】
低級アルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等の炭素数１〜６のアルキル基が挙げられる。
【００２３】
かかるオレフィン類（１）としては、例えばβ−メチルスチレン、アネトール、１−エトキシ−４−（１−プロペニル）ベンゼン、イソサフロール、４−イソプロピル−１−メチル−２−（１−プロペニル）ベンゼン、メチルイソオイゲノール、エチルイソオイゲノール、１，２，３−トリメトキシ−４−（１−プロペニル）ベンゼン、１−トリフルオロメチル−４−（１−プロペニル）ベンゼン等が挙げられる。
【００２４】
かかるオレフィン類（１）には、トランス体とシス体の二種類の幾何異性体が存在するが、本発明には、いずれか一方の幾何異性体を用いてもよいし、二種類の幾何異性体の混合物を用いてもよい。
【００２５】
オレフィン類（１）と過酸化水素との反応における金属酸化物触媒の使用量は、オレフィン類（１）に対して、通常０．００１モル倍以上であり、その上限は特にないが、経済的な面を考慮すると、実用的には、オレフィン類（１）に対して、１モル倍以下である。
【００２６】
過酸化水素は、通常水溶液として用いられる。もちろん過酸化水素の有機溶媒溶液を用いてもよい。過酸化水素水もしくは有機溶媒溶液中の過酸化水素濃度は特に制限されないが、容積効率、安全面等を考慮すると、実用的には１〜６０重量％である。過酸化水素水は、通常市販のものをそのままもしくは必要に応じて希釈、濃縮等により濃度調整を行なった後用いられる。過酸化水素の有機溶媒溶液は、例えば過酸化水素水を有機溶媒で抽出処理する、もしくは有機溶媒の存在下に過酸化水素水を蒸留処理する等の手段により、調製することができる。
【００２７】
過酸化水素の使用量は、オレフィン類（１）に対して、通常１モル倍以上であり、その使用量の上限は特にないが、経済的な面も考慮すると、実用的には、オレフィン類（１）に対して、１０モル倍以下である。なお、触媒として、金属酸化物を含む調製液を用いる場合は、該調製液中の過酸化水素量を含めて、過酸化水素の使用量を設定してもよい。
【００２８】
本反応は、通常水溶媒、有機溶媒もしくは有機溶媒と水の混合溶媒中で実施される。有機溶媒としては、例えばジエチルエーテル、メチルｔｅｒｔ−ブチルエーテル、テトラヒドロフラン等のエーテル系溶媒、例えば酢酸エチル等のエステル系溶媒、例えばメタノール、エタノール、ｔｅｒｔ−ブタノール等のアルコール系溶媒、例えばアセトニトリル、プロピオニトリル等のニトリル系溶媒等が挙げられる。水または有機溶媒の使用量は特に制限されないが、容積効率等を考慮すると、実用的には、オレフィン類（１）に対して、１００重量倍以下である。
【００２９】
なお、本反応においては、反応の進行に伴い水が副生するため、反応系内に脱水剤を共存させて、反応を実施してもよい。脱水剤としては、例えば無水硫酸マグネシウム、無水硫酸ナトリウム、無水ホウ酸、ポリリン酸、五酸化二リン等が挙げられ、その使用量は、反応系内に存在する水を脱水除去可能な量以上であればよい。
【００３０】
反応温度があまり低いと反応が進行しにくく、また反応温度があまり高いと、原料のオレフィン類（１）の重合等副反応が進行する恐れがあるため、実用的な反応温度は、０〜２００℃の範囲である。
【００３１】
本反応は、通常オレフィン類（１）、過酸化水素および金属酸化物触媒を接触、混合することにより実施されるが、その混合順序は特に制限されない。また、例えば金属化合物、過酸化水素およびオレフィン類（１）を接触、混合させて、金属酸化物触媒の調製操作と、オレフィン類（１）と過酸化水素との反応を、同時に行ってもよい。
【００３２】
本反応は、常圧条件下で実施してもよいし、加圧条件下で実施してもよい。また、反応の進行は、例えばガスクロマトグラフィ、高速液体クロマトグラフィ、薄層クロマトグラフィ、ＮＭＲ、ＩＲ等の通常の分析手段により確認することができる。
【００３３】
また、本反応は、例えば無水ホウ酸等のホウ素化合物の共存下に実施してもよい。ホウ素化合物としては、例えば無水ホウ酸、メタホウ酸、正ホウ酸、メタホウ酸アルカリ金属塩、メタホウ酸アルカリ土類金属塩、正ホウ酸アルカリ金属塩、正ホウ酸アルカリ土類金属塩等が挙げられ、その使用量は特に制限されないが、あまり多すぎても経済的に不利になるため、実用的には、オレフィン類（１）に対して、通常１モル倍以下である。
【００３４】
かくして一般式（２）
【００３５】
水に不溶の有機溶媒としては、例えばトルエン、キシレン等の芳香族炭化水素系溶媒、例えばジクロロメタン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素系溶媒、例えばジエチルエーテル、メチルｔｅｒｔ−ブチルエーテル、テトラヒドロフラン等のエーテル系溶媒、例えば酢酸エチル等のエステル系溶媒等が挙げられ、その使用量は特に制限されない。
【００３６】
また、目的とするケトン類（２）を晶析処理により取り出した後の濾液や反応液を抽出処理して得られる水層は、本反応の金属酸化物触媒を含んでおり、そのままもしくは必要に応じて濃縮処理等を行った後、再度本反応に使用することができる。
【００３７】
かかるケトン類（２）としては、例えばフェニルアセトン、４−メトキシフェニルアセトン、４−エトキシフェニルアセトン、３，４−メチレンジオキシフェニルアセトン、５−イソプロピル−２−メチルフェニルアセトン、３，４−ジメトキシフェニルアセトン、３−メトキシ−４−エトキシフェニルアセトン、２，３，４−トリメトキシフェニルアセトン、３−トリフルオロメチルフェニルアセトン等が挙げられる。
【００３８】
【実施例】
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれら実施例により限定されるものではない。なお、分析は、ガスクロマトグラフィ分析（内部標準法）により実施した。
【００３９】
実施例１
５０ｍＬフラスコに、タングステン金属１８ｍｇおよび３０重量％過酸化水素水４２０ｍｇを仕込み、内温６０℃に昇温し、同温度で０．５時間攪拌、保持し、タングステン酸化物水溶液を調製した。該水溶液に、メチルイソオイゲノール１．７８ｇ、ｔｅｒｔ−ブタノール８．９ｇおよび３０重量％過酸化水素水０．８３ｇを仕込み、内温８０℃に昇温し、同温度で４時間攪拌、保持し、反応させた。室温まで冷却し、メチルｔｅｒｔ−ブチルエーテル１０ｇおよび水１０ｇを加え、分液処理し、３，４−ジメトキシフェニルアセトンを含む有機層を得た。３，４−ジメトキシフェニルアセトンの収率は２５％で、原料のメチルイソオイゲノールの回収率は、５５％であった。
【００４０】
実施例２
５０ｍＬフラスコに、タングステン金属１８ｍｇおよび３０重量％過酸化水素水４２０ｍｇを仕込み、内温６０℃に昇温し、同温度で１時間攪拌、保持し、タングステン酸化物水溶液を調製した。該水溶液に、メチルイソオイゲノール１．７８ｇおよび３０重量％過酸化水素水０．８３ｇを仕込み、内温９５℃に昇温し、同温度で２時間攪拌、保持し、反応させた。室温まで冷却し、メチルｔｅｒｔ−ブチルエーテル１０ｇおよび水１０ｇを加え、分液処理し、３，４−ジメトキシフェニルアセトンを含む有機層を得た。３，４−ジメトキシフェニルアセトンの収率は１６％で、原料のメチルイソオイゲノールの回収率は、７１％であった。
【００４１】
実施例３
５０ｍＬフラスコに、ホウ化タングステン金属４０ｍｇ、無水ホウ酸３００ｍｇ、硫酸マグネシウム２．３ｇおよびｔｅｒｔ−ブタノール３ｇを仕込み、内温６０℃に昇温し、同温度で、イソサフロール３６０ｍｇとｔｅｒｔ−ブタノール１ｇと３０重量％過酸化水素水６００ｍｇとからなる混合液を２０分で滴下した。さらに同温度で２時間攪拌、保持し、反応させた。室温まで冷却し、メチルｔｅｒｔ−ブチルエーテル１０ｇおよび水１０ｇを加え、分液処理し、３，４−メチレンジオキシフェニルアセトンを含む有機層を得た。３，４−メチレンジオキシフェニルアセトンの収率は２１％で、原料のイソサフロールの回収率は、２０％であった。
【００４２】
実施例４
実施例１において、タングステン金属に代えて硫化タングステンを用いる以外は、実施例１と同様に実施することにより、３，４−ジメトキシフェニルアセトンが得られる。
【００４３】
実施例５
実施例１において、タングステン金属に代えて炭化タングステンを用いる以外は、実施例１と同様に実施することにより、３，４−ジメトキシフェニルアセトンが得られる。
【００４４】
実施例６
実施例１において、タングステン金属に代えて酸化タングステンを用いる以外は、実施例１と同様に実施することにより、３，４−ジメトキシフェニルアセトンが得られる。
【００４５】
実施例７
実施例１において、タングステン金属に代えてタングステン酸を用いる以外は、実施例１と同様に実施することにより、３，４−ジメトキシフェニルアセトンが得られる。
【００４６】
【発明の効果】
本発明の方法によれば、入手が容易なタングステン金属、ホウ化タングステン等のタングステン化合物と過酸化水素とを反応せしめてなる金属酸化物触媒の存在下に、アリール置換オレフィン類と安価な過酸化水素を反応させることにより、アラルキルケトン類を一段階で得ることができるため、経済的にも、また工業的にも有利である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing aralkyl ketones and a catalyst thereof.
[0002]
[Prior art]
General formula (2)
Are very important compounds as synthetic intermediates and fragrances of pharmaceuticals (for example, JP-A-2-131455). As a method for producing such aralkyl ketones represented by the general formula (2), for example, obtained by oxidizing an aryl-substituted olefin with an organic peracid in the presence of a carbonate using a halogenated hydrocarbon as a solvent. A method in which an intermediate is heated with a mineral acid (Japanese Patent Laid-Open No. 49-100044), an aryl-substituted olefin is reacted with N-bromosuccinimide and then treated with a base to obtain an epoxy, and the epoxy is brominated. Although a method (Tetrahedron, 43 , 5431 (1987)) in which a hydrogen acid aqueous solution is allowed to act has been reported, all of them are two-step reactions, and are not necessarily efficient methods.
[0003]
On the other hand, as a method for producing aralkyl ketones from aryl-substituted olefins in one step, a method using iodosylbenzenes (Japanese Patent Laid-Open No. 2-131435) has also been reported. However, it was not always an economically advantageous method.
[0004]
[Problems to be solved by the invention]
Under such circumstances, the present inventors are an inexpensive and easy-to-use method for producing aralkyl ketones economically and advantageously in one step from the aryl-substituted olefins represented by the general formula (1). easy, was intensive investigation to develop a method of using hydrogen peroxide is a clean oxidizing agent, comprising by reacting easy tungsten availability, and tungsten compounds such as boric tungsten and hydrogen peroxide The metal oxide was found to exhibit good catalytic activity in the process for producing aralkyl ketones by reacting the aryl-substituted olefins represented by the general formula (1) with hydrogen peroxide, leading to the present invention. It was.
[0005]
[Means for Solving the Problems]
That is, the present invention, in the presence of a metal oxide catalyst obtained by reacting hydrogen peroxide with at least one selected from the group consisting of tungsten metal , tungsten boride, tungsten sulfide, tungsten carbide, tungsten oxide and tungstic acid , General formula (1)
Wherein the aryl-substituted olefins represented by general formula (2) are reacted with hydrogen peroxide
[0006]
DETAILED DESCRIPTION OF THE INVENTION
First, the metal oxide catalyst used in the present invention will be described. As the catalyst, hydrogen peroxide is reacted with at least one selected from the group consisting of tungsten metal , tungsten boride, tungsten sulfide, tungsten carbide, tungsten oxide and tungstic acid (hereinafter abbreviated as a metal compound). comprising metal oxide Ru is used.
[0008]
When using the data tungsten acid, for example, may be used in which tungstic acid alkali metal salt of sodium tungstate and the like neutralized with an acid.
[0011]
Among these metal compounds, tungsten metal, tungsten boride, tungsten sulfide, tungsten oxide, and tungstic acid are preferable.
[0012]
As hydrogen peroxide to be reacted with such a metal compound, an aqueous solution is usually used. Of course, an organic solvent solution of hydrogen peroxide may be used, but it is preferable to use aqueous hydrogen peroxide in terms of easy handling. The concentration of hydrogen peroxide in the hydrogen peroxide solution or the organic solvent solution of hydrogen peroxide is not particularly limited, but is practically 1 to 60% by weight in consideration of volume efficiency, safety and the like. When using a hydrogen peroxide solution, a commercially available product may be used as it is or after adjusting the concentration by dilution, concentration or the like as necessary. When an organic solvent solution of hydrogen peroxide is used, a solution prepared by, for example, extracting hydrogen peroxide solution with an organic solvent or distilling hydrogen peroxide solution in the presence of an organic solvent is used. Use it.
[0013]
The amount of hydrogen peroxide to be reacted with the metal compound is usually at least 3 mol times, preferably at least 5 mol times the metal compound, and there is no particular upper limit.
[0014]
The reaction between the metal compound and hydrogen peroxide is usually carried out in an aqueous solution. Of course, ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and tert-butanol, nitrile solvents such as acetonitrile and propionitrile, etc. The reaction may be carried out in an organic solvent such as, or in a mixed solvent of the organic solvent and water.
[0015]
The reaction between the metal compound and hydrogen peroxide is usually carried out by mixing and contacting the two, and in order to further improve the contact efficiency between the metal compound and hydrogen peroxide, the metal compound is prepared in the metal oxide preparation solution. It is preferable to carry out the reaction with stirring so that is sufficiently dispersed. In addition, it is preferable to use a metal compound having a small particle diameter, such as a powdered metal compound, in order to increase the contact efficiency between the metal compound and hydrogen peroxide and to facilitate control during preparation of the metal oxide.
[0016]
The preparation temperature at the time of metal oxide preparation is usually −10 to 100 ° C.
[0017]
By reacting the metal compound and hydrogen peroxide in water, in an organic solvent, or in a mixed solvent of an organic solvent and water, all or part of the metal compound is dissolved to form a homogeneous solution or suspension containing the metal oxide. Although a turbid liquid can be prepared, the metal oxide may be taken out of the preparation liquid by, for example, concentration treatment and used as a catalyst, or the preparation liquid may be used as a catalyst as it is.
[0018]
Next, the general formula (1) using the metal oxide as a catalyst.
The reaction between the aryl-substituted olefins shown below (hereinafter abbreviated as olefins (1)) and hydrogen peroxide will be described.
[0019]
In the formula of olefins (1), R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and are each a hydrogen atom, an optionally substituted alkyl group or an optionally substituted alkoxy. Represents a group. R 6 represents a lower alkyl group.
[0020]
Examples of the alkyl group which may be substituted include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as decyl group, cyclopropyl group, 2,2-dimethylcyclopropyl group, cyclopentyl group, cyclohexyl group and menthyl group, and these alkyl groups Is substituted with a substituent such as an alkoxy group, an aryloxy group, an aralkyloxy group, a halogen atom, an acyl group, a carboalkoxy group, a carboaryloxy group, a carboaralkyloxy group, or a carboxyl group described below, for example, a chloromethyl group , Fluoromethyl group, trifluoromethyl group, methoxymethyl group, ethoxymethyl group, Tokishiechiru group, carbomethoxymethyl group, 1-carbethoxy-2,2-dimethyl-3-cyclopropyl group and the like.
[0021]
Examples of the optionally substituted alkoxy group include those composed of the optionally substituted alkyl group and an oxygen atom. For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-decyloxy group, cyclopentyloxy group, cyclohexyloxy group, menthyloxy group, etc. Cyclic C1-C20 alkoxy groups and these alkoxy groups substituted with substituents such as halogen atoms and alkoxy groups, for example, chloromethoxy group, fluoromethoxy group, trifluoromethoxy group, methoxymethoxy group, ethoxy A methoxy group, a methoxyethoxy group, etc. are mentioned.
[0022]
Examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. Examples thereof include an alkyl group having 1 to 6 carbon atoms.
[0023]
Examples of such olefins (1) include β-methylstyrene, anethole, 1-ethoxy-4- (1-propenyl) benzene, isosafrole, 4-isopropyl-1-methyl-2- (1-propenyl) benzene, Examples thereof include methylisoeugenol, ethylisoeugenol, 1,2,3-trimethoxy-4- (1-propenyl) benzene, 1-trifluoromethyl-4- (1-propenyl) benzene and the like.
[0024]
In the olefins (1), there are two types of geometric isomers, a trans isomer and a cis isomer. In the present invention, either one of the geometric isomers may be used, or two types of geometric isomers may be used. A mixture of bodies may be used.
[0025]
The amount of the metal oxide catalyst used in the reaction of the olefins (1) with hydrogen peroxide is usually 0.001 mol times or more with respect to the olefins (1), and there is no particular upper limit. Considering this aspect, it is practically 1 mole or less with respect to the olefin (1).
[0026]
Hydrogen peroxide is usually used as an aqueous solution. Of course, an organic solvent solution of hydrogen peroxide may be used. The concentration of hydrogen peroxide in the hydrogen peroxide solution or the organic solvent solution is not particularly limited, but is practically 1 to 60% by weight in consideration of volume efficiency, safety and the like. The hydrogen peroxide solution is usually used as it is or after adjusting the concentration by dilution, concentration or the like as it is. The organic solvent solution of hydrogen peroxide can be prepared, for example, by means of extraction treatment of hydrogen peroxide solution with an organic solvent or distillation treatment of hydrogen peroxide solution in the presence of the organic solvent.
[0027]
The amount of hydrogen peroxide used is usually 1 mol times or more with respect to the olefins (1), and there is no particular upper limit on the amount used, but in view of economic reasons, olefins are practically used. It is 10 mol times or less with respect to (1). In addition, when using the preparation liquid containing a metal oxide as a catalyst, you may set the usage-amount of hydrogen peroxide including the amount of hydrogen peroxide in this preparation liquid.
[0028]
This reaction is usually carried out in an aqueous solvent, an organic solvent, or a mixed solvent of an organic solvent and water. Examples of the organic solvent include ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol, and tert-butanol, such as acetonitrile and propionitrile. And nitrile solvents such as The amount of water or organic solvent used is not particularly limited, but considering volume efficiency and the like, it is practically 100 weight times or less with respect to the olefins (1).
[0029]
In this reaction, water is produced as a by-product as the reaction proceeds, and therefore the reaction may be carried out in the presence of a dehydrating agent in the reaction system. Examples of the dehydrating agent include anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous boric acid, polyphosphoric acid, diphosphorus pentoxide and the like, and the amount used is more than the amount capable of dehydrating and removing water present in the reaction system. I just need it.
[0030]
If the reaction temperature is too low, the reaction hardly proceeds. If the reaction temperature is too high, side reactions such as polymerization of the raw material olefins (1) may proceed. Therefore, a practical reaction temperature is 0 to 200. It is in the range of ° C.
[0031]
This reaction is usually carried out by contacting and mixing olefins (1), hydrogen peroxide and a metal oxide catalyst, but the mixing order is not particularly limited. Further, for example, a metal compound, hydrogen peroxide, and olefin (1) may be contacted and mixed, and the preparation operation of the metal oxide catalyst and the reaction between the olefin (1) and hydrogen peroxide may be performed simultaneously. .
[0032]
This reaction may be carried out under normal pressure conditions or under pressurized conditions. In addition, the progress of the reaction can be confirmed by ordinary analysis means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR, IR and the like.
[0033]
Further, this reaction may be carried out in the presence of a boron compound such as boric anhydride. Examples of the boron compound include boric anhydride, metaboric acid, normal boric acid, alkali metal metaborate, alkali earth metal borate, alkali metal normal borate, and alkaline earth metal borate. The amount to be used is not particularly limited, but it is economically disadvantageous if it is too much, so that it is practically 1 mole or less relative to the olefins (1).
[0034]
Thus, the general formula (2)
[0035]
Examples of the organic solvent insoluble in water include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as dichloromethane, chloroform, and chlorobenzene, and ethers such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran. Examples of the solvent include ester solvents such as ethyl acetate, and the amount used is not particularly limited.
[0036]
Further, the aqueous layer obtained by extracting the filtrate or reaction solution after the target ketones (2) are removed by crystallization treatment contains the metal oxide catalyst of this reaction, and is used as it is or necessary. Accordingly, after performing a concentration treatment or the like, it can be used again for this reaction.
[0037]
Examples of such ketones (2) include phenylacetone, 4-methoxyphenylacetone, 4-ethoxyphenylacetone, 3,4-methylenedioxyphenylacetone, 5-isopropyl-2-methylphenylacetone, 3,4-dimethoxy. Examples include phenylacetone, 3-methoxy-4-ethoxyphenylacetone, 2,3,4-trimethoxyphenylacetone, and 3-trifluoromethylphenylacetone.
[0038]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. The analysis was performed by gas chromatography analysis (internal standard method).
[0039]
Example 1
A 50 mL flask was charged with 18 mg of tungsten metal and 420 mg of 30 wt% hydrogen peroxide water, heated to an internal temperature of 60 ° C., and stirred and held at the same temperature for 0.5 hour to prepare an aqueous tungsten oxide solution. The aqueous solution was charged with 1.78 g of methylisoeugenol, 8.9 g of tert-butanol and 0.83 g of 30 wt% hydrogen peroxide solution, heated to an internal temperature of 80 ° C., stirred and held at the same temperature for 4 hours, Reacted. After cooling to room temperature, 10 g of methyl tert-butyl ether and 10 g of water were added, followed by liquid separation treatment to obtain an organic layer containing 3,4-dimethoxyphenylacetone. The yield of 3,4-dimethoxyphenylacetone was 25%, and the recovery rate of the raw material methylisoeugenol was 55%.
[0040]
Example 2
A 50 mL flask was charged with 18 mg of tungsten metal and 420 mg of 30 wt% hydrogen peroxide water, heated to an internal temperature of 60 ° C., and stirred and held at that temperature for 1 hour to prepare an aqueous tungsten oxide solution. The aqueous solution was charged with 1.78 g of methylisoeugenol and 0.83 g of 30 wt% hydrogen peroxide solution, heated to an internal temperature of 95 ° C., stirred and held at the same temperature for 2 hours, and reacted. After cooling to room temperature, 10 g of methyl tert-butyl ether and 10 g of water were added, followed by liquid separation treatment to obtain an organic layer containing 3,4-dimethoxyphenylacetone. The yield of 3,4-dimethoxyphenylacetone was 16%, and the recovery rate of the raw material methylisoeugenol was 71%.
[0041]
Example 3
A 50 mL flask was charged with 40 mg of tungsten boride, 300 mg of boric anhydride, 2.3 g of magnesium sulfate, and 3 g of tert-butanol. The temperature was raised to an internal temperature of 60 ° C. A mixed solution consisting of 600 mg of 30% by weight hydrogen peroxide was added dropwise over 20 minutes. Further, the mixture was stirred and held at the same temperature for 2 hours for reaction. After cooling to room temperature, 10 g of methyl tert-butyl ether and 10 g of water were added, followed by liquid separation treatment to obtain an organic layer containing 3,4-methylenedioxyphenylacetone. The yield of 3,4-methylenedioxyphenylacetone was 21%, and the recovery rate of the raw material isosafrole was 20%.
[0042]
Example 4
In Example 1, 3,4-dimethoxyphenylacetone is obtained by carrying out in the same manner as in Example 1 except that tungsten sulfide is used instead of tungsten metal.
[0043]
Example 5
In Example 1, 3,4-dimethoxyphenylacetone is obtained by carrying out in the same manner as in Example 1 except that tungsten carbide is used instead of tungsten metal.
[0044]
Example 6
In Example 1, 3,4-dimethoxyphenylacetone is obtained by carrying out in the same manner as in Example 1 except that tungsten oxide is used instead of tungsten metal.
[0045]
Example 7
In Example 1, 3,4-dimethoxyphenylacetone is obtained by carrying out in the same manner as in Example 1 except that tungstic acid is used instead of tungsten metal.
[0046]
【The invention's effect】
According to the method of the present invention, easily available tungsten metal, in the presence of a metal oxide catalyst comprising by reacting and hydrogen peroxide tungsten compound such as boric tungsten, inexpensive over-and aryl-substituted olefin By reacting with hydrogen oxide, aralkyl ketones can be obtained in one step, which is economically and industrially advantageous.
Claims (5)
で示されるアリール置換オレフィン類と過酸化水素とを反応させることを特徴とする一般式（２）
Wherein the aryl-substituted olefins represented by general formula (2) are reacted with hydrogen peroxide
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| WO2016104474A1 (en) * | 2014-12-26 | 2016-06-30 | 花王株式会社 | Method for producing cyclic diketone compound |
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