JPH0529378B2 - - Google Patents
Info
- Publication number
- JPH0529378B2 JPH0529378B2 JP1217066A JP21706689A JPH0529378B2 JP H0529378 B2 JPH0529378 B2 JP H0529378B2 JP 1217066 A JP1217066 A JP 1217066A JP 21706689 A JP21706689 A JP 21706689A JP H0529378 B2 JPH0529378 B2 JP H0529378B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- amines
- oximes
- solvent
- dmhba
- 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.)
- Expired - Lifetime
Links
- 150000007522 mineralic acids Chemical class 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 23
- 150000002923 oximes Chemical class 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 18
- -1 amines or amines Chemical class 0.000 claims description 17
- 150000002443 hydroxylamines Chemical class 0.000 claims description 17
- 239000005749 Copper compound Substances 0.000 claims description 16
- 150000001880 copper compounds Chemical class 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- UYGBSRJODQHNLQ-UHFFFAOYSA-N 4-hydroxy-3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C=O)=CC(C)=C1O UYGBSRJODQHNLQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 9
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 9
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 3
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 150000007824 aliphatic compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 50
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 10
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 6
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229960003280 cupric chloride Drugs 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- VTWKXBJHBHYJBI-SOFGYWHQSA-N (ne)-n-benzylidenehydroxylamine Chemical compound O\N=C\C1=CC=CC=C1 VTWKXBJHBHYJBI-SOFGYWHQSA-N 0.000 description 1
- 229940044613 1-propanol Drugs 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- VSNHCAURESNICA-UHFFFAOYSA-N Hydroxyurea Chemical compound NC(=O)NO VSNHCAURESNICA-UHFFFAOYSA-N 0.000 description 1
- GMPKIPWJBDOURN-UHFFFAOYSA-N Methoxyamine Chemical compound CON GMPKIPWJBDOURN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007013 Reimer-Tiemann formylation reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229960001330 hydroxycarbamide Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- WHIVNJATOVLWBW-SNAWJCMRSA-N methylethyl ketone oxime Chemical compound CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
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[Industrial Application Field] The present invention relates to a method for producing 3,5-dimethyl-4-hydroxybenzaldehyde, which is useful as a synthetic intermediate for perfumes, agricultural chemicals, pharmaceuticals, and the like. More specifically, the present invention provides a method for combining copper compounds and various nitrogen compounds in the liquid phase, namely amines or salts of amines and inorganic acids or mixtures thereof, hydroxylamines or salts of hydroxylamines and inorganic acids, or 2,4,6- The present invention relates to a method for efficiently oxidizing trimethylphenol (hereinafter referred to as TMP) with oxygen to produce 3,5-dimethyl-4-hydroxybenzaldehyde (hereinafter referred to as DMHBA). [Prior Art] DMHBA is an important substance that is a raw material for fragrances, agricultural chemicals, medicines, etc., but a high-efficiency synthesis method has not yet been established. In general, aromatic aldehydes are often used as raw materials for fragrances, agricultural chemicals, pharmaceuticals, etc., and various methods of synthesizing them are being investigated (RASheldon, âThe Role
of Oxygen in Chemistry and Biochemistryâ,
p243, Elsevier, Amsterdam, 1988), both methods have practical problems. For example, hydroxybenzaldehyde is synthesized by formylation of phenol, and the Reimer-Tiemann method or the RhÃŽne-Poulenc method both require auxiliary raw materials and have low reaction selectivity. This method has disadvantages in that side reactions are likely to occur and equipment is corroded. In recent years, many methods using oxidation reactions have been studied, but there are still many methods that use reagents as oxidizing agents. There are problems with the processing of materials, and even if relatively clean hydrogen peroxide or organic peroxide is used, the production cost increases and harmful metal compounds such as chromium and cerium must be used as catalysts. has. Also, the application of electrolytic oxidation method is being considered (S. Torii, âElectro-organic Synthesis,â
Part 1, Oxidations, âMonograph in Modern
Chemistry Series, Kodansha, Tokyo, 1985),
This method is not necessarily viable as an industrial manufacturing method because of problems with the durability of the electrodes and increased power costs. If oxygen in the air could be used as an oxidizing agent, it would be extremely advantageous in practical terms, but in the oxygen oxidation reaction, the generated benzaldehyde is likely to undergo sequential oxidation to produce an acid, making it difficult to control the reaction. An exceptionally successful example of this type of oxidation reaction is the oxygen oxidation of p-cresol using a cobalt chloride catalyst in the presence of a large amount of alkali in a methanol solvent to synthesize p-hydroxybenzaldehyde. is (Eur.Pat.Appl., 0,
012, 939 (1979)), but this case also has the disadvantage that a large amount of the solvent methanol and the added alkali are consumed. [Problems to be solved by the invention] Therefore, the present inventors oxidized TMP with oxygen.
As a result of intensive research on oxidation catalysts and oxidation reaction solvents for producing DMHBA, we have found that copper compounds and various nitrogen compounds, such as amines or salts of amines and inorganic acids, or mixtures thereof, hydroxylamines or hydroxyl A catalyst consisting of a salt of an amine and an inorganic acid or a mixture thereof or a combination of oximes or a mixture of an oxime and an inorganic acid is used, and a lower aliphatic alcohol having 1 to 8 carbon atoms or an aromatic hydrocarbon and a solvent are used. We have discovered that the desired DMHBA can be produced in high yield by using a mixture of lower aliphatic alcohols having 1 to 8 carbon atoms,
Based on this knowledge, the present invention was accomplished. [Means for solving the problem] That is, the present invention oxidizes TMP with oxygen.
In producing DMHBA, copper compounds and various nitrogen compounds, such as amines or salts of amines and inorganic acids or mixtures thereof, hydroxylamines or salts of hydroxylamines and inorganic acids or mixtures thereof, or oximes are used. A catalyst consisting of a mixture of oximes or oximes and an inorganic acid is used, and the solvent has 1 carbon number.
A DMHBA characterized by using a mixture of a lower aliphatic alcohol having ~8 carbon atoms or an aromatic hydrocarbon and a lower aliphatic alcohol having 1 to 8 carbon atoms.
The present invention provides a method for manufacturing. The present invention uses TMP as a lower aliphatic alcohol having 1 to 8 carbon atoms or an aromatic hydrocarbon and 1 to 8 carbon atoms.
~8 dissolved in a mixed solvent of lower aliphatic alcohols, containing molecular oxygen and a catalytic amount of a copper compound and various nitrogen compounds, namely amines or salts of amines and inorganic acids, or mixtures thereof, hydroxylamines. or in the presence of salts of hydroxylamines and inorganic acids or mixtures thereof, or oximes or mixtures of oximes and inorganic acids,
It is an extremely simple and safe oxidation method that can be easily achieved by simply stirring at room temperature to 200°C. In the present invention, in order to oxidize TMP, molecular oxygen as an oxidizing agent and a copper compound and various nitrogen compounds as catalysts, namely amines or salts of amines and inorganic acids, or mixtures thereof,
Hydroxylamines or salts of hydroxylamines and inorganic acids, or mixtures thereof, or combinations of oximes or mixtures of oximes and inorganic acids are used. As the molecular oxygen source, either pure oxygen gas or air may be used, and is effective in the range of normal pressure to 30 kg/cm 2 . As the copper compound used as a component of the catalyst, inorganic salts, organic salts, etc. can be used and there are no particular restrictions, but chlorides such as cuprous chloride and cupric chloride show particularly good reaction results. Regarding amines, which are nitrogen compounds used as other components of the catalyst, various derivatives such as cyclic amines, amino alcohols, and amino acids can be used regardless of whether they are primary, secondary, or tertiary, and there are no particular restrictions. However, relatively low molecular weight compounds give good reaction results. Regarding hydroxylamines, in addition to hydroxylamine itself, N,N-dialkylhydroxylamines such as N,N-dimethylhydroxylamine, N-alkylhydroxylamines such as N-methylhydroxylamine, O-methylhydroxylamine, etc. Although various hydroxylamine derivatives such as O-alkylhydroxylamines can be used, hydroxylamine, hydroxyurea or low molecular weight N,N-dialkylhydroxylamines show particularly good reaction results. Oximes include dialkyl ketones such as acetone, methyl ethyl ketone, and diethyl ketone, cyclic ketones such as cyclohexanone and cyclooctanone, aromatic ketones such as acetophenone and propiophenone, diketones such as diacetyl and acetylacetone, and dimedone. Oximes of any ketones such as cyclic diketones, aliphatic aldehydes such as formaldehyde, acetaldehyde, and propionaldehyde, and aromatic aldehydes such as benzaldehyde and phenylacetaldehyde can be used, but above all, oximes of aldehydes can be used. Relatively low molecular weight oximes such as acetaldoxime, benzaldoxime, acetone oxime, and 2-butanone oxime give good reaction results. In addition, when using salts with these inorganic acids, various inorganic acids such as sulfuric acid and halogen acids can be used, and there are no particular restrictions, but hydrochloric acid or sulfuric acid has yielded relatively good results. give. Addition of this inorganic acid is not essential, and sufficient catalytic activity can be obtained with a system of copper compound and oximes, but catalytic activity is often improved by further adding an inorganic acid. Furthermore, it is not necessary to prepare and use a mixture of hydroxylamines, oximes, amines, and inorganic acids in advance, and they may be added separately, and in either case, there are no particular restrictions on the composition ratio of each. However, a range of 0.2 to 5 moles of inorganic acid per mole of hydroxylamines and oximes gives good reaction results. There is no particular restriction on the amount of amines used in the copper compound when the amine is added as a salt or mixture with an inorganic acid, but if it is too little or too much, the reaction rate will be low, so A range of 0.3 to 3 moles is preferred. When adding amine alone, it is added per mole of copper compound.
The amount is preferably in the range of 0.5 to 1 mole, and addition of excess amine promotes side reactions and inhibits the production of p-hydroxybenzaldehyde, which is the target compound. There is no particular restriction on the amount of hydroxylamines and oximes to be used with respect to the copper compound, but if it is too little or too much, the reaction rate will be low, so in any case, it should be in the range of 0.3 to 3 mol per 1 mol of the copper compound. preferable. There is no particular restriction on the amount of the catalyst obtained in this way, but if it is too small, the reaction rate will be low, and if it is too large, problems will arise with separation after the reaction, etc. Therefore, the amount of copper compound should be 0.01 per mole of TMP. The use of Ë0.1 molar amounts gives favorable reaction results. In the method of the present invention, as for the solvent used in the reaction, lower aliphatic alcohols having 1 to 8 carbon atoms include methanol, ethanol, 1-
Propanol, isopropanol, 1-butanol, 2-butanol, tert-butanol, 1-amyl alcohol, 2-amyl alcohol, 3-amyl alcohol, sec-amyl alcohol, tert
-amyl alcohol, 1-hexanol, 1-octanol, 2-octanol, etc., including but not limited to, tert-butanol,
Tertiary alcohols such as tert-amyl alcohol give favorable results. When using a mixed solvent of aromatic hydrocarbons and lower aliphatic alcohols having 1 to 8 carbon atoms, there are no particular restrictions on the aromatic hydrocarbons; Those that are stable against oxidation are preferred. At this time, a mixture of one or more of the above-mentioned lower aliphatic alcohols having 1 to 8 carbon atoms, one or more aromatic hydrocarbons, and one or more aromatic hydrocarbons is used as a solvent. These solvents are highly effective in dissolving copper compounds as catalysts, amines, hydroxylamines, oximes, and/or inorganic acids, TMP as raw materials, and oxygen, and can be used to achieve the desired purpose simply by bringing them into contact. The production of DMHBA is extremely effective. The composition ratio of aromatic hydrocarbons and lower aliphatic alcohols cannot be determined unconditionally as it varies depending on the combination, but the volume ratio of lower aliphatic alcohols to aromatic hydrocarbons is 0.2 to 0.2.
1.5 is preferred, particularly preferably 0.25-0.8. The above catalysts can be used by directly dissolving them in a mixed solvent, but they can also be used as an aqueous solution. In addition, as the aliphatic alcohol having 1 to 8 carbon atoms used in this case, there is no particular problem as long as the aqueous solution is small, and butanol, pentanol, hexanol, heptanol, octanol, etc. containing various isomers can be used. . In either case, dissolved in the solvent
In order to efficiently bring TMP into contact with the catalyst dissolved in the aqueous phase and oxygen in the gas phase, it is necessary to provide an efficient stirring device and aeration device. The temperature of the reaction in the method of the invention is room temperature to 200 â
It can be carried out at a temperature around â, but if the temperature is too low, the reaction rate will be slow, while if it is too high, there will be a lot of solvent loss or side reactions.
Preferably, the temperature is 80°C. The reaction time depends on the reaction temperature, oxygen pressure, and amount of catalyst used, but 1 to 10 hours is usually sufficient. [Effects of the Invention] According to the method of the present invention, copper compounds such as cupric chloride, which are inexpensive commercially available general reagents, and nitrogen compounds such as amines, hydroxylamine, acetone oxime, etc. are used as catalysts, and Lower aliphatic alcohol or aromatic hydrocarbon with 1 or more carbon atoms
When a mixed solution formed with a preferable composition of lower aliphatic alcohols of 8 is used as a solvent and a catalyst is subjected to the reaction as an aqueous solution, a comparatively water-soluble aliphatic alcohol in the above-mentioned mixed solution or aliphatic alcohol having 1 to 8 carbon atoms is used as a solvent. It is possible to obtain DMHBA in one step by oxidizing TMP with molecular oxygen using a low-carbon solvent as a solvent, and with an extremely high reaction rate and yield.In addition, it is possible to circulate a large amount of catalyst, which was a drawback of the conventional method. This method is suitable as an industrial method for producing DMHBA because it eliminates the need for additional steps. Since the activity of the catalyst used in the present invention is extremely high, it is sufficient to use a small amount of the catalyst, and it is not necessarily necessary to recycle the catalyst. However, if this is necessary, the catalyst can be used as an aqueous solution. can be used repeatedly. in this case,
During the reaction, under stirring, in a mixed solvent system, due to the lipophilicity of aromatic hydrocarbons and the hydrophilicity of lower aliphatic alcohols, aliphatic alcohols, which are poorly water-soluble, are mixed with the lipophilicity of long-chain alkyl groups in the solvent. Due to the hydrophilic nature of the hydroxyl group, it forms a good suspension state with the catalyst in the aqueous phase, allowing the three-phase reaction of aqueous phase - organic phase - gas phase to proceed smoothly. However, when stirring is stopped after the reaction is completed, the organic phase The catalyst in the aqueous phase can be separated and recovered for reuse, and at the same time, the solvent can be removed from the organic phase by means such as distillation to produce the product.
DMHBA can be easily isolated. [Example] Next, the present invention will be explained in more detail with reference to Examples. Note that the examples of the present invention are representative examples for easier understanding of the present invention, and the present invention is not limited to these examples. In addition, the TMP shown in the following examples and comparative examples
The conversion rate of and the yield of DMHBA were determined by gas chromatography using o-dichlorobenzene as an internal standard. Examples 1 to 5 In a glass container with an internal volume of 10 ml, 2 mmol of TMP, 0.2 mmol of cupric chloride dihydrate as a catalyst, and predetermined amounts of various additives, and 2 ml of n-hexanol as a solvent were charged, and the reaction temperature was 60°C. to increase the oxygen pressure to 860mm
The reaction was carried out while maintaining the Hg level, and the amount of oxygen absorbed was measured using a gas filter. After the amount of oxygen absorption had almost stopped, the reaction was continued for about 1 to 2 hours to complete the reaction, and the products in the reaction solution were analyzed. Table 1 shows the conversion rate of TMP and the yield of DMHBA produced.
Shown below.
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AOïŒã¢ã»ãã³ãªãã·ã ïŒïŒCH3ïŒ2ïŒNOHïŒ
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DMHBAã®åçãè¡šïŒã«ç€ºãã[Table] The abbreviations used for additives in Table 1 indicate the following compounds. AO=acetone oxime ((CH 3 ) 2 C=NOH)
And 36% hydrochloric acid aqueous solution was used as HC1. Examples 6-7 In Example 1, cupric chloride dihydrate was added to 0.1 mm
ol, hydroxylamine hydrochloride 0.2 as additive
mmol, 2-pentanol or n- as solvent
A reaction was carried out in the same manner as in Example 1 using 2 ml of butanol. Conversion rate of TMP and produced
The yield of DMHBA is shown in Table 2.
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ãã³ã«çæããDMHBAã®åçãè¡šïŒã«ç€ºãã[Table] In Table 2, the abbreviations used for solvents indicate the following compounds. 2-PeOH=2-pentanol and n-
BuOH = n-butanol. Examples 8 to 9 In Examples 4 and 5, reactions were carried out in the same manner as in Examples 4 and 5, except that 0.1 mmol of hydroxylamine sulfate was used instead of hydroxylamine hydrochloride as a converting agent. Table 3 shows the conversion rate of TMP and the yield of DMHBA produced.
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ãè¡šïŒã«ç€ºãã[Table] Examples 10 to 11 In Example 1, 0.1 mmol of cupric chloride hydrate,
Example 1 Using 2 ml of tertiary butanol instead of n-hexanol as a solvent and 0.2 mmol of hydroxylamine hydrochloride or 0.1 mmol of hydroxylamine sulfate as an additive, the reaction temperature was 40°C.
The reaction was carried out in the same manner. Table 4 shows the conversion rate of TMP and the yield of DMHBA produced. Comparative Examples 1-2 In Example 10, lithium chloride was used as an additive.
The reaction was carried out in the same manner as in Example 10 using 0.1 mmol or 0.2 mmol of diethylamine hydrochloride.
Table 4 shows the addition rate of TMP and the yield of DMHBA produced.
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OHã»HC1ïŒããã³HASïŒããããã·ã«ã¢ãã³
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å®æœäŸ 12ã21
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åçãè¡šïŒã«ç€ºãã[Table] In Table 4, the abbreviations used for additives indicate the following compounds. HAH=Hydroxylamine hydrochloride ( NH2
OHã»HC1) and HAS=hydroxylamine sulfate ((NH 2 OH) 2ã»H 2 SO 4 ). Examples 12-21 In Example 10, using various aliphatic alcohols instead of tertiary butanol as the solvent,
The reaction was carried out in the same manner as in Example 10. The TMP conversion rate and the yield of DMHBA produced are shown in Table 5. Comparative Example 3 In Example 17, the reaction was carried out in the same manner as in Example 17 without adding hydroxylamine hydrochloride. Table 5 shows the conversion rate of TMP and the yield of DMHBA produced.
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HeOHïŒïœâãããµããŒã«ã
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ãDMHBAã®åçãè¡šïŒã«ç€ºãã[Table] In Table 5, the abbreviations used for solvents indicate the following compounds. EtOH = ethanol, n-propanol, i-
PrOH=isopropanol, i-BuOH=i-butanol, n-AmOH=n-amyl alcohol,
s-AmOH=s-amyl alcohol, t-
AmOH = t-amyl alcohol and n-
HeOH=n-hexanol. Example 22 In Example 20, a reaction was carried out for 3 hours in the same manner as in Example 20 using 0.4 mmol of hydroxylamine hydrochloride, and the conversion rate of TMP was 98.6%.
A value of 58.6% DMHBA was obtained. Examples 23 to 24 In Example 10, the reaction was carried out in the same manner as in Example 10, using a mixed solvent of isopropanol and toluene (Tol) instead of 2 ml of tertiary butanol as the solvent. Table 6 shows the conversion rate of TMP and the yield of DMHBA produced.
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ãªãã³ã«çæããDMHBAã®åçãè¡šïŒã«ç€ºãã[Table] Examples 25-32 In Example 11, using various aliphatic alcohols as solvents instead of tertiary butanol,
The reaction was carried out in the same manner as in Example 11. Table 7 shows the conversion rate of TMP and the yield of DMHBA produced.
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å®æœäŸ 33
å®æœäŸ11ã«ãããŠã第äžçŽãã¿ããŒã«ã®ããã
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å溶åªãçšããŠãå®æœäŸ11ãšåæ§ã«ïŒæéåå¿ã
è¡ã€ããšãããTMPã®è»¢åç100ïŒ
ãªãã³ã«çæ
ããDMHBAã®åç78.0ïŒ
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å®æœäŸ 34ã37
å®æœäŸïŒã«ãããŠæ·»å å€ãšããŠãžãšãã«ã¢ãã³
ïŒEt2NHïŒããžâïœâãããã«ã¢ãã³ïŒPr2NHïŒ
ãããã¯ãžâïœâããã«ã¢ãã³ïŒBu2NHïŒãçš
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åçãªãã³ã«çæããDMHBAåçãè¡šïŒã«ç€º
ãã[Table] In Table 7, the abbreviations used for solvents indicate the following compounds. 2-OcOH=2-octanol. Example 33 In Example 11, when a mixed solvent of 1.0 ml of toluene and 1.0 ml of isopropanol was used instead of tertiary butanol and the reaction was carried out for 1 hour in the same manner as in Example 11, the conversion rate of TMP was 100%. In addition, a value of 78.0% yield of DMHBA was obtained. Examples 34 to 37 In Example 1, diethylamine (Et 2 NH) and di-n-propylamine (Pr 2 NH) were used as additives.
Alternatively, the reaction was carried out in the same manner as in Example 1 using di-n-butylamine (Bu 2 NH). The TMP conversion rate and the yield of DMHBA produced are shown in Table 8.
Claims (1)
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ã®è£œé æ¹æ³ã[Claims] 1. In producing 3,5-dimethyl-4-hydroxybenzaldehyde by oxidizing 2,4,6-trimethylphenol with oxygen, a copper compound and various nitrogen compounds, namely amines or amines, and A catalyst consisting of a salt with an inorganic acid or a mixture thereof, a hydroxylamine or a salt of a hydroxylamine with an inorganic acid or a mixture thereof, or a combination of oximes or a mixture of an oxime and an inorganic acid is used. A method for producing 3,5-dimethyl-4-hydroxybenzaldehyde. 2 2,4,6-trimethylphenol is combined with a copper compound and various nitrogen compounds, namely amines or salts of amines and inorganic acids, or mixtures thereof, hydroxylamines or salts of hydroxylamines and inorganic acids, or the like. a mixture of
Alternatively, in a method for producing 3,5-dimethyl-4-hydroxybenzaldehyde by oxygen oxidation using a catalyst consisting of oximes or a combination of oximes and an inorganic acid, lower aliphatic compounds having 1 to 8 carbon atoms are used as the solvent. 3, characterized in that a mixture of alcohol or aromatic hydrocarbon and lower aliphatic alcohol having 1 to 8 carbon atoms is used;
A method for producing 5-dimethyl-4-hydroxybenzaldehyde.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1217066A JPH0381241A (en) | 1989-08-23 | 1989-08-23 | Production of 3,5-dimethyl-4-hydroxybenzaldehyde |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1217066A JPH0381241A (en) | 1989-08-23 | 1989-08-23 | Production of 3,5-dimethyl-4-hydroxybenzaldehyde |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0381241A JPH0381241A (en) | 1991-04-05 |
JPH0529378B2 true JPH0529378B2 (en) | 1993-04-30 |
Family
ID=16698301
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1217066A Granted JPH0381241A (en) | 1989-08-23 | 1989-08-23 | Production of 3,5-dimethyl-4-hydroxybenzaldehyde |
Country Status (1)
Country | Link |
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JP (1) | JPH0381241A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5475156A (en) * | 1994-06-06 | 1995-12-12 | General Electric Company | Method for making a 2,6-dialkylphenol |
DE19723890A1 (en) * | 1997-06-06 | 1998-12-10 | Consortium Elektrochem Ind | Process for the preparation of aromatic and heteroaromatic aldehydes and ketones |
JP4315548B2 (en) | 1999-11-19 | 2009-08-19 | æ ªåŒäŒç€Ÿããªãã¹ãã³ | Tire carcass forming apparatus and forming method |
JP3574844B2 (en) * | 2000-07-19 | 2004-10-06 | 倧éªå€§åŠé· | Method for oxidizing a compound using an aldehyde in the presence of a copper catalyst comprising a copper salt and a nitrogen-containing compound |
-
1989
- 1989-08-23 JP JP1217066A patent/JPH0381241A/en active Granted
Also Published As
Publication number | Publication date |
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JPH0381241A (en) | 1991-04-05 |
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