JP6561049B2 - 2,3,6−トリメチルフェノールの酸化による2,3,5−トリメチルベンゾキノンの製造方法 - Google Patents
2,3,6−トリメチルフェノールの酸化による2,3,5−トリメチルベンゾキノンの製造方法 Download PDFInfo
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- JP6561049B2 JP6561049B2 JP2016522475A JP2016522475A JP6561049B2 JP 6561049 B2 JP6561049 B2 JP 6561049B2 JP 2016522475 A JP2016522475 A JP 2016522475A JP 2016522475 A JP2016522475 A JP 2016522475A JP 6561049 B2 JP6561049 B2 JP 6561049B2
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- Prior art keywords
- oxidation
- catalyst
- trimethylbenzoquinone
- mixture
- trimethylphenol
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- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 title claims description 41
- QIXDHVDGPXBRRD-UHFFFAOYSA-N 2,3,5-trimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C(C)=C(C)C1=O QIXDHVDGPXBRRD-UHFFFAOYSA-N 0.000 title claims description 38
- 238000007254 oxidation reaction Methods 0.000 title claims description 35
- 230000003647 oxidation Effects 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims description 56
- 239000003054 catalyst Substances 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- -1 copper (II) halide Chemical class 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000012429 reaction media Substances 0.000 claims description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 3
- 150000008045 alkali metal halides Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 150000003138 primary alcohols Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 8
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 8
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 7
- 150000003333 secondary alcohols Chemical class 0.000 description 7
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229930003427 Vitamin E Natural products 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229940046009 vitamin E Drugs 0.000 description 4
- 239000011709 vitamin E Substances 0.000 description 4
- 235000019165 vitamin E Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- 239000005968 1-Decanol Substances 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012455 biphasic mixture Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000003509 tertiary alcohols Chemical class 0.000 description 2
- GVJHHUAWPYXKBD-IEOSBIPESA-N (R)-alpha-Tocopherol Natural products OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- AOBORMOPSGHCAX-DGHZZKTQSA-N tocofersolan Chemical compound OCCOC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C AOBORMOPSGHCAX-DGHZZKTQSA-N 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
- C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/02—Quinones with monocyclic quinoid structure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/02—Quinones with monocyclic quinoid structure
- C07C50/04—Benzoquinones, i.e. C6H4O2
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Description
例示的な実験の最後には、相を分離し、別々に秤量し、有機相を分析した。有機相中の(1)及び(4)の量の定量分析はガスクロマトグラフィーにより実施した。塩素の総含有量は元素分析により測定し、塩素イオン量は硝酸銀溶液による電位差滴定法により測定した。2つの値の差異は、有機結合塩素の量を示す。銅及びリチウムの定量分析は原子発光分析(ICP-OES)により実施した。
4 Lの鋼製反応器に、151 gのCuCl2・2H2O、150 gのLiCl、及び365 gの水からなる657 gの水性反応媒体を仕込み、さらに溶媒として機能する818 gのアルコールを仕込んだ。撹拌しながら、この二相混合物を所望の開始温度TDにし、そこに、大気圧下で、酸素含有ガス混合物を通過させた。温度TDに到達したら、溶媒として機能するアルコール中の2,3,5-トリメチルフェノール(4)の60重量%濃度の溶液500 gをtDの時間にわたって一定速度で供給する。反応を完了させるために、撹拌を温度TRで、時間間隔tRの間、継続する。
実施例I7から得られた反応流出物(3-ヘプタノール中の反応)を、最初に水で洗浄する。相分離を実施してから、有機相をHCl水溶液(25重量%)で振とうにより抽出し、その後再度水で洗浄する。水酸化ナトリウム溶液(2重量%)を添加して溶液をpH6にし、トリメチルキノン(1)の約75重量%濃度の溶液が得られる程度まで、減圧下で溶媒を除去する。
実施例11を比較例C1からの流出物で繰り返した(1-ヘキサノール(溶媒)中の反応)。110℃に加熱したところ、125時間後には、最初に存在したキノン(1)の44%が分解した。
(付記)
(付記1)
以下のステップ:
(i)二相又は多相の反応媒体中、ハロゲン化銅(II)を少なくとも含む触媒又は触媒系の存在下で、酸素又は酸素含有ガスにより2,3,6-トリメチルフェノールを2,3,5-トリメチルベンゾキノンに酸化させて、2,3,5-トリメチルベンゾキノンを含む混合物を得るステップであって、
反応媒体が、水、及び6個以上、好ましくは7個以上の炭素原子を有する少なくとも1種の脂肪族非環式第二級アルコールを含む、前記ステップ
を含む、2,3,5-トリメチルベンゾキノン又は2,3,5-トリメチルベンゾキノンを含む混合物の製造方法。
(付記2)
触媒又は触媒系が、塩化銅(II)を含む、付記1に記載の方法。
(付記3)
触媒又は触媒系が、少なくとも1種のアルカリ金属のハロゲン化物、好ましくは塩化リチウムをさらに含む、付記1〜2の少なくとも一つに記載の方法。
(付記4)
反応媒体が、3-ヘプタノールを含む、付記1〜3の少なくとも一つに記載の方法。
(付記5)
方法を、バッチ式で実施する、付記1〜4の少なくとも一つに記載の方法。
(付記6)
ステップ(ii)において、2,3,5-トリメチルベンゾキノンを含む混合物を、アルカリ性水溶液により洗浄する、付記1〜5の少なくとも一つに記載の方法。
(付記7)
酸化を、50℃〜65℃の温度、好ましくは53℃〜58℃の温度で実施する、付記1〜6の少なくとも一つに記載の方法。
(付記8)
酸化を、4〜8時間にわたって、好ましくは4〜7時間にわたって実施する、付記1〜7の少なくとも一つに記載の方法。
(付記9)
ステップ(iii)において、酸化を実施した後の反応媒体を相分離させて、有機相を、有機相の溶液中の触媒の回収のために抽出する、付記1〜8の少なくとも一つに記載の方法。
(付記10)
付記1〜9の少なくとも一つに記載の方法により製造可能であるか、又は製造される、2,3,5-トリメチルベンゾキノンを含む混合物。
(付記11)
0.5 g/100 g未満の塩素含有量である、付記10に記載の混合物。
(付記12)
0.3 g/100 g未満のリチウム含有量である、付記10に記載の混合物。
(付記13)
240 mg/kg未満の銅含有量である、付記10に記載の混合物。
(付記14)
2,3,6-トリメチルフェノールの2,3,5-トリメチルベンゾキノンへの酸化における、溶媒としての、6個以上、好ましくは7個以上の炭素原子を有する脂肪族非環式第二級アルコールの使用。
(付記15)
ビタミンEの合成、より特には2,3,6-トリメチルヒドロキノンの製造における、付記1〜9の少なくとも一つに記載の方法により製造された2,3,5-トリメチルベンゾキノンの、又は付記1〜9の少なくとも一つに記載の方法により製造された2,3,5-トリメチルベンゾキノンを含む混合物の使用。
Claims (13)
- 以下のステップ:
(i)二相又は多相の反応媒体中、ハロゲン化銅(II)を少なくとも含む触媒又は触媒系の存在下で、酸素又は酸素含有ガスにより2,3,6-トリメチルフェノールを2,3,5-トリメチルベンゾキノンに酸化させて、2,3,5-トリメチルベンゾキノンを含む混合物を得るステップであって、
反応媒体が、水、及び7個以上の炭素原子を有する少なくとも1種の脂肪族非環式第二級アルコールを含む、前記ステップ
を含む、2,3,5-トリメチルベンゾキノン又は2,3,5-トリメチルベンゾキノンを含む混合物の製造方法。 - 触媒又は触媒系が、塩化銅(II)を含む、請求項1に記載の方法。
- 触媒又は触媒系が、少なくとも1種のアルカリ金属のハロゲン化物をさらに含む、請求項1又は2に記載の方法。
- 少なくとも1種のアルカリ金属のハロゲン化物が、塩化リチウムを含む、請求項3に記載の方法。
- 反応媒体が、3-ヘプタノールを含む、請求項1〜4のいずれか一項に記載の方法。
- 方法を、バッチ式で実施する、請求項1〜5のいずれか一項に記載の方法。
- 2,3,5-トリメチルベンゾキノンを含む混合物を、アルカリ性水溶液により洗浄するステップ(ii)を含む、請求項1〜6のいずれか一項に記載の方法。
- 酸化を、50℃〜65℃の温度で実施する、請求項1〜7のいずれか一項に記載の方法。
- 酸化を、53℃〜58℃の温度で実施する、請求項1〜8のいずれか一項に記載の方法。
- 酸化を、4〜8時間にわたって実施する、請求項1〜9のいずれか一項に記載の方法。
- 酸化を、4〜7時間にわたって実施する、請求項1〜10のいずれか一項に記載の方法。
- 酸化を実施した後の反応媒体を相分離させて、有機相を、有機相の溶液中の触媒の回収のために抽出するステップ(iii)を含む、請求項1〜11のいずれか一項に記載の方法。
- 二相又は多相の反応媒体中、ハロゲン化銅(II)を少なくとも含む触媒又は触媒系の存在下での酸素又は酸素含有ガスによる2,3,6-トリメチルフェノールの2,3,5-トリメチルベンゾキノンへの酸化における、溶媒としての、7個以上の炭素原子を有する脂肪族非環式第二級アルコールの使用。
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Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL39225A (en) | 1971-05-17 | 1975-07-28 | Sparamedica Ag | Process for the manufacture of methyl substituted p-benzoquinones |
DE2139692A1 (de) | 1971-08-07 | 1973-02-15 | Basf Ag | Verfahren zur herstellung von heptanol |
JPS5572136A (en) | 1978-11-24 | 1980-05-30 | Kuraray Co Ltd | Preparation of 2,3,5-trimethylquinone |
JPS6117532A (ja) | 1984-07-03 | 1986-01-25 | Mitsubishi Gas Chem Co Inc | 2,3,5−トリメチルベンゾキノンの製造法 |
US4828762A (en) * | 1983-06-06 | 1989-05-09 | Mitsubishi Gas Chemical Company, Inc. | Process for the production of 2,3,5-trimethylbenzoquinone |
JPS59225137A (ja) | 1983-06-06 | 1984-12-18 | Mitsubishi Gas Chem Co Inc | 2,3,5−トリメチルベンゾキノンの製造方法 |
JPS60255746A (ja) * | 1984-05-30 | 1985-12-17 | Mitsubishi Gas Chem Co Inc | 2,3,5−トリメチルベンゾキノンの製造法 |
JPS60255745A (ja) * | 1984-05-30 | 1985-12-17 | Mitsubishi Gas Chem Co Inc | 2,3,5−トリメチルベンゾキノンの製造法 |
JPS6140239A (ja) * | 1984-08-02 | 1986-02-26 | Mitsubishi Gas Chem Co Inc | 触媒の回収方法 |
JPH0645567B2 (ja) * | 1985-09-24 | 1994-06-15 | 三菱瓦斯化学株式会社 | 酸化反応液の精製法 |
JPH0776192B2 (ja) * | 1986-07-11 | 1995-08-16 | 三井東圧化学株式会社 | キノン類の製造方法 |
JPS63280040A (ja) | 1987-05-13 | 1988-11-17 | Eisai Co Ltd | 2,3,5−トリメチルベンゾキノンの製造方法 |
JPH02174744A (ja) * | 1988-11-18 | 1990-07-06 | Agency Of Ind Science & Technol | 2,3,5−トリメチルベンゾキノンの製造方法 |
JPH02264739A (ja) * | 1989-04-05 | 1990-10-29 | Agency Of Ind Science & Technol | 2,3,5―トリメチルベンゾキノンの製造方法 |
EP0369823B1 (en) | 1988-11-18 | 1993-06-16 | THE STATE OF JAPAN, as Represented by the DIRECTOR GENERAL of the AGENCY of INDUSTRIAL SCIENCE and TECHNOLOGY | Method for the preparation of 2,3,5-trimethylbenzoquinone |
DE4029198A1 (de) | 1990-09-14 | 1992-03-19 | Basf Ag | Verfahren zur herstellung von 2,3,5-trimethyl-p-benzochinon |
DE19846003A1 (de) * | 1998-10-06 | 2000-04-13 | Basf Ag | Verfahren zur Reinigung und Isolierung von 2,3,5-Trimethyl-p-benzochinon |
RU2163600C2 (ru) * | 1998-12-04 | 2001-02-27 | Общество с ограниченной ответственностью конструкторское бюро "Пульс" | СПОСОБ ПОЛУЧЕНИЯ α-ТОКОФЕРОЛА (ВИТАМИНА E) |
DE19949795A1 (de) | 1999-10-15 | 2001-04-19 | Degussa | Verfahren zur Herstellung von 2,3,5-Trimethyl-p-benzochinon |
RU2165406C1 (ru) * | 2000-04-10 | 2001-04-20 | Институт катализа им. Г.К. Борескова СО РАН | Способ получения 2,3,5-триметил-1,4-бензохинона и катализатор для его осуществления |
CN1986513A (zh) * | 2006-12-25 | 2007-06-27 | 浙江大学 | 一种2,3,5-三甲基苯醌的制备方法 |
CN102108047B (zh) * | 2010-12-06 | 2013-10-02 | 上海海嘉诺医药发展股份有限公司 | 制备2,3,5-三甲基对苯醌的方法 |
CN102898282B (zh) * | 2012-10-24 | 2014-07-09 | 南通柏盛化工有限公司 | 三甲基氢醌的制备方法 |
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