JP2000095740A - Production of n-alkyl substituted aromatic amino compound - Google Patents
Production of n-alkyl substituted aromatic amino compoundInfo
- Publication number
- JP2000095740A JP2000095740A JP10273619A JP27361998A JP2000095740A JP 2000095740 A JP2000095740 A JP 2000095740A JP 10273619 A JP10273619 A JP 10273619A JP 27361998 A JP27361998 A JP 27361998A JP 2000095740 A JP2000095740 A JP 2000095740A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- aromatic amino
- amino compound
- paraformaldehyde
- hydrogen
- 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.)
- Pending
Links
- -1 aromatic amino compound Chemical class 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 25
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 27
- 238000005932 reductive alkylation reaction Methods 0.000 claims description 15
- NEGFNJRAUMCZMY-UHFFFAOYSA-N 3-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC(C(O)=O)=C1 NEGFNJRAUMCZMY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 10
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 claims description 6
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 description 3
- ZCCNWBPFIBQFQX-UHFFFAOYSA-N 3-(methylamino)benzoic acid Chemical compound CNC1=CC=CC(C(O)=O)=C1 ZCCNWBPFIBQFQX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- WVMBPWMAQDVZCM-UHFFFAOYSA-N N-methylanthranilic acid Chemical compound CNC1=CC=CC=C1C(O)=O WVMBPWMAQDVZCM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- ULHFFAFDSSHFDA-UHFFFAOYSA-N 1-amino-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1N ULHFFAFDSSHFDA-UHFFFAOYSA-N 0.000 description 1
- MYGRPGMUMHJDGG-UHFFFAOYSA-N 1-aminocyclohexa-3,5-diene-1,3-diol Chemical compound NC1(O)CC(O)=CC=C1 MYGRPGMUMHJDGG-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- DVVXXHVHGGWWPE-UHFFFAOYSA-N 2-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC=C1C(O)=O DVVXXHVHGGWWPE-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- WASQBNCGNUTVNI-UHFFFAOYSA-N 2-amino-4,6-dichlorophenol Chemical compound NC1=CC(Cl)=CC(Cl)=C1O WASQBNCGNUTVNI-UHFFFAOYSA-N 0.000 description 1
- JEPCLNGRAIMPQV-UHFFFAOYSA-N 2-aminobenzene-1,3-diol Chemical compound NC1=C(O)C=CC=C1O JEPCLNGRAIMPQV-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- CKQHAYFOPRIUOM-UHFFFAOYSA-N 3'-Aminoacetophenone Chemical compound CC(=O)C1=CC=CC(N)=C1 CKQHAYFOPRIUOM-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- QMIJLOSXZVDDAT-UHFFFAOYSA-N 3-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=CC(N)=CC(O)=C21 QMIJLOSXZVDDAT-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- WEZAHYDFZNTGKE-UHFFFAOYSA-N 3-ethoxyaniline Chemical compound CCOC1=CC=CC(N)=C1 WEZAHYDFZNTGKE-UHFFFAOYSA-N 0.000 description 1
- AMKPQMFZCBTTAT-UHFFFAOYSA-N 3-ethylaniline Chemical compound CCC1=CC=CC(N)=C1 AMKPQMFZCBTTAT-UHFFFAOYSA-N 0.000 description 1
- MBDUKNCPOPMRJQ-UHFFFAOYSA-N 4-amino-2-chlorobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(Cl)=C1 MBDUKNCPOPMRJQ-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- ROCVGJLXIARCAC-UHFFFAOYSA-N 4-aminobenzene-1,3-diol Chemical compound NC1=CC=C(O)C=C1O ROCVGJLXIARCAC-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000013078 crystal Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、染料、色素、顔料
などの中間体として有用なＮ−アルキル置換芳香族アミ
ノ化合物の製造方法に関する。[0001] The present invention relates to a method for producing an N-alkyl-substituted aromatic amino compound useful as an intermediate such as a dye, a pigment or a pigment.
【０００２】[0002]
【従来の技術】芳香族アミノ化合物にホルムアルデヒド
と水素を用いて還元アルキル化を行ない、Ｎ−アルキル
置換芳香族アミノ化合物を得る製造法は数多く知られて
いる。例えば、多量のパラジウム／カ−ボン触媒の存在
下、３−アミノ安息香酸のアルカリ性水溶液にホルマリ
ンを逐次的に供給し、還元アルキル化する方法（特開昭
５２−７１４２４号公報）、有効量のパラジウム触媒及
び酢酸の存在下にメタノ−ル溶媒中で３−ニトロ安息香
酸を水添したのち、メチルホルムセル溶液（ホルムアル
デヒドのメタノ−ル溶液）を供給して還元アルキル化す
る方法（特開昭５５−２０７７３号公報）、パラジウム
／カ−ボン触媒の存在下、エタノ−ル溶媒中で３−ニト
ロ安息香酸を水添したのち、ホルマリンを誘導期を除き
水素の吸収に対応して供給し還元アルキル化する方法
（特開昭５７−８１４４４号公報）などが知られてい
る。これらの製法は多量の触媒を必要とする点や反応完
結に長時間を要することなどから経済的な製法としては
満足できるものではなかった。また反応の方法として
は、ホルムアルデヒドが触媒毒となることを避けるた
め、芳香族アミノ化合物存在下にホルムアルデヒドの供
給速度を規制しながら、加圧下の反応釜中に装入してい
く方法を行なっている。この様な反応方法は工業的見地
から考えると、反応機の他にホルムアルデヒドを装入す
るための付帯設備が必要になるなど、設備的な面から見
ても経済的ではなく、満足のいく製法とはいえなかっ
た。2. Description of the Related Art There are many known methods for producing an N-alkyl-substituted aromatic amino compound by subjecting an aromatic amino compound to reductive alkylation using formaldehyde and hydrogen. For example, a method of sequentially supplying formalin to an aqueous alkaline solution of 3-aminobenzoic acid in the presence of a large amount of a palladium / carbon catalyst to carry out reductive alkylation (JP-A-52-71424). A method of hydrogenating 3-nitrobenzoic acid in a methanol solvent in the presence of a palladium catalyst and acetic acid, followed by supplying a methylformel solution (formaldehyde solution in methanol) to carry out reductive alkylation (Japanese Patent Laid-Open No. No. 55-20773), hydrogenation of 3-nitrobenzoic acid in an ethanol solvent in the presence of a palladium / carbon catalyst, and then formalin is supplied in response to the absorption of hydrogen except for the induction period and reduced. An alkylation method (JP-A-57-81444) and the like are known. These processes are not satisfactory as economical processes because they require a large amount of catalyst and require a long time to complete the reaction. As a reaction method, in order to prevent formaldehyde from becoming a catalyst poison, a method of charging the reaction vessel under pressure while controlling the supply rate of formaldehyde in the presence of the aromatic amino compound was performed. I have. From the industrial point of view, such a reaction method is not economical in terms of equipment, such as requiring additional equipment for charging formaldehyde in addition to the reactor. I couldn't say.
【０００３】[0003]
【発明が解決しようとする課題】本発明の課題は、反応
が極めて短時間、且つ高収率で進行し、工業的にも有用
なＮ−アルキル置換芳香族アミノ化合物の製造方法を提
供することである。An object of the present invention is to provide a process for producing an N-alkyl-substituted aromatic amino compound which is industrially useful, in which the reaction proceeds in a very short time and in a high yield. It is.
【０００４】[0004]
【課題を解決するための手段】本発明者等は上記した課
題を解決するために鋭意検討した結果、パラホルムアル
デヒドが触媒毒とならないことを見出し本発明に到っ
た。つまり、芳香族アミノ化合物に有機溶媒中、パラホ
ルムアルデヒド及び水素を反応させることにより、更に
は、芳香族ニトロ化合物とパラホルムアルデヒド共存
下、有機溶媒中貴金属触媒存在下に水素による還元及び
還元アルキル化反応を行なうことにより、短時間、高収
率でＮ−アルキル置換芳香族アミノ化合物が得られるこ
とを見出し、本発明を完成するに到った。Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that paraformaldehyde does not become a catalyst poison, and arrived at the present invention. In other words, by reacting an aromatic amino compound with paraformaldehyde and hydrogen in an organic solvent, furthermore, in the presence of an aromatic nitro compound and paraformaldehyde, a reduction and reductive alkylation reaction with hydrogen in the presence of a noble metal catalyst in an organic solvent. By carrying out, the present inventors have found that an N-alkyl-substituted aromatic amino compound can be obtained in a short time and with high yield, and have completed the present invention.
【０００５】即ち、本発明は、（１）芳香族アミノ化合
物に、有機溶媒中、パラホルムアルデヒド及び水素を反
応させることを特徴とするＮ−アルキル置換芳香族アミ
ノ化合物の製造方法、（２）芳香族アミノ化合物が、ｍ
−アミノ安息香酸である（１）記載の製造方法、（３）
有機溶媒がメタノ−ルである（１）記載の製造方法、
（４）Ｎ−アルキル置換芳香族アミノ化合物が、ｍ−ジ
メチルアミノ安息香酸である（１）記載の製造方法、
（５）反応温度が６０〜１１０℃である（１）〜（４）
記載の製造方法、（６）芳香族ニトロ化合物にパラホル
ムアルデヒドを加え、有機溶媒中貴金属触媒存在下、水
素と反応させることにより還元反応、次いで還元アルキ
ル化反応を行なうことを特徴とするＮ−アルキル置換芳
香族アミノ化合物の製造方法、（７）芳香族ニトロ化合
物がｍ−ニトロ安息香酸である（６）記載の製造方法、
（８）有機溶媒がメタノ−ルである（６）記載の方法、
（９）Ｎ−アルキル置換芳香族アミノ化合物がｍ−ジメ
チルアミノ安息香酸である（６）記載の製造方法、（１
０）芳香族ニトロ化合物の還元反応を６０℃以下で行な
い、パラホルムアルデヒドとの還元アルキル化反応を６
０〜１１０℃で行なうことを特徴とする（６）〜（９）
記載の製造方法に関する。That is, the present invention provides (1) a method for producing an N-alkyl-substituted aromatic amino compound, which comprises reacting an aromatic amino compound with paraformaldehyde and hydrogen in an organic solvent; Group m amino compound is m
-The production method according to (1), which is aminobenzoic acid, (3)
(1) The method according to (1), wherein the organic solvent is methanol.
(4) The method according to (1), wherein the N-alkyl-substituted aromatic amino compound is m-dimethylaminobenzoic acid.
(5) The reaction temperature is from 60 to 110 ° C (1) to (4).
(6) N-alkyl characterized by performing a reduction reaction by adding paraformaldehyde to an aromatic nitro compound and reacting with hydrogen in an organic solvent in the presence of a noble metal catalyst, followed by a reductive alkylation reaction. A process for producing a substituted aromatic amino compound, (7) the process for producing (6), wherein the aromatic nitro compound is m-nitrobenzoic acid,
(8) The method according to (6), wherein the organic solvent is methanol.
(9) The method according to (6), wherein the N-alkyl-substituted aromatic amino compound is m-dimethylaminobenzoic acid.
0) The reduction reaction of the aromatic nitro compound is carried out at 60 ° C. or lower, and the reductive alkylation reaction with paraformaldehyde is carried out at 6 ° C.
(6) to (9), which is performed at 0 to 110 ° C.
The present invention relates to the production method described above.
【０００６】[0006]
【発明の実施の形態】以下に、具体的に本発明を説明す
る。本発明において実施される反応の形態としては、例
えば芳香族アミノ化合物を有機溶媒中に溶解させ、貴
金属触媒及びパラホルムアルデヒドを装入し、水素を供
給して６０〜１１０℃で反応させる方法、芳香族ニト
ロ化合物を有機溶媒中に溶解させ、貴金属触媒及びパラ
ホルムアルデヒドを装入し、水素を供給して０〜６０℃
でニトロ基の還元を行なったのち、６０〜１１０℃で還
元アルキル化反応を実施する方法等が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. Examples of the form of the reaction performed in the present invention include a method in which an aromatic amino compound is dissolved in an organic solvent, a noble metal catalyst and paraformaldehyde are charged, hydrogen is supplied, and the reaction is performed at 60 to 110 ° C. A group nitro compound is dissolved in an organic solvent, a noble metal catalyst and paraformaldehyde are charged, hydrogen is supplied and
And then a reductive alkylation reaction at 60 to 110 ° C.
【０００７】本発明における原料である芳香族アミノ化
合物の置換基は、置換基として、カルボキシル基、スル
ホン酸基、水酸基、アルキル基、アルコキシ基、アシル
基、ハロゲン原子等の反応に不活性な置換基を有してい
ても良い。In the present invention, the substituent of the aromatic amino compound, which is a raw material, is a substituent which is inactive to a reaction such as a carboxyl group, a sulfonic acid group, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, and a halogen atom. It may have a group.
【０００８】この様な化合物としては、例えば２−アミ
ノ安息香酸、３−アミノ安息香酸、４−アミノ安息香
酸、Ｎ−メチル−２−アミノ安息香酸、２，３−ジアミ
ノ安息香酸、２−アミノベンゼンスルホン酸、３−アミ
ノベンゼンスルホン酸、４−アミノベンゼンスルホン
酸、２−アミノフェノ−ル、３−アミノフェノ−ル、４
−アミノフェノ−ル、２−アミノレゾルシン、３−アミ
ノレゾルシン、４−アミノレゾルシン、ｏ−トルイジ
ン、ｍ−トルイジン、ｐ−トルイジン、２−エチルアニ
リン、３−エチルアニリン、４−エチルアニリン、ｏ−
フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フ
ェニレンジアミン、２−メトキシアニリン、３−メトキ
シアニリン、４−メトキシアニリン、２−エトキシアニ
リン、３−エトキシアニリン、４−エトキシアニリン、
２−アミノアセトフェノン、３−アミノアセトフェノ
ン、４−アミノアセトフェノン、２−クロロアニリン、
３−クロロアニリン、４−クロロアニリン、４，６−ジ
クロロ−２−アミノフェノ−ル、２−クロロ−４−アミ
ノ安息香酸、３−アミノ−１−ナフト−ル等が挙げられ
が、これらに限定されるものではない。Examples of such compounds include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, N-methyl-2-aminobenzoic acid, 2,3-diaminobenzoic acid, and 2-aminobenzoic acid. Benzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminophenol, 3-aminophenol, 4
-Aminophenol, 2-aminoresorcin, 3-aminoresorcin, 4-aminoresorcin, o-toluidine, m-toluidine, p-toluidine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, o-
Phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-ethoxyaniline, 3-ethoxyaniline, 4-ethoxyaniline,
2-aminoacetophenone, 3-aminoacetophenone, 4-aminoacetophenone, 2-chloroaniline,
3-chloroaniline, 4-chloroaniline, 4,6-dichloro-2-aminophenol, 2-chloro-4-aminobenzoic acid, 3-amino-1-naphthol, and the like, but are not limited thereto. It is not something to be done.
【０００９】また、これらの芳香族アミノ化合物の前駆
体、即ち反応系において水素添加されてこれらのアミン
を形成する芳香族ニトロ化合物も、原料として使用する
ことができる。本発明における芳香族ニトロ化合物と
は、前記芳香族アミノ化合物に対応するニトロ化合物を
表す。Also, precursors of these aromatic amino compounds, that is, aromatic nitro compounds which form hydrogen by being hydrogenated in the reaction system, can be used as raw materials. The aromatic nitro compound in the present invention represents a nitro compound corresponding to the aromatic amino compound.
【００１０】反応に使用される貴金属触媒としては、例
えばラネ−ニッケル、酸化白金、銅−クロム酸化物、ニ
ッケル、白金、パラジウム等の金属を担体に担持させた
触媒など、通常の水添反応に使用される任意のものを使
用することができるが、その中でもパラジウム／カ−ボ
ン担持触媒が好ましい。The noble metal catalyst used in the reaction includes, for example, a catalyst in which a metal such as Raney-nickel, platinum oxide, copper-chromium oxide, nickel, platinum and palladium is supported on a carrier. Any of those used can be used, but among them, a palladium / carbon supported catalyst is preferred.
【００１１】反応に使用される貴金属触媒の使用量とし
ては、使用する原料に対し金属原子として０．００５〜
０．５ｗｔ％、好ましくは０．０２５〜０．１ｗｔ％で
ある。The amount of the noble metal catalyst used in the reaction is from 0.005 to 5
0.5 wt%, preferably 0.025 to 0.1 wt%.
【００１２】反応に使用される有機溶媒としては、メタ
ノ−ル、エタノ−ル、イソプロピルアルコ−ル等のアル
コ−ル系溶媒、及び１，３−ジメチル−２−イミダゾリ
ジノン、Ｎ，Ｎ−ジメチルホルムアミドなどの極性溶媒
などを用いることができる。その中でも使用する原料に
対して高い溶解度を有し、さらに溶媒回収の容易さなど
から考慮するとメタノ−ルが好ましい。The organic solvent used in the reaction includes alcohol solvents such as methanol, ethanol and isopropyl alcohol, and 1,3-dimethyl-2-imidazolidinone, N, N- A polar solvent such as dimethylformamide can be used. Among them, methanol has a high solubility in the raw materials used, and methanol is preferable in consideration of ease of solvent recovery.
【００１３】溶媒の使用量は使用する原料に対して２〜
１０倍重量、好ましくは４〜８倍重量である。この範囲
内では、反応は良好に進行する。The amount of the solvent used is 2 to the raw materials used.
The weight is 10 times, preferably 4 to 8 times the weight. Within this range, the reaction proceeds well.
【００１４】本発明における反応温度は、芳香族ニトロ
化合物を原料として使用した場合、ニトロ基の還元反応
は６０℃以下、好ましくは０〜５０℃で実施される。こ
の温度範囲内では、反応は発熱を伴って速やかに進行す
る。また、ニトロ基を還元するに必要な理論水素吸収量
に達したところで、水素吸収が停止し、発熱もなくなる
ことから還元反応の終点を確認することができる。この
温度を越えて還元を行なった場合、ニトロ基の還元が終
了しないうちに、パラホルムアルデヒドの分解が進行
し、副反応が促進されるため好ましくない。In the present invention, when an aromatic nitro compound is used as a raw material, the reduction reaction of the nitro group is carried out at 60 ° C. or lower, preferably 0 to 50 ° C. Within this temperature range, the reaction proceeds rapidly with exotherm. Further, when the theoretical amount of hydrogen absorption necessary for reducing the nitro group is reached, the absorption of hydrogen is stopped and no heat is generated, so that the end point of the reduction reaction can be confirmed. If the reduction is carried out over this temperature, the decomposition of paraformaldehyde proceeds before the reduction of the nitro group is completed, and a side reaction is unfavorably promoted.
【００１５】続くパラホルムアルデヒドとの還元アルキ
ル化反応は６０〜１１０℃で実施されるが、より好まし
くは７０〜１００℃である。反応温度が６０℃より低い
場合はパラホルムアルデヒド分解速度の低下、及び反応
速度の低下を招き、反応中間体が反応系内に滞留し易く
なるなどして副反応を促進し、好ましくない。また、反
応温度が１１０℃より高い場合は、反応時間は短くなる
ものの、副生物の生成が増大し、これらの副生物が触媒
を被毒して触媒活性を低下させるため好ましくない。[0015] The subsequent reductive alkylation reaction with paraformaldehyde is carried out at 60 to 110 ° C, more preferably at 70 to 100 ° C. If the reaction temperature is lower than 60 ° C., the rate of decomposition of paraformaldehyde and the rate of reaction are reduced, and the reaction intermediate is liable to stay in the reaction system. On the other hand, when the reaction temperature is higher than 110 ° C., although the reaction time is shortened, the generation of by-products increases, and these by-products poison the catalyst and lower the catalytic activity, which is not preferable.
【００１６】原料に芳香族アミンを使用する場合は反応
温度を６０〜１１０℃、より好ましくは７０〜１００℃
で反応を開始することにより、本発明の効果が得られ
る。When an aromatic amine is used as a raw material, the reaction temperature is 60 to 110 ° C., more preferably 70 to 100 ° C.
The effect of the present invention can be obtained by initiating the reaction.
【００１７】本発明は常圧でも行なえるが、水素加圧下
で行なうのが有利であり、通常、常圧〜１０ｋｇ／ｃｍ
2（常圧〜０．９８ＭＰａ）、好ましくは３〜５ｋｇ／
ｃｍ2（０．２９〜０．４９ＭＰａ）の範囲である。Although the present invention can be carried out at normal pressure, it is advantageous to carry out the reaction under hydrogen pressure, and usually, normal pressure to 10 kg / cm.
2 (normal pressure to 0.98 MPa), preferably 3 to 5 kg /
cm 2 (0.29 to 0.49 MPa).
【００１８】本発明で使用されるパラホルムアルデヒド
はｎ＝８〜１００のホルムアルデヒドの重合体であっ
て、ポリオキシメチレングリコ−ルの混合物である。使
用するパラホルムアルデヒドの純度としては特に規定は
されないが、６０％以上が好ましく、より好ましくは８
０％以上であれば良好に反応は進行する。パラホルムア
ルデヒドの形状は、粒状でも微粉でも良く、本発明にお
いては特に限定されない。The paraformaldehyde used in the present invention is a polymer of formaldehyde where n = 8 to 100, and is a mixture of polyoxymethylene glycol. Although the purity of paraformaldehyde used is not particularly limited, it is preferably 60% or more, more preferably 8% or more.
If it is 0% or more, the reaction proceeds well. The form of paraformaldehyde may be granular or fine powder, and is not particularly limited in the present invention.
【００１９】パラホルムアルデヒドの使用量は原料のア
ミノ基、もしくはニトロ基に対して２倍モル以上あれば
良く、好ましくは２倍モル〜２．２倍モルで十分であ
る。The amount of paraformaldehyde used should be at least twice the molar amount of the amino group or nitro group of the raw material, and preferably 2 to 2.2 times the molar amount.
【００２０】本発明は理論量の水素が吸収された時点を
反応終了点とする。反応終了マスからの目的生成物の取
り出しは、まず触媒を沈降分離や濾過等の手段で反応液
から分離する。分離した反応液は生成物が常温で液体の
場合は蒸留等の方法で取り出すことができ、目的生成物
が常温で固体の場合は、反応液をそのまま冷却し再結晶
するか、或いは溶媒を濃縮乾固させるなどして生成物の
結晶を得ることができる。In the present invention, the point at which the theoretical amount of hydrogen has been absorbed is defined as the reaction end point. To take out the target product from the reaction-completed mass, first, the catalyst is separated from the reaction solution by means such as sedimentation or filtration. The separated reaction solution can be taken out by distillation or the like if the product is liquid at room temperature. If the target product is solid at room temperature, the reaction solution can be cooled and recrystallized, or the solvent can be concentrated. The crystals of the product can be obtained, for example, by drying.
【００２１】[0021]
【実施例】以下、実施例により本発明をさらに具体的に
説明するが、本発明は実施例のみに限定されるものでは
ない。 （実施例１）０．５ｌのオ−トクレ−ブに３−ニトロ安
息香酸２５．１ｇと５％Ｐｄ／Ｃ（エヌ・イ−・ケムキ
ャット社製／５０％ｗｅｔ品）０．５ｇ、純度９４％の
パラホルムアルデヒド（水分６％含有）９．６ｇをメタ
ノ−ル１００．４ｇとともに仕込み、窒素置換終了後、
水素で置換したのち圧力を５ｋｇ／ｃｍ2（０．４９Ｍ
Ｐａ）まで昇圧した。室温で攪拌を開始したところ、同
時に水素吸収及び発熱が見られ、原料に対して３倍モル
の水素を吸収したところで、水素の吸収は止まった。こ
の間反応温度は最高４８℃まで上がったところで低下し
始めた。この時、反応開始から１６分経過していた（還
元反応）。その後、温度を１００℃に昇温すると再び水
素吸収が始まり、約３０分で原料に対して２倍モルの水
素を吸収し、水素の吸収が停止した（還元アルキル化反
応）。同温度で３０分熟成したのち、反応液を濾過して
触媒を分離した。得られた反応液を液体クロマトグラフ
ィ−で定量分析したところ、３−ジメチルアミノ安息香
酸の生成量は２４．１６ｇ（収率９７．５％）であり、
３−モノメチルアミノ安息香酸の生成は見られなかっ
た。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to Examples. (Example 1) In 0.5 l of autoclave, 25.1 g of 3-nitrobenzoic acid and 0.5 g of 5% Pd / C (manufactured by N-Chemcat / 50% wet product), purity 94 % Paraformaldehyde (water content 6%) 9.6 g was charged together with methanol 100.4 g.
After replacing with hydrogen, the pressure was increased to 5 kg / cm 2 (0.49M
The pressure was increased to Pa). When stirring was started at room temperature, hydrogen absorption and heat generation were observed at the same time, and absorption of hydrogen stopped when hydrogen was absorbed three times the amount of the raw material. During this time, the reaction temperature began to drop when it rose to a maximum of 48 ° C. At this time, 16 minutes had elapsed since the start of the reaction (reduction reaction). Thereafter, when the temperature was raised to 100 ° C., hydrogen absorption started again, and in about 30 minutes, twice the amount of hydrogen with respect to the raw material was absorbed, and the absorption of hydrogen was stopped (reductive alkylation reaction). After aging at the same temperature for 30 minutes, the reaction solution was filtered to separate the catalyst. When the obtained reaction solution was quantitatively analyzed by liquid chromatography, the amount of 3-dimethylaminobenzoic acid produced was 24.16 g (yield 97.5%),
No formation of 3-monomethylaminobenzoic acid was observed.
【００２２】（実施例２）０．５ｌのオ−トクレ−ブに
３−アミノ安息香酸２０．７ｇと５％Ｐｄ／Ｃ（５０％
ｗｅｔ品）０．５ｇ、純度９４％のパラホルムアルデヒ
ド９．６ｇをメタノ−ル１００．４ｇとともに仕込み、
窒素置換終了後、水素置換したのち圧力を５ｋｇ／ｃｍ
2まで昇圧した。室温で攪拌を開始し、そのまま１００
℃に昇温して反応を行なったところ、約６０分で原料に
対して２倍モルの水素を吸収し、水素の吸収が停止した
（還元アルキル化反応）。そのまま３０分熟成したの
ち、反応液を濾過して触媒を分離した。得られた反応液
を液体クロマトグラフィ−で定量分析したところ、３−
ジメチルアミノ安息香酸の生成量は２４．０４ｇ（収率
９７．０％）であり、モノメチル安息香酸の生成は見ら
れなかった。(Example 2) In 0.5 l of autoclave, 20.7 g of 3-aminobenzoic acid and 5% Pd / C (50%
Wet product) 0.5 g, 9.6 g of 94% pure paraformaldehyde were charged together with 100.4 g of methanol,
After completion of the nitrogen replacement, the pressure is reduced to 5 kg / cm after hydrogen replacement.
Pressurized to 2 . Start stirring at room temperature.
When the temperature was raised to ° C. and the reaction was carried out, hydrogen was absorbed twice as much as the raw material in about 60 minutes, and the absorption of hydrogen was stopped (reductive alkylation reaction). After aging for 30 minutes, the reaction solution was filtered to separate the catalyst. When the obtained reaction solution was quantitatively analyzed by liquid chromatography, 3-
The amount of dimethylaminobenzoic acid produced was 24.04 g (yield 97.0%), and no monomethylbenzoic acid was produced.
【００２３】（実施例３）実施例１の還元アルキル化反
応温度を１００℃から８５℃へ変更した以外は実施例１
と同様に反応を行なった。３−ジメチルアミノ安息香酸
の生成量は２３．５４ｇ（収率９５．０％）であり、３
−モノメチルアミノ安息香酸の生成量は０．６８ｇ（収
率３．０％）であった。(Example 3) Example 1 was repeated except that the reductive alkylation reaction temperature in Example 1 was changed from 100 ° C to 85 ° C.
The reaction was carried out in the same manner as described above. The amount of 3-dimethylaminobenzoic acid produced was 23.54 g (yield 95.0%).
The amount of monomethylaminobenzoic acid produced was 0.68 g (3.0% yield).
【００２４】（実施例４）実施例１の還元アルキル化反
応温度を１００℃から６０℃へ変更した以外は実施例１
と同様に反応を行なった。３−ジメチルアミノ安息香酸
の生成量は２２．４２ｇ（収率９０．５％）であり、３
−モノメチルアミノ安息香酸の生成量は０．６６ｇ（収
率２．９％）であった。(Example 4) Example 1 was repeated except that the reductive alkylation reaction temperature in Example 1 was changed from 100 ° C to 60 ° C.
The reaction was carried out in the same manner as described above. The amount of 3-dimethylaminobenzoic acid produced was 22.42 g (90.5% yield).
-The production amount of monomethylaminobenzoic acid was 0.66 g (yield 2.9%).
【００２５】（実施例５）実施例１の純度９４％のパラ
ホルムアルデヒドの代えて、純度８０．０％のパラホル
ムアルデヒド（水分２０％含有）１１．２８ｇを用いた
以外は実施例１と同様に反応を行なった。３−ジメチル
アミノ安息香酸の生成量は２３．８１ｇ（収率９６．１
％）であり、３−モノメチルアミノ安息香酸の生成量は
０．４５ｇ（収率２．０％）であった。Example 5 The procedure of Example 1 was repeated except that paraformaldehyde having a purity of 94% was replaced by 11.28 g of paraformaldehyde having a purity of 80.0% (containing 20% of water). The reaction was performed. The amount of 3-dimethylaminobenzoic acid produced was 23.81 g (yield 96.1).
%), And the amount of 3-monomethylaminobenzoic acid produced was 0.45 g (yield 2.0%).
【００２６】（比較例１）実施例１のパラホルムアルデ
ヒドに代えて、３７％ホルマリン２４．３５ｇを用いた
以外は実施例１と同様に反応を行なった。ところが、ニ
トロ基を還元するに必要な理論水素吸収量に達しても水
素の吸収が停止することなく継続したため、そのまま反
応温度を１００℃まで上げ、水素吸収が停止するまで反
応を行なった。反応後、触媒を濾過し反応液を分析した
ところ、３−ジメチルアミノ安息香酸１９．８７ｇ（収
率８０．２％）、３−モノメチルアミノ安息香酸１．１
３ｇ（収率５．０％）の生成が見られたが、その他に副
生物の生成が多数確認された。Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that 24.35 g of 37% formalin was used instead of paraformaldehyde of Example 1. However, even if the theoretical hydrogen absorption required for reducing the nitro group was reached, the absorption of hydrogen continued without stopping, so the reaction temperature was raised to 100 ° C. and the reaction was continued until the absorption of hydrogen stopped. After the reaction, the catalyst was filtered and the reaction solution was analyzed. As a result, 19.87 g (yield: 80.2%) of 3-dimethylaminobenzoic acid and 3-monomethylaminobenzoic acid 1.1 were obtained.
Although 3 g (yield 5.0%) was produced, many other by-products were confirmed.
【００２７】（比較例２）実施例１と同様の仕込みで、
系内の温度を一気に１００℃に昇温した。ニトロ基をジ
メチルアミノ基まで還元アルキル化するのに必要な理論
水素吸収量に対して約１０％の水素吸収が見られたとこ
ろで、水素吸収が完全に停止した。反応液より触媒を濾
過し、分析したところ、３−ジメチルアミノ安息香酸の
生成は１．３１ｇ（収率５．３％）見られ、８２．７％
の３−ニトロ安息香酸が残存しており、更に、多数の副
生物の生成が見られた。(Comparative Example 2) With the same preparation as in Example 1,
The temperature in the system was raised to 100 ° C at a stretch. When about 10% of the hydrogen absorption required for reductive alkylation of the nitro group to the dimethylamino group was observed, the hydrogen absorption was completely stopped. When the catalyst was filtered from the reaction solution and analyzed, 1.31 g (yield 5.3%) of 3-dimethylaminobenzoic acid was found, and 82.7%.
Of 3-nitrobenzoic acid remained, and generation of many by-products was observed.
【００２８】[0028]
【発明の効果】本発明の方法により、芳香族アミノ化合
物または、その前駆体である芳香族ニトロ化合物を還元
アルキル化して、Ｎ−アルキル置換芳香族アミノ化合物
を製造する際に、短時間、高収率で進行し、なお且つ工
業的にも有用な製造方法を提供することができた。According to the method of the present invention, an aromatic amino compound or an aromatic nitro compound which is a precursor thereof is reductively alkylated to produce an N-alkyl-substituted aromatic amino compound in a short period of time. It was possible to provide a production method which proceeded with a high yield and was industrially useful.
フロントページの続き (72)発明者 金村 芳信 福岡県大牟田市浅牟田町30番地 三井化学 株式会社内 Ｆターム(参考） 4H006 AA02 AC52 BA05 BA14 BA21 BA25 BA26 BA30 BA55 BA70 BB14 BC10 BE20 BJ50 BS30 BU46 Continued on the front page (72) Inventor Yoshinobu Kanamura 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. F-term (reference) 4H006 AA02 AC52 BA05 BA14 BA21 BA25 BA26 BA30 BA55 BA70 BB14 BC10 BE20 BJ50 BS30 BU46
Claims (10)
ラホルムアルデヒド及び水素を反応させることを特徴と
するＮ−アルキル置換芳香族アミノ化合物の製造方法。1. A method for producing an N-alkyl-substituted aromatic amino compound, which comprises reacting an aromatic amino compound with paraformaldehyde and hydrogen in an organic solvent.
香酸である請求項１記載の製造方法。2. The method according to claim 1, wherein the aromatic amino compound is m-aminobenzoic acid.
載の製造方法。3. The method according to claim 1, wherein the organic solvent is methanol.
が、ｍ−ジメチルアミノ安息香酸である請求項１記載の
製造方法。4. The method according to claim 1, wherein the N-alkyl-substituted aromatic amino compound is m-dimethylaminobenzoic acid.
１〜４記載の製造方法。5. The method according to claim 1, wherein the reaction temperature is 60 to 110 ° C.
ヒドを加え、有機溶媒中貴金属触媒存在下、水素と反応
させることにより、還元反応、次いで還元アルキル化反
応を行なうことを特徴とするＮ−アルキル置換芳香族ア
ミノ化合物の製造方法。6. An N-alkyl-substituted aromatic compound, comprising adding paraformaldehyde to an aromatic nitro compound and reacting with hydrogen in an organic solvent in the presence of a noble metal catalyst to carry out a reduction reaction and then a reductive alkylation reaction. A method for producing an aromatic amino compound.
酸である請求項６記載の製造方法。7. The method according to claim 6, wherein the aromatic nitro compound is m-nitrobenzoic acid.
載の方法。8. The method according to claim 6, wherein the organic solvent is methanol.
ｍ−ジメチルアミノ安息香酸である請求項６記載の製造
方法。9. The method according to claim 6, wherein the N-alkyl-substituted aromatic amino compound is m-dimethylaminobenzoic acid.
℃以下で行ない、パラホルムアルデヒドとの還元アルキ
ル化反応を６０〜１１０℃で行なうことを特徴とする請
求項６〜９記載の製造方法。10. The reduction reaction of an aromatic nitro compound is carried out by 60
10. The process according to claim 6, wherein the reaction is carried out at a temperature of not higher than 60 DEG C., and the reductive alkylation reaction with paraformaldehyde is carried out at a temperature of 60 to 110 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10273619A JP2000095740A (en) | 1998-09-28 | 1998-09-28 | Production of n-alkyl substituted aromatic amino compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10273619A JP2000095740A (en) | 1998-09-28 | 1998-09-28 | Production of n-alkyl substituted aromatic amino compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000095740A true JP2000095740A (en) | 2000-04-04 |
Family
ID=17530256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10273619A Pending JP2000095740A (en) | 1998-09-28 | 1998-09-28 | Production of n-alkyl substituted aromatic amino compound |
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| Country | Link |
|---|---|
| JP (1) | JP2000095740A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009086034A1 (en) | 2007-12-20 | 2009-07-09 | E. I. Du Pont De Nemours And Company | Process for producing a multilayer coating |
| CN103159634A (en) * | 2011-12-13 | 2013-06-19 | 北京莫伊克科技有限公司 | Manufacturing method of N-alkyl aminophenol low in cost and free of waste water and waste gas |
-
1998
- 1998-09-28 JP JP10273619A patent/JP2000095740A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009086034A1 (en) | 2007-12-20 | 2009-07-09 | E. I. Du Pont De Nemours And Company | Process for producing a multilayer coating |
| CN103159634A (en) * | 2011-12-13 | 2013-06-19 | 北京莫伊克科技有限公司 | Manufacturing method of N-alkyl aminophenol low in cost and free of waste water and waste gas |
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