JP4072651B2 - Process for producing 4-aminoresorcinol or a salt thereof - Google Patents
Process for producing 4-aminoresorcinol or a salt thereof Download PDFInfo
- Publication number
- JP4072651B2 JP4072651B2 JP32431997A JP32431997A JP4072651B2 JP 4072651 B2 JP4072651 B2 JP 4072651B2 JP 32431997 A JP32431997 A JP 32431997A JP 32431997 A JP32431997 A JP 32431997A JP 4072651 B2 JP4072651 B2 JP 4072651B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- salt
- substituted phenyl
- aminoresorcinol
- 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
- ROCVGJLXIARCAC-UHFFFAOYSA-N 4-aminobenzene-1,3-diol Chemical compound NC1=CC=C(O)C=C1O ROCVGJLXIARCAC-UHFFFAOYSA-N 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 13
- 150000003839 salts Chemical class 0.000 title claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000001448 anilines Chemical class 0.000 claims description 8
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical class N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- 229910021472 group 8 element Inorganic materials 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- -1 azo resorcinol Chemical compound 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- CLRSZXHOSMKUIB-UHFFFAOYSA-M benzenediazonium chloride Chemical compound [Cl-].N#[N+]C1=CC=CC=C1 CLRSZXHOSMKUIB-UHFFFAOYSA-M 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LLJMPRKYLLJAEB-UHFFFAOYSA-N 4-aminobenzene-1,3-diol;hydron;chloride Chemical compound Cl.NC1=CC=C(O)C=C1O LLJMPRKYLLJAEB-UHFFFAOYSA-N 0.000 description 2
- BPTKLSBRRJFNHJ-UHFFFAOYSA-N 4-phenyldiazenylbenzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1N=NC1=CC=CC=C1 BPTKLSBRRJFNHJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- NNNDGNSOCBWTJG-UHFFFAOYSA-N aniline;benzoic acid Chemical compound NC1=CC=CC=C1.OC(=O)C1=CC=CC=C1 NNNDGNSOCBWTJG-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- HDSUWQLDQNJISD-UHFFFAOYSA-N iridium;triphenylphosphane Chemical compound [Ir].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HDSUWQLDQNJISD-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JDEJGVSZUIJWBM-UHFFFAOYSA-N n,n,2-trimethylaniline Chemical compound CN(C)C1=CC=CC=C1C JDEJGVSZUIJWBM-UHFFFAOYSA-N 0.000 description 1
- SLFVYFOEHHLHDW-UHFFFAOYSA-N n-(trifluoromethyl)aniline Chemical compound FC(F)(F)NC1=CC=CC=C1 SLFVYFOEHHLHDW-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 description 1
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- MGNPLIACIXIYJE-UHFFFAOYSA-N n-fluoroaniline Chemical compound FNC1=CC=CC=C1 MGNPLIACIXIYJE-UHFFFAOYSA-N 0.000 description 1
- CDZOGLJOFWFVOZ-UHFFFAOYSA-N n-propylaniline Chemical compound CCCNC1=CC=CC=C1 CDZOGLJOFWFVOZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- JLXXLCJERIYMQG-UHFFFAOYSA-N phenylcyanamide Chemical compound N#CNC1=CC=CC=C1 JLXXLCJERIYMQG-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、４−アミノレゾルシノール及びその塩並びにその中間体である４−（置換フェニル）アゾレゾルシノールの製造法に関する。更に詳しくは、一般式（２）
【０００２】
【化８】
（式中、Ｒは水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、ハロゲン原子、スルホ基、シアノ基、カルボキシル基、炭素数２〜１１のカルボアルコキシ基を表し、ｎは０〜５の整数である。）で表される置換アニリンと亜硝酸アルカリを酸水溶液中で反応させて一般式（３）
【０００４】
【化９】
（式中、Ｒ及びｎは式（２）と同じ意味を表し、ＸはＣｌ、Ｂｒ、ＯＳＯ3Ｈ又はＯＰＯ3Ｈ2を表す。）で表される置換フェニルジアゾニウム塩を生成させた後、ｐＨ７〜１２を維持しながらレゾルシノールと反応させることを特徴とする一般式（１）
【０００６】
【化１０】
（式中、Ｒ及びｎは式（２）と同じ意味を表す。）で表される４−（置換フェニル）アゾレゾルシノールの製造法及びこの４−（置換フェニル）アゾレゾルシノールを金属触媒を用いて接触還元法によって水素化分解することを特徴とする４−アミノレゾルシノール又はその塩の製造法に関する。
【０００８】
【従来の技術】
これまで前記一般式（１）で表される４−（置換フェニル）アゾレゾルシノールの還元による４−アミノレゾルシノールの製造法としては、錫と塩酸による方法が知られている(Chem.Ber.,16(1883)1330)。この方法は、高価な塩化第一錫を試薬量必要であり、また有機物を含む塩化第二錫の塩酸水溶液の処理が課題であった。
【０００９】
更に、置換アニリン誘導体と亜硝酸アルカリ及びレゾルシノールから４−（置換フェニル）アゾレゾルシノールを得る行程では、異性体やビス（置換フェニル）アゾレゾルシノール等の副生物が見られ、目的物の選択率が低かった。
【００１０】
【発明が解決しようとする課題】
本発明の目的は、４−（置換フェニル）アゾレゾルシノールの実用的還元法による４−アミノレゾルシノールの製造法の提供及び原料の４−（置換フェニル）アゾレゾルシノールを高選択率で得るカップリング方法の提供にある。
【００１１】
【課題を解決するための手段】
本発明者等は、上記課題を解決するために鋭意研究を重ねた結果、本発明を完成するに至った。即ち、本発明は、一般式（２）
【００１２】
【化１１】
（式中、Ｒ及びｎは式（１）と同じ意味を表す。）で表される置換アニリンと亜硝酸アルカリを酸水溶液中で反応させて一般式（３）
【００１４】
【化１２】
（式中、Ｒ及びｎは式（１）と同じ意味を表し、ＸはＣｌ、Ｂｒ、ＯＳＯ3Ｈ又はＯＰＯ3Ｈ2を表す。）で表される置換フェニルジアゾニウム塩を生成させた後、ｐＨ７〜１２を維持しながらレゾルシノールと反応させ前記一般式（１）で表される４−（置換フェニル）アゾレゾルシノールを得、この４−（置換フェニル）アゾレゾルシノール金属触媒を用いて水素化分解することを特徴とする４−アミノレゾルシノール又はその塩の製造法に関する。
【００１６】
【発明の実施の形態】
まず、還元反応の原料である一般式（１）で表される４−（置換フェニル）アゾレゾルシノールの製造法について述べる。４−（置換フェニル）アゾレゾルシノールの製造法は下記の反応式で表される。
【００１７】
【化１３】
（式中、Ｒ、ｎ及びＸは前記と同じ意味を表す。Ａはアルカリ金属を表す。）
本発明で用いる一般式（２）で表されるアニリン誘導体のＲは水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、ハロゲン原子、スルホン酸基、シアノ基、カルボキシル基、炭素数２〜１１のカルボアルコキシ基を表し、ｎは０〜５の整数である。具体的には、アニリン、トルイジン、アニシジン、ジメチルアニリン、エチルアニリン、トリメチルアニリン、プロピルアニリン、ブチルアニリン、フルオロアニリン、クロルアニリン、ブロモアニリン、アニリン安息香酸及びそのエステル類、シアノアニリン、トリフロロメチルアニリン等が挙げられる。特に好ましいのはアニリンである。
【００１９】
ＡＮＯ2で表される亜硝酸アルカリとしては、亜硝酸リチウム、亜硝酸ナトリウム及び亜硝酸カリウムなどが挙げられる。特には安価な亜硝酸ナトリウムが好ましい。その使用量、置換アニリンに対し１〜２当量、より好ましくは１〜１．３当量である。酸量は、置換アニリンに対し１〜１０当量、より好ましくは、２〜３当量である。酸としては塩酸の他に、臭化水素酸、硫酸及び燐酸などの他の酸も使用可能であるが塩酸が好ましい。
【００２０】
反応温度は０〜２０℃、好ましくは０〜１０℃で置換フェニルジアゾニウム塩を製造するのが良い。置換フェニルジアゾニウム塩とレゾルシノールのカップリング反応は、通常、置換フェニルジアゾニウム塩の溶液を、レゾルシノールの溶液中に滴下混合する。この際に本反応は酸性でも可能であるが、反応が遅くなり副生物も見られることから中性から塩基性下で行うことが好ましい。従って、アルカリ水溶液を添加し、実用的には、連続同時添加方式が望ましい。好ましいｐＨ領域としてはｐＨ５〜１２であるが、特には、ｐＨ６〜１０付近でカップリング反応を行うのが良い。また、レゾルシノールに対する置換フェニルジアゾニウム塩の仕込み量は置換フェニルジアゾニウム塩の一部分解を考慮して通常１．０〜１．２０モル倍使用するのが好ましい。
【００２１】
反応温度も低温が好ましく、アルカリ性では０〜１０℃、酸性では、反応が遅くなるので０〜６０℃が好ましい。生成物は、反応終了後に酸性化し、濾過水洗することにより目的とする４−（置換フェニル）アゾレゾルシノールを得ることが出来る。更に、純度を上げる場合は、炭酸ナトリウム水溶液で抽出した後、酸沈するか、メタノール／水、トルエンやジオキサン等の溶媒から、再結晶させることにより精製することができる。
【００２２】
次に、４−（置換フェニル）アゾレゾルシノールの還元行程について述べる。
【００２３】
【化１４】
触媒としては、周期律表第８族のパラジウム、ルテニウム、ロジウム、白金、ニッケル、コバルト及び鉄、又第１族の銅等が使用できる。これらの金属は単独で、又は他の元素と複合された多元系で使用される。それらの使用形態は、各金属単身、ラネー型触媒、ケイソウ土、アルミナ、ゼオライト、炭素及びその他の担体に担持させた触媒及び錯体触媒などが挙げられる。
【００２５】
具体的には、パラジウム−炭素、ルテニウム−炭素、ロジウム−炭素、白金−炭素、パラジウム−アルミナ、ルテニウム−アルミナ、ロジウム−アルミナ、白金−アルミナ、還元ニッケル、還元コバルト、ラネーニッケル、ラネーコバルト、ラネー銅、酸化銅、銅クロマイト、クロロトリス（トリフェニルホスフィン）ロジウム、クロロヒドリドトリス（トリフェニルホスフィン）ルテニウム、ジクロロトリス（トリフェニルホスフィン）ルテニウム及びヒドリドカルボニルトリス（トリフェニルホスフィン）イリジウムなどが挙げられる。これらの中で特に好ましいものはパラジウム−炭素及びルテニウム−炭素である。
【００２６】
触媒の使用量は、５％金属担持触媒として基質に対し０．１〜３０重量％が、特には、０．５〜２０重量％が好ましい。溶媒は、メタノール、エタノール及びプロパノールなどに代表されるアルコール類、ジオキサン、テトラヒドロフラン及びジメトキシエタンなどに代表されるエーテル類、酢酸エチル及び酢酸プロピルに代表されるエステル類、アセトニトリル、プロピオニトリルなどに代表される脂肪族ニトリル類、更にベンゼン、トルエン及びキシレンなどに代表される芳香族炭化水素類及び水と前記溶媒との混合溶媒が使用できる。
【００２７】
その使用量は、原料に対し１〜５０重量倍の範囲が、特には、３〜１０重量倍の範囲が好ましい。水素圧は常圧から１０4ｋＰａの範囲が、特には、常圧から３０００ｋＰａの範囲が好ましい。反応温度は、０〜１５０℃の範囲が、特には、１０〜１００℃の範囲が好ましい。
【００２８】
反応は、水素の吸収量によって追跡することができ、理論水素量の吸収後サンプリングし液体クロマトクラフィーで分析し確認することができる。本発明は、回分式でも連続反応でも可能である。反応後は、濾過により触媒を除いた後、酸での沈澱及び再結晶を繰り返すことによって精製することができる。
【００２９】
尚、通常は、４−アミノレゾルシノールは、無機酸又は有機酸溶液で、その無機酸塩又は有機酸塩として単離する方が、４−アミノレゾルシノールの安定性上好ましいが、これを塩基によって中和すれば４−アミノレゾルシノールも容易に単離できる。以下に実施例を挙げ、本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
【００３０】
【実施例】
実施例１
水５０．０g、３５％塩酸塩酸水溶液２６．１ｇを反応器に加え、撹拌しながら、アニリン９．３ｇを滴下しアニリン塩酸塩を含む塩酸水溶液を調整した。５℃にし氷冷したアニリン塩酸塩を含む塩酸水溶液に、別途調整した、亜硝酸ソーダ６．９ｇの水５０ｇに溶かした亜硝酸ソーダ水溶液を１０℃を越えないように滴下し塩化ベンゼンジアゾニウム水溶液を調整した。
【００３１】
この調整した塩化ベンゼンジアゾニウム水溶液６４ｇを、別途調整した、メタノール３３０ｇ、レゾルシノール１１．０ｇ、３３．３％苛性ソーダ水溶液７ｍｌを混合した溶液に滴下し、更に３３．３％苛性ソーダ水溶液２．５ｍｌを加えた。そして、塩化ベンゼンジアゾニウム水溶液２６ｇを滴下し、３３．３％苛性ソーダ水溶液２．５ｍｌを加えた。更に塩化ベンゼンジアゾニウム水溶液２６ｇを滴下し、３３．３％苛性ソーダ水溶液２．５ｍｌを加えｐＨ７付近に調整した。この滴下終了後、室温で撹拌しながら、１時間反応させた。
【００３２】
反応混合物からのメタノールを減圧留去し、１７．４重量％の炭酸ソーダ水溶液１２１ｇを加え、更にクロロホルム１５０ｇを加え室温で１０分間撹拌し分液した。下層のクロロホルム層を抜き出し、再びクロロホルム５０ｇを加え、同様に分液操作をした。上層の水層を撹拌しながら、この水層に３５％塩酸水溶液５６．０ｇを滴下し、ｐＨ２付近にし、結晶を析出させた。この結晶をろ過し、ろ過ケーキを温水３００ｇで洗浄した後、ろ過ケーキを反応器に取りだし、メタノール２００ｇ加え、撹拌しながら５５℃に加熱し、溶解させた。そして、水２００ｇを加え、撹拌しながら室温に戻した。析出した結晶をろ過し、ろ過ケーキを取りだし、減圧乾燥して、純度９９．５％の４−フェニルアゾレゾルシノール１９．２ｇが得られた。収率９０％
【００３３】
実施例２
実施例１の方法を繰り返して得た４−フェニルアゾレゾルシノール２１．４ｇ、トルエン１６０．５ｇ、イソプロパノール２１．４ｇ、水５３．５ｇ、５０％ウエット−５％パラジウムカーボン２．１４ｇ及び３５％塩酸１２．５ｇを撹拌装置、温度計を備えた反応器中に仕込んだ。容器内を窒素置換した後、続いて水素置換した後、水素を常圧で供給し、撹拌下、室温で反応させた。４．５時間後、水素の吸収が停止し、反応が終了した。反応雰囲気を窒素置換し、触媒ろ過を行い、続いて分液ロートで水層とトルエン層を分離した。得られた水層中にトルエン８０ｇを加え、分液を行った。この操作をさらにもう一度繰り返した。この分液した水層に、３５％塩酸及び塩化第一スズ水和物０．１３ｇを加え、この塩酸酸性水溶液を５℃に冷却し、析出した結晶をろ過した。得られた結晶を減圧乾燥し、純度９８．５％の４−アミノレゾルシノール一塩酸塩の結晶１３．０ｇを得た。
【００３４】
実施例３
実施例２の仕込み量の１／１０にて、ハステロイ製オートクレーブ中で、水素圧３００ｋＰａで反応を行った。１時間で水素吸収がなくなった。反応終了後、実施例２と同様な後処理操作を行い、純度９９．０％の４−アミノレゾルシノール一塩酸塩の結晶を１．２ｇを得た。
【００３５】
【発明の効果】
本発明によれば、４−（置換フェニル）アゾレゾルシノールから、あるいは置換アニリンとレゾルシノールとから、４アミノレゾルシノールまたはその塩を高収率にまた、高純度の４−アミノレゾルシノールの塩を製造することができる。更に中間体の４−（置換フェニル）アゾレゾルシノールを高選択率で得るカップリング反応させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing 4-aminoresorcinol and a salt thereof and an intermediate thereof, 4- (substituted phenyl) azoresorcinol. More specifically, the general formula (2)
[0002]
[Chemical 8]
(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a sulfo group, a cyano group, a carboxyl group, or a carboalkoxy group having 2 to 11 carbon atoms. , N is an integer of 0 to 5.) The substituted aniline represented by formula (3) is reacted with an alkali nitrite in an aqueous acid solution.
[0004]
[Chemical 9]
(Wherein, R and n are as defined formula (2), X Cl, Br, represents. A OSO 3 H or OPO 3 H 2) After generating the substituted phenyl diazonium salt represented by, formula which comprises reacting resorcinol while maintaining pH7~12 (1)
[0006]
[Chemical Formula 10]
(In the formula, R and n represent the same meaning as in formula (2).) A process for producing 4- (substituted phenyl) azoresorcinol represented by formula (4) and the 4- (substituted phenyl) azoresorcinol using a metal catalyst The present invention relates to a process for producing 4-aminoresorcinol or a salt thereof, which is hydrocracked by a catalytic reduction method.
[0008]
[Prior art]
So far, as a method for producing 4-aminoresorcinol by reduction of 4- (substituted phenyl) azoresorcinol represented by the general formula (1), a method using tin and hydrochloric acid is known (Chem. Ber., 16 (1883) 1330). This method requires a reagent amount of expensive stannous chloride, and treatment of a stannic chloride-containing aqueous hydrochloric acid solution containing organic substances has been a problem.
[0009]
Furthermore, in the process of obtaining 4- (substituted phenyl) azoresorcinol from a substituted aniline derivative, alkali nitrite and resorcinol, by-products such as isomers and bis (substituted phenyl) azoresorcinol are seen, and the selectivity of the target product is low. It was.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing 4-aminoresorcinol by a practical reduction method of 4- (substituted phenyl) azoresorcinol and a coupling method for obtaining 4- (substituted phenyl) azoresorcinol as a raw material with high selectivity. On offer.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention relates to the general formula (2)
[0012]
Embedded image
(In the formula, R and n have the same meaning as in formula (1).) A substituted aniline represented by formula (3) is reacted with an alkali nitrite in an acid aqueous solution to form a general formula (3)
[0014]
Embedded image
(Wherein R and n represent the same meaning as in formula (1), X represents Cl, Br, OSO 3 H or OPO 3 H 2 ), and then a substituted phenyldiazonium salt represented by pH7~12 reacted with resorcinol while maintaining represented by the general formula (1) 4- give (substituted phenyl) azo resorcinol, decomposed hydrogenated using the 4- (substituted phenyl) azo resorcinol metal catalyst The present invention relates to a process for producing 4-aminoresorcinol or a salt thereof.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
First, a method for producing 4- (substituted phenyl) azoresorcinol represented by the general formula (1) as a raw material for the reduction reaction will be described. A method for producing 4- (substituted phenyl) azoresorcinol is represented by the following reaction formula.
[0017]
Embedded image
(In the formula, R, n and X represent the same meaning as described above. A represents an alkali metal.)
R of the aniline derivative represented by the general formula (2) used in the present invention is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a sulfonic acid group, a cyano group, or a carboxyl group. Represents a carboalkoxy group having 2 to 11 carbon atoms, and n is an integer of 0 to 5. Specifically, aniline, toluidine, anisidine, dimethylaniline, ethylaniline, trimethylaniline, propylaniline, butylaniline, fluoroaniline, chloraniline, bromoaniline, aniline benzoic acid and its esters, cyanoaniline, trifluoromethylaniline Etc. Particularly preferred is aniline.
[0019]
Examples of the alkali nitrite represented by ANO 2 include lithium nitrite, sodium nitrite, and potassium nitrite. In particular, inexpensive sodium nitrite is preferable. The amount used is 1 to 2 equivalents, more preferably 1 to 1.3 equivalents, relative to the substituted aniline. The acid amount is 1 to 10 equivalents, more preferably 2 to 3 equivalents, with respect to the substituted aniline. In addition to hydrochloric acid, other acids such as hydrobromic acid, sulfuric acid and phosphoric acid can be used as the acid, but hydrochloric acid is preferred.
[0020]
The substituted phenyldiazonium salt may be produced at a reaction temperature of 0 to 20 ° C, preferably 0 to 10 ° C. In the coupling reaction between the substituted phenyldiazonium salt and resorcinol, a solution of the substituted phenyldiazonium salt is usually added dropwise to the resorcinol solution. In this case, this reaction can be carried out in an acidic manner, but it is preferably carried out from neutral to basic, since the reaction is slow and by-products are also observed. Therefore, an alkaline aqueous solution is added, and a continuous simultaneous addition method is desirable for practical use. A preferable pH range is pH 5 to 12, but it is particularly preferable to perform the coupling reaction at around pH 6 to 10. In addition, the amount of the substituted phenyldiazonium salt charged relative to resorcinol is preferably 1.0 to 1.20 mole times considering the partial decomposition of the substituted phenyldiazonium salt .
[0021]
The reaction temperature is also preferably low, and is 0 to 10 ° C. for alkali, and 0 to 60 ° C. for acid because the reaction slows down. The product is acidified after completion of the reaction, and the desired 4- (substituted phenyl) azoresorcinol can be obtained by washing with filtered water. Furthermore, when raising purity, it can refine | purify by recrystallizing from solvent, such as methanol / water, toluene, a dioxane, after acid extraction after extracting with sodium carbonate aqueous solution.
[0022]
Next, the reduction process of 4- (substituted phenyl) azoresorcinol will be described.
[0023]
Embedded image
As the catalyst, Group 8 palladium, ruthenium, rhodium, platinum, nickel, cobalt and iron, Group 1 copper, etc. can be used. These metals are used alone or in multicomponent systems complexed with other elements. Examples of their use include single metals, Raney-type catalysts, diatomaceous earth, alumina, zeolite, carbon and other catalysts supported on carriers and complex catalysts.
[0025]
Specifically, palladium-carbon, ruthenium-carbon, rhodium-carbon, platinum-carbon, palladium-alumina, ruthenium-alumina, rhodium-alumina, platinum-alumina, reduced nickel, reduced cobalt, Raney nickel, Raney cobalt, Raney copper , Copper oxide, copper chromite, chlorotris (triphenylphosphine) rhodium, chlorohydridotris (triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) ruthenium, and hydridocarbonyltris (triphenylphosphine) iridium. Of these, palladium-carbon and ruthenium-carbon are particularly preferred.
[0026]
The amount of the catalyst used is preferably 0.1 to 30% by weight, particularly 0.5 to 20% by weight based on the substrate as a 5% metal-supported catalyst. Solvents include alcohols typified by methanol, ethanol and propanol, ethers typified by dioxane, tetrahydrofuran and dimethoxyethane, esters typified by ethyl acetate and propyl acetate, acetonitrile, propionitrile and the like. Aliphatic nitriles, aromatic hydrocarbons represented by benzene, toluene, xylene and the like, and mixed solvents of water and the above solvents can be used.
[0027]
The amount used is preferably in the range of 1 to 50 times by weight, particularly in the range of 3 to 10 times by weight with respect to the raw material. The hydrogen pressure is preferably in the range of normal pressure to 10 4 kPa, and particularly preferably in the range of normal pressure to 3000 kPa. The reaction temperature is preferably in the range of 0 to 150 ° C, particularly preferably in the range of 10 to 100 ° C.
[0028]
The reaction can be traced by the amount of hydrogen absorbed, and can be confirmed by sampling after absorption of the theoretical amount of hydrogen, and analyzing by liquid chromatography. The present invention can be used batchwise or continuously. After the reaction, the catalyst can be removed by filtration, followed by purification by repeated precipitation with acid and recrystallization.
[0029]
Normally, 4-aminoresorcinol is preferably isolated as an inorganic acid salt or organic acid salt with an inorganic acid or organic acid solution in terms of the stability of 4-aminoresorcinol. 4-aminoresorcinol can be easily isolated by adding. EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0030]
【Example】
Example 1
50.0 g of water and 26.1 g of 35% hydrochloric acid aqueous hydrochloric acid solution were added to the reactor, and 9.3 g of aniline was added dropwise with stirring to prepare an aqueous hydrochloric acid solution containing aniline hydrochloride. A sodium nitrite aqueous solution dissolved in 50 g of sodium nitrite 6.9 g of water was added dropwise to a hydrochloric acid aqueous solution containing aniline hydrochloride cooled to 5 ° C. with ice cooling so as not to exceed 10 ° C., and a benzenediazonium chloride aqueous solution was added. It was adjusted.
[0031]
64 g of this adjusted aqueous solution of benzenediazonium chloride was added dropwise to a solution prepared by mixing 330 g of methanol, 11.0 g of resorcinol and 7 ml of 33.3% aqueous sodium hydroxide solution, and 2.5 ml of 33.3% aqueous sodium hydroxide solution was further added. . Then, 26 g of a benzenediazonium chloride aqueous solution was dropped, and 2.5 ml of a 33.3% caustic soda aqueous solution was added. Further, 26 g of a benzenediazonium chloride aqueous solution was added dropwise, and 2.5 ml of 33.3% aqueous sodium hydroxide solution was added to adjust the pH to around 7. After completion of the dropping, the reaction was allowed to proceed for 1 hour with stirring at room temperature.
[0032]
Methanol from the reaction mixture was distilled off under reduced pressure, 121 g of a 17.4% by weight aqueous sodium carbonate solution was added, 150 g of chloroform was further added, and the mixture was stirred at room temperature for 10 minutes and separated. The lower chloroform layer was extracted, 50 g of chloroform was added again, and a liquid separation operation was performed in the same manner. While stirring the upper aqueous layer, 56.0 g of 35% aqueous hydrochloric acid solution was added dropwise to this aqueous layer to adjust the pH to around 2 to precipitate crystals. The crystals were filtered, and the filter cake was washed with 300 g of hot water. The filter cake was taken out into a reactor, 200 g of methanol was added, and the mixture was heated to 55 ° C. with stirring to be dissolved. And 200g of water was added and it returned to room temperature, stirring. The precipitated crystals were filtered, and the filter cake was taken out and dried under reduced pressure to obtain 19.2 g of 4-phenylazoresorcinol having a purity of 99.5%. Yield 90%
[0033]
Example 2
4-phenylazoresorcinol 21.4 g obtained by repeating the method of Example 1, toluene 160.5 g, isopropanol 21.4 g, water 53.5 g, 50% wet-5% palladium carbon 2.14 g and 35% hydrochloric acid 12 .5 g was charged into a reactor equipped with a stirrer and a thermometer. After substituting the inside of the container with nitrogen and subsequently substituting with hydrogen, hydrogen was supplied at normal pressure and reacted at room temperature with stirring. After 4.5 hours, hydrogen absorption stopped and the reaction was completed. The reaction atmosphere was replaced with nitrogen, catalyst filtration was performed, and then the aqueous layer and the toluene layer were separated with a separatory funnel. To the obtained aqueous layer, 80 g of toluene was added for liquid separation. This operation was repeated once more. To this separated aqueous layer, 35% hydrochloric acid and stannous chloride hydrate (0.13 g) were added, the hydrochloric acid aqueous solution was cooled to 5 ° C., and the precipitated crystals were filtered. The obtained crystals were dried under reduced pressure to obtain 13.0 g of 4-aminoresorcinol monohydrochloride crystals having a purity of 98.5%.
[0034]
Example 3
The reaction was carried out at 1/10 the charge of Example 2 in a Hastelloy autoclave at a hydrogen pressure of 300 kPa. Hydrogen absorption disappeared in 1 hour. After completion of the reaction, the same post-treatment operation as in Example 2 was performed to obtain 1.2 g of 4-aminoresorcinol monohydrochloride crystals having a purity of 99.0%.
[0035]
【The invention's effect】
According to the present invention, 4-aminoresorcinol or a salt thereof is produced in high yield from 4- (substituted phenyl) azoresorcinol or from substituted aniline and resorcinol, and also to produce a highly pure salt of 4-aminoresorcinol. Can do. Furthermore, it is possible to carry out a coupling reaction to obtain an intermediate 4- (substituted phenyl) azoresorcinol with high selectivity.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32431997A JP4072651B2 (en) | 1997-11-26 | 1997-11-26 | Process for producing 4-aminoresorcinol or a salt thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32431997A JP4072651B2 (en) | 1997-11-26 | 1997-11-26 | Process for producing 4-aminoresorcinol or a salt thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11158124A JPH11158124A (en) | 1999-06-15 |
| JP4072651B2 true JP4072651B2 (en) | 2008-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP32431997A Expired - Lifetime JP4072651B2 (en) | 1997-11-26 | 1997-11-26 | Process for producing 4-aminoresorcinol or a salt thereof |
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| JP5581927B2 (en) * | 2010-09-14 | 2014-09-03 | オリヱント化学工業株式会社 | Process for producing 4-amino-m-cresol |
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