CN104341275B - A kind of synthetic method of 2,6-orcin - Google Patents
A kind of synthetic method of 2,6-orcin Download PDFInfo
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- CN104341275B CN104341275B CN201410592108.4A CN201410592108A CN104341275B CN 104341275 B CN104341275 B CN 104341275B CN 201410592108 A CN201410592108 A CN 201410592108A CN 104341275 B CN104341275 B CN 104341275B
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- ZUVPLKVDZNDZCM-UHFFFAOYSA-N 3-chloro-2-methylaniline Chemical compound CC1=C(N)C=CC=C1Cl ZUVPLKVDZNDZCM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- 238000009413 insulation Methods 0.000 claims description 19
- 239000010410 layer Substances 0.000 claims description 19
- 239000012044 organic layer Substances 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 239000012485 toluene extract Substances 0.000 claims description 9
- 239000004280 Sodium formate Substances 0.000 claims description 7
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 7
- 235000019254 sodium formate Nutrition 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 229940045803 cuprous chloride Drugs 0.000 claims description 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000012264 purified product Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000005457 optimization Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002932 luster Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XDZPCIROQHEUDI-UHFFFAOYSA-N CI.C1(O)=CC(O)=CC=C1 Chemical compound CI.C1(O)=CC(O)=CC=C1 XDZPCIROQHEUDI-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- -1 Methyl Chemical group 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- PKAUVIXBZJUYRV-UHFFFAOYSA-N methane;hydroiodide Chemical compound C.I PKAUVIXBZJUYRV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic method of 2,6-orcin. Taking 3-chloro-2-methyl aniline as raw material,, acidifying 4 steps molten through diazo-reaction, lanthanum orthophosphate catalyzing hydrolysis, alkali, obtain 2,6-orcin. Advantage of the present invention is: (1) raw material sources are extensive, the simple easy operating of (2) technique; (3) can optimizing product color and luster as catalyst with active rare earth; (4) reaction condition is relatively gentle, and safety coefficient is high; (5) total recovery is up to more than 65%, and purity reaches more than 99.0%, and solvent can recovery, and effects of energy saving and emission reduction is obvious.
Description
One technical field
The synthetic method that the present invention relates to a kind of 2,6-orcin, belongs to chemical material preparing technical field. WeMethod is applicable to taking 3-chloro-2-methyl aniline as raw material, the occasion of synthetic 2,6-orcin.
Two background technologies
2,6-orcin is a kind of important fine-chemical intermediate, is widely used in pigment, dyestuff, hair dye, closesThe fields such as resin, medicine, agricultural chemicals, photography.
At present, 2,6-orcin mainly contains following several synthetic method:
(1) be raw material high-pressure hydrogenation Hydrolyze method with 2,6-dinitrotoluene (DNT).
The method is divided into two steps, first uses 2,6-dinitrotoluene (DNT) under high-temperature and high-pressure conditions, to carry out hydrogenation reaction, then existsUnder acetate system, use palladium. carbon is as catalyst, then be hydrolyzed 2,6-orcin. But the method need be at acidity and high temperatureUnder the condition of high pressure, carry out, make equipment selection difficulty, the catalyst of employing is expensive, makes on the production cost of productRise, the purity that simultaneously makes product is low, is not suitable for suitability for industrialized production.
(2), with 1, hydroresorcinol is that raw material passes through CH3Methyl dehydrogenation is again introduced in I or Mannich reaction in 2-position.
This circuit needs to carry out hydrogenation and dehydrogenation reaction in building-up process, and these two processes all need to use a large amount ofPalladium carbon catalyst, and reaction yield is low, makes product cost higher.
(3) resorcinol methyl alcohol methylation reaction.
The method is that resorcinol and methyl alcohol are at ammonium chloride. in the medium of methyl alcohol, through HTHP directly reaction producedProduct. Reaction is carried out under the condition of high temperature, high pressure, and especially reaction temperature is up to 530 DEG C, and this type selecting to equipment has increased tiredDifficulty, and the yield of reaction is low, and the accessory substance of generation is many, and separation difficulty is not suitable for the needs of suitability for industrialized production.
(4) resorcinol iodomethane methylation method.
The method is the industrial method using at present. It is classical anti-that three reactions steps of this method all belong toShould. The yield of every step product is also higher, but catalyst iodine methane is expensive, and belongs to hypertoxic raw material, and this makes to produceThe cost of product raises, and potential safety hazard is serious, causes the market competitiveness of target product not strong.
(5) resorcinol formaldehyde methylation method
This circuit and other several circuit contrasts, reactions steps is more, and total recovery is lower, complex manufacturing, realityOperating difficulties.
(6) taking glutaric acid as raw material
The catalyst of this reaction is nitrobenzene and aluminium chloride. The acetic anhydride steam using in this route is poisonous, and thisBar synthetic route more complicated, can produce more accessory substance, is not easy to the separating-purifying of product, and post-processed is also becomeRelatively send out and mix, also comparatively serious to the pollution of environment, reaction condition is difficult to control.
Three summary of the invention
The object of the invention is to select reaction condition gentleness, safety coefficient is high, product yield is high, product purity is high closesOne-tenth method.
The technical solution that realizes the object of the invention is: a kind of synthetic method of 2,6-orcin, and with the chloro-2-of 3-Methylaniline is initiation material, and, acidifying 4 steps reactions molten through diazo-reaction, hydrolysis, alkali, obtain 2,6-orcin:
Step 1): diazo-reaction. In diazotising still, first sulfuric acid is mixed with to 40% (mass percent) aqueous solution, risesTemperature starts to drip 3-chloro-2-methyl aniline during to 90-95 DEG C, in 1.5-2h, dropwises, and after insulation 1.0h, logical salt water for coolingTo below 5 DEG C. Control temperature at 0-5 DEG C, in 3-4h, drip mass percent and be 30% sodium nitrite in aqueous solution, after finishingInsulation 1.0h, it is for subsequent use that suction filtration obtains diazo liquid filtrate.
Step 2): hydrolysis. The mother liquid coming of injected water or recovery in still, adds active rare earth catalyst lanthanum orthophosphate, opensOpen stirring, at the uniform velocity drip the concentrated sulfuric acid, the toluene extract that toluene or reextraction are used, is warming up to backflow, in 3-4h, dripsBy step 1) diazo liquid that obtains, after insulation 0.5h, lower the temperature, leave standstill point water layer and an organic layer, a water layer part is followed as mother liquid comingRing uses, and remainingly after toluene reextraction, puts to waste water processing station, and the toluene extract that reextraction is used can circulate and makeWith; Organic layer needn't be dried directly and beat to the molten still of alkali, is warming up to 60 DEG C, at the uniform velocity drips sheet alkali 11% (mass percent) aqueous solutionAbout 1h, leaves standstill point water layer and an organic layer, and sodium phenolate solution water layer is placed in bucket, treats the high pressure use that feeds intake, and organic layer is through distilling backThe toluene of receiving can recycle.
Step 3): alkali is molten. Suction successively in autoclave: step 2) the sodium phenolate solution that obtains, mass percent63.5% sodium hydrate aqueous solution, sodium formate, sodium sulfite, the cuprous chloride catalyst that sour water was washed. Heating, 195～200DEG C, still internal pressure is under 1.0～1.2Mpa condition, and insulation 1.5-2h, is then cooled to 100 DEG C and carries out suction filtration, and elimination solid is uselessSlag, unified collection. Filtrate is for subsequent use.
Step 4): acidifying. In advance hydrochloric acid and water are made into aqueous hydrochloric acid solution, step 3 according to 1: 1.2～1.3 ratios) obtainFiltrate enter in acidifying still, in 0.5-1.0h, fast dripping aqueous hydrochloric acid solution to pH value is 1.5-2. Be cooled to room temperature, take outFilter, ethyl acetate extraction, saturated soda water washing is neutral, steams except after ethyl acetate and adds toluene, crystallisation by cooling, centrifugationObtain crude product, after recrystallization decolouring, obtain purified product.
The raw materials used ratio of the present invention is respectively:
Step 1): the mass percent of 3-chloro-2-methyl aniline, the concentrated sulfuric acid, natrium nitrosum be 1: 3.1～3.5: 0.49～0.53；
Step 2): the mass percent of toluene, the concentrated sulfuric acid, catalyst P 1 is 1: 0.80～0.85: 0.014～0.021;
Step 3): the mass percent of sodium phenolate solution, stannous chloride, sodium sulfite, sodium formate is 1: 1.2～1.4:1.6～1.8∶1.2～1.4；
Step 4): all drying processes are all used homemade boiling drying equipment, dry product at 40-50 DEG C, and every batch is dryTime 0.5h, solvent energy recovery.
According to provided by the invention a kind of 2, the synthetic method of 6-orcin, its key problem in technology is to adopt the chloro-2-of 3-Methylaniline is initiation material, and, acidifying 4 steps reactions molten through diazo-reaction, hydrolysis, alkali obtain target product;
According to provided by the invention a kind of 2, the synthetic method of 6-orcin, wherein step 2) the chloro-2-of 3-that generatesMethylphenol not drying directly drips sodium phenolate throwing autoclave processed with alkali lye;
According to provided by the invention a kind of 2, the synthetic method of 6-orcin, step 2) adopt active rare earth as urgingAgent;
According to provided by the invention a kind of 2, the synthetic method of 6-orcin, adopts homemade boiling drying equipment,Save drying time and loss on drying effect better.
Compared with prior art, its advantage is in the present invention: (1) raw material sources are extensive, the simple easy operating of (2) technique; (3)With active rare earth can optimizing product color and luster as catalyst; (4) reaction condition is relatively gentle, and safety coefficient is high; (5) total recovery is highReach more than 65%, purity reaches more than 99.0%; (6) adopt homemade boiling drying equipment, save drying time and loss on dryingBetter effects if, and solvent can recovery, and effects of energy saving and emission reduction is obvious.
Four detailed description of the invention
The present invention is described in detail in detail by the following examples, and these embodiment are only clear open the present invention, and conduct is not to the present inventionRestriction.
Embodiment 1
Step 1): in 2000L diazo reaction still, adding mass percent is 40% aqueous sulfuric acid 1750kg, steamsVapour heating starts at the uniform velocity to drip 3-chloro-2-methyl aniline 225kg in the time that temperature rises to 90-95 DEG C, in 1.5-2h, dripsFinish insulation reaction 1.0h. Logical salt solution is cooled to below 5 DEG C. Control temperature at 0-5 DEG C, in 3-4h, drip mass percent and be30% sodium nitrite in aqueous solution 380kg, finishes rear insulation 1.0h, and it is for subsequent use that suction filtration obtains suction filtration diazo liquid.
Step 2): in hydrolysis kettle, inject the mother liquid coming of 780kg water or recovery, add the active rare earth catalyst phosphorus of 10kgAcid lanthanum, opens and stirs, and at the uniform velocity drips the 560kg concentrated sulfuric acid, and the toluene extract of 700kg toluene or reextraction, is warming up to backStream drips step 1 in 3-4h) diazo liquid that obtains, after insulation 0.5h, lower the temperature, leave standstill point water layer and an organic layer, water layer is got780kg recycles as mother liquid coming, remainingly after toluene reextraction, puts to waste water processing station the toluene extraction of reextractionGetting liquid goes to hydrolysis kettle head tank and recycles; Organic layer is directly beaten to the molten still of alkali, is warming up to 60 DEG C, at the uniform velocity drips 675kg. sheetThe about 1h of alkali 11% (mass percent) aqueous solution, leaves standstill point water layer and an organic layer, and sodium phenolate solution water layer is placed in bucket, treats heightThe pressure use that feeds intake, the toluene solvant that organic layer can be used as reextraction through the toluene of Distillation recovery recycles.
Step 3): suction successively in autoclave: 550kg step 2) the sodium phenolate solution that obtains, 275kg mass percent63.5% sodium hydrate aqueous solution, 8kg sodium formate, 10kg sodium sulfite, the cuprous chloride catalyst that 8kg sour water was washed. Heating,At 195～200 DEG C, still internal pressure is under 1.0～1.2Mpa condition, and insulation 1.5-2h, is then cooled to 100 DEG C and carries out suction filtration,Elimination solid slag, unified collection. Filtrate is for subsequent use.
Step 4): in advance by 650kg hydrochloric acid and 800kg water wiring solution-forming, step 3) filtrate that obtains enters in acidifying still,In 0.5-1.0h, dripping aqueous hydrochloric acid solution to pH value is fast 1.5-2. Be cooled to room temperature, suction filtration, 800kg ethyl acetate extractionGet, saturated soda water washing is neutral, and steam except after ethyl acetate and add 350kg toluene, crystallisation by cooling, centrifugation obtains slightlyProduct, obtain purified product after recrystallization decolouring. Total recovery reaches more than 65%, and purity reaches more than 99.0%.
Embodiment 2
Step 1): in 2000L diazo reaction still, adding mass percent is 40% aqueous sulfuric acid 1969kg, steamsVapour heating starts at the uniform velocity to drip 3-chloro-2-methyl aniline 225kg in the time that temperature rises to 90-95 DEG C, in 1.5-2h, dripsFinish insulation reaction 1.0h. Logical salt solution is cooled to below 5 DEG C. Control temperature at 0-5 DEG C, in 3-4h, drip mass percent and be30% sodium nitrite in aqueous solution 390kg, finishes rear insulation 1.0h, and it is for subsequent use that suction filtration obtains suction filtration diazo liquid.
Step 2): in hydrolysis kettle, inject the mother liquid coming that 780kg reclaims, add the active rare earth catalyst lanthanum orthophosphate of 15kg,Open and stir, at the uniform velocity drip the 600kg concentrated sulfuric acid, the toluene extract of 700kg reextraction, is warming up to backflow, in 3-4h, dripsAdd step 1) diazo liquid that obtains, after insulation 0.5h, lower the temperature, leave standstill point water layer and an organic layer, water layer is got 780kg as mother liquid comingRecycle, remainingly after toluene reextraction, put to waste water processing station, the toluene extract of reextraction goes to hydrolysis kettleHead tank recycles; Organic layer is directly beaten to the molten still of alkali, is warming up to 60 DEG C, at the uniform velocity drips 675kg sheet alkali 11% (quality percentageThan) the about 1h of the aqueous solution, leave standstill point water layer and an organic layer, sodium phenolate solution water layer is placed in bucket, treat the high pressure use that feeds intake, organic layerThe toluene solvant that can be used as reextraction through the toluene of Distillation recovery recycles.
Step 3): suction successively in autoclave: 570kg step 2) the sodium phenolate solution that obtains, 275kg mass percent63.5% sodium hydrate aqueous solution, 7kg sodium formate, 9kg sodium sulfite, the cuprous chloride catalyst that 7kg sour water was washed. Heating,At 195～200 DEG C, still internal pressure is under 1.0～1.2Mpa condition, and insulation 1.5-2h, is then cooled to 100 DEG C and carries out suction filtration,Elimination solid slag, unified collection. Filtrate is for subsequent use.
Step 4): in advance by 700kg hydrochloric acid and 900kg water wiring solution-forming, step 3) filtrate that obtains enters in acidifying still,In 0.5-1.0h, dripping aqueous hydrochloric acid solution to pH value is fast 1.5-2. Be cooled to room temperature, suction filtration, 800kg ethyl acetate extractionGet, saturated soda water washing is neutral, and steam except after ethyl acetate and add 350kg toluene, crystallisation by cooling, centrifugation obtains slightlyProduct, obtain purified product after recrystallization decolouring. Total recovery reaches more than 65%, and purity reaches more than 99.0%.
Embodiment 3
Step 1): in 2000L diazo reaction still, adding mass percent is 40% aqueous sulfuric acid 1850kg, steamsVapour heating starts at the uniform velocity to drip 3-chloro-2-methyl aniline 225kg in the time that temperature rises to 90-95 DEG C, in 1.5-2h, dripsFinish insulation reaction 1.0h. Logical salt solution is cooled to below 5 DEG C. Control temperature at 0-5 DEG C, in 3-4h, drip mass percent and be30% sodium nitrite in aqueous solution 385kg, finishes rear insulation 1.0h, and it is for subsequent use that suction filtration obtains suction filtration diazo liquid.
Step 2): in hydrolysis kettle, inject the mother liquid coming that 780kg reclaims, add the active rare earth catalyst lanthanum orthophosphate of 13kg,Open and stir, at the uniform velocity drip the 560kg concentrated sulfuric acid, the toluene extract of 700kg reextraction, is warming up to backflow, in 3-4h, dripsAdd step 1) diazo liquid that obtains, after insulation 0.5h, lower the temperature, leave standstill point water layer and an organic layer, water layer is got 780kg as mother liquid comingRecycle, remainingly after toluene reextraction, put to waste water processing station, the toluene extract of reextraction goes to hydrolysis kettleHead tank recycles; Organic layer is directly beaten to the molten still of alkali, is warming up to 60 DEG C, at the uniform velocity drips 675kg sheet alkali 11% (quality percentageThan) the about 1h of the aqueous solution, leave standstill point water layer and an organic layer, sodium phenolate solution water layer is placed in bucket, treat the high pressure use that feeds intake, organic layerThe toluene solvant that can be used as reextraction through the toluene of Distillation recovery recycles.
Step 3): suction successively in autoclave: 560kg step 2) the sodium phenolate solution that obtains, 275kg mass percent63.5% sodium hydrate aqueous solution, 7.5kg sodium formate, 9.5kg sodium sulfite, the cuprous chloride catalyst that 7.5kg sour water was washed.Heating, at 195～200 DEG C, still internal pressure is under 1.0～1.2Mpa condition, insulation 1.5-2h, is then cooled to 100 DEG C and carries outSuction filtration, elimination solid slag, unified collection. Filtrate is for subsequent use.
Step 4): in advance by 675kg hydrochloric acid and 850kg water wiring solution-forming, step 3) filtrate that obtains enters in acidifying still,In 0.5-1.0h, dripping aqueous hydrochloric acid solution to pH value is fast 1.5-2. Be cooled to room temperature, suction filtration, 800kg ethyl acetate extractionGet, saturated soda water washing is neutral, and steam except after ethyl acetate and add 350kg toluene, crystallisation by cooling, centrifugation obtains slightlyProduct, obtain purified product after recrystallization decolouring. Total recovery reaches more than 65%, and purity reaches more than 99.0%.
Claims (4)
1. one kind 2, the synthetic method of 6-orcin, is characterized in that: taking 3-chloro-2-methyl aniline as initiation material, and warpDiazo-reaction, hydrolysis, alkali are molten, 4 steps of acidifying, obtain 2,6-orcin, and synthesis step is as follows:
Step 1): in diazotising still, first sulfuric acid is mixed with to mass concentration and is 40% the aqueous solution, while being warming up to 90-95 DEG C, openBegin to drip 3-chloro-2-methyl aniline, in 1.5-2h, dropwise, after insulation 1.0h, logical salt solution is cooled to below 5 DEG C, controlsTemperature is at 0-5 DEG C, drips mass concentration and be 30% sodium nitrite in aqueous solution in 3-4h, finishes rear insulation 1.0h, and suction filtration obtainsFor subsequent use to diazo liquid filtrate;
Wherein, the mass ratio of 3-chloro-2-methyl aniline, the concentrated sulfuric acid, natrium nitrosum is 1: 3.1～3.5: 0.49～0.53;
Step 2): the mother liquid coming of injected water or recovery in still, adds active rare earth catalyst lanthanum orthophosphate to open and stirs, at the uniform velocityDrip the concentrated sulfuric acid, the toluene extract that toluene or reextraction are used, is warming up to backflow, in 3-4h, drips by step 1) obtainDiazo liquid, insulation is lowered the temperature after 0.5h, leaves standstill point water layer and an organic layer, a water layer part recycles as mother liquid coming, residueAfter toluene reextraction, put to waste water processing station, the toluene extract that reextraction is used can recycle; Organic layer is notMust be dried directly and beat to the molten still of alkali, be warming up to 60 DEG C, at the uniform velocity drip mass concentration and be 11% sheet aqueous alkali 1h, leave standstill a point waterLayer and organic layer, place sodium phenolate solution water layer in bucket, treats the high pressure use that feeds intake, and organic layer can follow through the toluene of Distillation recoveryRing uses; Wherein, the mass ratio of toluene, the concentrated sulfuric acid, catalyst lanthanum orthophosphate is 1: 0.80～0.85: 0.014～0.021;
Step 3): suction step 2 successively in autoclave) the sodium phenolate solution, the mass concentration that obtain be 63.5% NaOHThe cuprous chloride catalyst that the aqueous solution, sodium formate, sodium sulfite, sour water were washed, is warming up to 195～200 DEG C, and still internal pressure isUnder 1.0～1.2Mpa condition, insulation 1.5-2h, is then cooled to 100 DEG C and carries out suction filtration, elimination solid slag, unified collection, filterLiquid is for subsequent use; Wherein, the mass ratio of sodium phenolate solution, stannous chloride, sodium sulfite, sodium formate is 1: 1.2～1.4: 1.6～1.8:1.2～1.4；
Step 4): in advance hydrochloric acid and water are made into aqueous hydrochloric acid solution, step 3 according to mass ratio 1: 1.2～1.3) filtrate that obtainsEnter in acidifying still, in 0.5-1.0h, dripping aqueous hydrochloric acid solution to pH value is fast 1.5-2, is cooled to room temperature, suction filtration, acetic acidEthyl ester extraction, saturated soda water washing is neutral, and steam except after ethyl acetate and add toluene, crystallisation by cooling, centrifugation obtains slightlyProduct, obtain purified product after recrystallization, decolouring, and all drying processes are all used homemade boiling drying equipment, solvent energy recovery setWith;
2. according to claim 1 a kind of 2, the synthetic method of 6-orcin, is characterized in that: step 2) generate3-chloro-2-methyl phenol not drying directly drips sodium phenolate throwing autoclave processed with alkali.
3. according to claim 1 a kind of 2, the synthetic method of 6-orcin, is characterized in that: step 2 is with activeRare earth lanthanum orthophosphate is as catalyst optimization product color.
4. according to claim 1 a kind of 2, the synthetic method of 6-orcin, is characterized in that: self-control for step 4Boiling drying equipment, 40-50 DEG C dry product, every batch drying time 0.5h, the solvent of volatilization is wanted recovery.
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| CN105152870A (en) * | 2015-08-27 | 2015-12-16 | 河南黑马动物药业有限公司 | Method for preparing pyroline by means of water re-crystallization |
| CN107473943A (en) * | 2017-08-22 | 2017-12-15 | 江苏鼎烨药业有限公司 | A kind of preparation method of 2,6 orcin |
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| CN114085132B (en) * | 2021-12-02 | 2023-10-24 | 湖北文理学院 | Preparation method of 2, 6-dihydroxytoluene |
| CN115055130A (en) * | 2022-05-13 | 2022-09-16 | 丁兴立 | System for preparing 2-methylresorcinol and method for preparing 2-methylresorcinol |
| CN115784846B (en) * | 2022-11-28 | 2024-01-16 | 安徽英特美科技有限公司 | Preparation method of 2,6-dihydroxytoluene |
| CN116283500B (en) * | 2023-02-13 | 2024-05-07 | 内蒙古源宏精细化工有限公司 | Synthesis method of high-purity 2, 6-dihydroxytoluene |
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