CN101462967B - Method for converting arylamine polyhalide - Google Patents
Method for converting arylamine polyhalide Download PDFInfo
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- CN101462967B CN101462967B CN200910000528.8A CN200910000528A CN101462967B CN 101462967 B CN101462967 B CN 101462967B CN 200910000528 A CN200910000528 A CN 200910000528A CN 101462967 B CN101462967 B CN 101462967B
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000004982 aromatic amines Chemical class 0.000 title 1
- -1 aromatic amine compound Chemical class 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract 3
- 238000005984 hydrogenation reaction Methods 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 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Polymers C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006298 dechlorination reaction Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- 208000006278 hypochromic anemia Diseases 0.000 claims 3
- 230000001131 transforming effect Effects 0.000 claims 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 235000011118 potassium hydroxide Nutrition 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- YGUFQYGSBVXPMC-UHFFFAOYSA-N 4-chloro-2,5-dimethoxyaniline Chemical compound COC1=CC(Cl)=C(OC)C=C1N YGUFQYGSBVXPMC-UHFFFAOYSA-N 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000011426 transformation method Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 17
- 238000005695 dehalogenation reaction Methods 0.000 description 15
- 229910052763 palladium Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- GJQPMPFPNINLKP-UHFFFAOYSA-N diclofenamide Chemical compound NS(=O)(=O)C1=CC(Cl)=C(Cl)C(S(N)(=O)=O)=C1 GJQPMPFPNINLKP-UHFFFAOYSA-N 0.000 description 3
- 229960005081 diclofenamide Drugs 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LUNUTDXQTSGSJG-LFABVHOISA-N (2S)-2-amino-2-cyclohexyl-N-(1-diphenoxyphosphorylethyl)acetamide Chemical compound C1([C@H](N)C(=O)NC(C)P(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)CCCCC1 LUNUTDXQTSGSJG-LFABVHOISA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- NATVSFWWYVJTAZ-UHFFFAOYSA-N 2,4,6-trichloroaniline Chemical compound NC1=C(Cl)C=C(Cl)C=C1Cl NATVSFWWYVJTAZ-UHFFFAOYSA-N 0.000 description 1
- QMXZSRVFIWACJH-UHFFFAOYSA-N 2-chloro-1,4-dimethoxybenzene Chemical compound COC1=CC=C(OC)C(Cl)=C1 QMXZSRVFIWACJH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides transformation method for poly-halogenated aromatic amine compound. In the method, a hydrodechlorination reaction is carried out on the poly-chloraniline compound (I) rich in the rectification residue, with the existence of H2, liquid solvent and alkali, by taking the rectification residue generated in the process of synthesizing 2, 5 dimethoxy-4-chloraniline as raw materials and by adopting a support catalyst with group VIII metals as active components. The method has the advantage that the rectification residue generated in the process of synthesizing 2, 5 dimethoxy-4-chloraniline can be recycled at utmost, so that the environmental pollution caused by the discharge of rectification residue is reduced.
Description
Technical field
The present invention relates to a kind of method for transformation of many halogen aromatic amines compound, particularly a kind of with phenyl-monohalide amine compound---2, the rectification residue producing in the production process of 5-dimethoxy-4 '-chloroaniline is raw material, the phenyl polychloride aminated compounds being wherein rich in is converted into monochloro-benzene amine compound by the partial hydrogenation dehalogenation reaction and the method recycled.
Background technology
As 2 of monochloro-benzene amine compound, 5-dimethoxy-4 '-chloroaniline is a kind of important pigment dyestuff intermediate, can by diazotization reaction prepare permanent yellow HR (Colour index number C.I.PigmentYellow 83 (21108)) and forever solid pink FBB-B (Colour index number C.I.Pigment Red 146 (12485), for senior ink and plastics.
The starting raw material of 2,5-dimethoxy-4 '-chloroaniline is Resorcinol.Resorcinol becomes terephthaldehyde's ether (being Isosorbide-5-Nitrae-dimethoxy benzene) through etherificate (methylating) reaction.Isosorbide-5-Nitrae-dimethoxy benzene reacts with SULPHURYL CHLORIDE and generates 2,5-dimethoxy-1-chlorobenzene, then through nitrated, reduction, generates 2,5-dimethoxy-4 '-chloroaniline.Yet, i.e. 2, the 5-dimethoxy-4 '-chloroaniline association of object product monochloro-benzene amine compound has more phenyl polychloride amine compound, and these phenyl polychloride amine compound are rich in 2, in the rectification residue of 5-dimethoxy-4 '-chloroaniline, content is up to more than 95% conventionally.If this rectification residue is treated, do not arrange outward, will cause severe contamination to environment.At present, the synthetic formed rectification residue that is rich in phenyl polychloride amine compound of 2,5-dimethoxy-4 '-chloroaniline does not also have a kind of good treatment process.
Under shortening dehalogenation condition, the hydro carbons of Halogen and derivative thereof can carry out the dehalogenation reaction.For example, US Patent No. 3579596 adopts noble metal catalysts, by CCl
4carry out selective hydrogenation dechlorination and produce CH
2cl
2and CHCl
3; US Patent No. 4618686 is usingd active carbon-supported palladium as catalyzer, makes polychlorinated biphenyl dechlorination; Chinese patent CN02132909.5 and CN200510054509.5 adopt transition-metal catalyst, make halogenated phenol compound carry out hydrodehalogenation reaction.Yet in document, yet there are no the report that three halogen aromatic amines compounds is carried out to hydrodehalogenation at present, particularly have no pigment dyestuff intermediate---monochloro-benzene amine compound 2, thus the rectification residue of 5-dimethoxy-4 '-chloroaniline is raw material to carry out the partial hydrogenation dehalogenation reaction phenyl polychloride amine compound being wherein rich in is converted into the report that monochloro-benzene amine compound is recycled.
Summary of the invention
The inventor thinks, if can be to the pigment dyestuff intermediate 2 as monochloro-benzene amine compound, the rectification residue that is rich in phenyl polychloride amine compound in 5-dimethoxy-4 '-chloroaniline production process is processed, thereby by product phenyl polychloride amine compound is wherein converted into monochloro-benzene amine compound through the partial hydrogenation dehalogenation reaction to be recycled, both reduced the degree of environmental pollution, improved again the yield of object product monochloro-benzene amine compound, a kind of method effectively with industrial value of can yet be regarded as.The inventor is surprised to find, and under shortening condition, described phenyl polychloride amine compound can carry out part dechlorination reaction, and other substituting group on phenyl ring is not subject to the impact of hydrodechlorination reaction.Therefore described phenyl polychloride amine compound is used can be converted into monochloro-benzene amine compound product after partial hydrogenation dehalogenation is processed.
So, the object of this invention is to provide a kind of with pigment dyestuff intermediate 2, rectification residue in 5-dimethoxy-4 '-chloroaniline production process is raw material, the phenyl polychloride amine compound being wherein rich in is converted into monochloro-benzene amine compound by the partial hydrogenation dehalogenation reaction and the method that recycled.
Technical scheme provided by the invention is: with 2, the rectification residue producing in the production process of 5 dimethoxy-4 's-chloroaniline is raw material, adopt carrier-borne transition metal catalysts, under organic solvent and hydrogen condition, carry out the partial hydrogenation dehalogenation reaction, the phenyl polychloride amine compound being rich in residue is converted into monochloro-benzene amine compound.
(I) is as follows for the structural formula of phenyl polyhalide amine compound of the present invention:
Wherein, the substituent R on phenyl ring
1～R
5can be identical or different, and to have two substituting groups at least be halogen atom, and the substituting group except halogen atom can be hydrogen atom, alkyl, hydroxyl or alkoxyl group.
The present invention processes 2, the condition that 5-dimethoxy-4 '-chloroaniline rectification residue, the phenyl polychloride amine compound that makes to be wherein rich in are converted into monochloro-benzene amine compound by the partial hydrogenation dehalogenation reaction is as follows: temperature of reaction is 0～250 ℃ of room temperature, preferably 50～120 ℃, reaction pressure 0.5～5MPa, preferred 1.5～2.5MPa, as the rectification residue of reaction raw materials and the weight ratio of organic solvent, it is 1: 5～1: 20, preferably 1: 10～1: 15, the mol ratio of the rectification residue of hydrogen and reaction raw materials is 1: 2～1: 12, preferably 1: 4～1: 6.
Partial hydrogenation dehalogenate activator of the present invention adopts take the loaded catalyst that transition metal is active ingredient, take porous material as carrier.Described catalyst activity component is selected from periodic table of elements VI, VII, the transition metal of VIIIB family, precious metal, comprises Pd, Rh, Pt, Co, Cu, Fe, Zr, Ni etc., preferably Pd.The transition metal oxide that the described porous material as support of the catalyst is selected from aluminum oxide, silicon-dioxide, silico-aluminate, carbonaceous material, natural or artificial clay, alkaline earth metal oxide and is suitable as carrier is as TiO
2with ZrO
2deng, preferred carbonaceous material, more preferably gac.Take catalyzer as benchmark, and described active metal total content is 0.01～5 heavy %, preferably 0.05～0.6 heavy %.The preferred impregnation method of preparation of described partial hydrogenation dehalogenate activator.
According to method provided by the invention, described partial hydrogenation dehalogenate activator adopts dipping technique preparation, and with the solution impregnation porous carrier containing catalyst activity component, then catalyzer is prepared in dry, roasting.Concrete steps are as follows:
By the solution direct impregnation porous carrier containing catalyst activity component, under room temperature, deposit 1～6hr, 100～150 ℃ of dry 1～6hr, 200～400 ℃ of roasting 2～6hr, roasting can be carried out in air or water vapour, also can be at rare gas element N
2in atmosphere, carry out.
The described solution containing catalyst activity component can be selected from its water miscible all kinds of inorganic or organic compound that maybe can be dissolved in ammoniacal liquor, nitric acid or hydrochloric acid, if the solution containing Pd is preferably from the acid of chlorine palladium, Palladous chloride.
The described partial hydrogenation dehalogenation reaction is to carry out under the condition existing at organic solvent.Described organic solvent is selected from one or more in hydro carbons, heterogeneous ring compound, alcohols, preferably alcohols.Described hydro carbons comprises alkane and aromatic hydrocarbons, and as normal hexane, hexanaphthene, sherwood oil, benzene,toluene,xylene etc., described heterogeneous ring compound comprises tetrahydrofuran (THF), dioxane, pyridine etc., and described alcohols comprises methyl alcohol, ethanol, Virahol, ethylene glycol etc.The rectification residue of described reaction raw materials and the weight ratio of organic solvent are 1: 5～1: 20, preferably 1: 10～1: 15.
Described partial hydrogenation dehalogenation reaction process is accompanied by the generation of hydrogen halide, and hydrogen halide can cause catalyst deactivation, therefore must be removed to guarantee carrying out continuously of hydrodehalogenation reaction.The dehalogenation reaction of partial hydrogenation described in the present invention system adds alkaline matter in order to absorb hydrogen halide.Described alkaline matter can be selected from one or more of inorganic base, organic bases, described inorganic base comprises carbonate, ammoniacal liquor of the oxyhydroxide of alkali-metal oxyhydroxide, alkaline-earth metal, alkali-metal carbonate, alkaline-earth metal etc., and described organic bases comprises pyridine, pyrroles, ethamine, diethylamine, triethylamine, thanomin etc.It is 1: 4～2: 1 that the consumption of described alkaline matter be take the mol ratio of alkaline matter and reaction raw materials, preferably 1: 2～1: 1.
The described partial hydrogenation dehalogenation reaction can adopt continuous fixed bed mode to carry out, and also can adopt intermittently autoclave to carry out.The partial hydrogenation dehalogenation reaction of the present invention adopts intermittently autoclave to carry out, reaction times 0.1～24h, preferably 3～8h.
Advantage of the present invention is, with 2, the rectification residue producing in the production process of 5-dimethoxy-4 '-chloroaniline is raw material, the phenyl polychloride amine compound being wherein rich in is converted into monochloro-benzene amine compound by the partial hydrogenation dehalogenation reaction, both reduced the degree that causes environmental pollution because of the discharge of described rectification residue, improved again the yield of object product monochloro-benzene amine compound, thereby made to obtain maximum recycling as the described rectification residue of refuse.
Embodiment
In embodiment, use 2, the rectification residue of 5-dimethoxy-4 '-chloroaniline is provided by Qingdao Tianyuan Chemical Co., Ltd., other reagent used is commercially available chemical.
Below by example, method of the present invention is further described, but does not limit therefrom protection scope of the present invention.
Embodiment 1
The present embodiment is for illustrating the preparation of catalyzer.
According to catalyzer, finally form, take appropriate group VIII metal chloride (as Palladous chloride) and be dissolved in 20ml concentrated hydrochloric acid, be diluted with water to 100ml.Get the mixing solutions that 50ml should configure, add in the 100g absorbent charcoal carrier of crossing through nitric acid treatment, at 25 ℃, flood 8 hours, after filtration in furnace pot in water-bath evaporate to dryness, finally be placed in 120 ℃ of oven dry of baking oven, the activated carbon supported type catalyzer that to obtain take group VIII metal be active ingredient.Catalyzer needs through H before using
2reduction.
Embodiment 2
The effect of this example explanation the inventive method.
In 1L autoclave, add 100 gram 2,4,6-trichloroaniline, 0.38 gram of activated carbon supported palladium catalyst (containing the heavy % of palladium 0.1) and 300ml alcohol solvent, 10 grams, sodium hydroxide.Under 3.5MPa hydrogen pressure, 120 ℃ of temperature controls, stir, and carry out partial hydrogenation dechlorination reaction, and reaction was carried out after 4 hours, obtained 85 grams of reacting final products, and wherein dichlorphenamide bulk powder 12%, mono chloro benzene amine 88%.
Embodiment 3
In 1L autoclave, add 100 grams of 2,6-DCAs, 0.2 gram of activated carbon supported palladium catalyst (containing the heavy % of palladium 0.1) and 300ml alcohol solvent, 10 grams, sodium hydroxide.Under 2.5MPa hydrogen pressure, 100 ℃ of temperature controls, stir, and carry out partial hydrogenation dechlorination reaction, and reaction was carried out after 5 hours, obtained 80 grams of reacting final products, and wherein mono chloro benzene amine 100%.
Embodiment 4
In 1L autoclave, add 100 gram 2,5-dimethoxy-4 '-chloroaniline rectification residue, 0.1 gram of activated carbon supported catalyzer (containing the heavy % of the heavy % of palladium 0.1 nickeliferous 1.0) and 200ml methanol solvate, 10 grams, sodium hydroxide, under 3.0MPa hydrogen pressure, 80 ℃ of temperature controls, stir, reaction 6h, obtains 75 grams of reacting final products, and wherein dichlorphenamide bulk powder compound 30%, mono chloro benzene amine compound 68.5%, aniline compound 1.5%.
Embodiment 5
In stainless steel autoclave (1L), add the catalyzer 0.5g (containing the heavy % of the heavy % of palladium 0.05 nickeliferous 1.0) of preparation, 100 grams of chloroaniline rectification residues, anhydrous methanol 200ml, 10 grams, sodium hydroxide.Then 120 ℃ of temperature of reaction, under the condition of reaction pressure 3.0MPa, isothermal reaction 6h, stopped reaction, obtains product 85g, and the content of each component is: dichlorphenamide bulk powder compound 9.5%, mono chloro benzene amine compound 89.6%, aniline compound 0.9%, polystream amine compound 0%.
Claims (5)
1. the method that chloro aromatic amine compound more than a kind transforms, it is characterized in that synthesizing 2, the rectification residue that is rich in polystream amine compound (I) producing in 5-dimethoxy-4 '-chloroaniline process is raw material, adopts to take the loaded catalyst that group VIII metal is active ingredient, at H
2, organic solvent and alkali existence under, the polystream amine compound (I) being rich in rectification residue is carried out to partial hydrogenation dechlorination reaction;
The structural formula of described polystream amine compound (I) is as follows:
Wherein, the substituent R on phenyl ring
1～R
5can be identical or different, and to have two substituting groups at least be chlorine atom, and the substituting group beyond dechlorination atom is hydrogen atom, alkyl, hydroxyl or alkoxyl group;
Temperature of reaction is 80～120 ℃, and reaction pressure is 1.5～3.0MPa;
In described catalyzer, active ingredient accounts for 0.5～10% of catalyzer total amount;
Described catalyst activity component is Pd and/or Ni;
The concentration of described catalyzer in reaction soln is 0.05g/100mL;
The mol ratio of alkali and described polystream amine compound is 2: 1～1: 4;
Described organic solvent is methyl alcohol, ethanol, Virahol or ethylene glycol.
2. the method transforming according to many chloros aromatic amine compound claimed in claim 1, is characterized in that, the carrier of described catalyzer is gac.
3. in accordance with the method for claim 1, it is characterized in that, described alkali is ammoniacal liquor, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, one or more in pyridine, pyrroles, ethamine, diethylamine, triethylamine thanomin.
4. the method transforming according to many chloros aromatic amine compound claimed in claim 1, is characterized in that, the mol ratio of described alkali and polystream aminated compounds is 1: 4～2: 1.
5. the method transforming according to many chloros aromatic amine compound claimed in claim 4, is characterized in that, the mol ratio of described alkali and polystream aminated compounds is 1: 2～1: 1.
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| CN102512781B (en) * | 2011-10-19 | 2014-04-16 | 中国科学院烟台海岸带研究所 | Combined degradation method for processing high concentration halogenated phenol compounds |
| CN103664755B (en) * | 2013-12-31 | 2016-07-13 | 沈阳化工研究院有限公司 | A kind of preparation method of dichloromethyl substituted pyridines |
| CN105749936A (en) * | 2016-04-05 | 2016-07-13 | 宁夏蓝丰精细化工有限公司 | Metal composite catalyst for selective dechloridation and preparation method thereof |
| CN107032942A (en) * | 2017-05-22 | 2017-08-11 | 江苏科菲特生化技术股份有限公司 | A kind of method of rectifying organic solid residue conduction oil in utilization biphenyl alcohol production |
| CN109603834A (en) * | 2018-12-17 | 2019-04-12 | 上海应用技术大学 | A kind of catalyst and preparation method thereof for hydrogen production from methanol-steam reforming |
| CN110407664B (en) * | 2019-07-30 | 2020-10-16 | 厦门大学 | Method for synthesizing dichlorobenzene |
| CN110407665B (en) * | 2019-07-30 | 2021-01-26 | 厦门大学 | Chlorinated aromatic compound (R)1-Xm) Dechlorination method of |
| CN110407663B (en) * | 2019-07-30 | 2021-01-26 | 厦门大学 | Dechlorination method of chlorine-containing aromatic compound |
| CN112079734B (en) * | 2020-09-30 | 2022-03-18 | 常州大学 | Preparation method of 4-chloro-2, 5-dimethoxyaniline |
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