CN102952021B - Synthesis method of 3,4-dimethylaniline - Google Patents
Synthesis method of 3,4-dimethylaniline Download PDFInfo
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- CN102952021B CN102952021B CN201110254637.XA CN201110254637A CN102952021B CN 102952021 B CN102952021 B CN 102952021B CN 201110254637 A CN201110254637 A CN 201110254637A CN 102952021 B CN102952021 B CN 102952021B
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- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical compound CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 23
- 239000002262 Schiff base Substances 0.000 claims abstract description 8
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 14
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000012074 organic phase Substances 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 5
- HBCZMIJXNQCIDC-UHFFFAOYSA-N 2-(chloromethyl)-1-methyl-4-nitrobenzene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1CCl HBCZMIJXNQCIDC-UHFFFAOYSA-N 0.000 abstract 1
- 238000011033 desalting Methods 0.000 abstract 1
- ZKZPFRYNEJTLDV-UHFFFAOYSA-N ethane-1,2-diamine;2-hydroxybenzaldehyde Chemical compound NCCN.OC1=CC=CC=C1C=O ZKZPFRYNEJTLDV-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005591 Pendimethalin Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- CHIFOSRWCNZCFN-UHFFFAOYSA-N pendimethalin Chemical compound CCC(CC)NC1=C([N+]([O-])=O)C=C(C)C(C)=C1[N+]([O-])=O CHIFOSRWCNZCFN-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 108010020056 Hydrogenase Proteins 0.000 description 1
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPWHTZKZQNXVAE-UHFFFAOYSA-N Tetracaine hydrochloride Chemical compound Cl.CCCCNC1=CC=C(C(=O)OCCN(C)C)C=C1 PPWHTZKZQNXVAE-UHFFFAOYSA-N 0.000 description 1
- 229930003471 Vitamin B2 Natural products 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YTXAYGAYACWVGD-UHFFFAOYSA-N palladium;hydrate Chemical compound O.[Pd] YTXAYGAYACWVGD-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000011716 vitamin B2 Substances 0.000 description 1
- 235000019164 vitamin B2 Nutrition 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
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing 3,4-dimethylaniline by catalytic hydrogenation reduction. The method comprises steps as follows: (1) a water-soluble ethylenediamine salicylaldehyde Schiff base palladium complex catalyst is synthesized; (2) 3-chloromethyl-4-methylnitrobenzene is subjected to catalytic hydrogenation reaction under alkaline two-phase conditions, and meanwhile, dechlorination and nitroreduction reaction are carried out to obtain the 3,4-dimethylaniline; liquid separation is carried out, wherein the organic phase is the product; and (3) the water phase after liquid separation, which contains the palladium complex catalyst, can be directly recovered and reutilized repeatedly with constant catalytic activity. After being reutilized repeatedly, the catalyst can be concentrated for desalting without influencing the recovery and reutilization of the catalyst.
Description
Technical field
The present invention relates to Chemicals 3, a kind of synthetic method of 4-xylidine.Especially relate to the synthetic method of with the water-soluble quadrol double salicylaldehyde of homogeneous phase Schiff-base Palladium composition catalyst, 3-chloromethyl-4-methyl oil of mirbane being carried out hydrogenating reduction nitro dechlorination and obtained 3,4-xylidine.
Background technology
3,4-xylidine is a kind of important Chemicals, is the intermediate of synthetic pesticide pendimethalin and medical Lin Suanna Vitamin B2 Sodium Phosphate.Pendimethalin is a kind of important selective herbicide.Then o-Xylol reduces nitro to nitrated in position is that amido is the most traditional synthetic method of 3,4-xylidine.When the shortcoming of this synthetic route is o-Xylol mono-nitration, mainly generate the nitrated isomer in ortho position, must carry out isomer separation and find the purposes of ortho isomer.J.Am.Chem.Sco., 63:2532 (1941) has reported the then synthetic method of ammonia solution of o-Xylol bromo, but the method cost is too high uneconomical.By chloromethylation, can obtain 3-chloromethyl-4-methyl oil of mirbane by para-nitrotoluene, the dechlorination simultaneously of 3-chloromethyl-4-methyl hydrogenation of chloronitrobenzene reduction nitro can obtain 3,4-xylidine, Raney Ni catalyzer for this reaction need to react under 35-70atm hydrogen-pressure.Dangerous and the easy inactivation of Raney Ni catalyzer of the operation of high pressure hydrogen.The reduction of nitro-compound is an important chemical process.Organic chemical industry is the earliest from Perkin uses iron powder reducing nitro-aromatic.Iron powder reducing nitro is because iron sludge-polluted is seriously and gradually superseded.The method of various hydrogenating reduction nitros develops gradually.The catalyzer of the most frequently used hydrogenating reduction nitro has Raney Ni catalyzer and palladium-carbon catalyst.Raney Ni catalyzer is used and easy inactivation conventionally under comparatively high temps and pressure.Palladium-carbon catalyst is easily efflorescence and become bad recovery in stirred autoclave.U.S. Pat 3832401 and US3906045 have reported the method with homogeneous phase complexing Ru catalyst hydrogenation reduction nitro.But homogeneous catalyst is more difficult, from product, reclaim.U.S. Pat 6054617 use water soluble ligand TPPPS coordinate Ru catalyst hydrogenations reduction nitros, and after having reacted, separating that water recycles is recyclable catalyzer.But this catalyzer need to be under the high hydrogen-pressure of 20bar 100 ℃ react.The operation of high pressure hydrogen is dangerous.The present invention with water-soluble schiff base of salicylaldehyde palladium complex catalyst in alkaline aqueous solution to 3-chloromethyl-4-methyl hydrogenation of chloronitrobenzene, carry out nitroreduction and dechlorination reaction simultaneously, reaction at normal pressure, carry out, reaction yield is high.Having reacted rear water phase separated is recyclable catalyzer.
Summary of the invention
Quadrol double salicylaldehyde Schiff-base Palladium title complex is a kind of palladium complex that has catalytic activity, the hydrogenation reaction of energy catalysis Heck reaction and organic compound etc.J.Mol.Catal., report the hydrogenation reaction of this palladium complex catalyst and hydrogenase have similarity at 1 (2): 121 (1976), has pH value dependency, and hydrogen can exchange occur with heavy water and generate heavy hydrogen under this catalyst action.This palladium complex has certain water-soluble but in organic phase, also have certain solubleness, in two-phase, distributes and makes the recovery of this catalyzer more difficult.The present invention is part with the salicylic aldehyde of sulfonation, after same quadrol forms Schiff's base and Palladous chloride form title complex, due to sulfonic water-soluble, under alkaline condition, new title complex is completely water-soluble and be insoluble to organic phase.The present invention for the hydrogenation of 3-chloromethyl-4-methyl oil of mirbane, finds that reaction can carry out under normal pressure by this water-soluble complexes, carries out nitroreduction simultaneously and become the reaction of amino and hydrodechlorination.After having reacted, water phase separated recycles can recovery catalyzer.
The present invention achieves the above object by the following technical solutions:
4-sulfonic group salicylic aldehyde and reacting ethylenediamine form Schiff's base, and Schiff's base solution drips palladium chloride solution, the water miscible palladium complex that reaction obtains.This palladium complex is dissolved in to alkaline aqueous solution and adds the heating of 3-chloromethyl-4-methyl nitro benzo, pass into hydrogen stirring simultaneously and react.In reaction process, constantly add alkali and keep solution alkalescence.Reacted rear separatory.After organic phase is cooling, obtain 3,4-xylidine white crystalline solid.Water separates rear recycled, and catalyzer does not lose.The sodium chloride salt that time produces with rear water evolution reaction.Can remove by filtering separation.
Now describe technical solution of the present invention in detail:
One, the preparation of water-soluble quadrol double salicylaldehyde Schiff-base Palladium composition catalyst
The sylvite of 4-sulfonic group salicylic aldehyde is dissolved in ethanol water mixed solvent, adds quadrol, heated and stirred several hours.The cooling yellow solid that obtains is sulfo group salicylidene quadrol Schiff's base (Schiff base).This Schiff's base heating for dissolving, in ethanol water mixed solvent, is dripped to the hydrochloric acid soln of Palladous chloride, and then hydro-oxidation sodium solution tune pH is 7, then heated and stirred reaction several hours, and cold filtration crystalline solid, obtains palladium complex catalyst.
Two, hydrogenation reaction
By soluble in water palladium complex catalyst obtained in the previous step, adjust pH is 10, is heated to 60-100 ℃, passes into hydrogen stirring reaction for some time, then adds 3-chloromethyl-4-methyl oil of mirbane of fusing, logical hydrogen stirring reaction.In reaction process, drip the alkalescence that 40% sodium hydroxide solution keeps reaction system.After 5-15 hour, liquid chromatograph detects organic phase not containing reaction raw materials.Stop logical hydrogen and stop stirring, separatory separates lower floor's water.Upper organic phase is being as cold as after room temperature, obtains 3,4-xylidine white crystalline solid.Conventionally yield and purity are all greater than 95%.
Three, catalyst recirculation is used
The logical hydrogen of water direct heating that after reaction, separatory obtains, then add next batch 3-chloromethyl-4-methyl oil of mirbane to react.Repeatedly the catalytic effect of reaction is constant.Repeatedly react post chlorization sodium and accumulate at water, can it be separated out concentrating under reduced pressure, cross catalyzer loss in the aqueous solution that filters out sodium-chlor and can continue recycled.
Technical scheme of the present invention is further characterized in that, carries out the hydrogenation reaction of 3-chloromethyl-4-methyl oil of mirbane with water-soluble quadrol double salicylaldehyde Schiff-base Palladium composition catalyst.After having reacted, can simply reclaim catalyzer by water phase separated.The high yield of catalyzed reaction selectivity is high.
Compared with prior art, the present invention has following remarkable advantage:
The present invention carries out hydrogenation reaction with normal pressure or low pressure hydrogen, has avoided the danger in high pressure hydrogen operation.The present invention reacts with water-soluble catalyst, and post catalyst reaction only need just can reclaim through simple separatory operation, and the catalyzer time of recovery is constant with catalytic effect.
Embodiment
Embodiment 1: the preparation of water-soluble palladium composition catalyst: by the sylvite (content 94% of 25.5 grams of 4-sulfonic group salicylic aldehydes, 0.1mol) add in the mixed solvent of 200 grams of dehydrated alcohols and 100 grams of water, stir the 60 ℃ of dissolvings that heat up, then slowly drip the solution that 3.6 grams of quadrols (0.06mol) are dissolved in 80 grams of dehydrated alcohols, be added dropwise to complete rear solution 60 ℃ of stirring reactions 3 hours.Then cooling solution has yellow solid to separate out.After yellow solid water and ethyl alcohol recrystallization, filtration drying obtains the sylvite that 17 grams of yellow crystals are sulfo group salicylidene quadrol Schiff's base, and yield is 67%.Get the sylvite of 13 grams of above-mentioned Schiff's base, be dissolved in the mixing solutions of 150 grams of ethanol and 150 grams of water, the 40 ℃ of stirrings that heat up, drip 4.43 grams of Palladous chlorides and are dissolved in the solution of 10ml concentrated hydrochloric acid and 45ml water, and when dripping palladium chloride solution, dripping 10% sodium hydroxide solution adjust pH is 6-7.After dripping, pH value is transferred to neutrality, 70 ℃ of reactions 16 hours heat up.After cooling solution, separating out dark solid is palladium complex.Adding ethanol and Repone K can promote palladium complex to separate out.Conventionally do not separate palladium complex solid, but ethanol in solution is steamed, then add water dissolution all solids, the concentration of the palladium complex of the demarcation aqueous solution is standby.
Embodiment 2: catalytic hydrogenation reaction: 1000ml is equipped with in the mechanical stirring reaction flask of condenser, add containing 200 grams of the aqueous solution of palladium complex 1mmol, with the careful adjust pH of sodium hydroxide solution be 10, stir and heat up 90 ℃, with 200ml/min flow velocity, by under liquid level, pass into hydrogen, after 30 minutes, add 200 grams of 3-chloromethyl-4-methyl oil of mirbane, keep logical hydrogen, material melting stirs into emulsus.With injection needles, see through soft rubber ball and drip 40wt% aqueous sodium hydroxide solution toward reaction flask, be controlled at approximately 110 grams of solution of even dropping in 8 hours and make reaction soln remain alkalescence.The excess hydrogen of emitting on prolong is returned to water seal bomb, and bomb is by constant flow air pump toward reactor hydrogen supply, and the hydrogen that reaction consumes is supplemented to bomb by steel cylinder.After 8 hours, liquid chromatography sampling demonstration reaction is carried out completely.Stop logical hydrogen, reaction solution separatory, lower layer of water liquid reclaims standby, is 129 grams of white crystalline solid after the organic liquor cool to room temperature of upper strata, liquid-phase chromatographic analysis 3,4-dimethyl benzene amine content 96%.Reaction yield is 95%.Product by ethyl alcohol recrystallization obtain content be greater than 99% 3,120 grams of 4-xylidines.
Embodiment 3: the recycled of water-soluble palladium composition catalyst: the water that first set reaction separatory obtains is directly applied mechanically, the logical hydrogen of water liquid stirs to heat up after 90 ℃ and directly adds 200 grams of 3-chloromethyl-4-methyl oil of mirbane to react, reaction conditions is with also dripping for the first time approximately 110 grams of 40wt% aqueous sodium hydroxide solutions, and reaction finished at 6-10 hour conventionally.Reaction for the second time salts out.Reacted rear isolation separatory again.Organic phase condensation obtains product.Approximately 220 grams of water vacuum hydro-extractions, again have in a large number and salt out, and after isolation, water liquid make up water to 200 gram is for recycled for the third time.The reaction conditions of at every turn applying mechanically, with for the first time, carries out a desalination operation after every applying mechanically for twice.Through 20 recycleds, reactive behavior and selectivity are substantially constant, and reaction yield keeps 94-96%, and product purity keeps 95-98%.Time does not almost reduce with the content of the water-soluble palladium composition catalyst of post analysis water, illustrates that palladium complex catalyst does not lose substantially in separatory and desalination operation.
Claims (7)
1. one kind 3, the synthetic method of 4-xylidine, is characterized in that the method comprises the following steps: (1) synthesizes 4-sulfonic group sal-en schiff base palladium complex catalyst; (2) pass into hydrogen, aqueous catalyst solution and 3-chloromethyl-4-methyl oil of mirbane carry out catalytic hydrogenation reaction at alkaline condition, carry out dechlorination and nitro-reduction reaction simultaneously and obtain 3,4-xylidine; (3) separatory recycle-water phase catalyst, recycled; After time use, by aqueous solution concentrating and desalinating, then add water and apply mechanically, catalyzer does not lose.
2. synthetic method according to claim 1, is characterized in that the described catalyzer of step (1) reacts formed title complex again for 4-sulfonic group salicylic aldehyde and quadrol condensation with Palladous chloride.
3. preparation method according to claim 1, is characterized in that the described temperature of reaction of step (2) is 60-100 ℃, and the reaction times is 5-15 hour.
4. preparation method according to claim 1, it is characterized in that the described required hydrogen pressure of reaction of step (2) is 1 normal atmosphere, hydrogen is by circulation pump high volume continuously by reaction system, and the water that air-flow takes up and organic vapo(u)r are by condensation Returning reactor.
5. preparation method according to claim 1, is characterized in that the water that step (3) separatory reclaims contains whole catalyzer, recycled and catalytic activity is constant.
6. preparation method according to claim 1, is characterized in that the salt of accumulating in water that step (3) separatory reclaims operates separation by condensing crystal, and operating process catalyzer is stayed in the aqueous solution and do not lost.
7. preparation method according to claim 1, it is characterized in that step (2) obtains 3,4-xylidine yield and purity are all greater than 95%, can obtain the pharmaceutical grade product that purity is greater than 99% after a recrystallization.
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