CN104098450A - Chemosynthesis preparation method for methyl catechol - Google Patents
Chemosynthesis preparation method for methyl catechol Download PDFInfo
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Abstract
The invention relates to a chemosynthesis preparation method for methyl catechol. The preparation technology comprises the following steps: adding 95-115 parts of methyl benzene and 420-480 parts of soda in a reaction still at the room temperature; adding 450-550 parts of pyrocatechol while stirring; starting steam heating after batch charging is fulfilled; dripping 450-550 parts of methyl sulfate at the same time; then adding 100-120 parts of sodium hydroxide to conduct alkali washing; generating by-product crude methanol solution by generated tail gas; stopping stirring after insulation is fulfilled; still standing for 20 minutes to conduct delamination; putting water layer into a geosyncline; conducting extraction, exsolution and distillation on an organic phase to obtain the product. The chemosynthesis preparation method has the benefits that hydrous free radical reaction is replaced by anhydrous free radical reaction; benzenediol is adopted as a starting material; various raw materials are added to synthesize the product; the technology has the excellent characteristics of advanced technology, safety, reliability, low cost, cleanness, low pollution and the like; serious environmental pollution of an original technology is avoided.
Description
Technical field
The present invention relates to a kind of manufacture craft of methyl catechol, particularly a kind of chemical synthesis and preparation method of methyl catechol.
Background technology
Methyl catechol has special fragrant and sweet smell, and slightly phenol taste, is medicine and the important intermediate of spices.By more creating
Wood phenol can synthesize multiple anti-inflammatory, antibacterials, also can directly be used as spices, also can be by its synthetic multiple food of multiple one-tenth
With with daily spices, as synthetic musk and be widely used in food, tobacco and wine and perfume industry vanillin food grade,1000.000000ine mesh etc., in recent years, more
Create wooden phenol and in the research of the first-class series product of perfume industry, close application aspect and obtained very large breakthrough, application market obtains
Huge extension space, in a word, methyl catechol is as a kind of excellent property, broad-spectrum medical material, by tool
There is vast potential for future development.
From Japanese, develop Ortho Anisidine diazotization method and produce after methyl catechol, by the extensive industrialization in various countries, but in recent years due to environmental requirement, developed country has stopped using the method.It is mainly also to take this method and pyrocatechol, monochloro methane method as main that current domestic methyl catechol is produced.This two classes explained hereafter cycle is long, and transformation efficiency, yield are all very low, and high to equipment requirements, environmental pollution is serious, and production cost and danger are higher.For improving content, the yield of product, reduce production costs, finding new clean oligosaprobic synthetic route has become the task of top priority in the industry.
Traditional technology is used 30% sodium hydroxide as reaction raw materials, for the esterification that has water to participate in, reaction mechanism is mainly that the free movement collision contact of effects of ion occurs, because raw materials used pyrocatechol ionizes poor effect when the low temperature in water, temperature is higher, molecular motion is faster, it is fiercer to react, but due to molecular motion irregularities, it is more passive to react, the transformation ratio of pyrocatechol is slower, the process controllability that generates methyl catechol and veratrole is poor, selectivity is corresponding poor, the probability that generates by product veratrole increases greatly, because feedstock conversion is slow, cause the reaction times longer, all can the oxidation by air rotten tar that generates of the methyl catechol generating under comparatively high temps and veratrole, tar can aqueous suspension in, can mix again with organic methyl catechol etc., cause organic phase and water layering difficulty, corresponding organic phase tar is more, in water, methyl catechol is more, cause the loss of product, quality product declines, and the water generating is coal-tar middle oil too much, the saltcake generating after multi-effect distilling is without recovery value.Reclaiming increases production cost, does not reclaim that wastewater flow rate is larger, and contaminate environment is serious.
Through retrieval, Chinese patent literature number is 103694090A, patent name is the preparation method > > of a < < methyl catechol, adopt the method for two-step reaction to prepare methyl catechol, the first step by epoxy cyclohexane, methyl alcohol according to certain ratio, by being equipped with in the fixed-bed reactor of load-type solid acid catalyst, under protection of inert gas, successive reaction obtains O-methoxy hexalin; Second step O-methoxy hexalin activates by H2 after inert gas dilution take the dehydrogenation catalyst bed that Pd is active ingredient, and thick product obtains methyl catechol through rectifying.This process has that raw materials cost is low, Atom economy is high, product yield is high, the simple feature of separating technology.
Chinese patent literature number is 101492353, patent name is the method > > of a < < producing guaiacol with methanol method, be take methyl alcohol as methylating reagent and pyrocatechol under solid acid catalyst effect in autoclave synthesizing guaiacol.The solid acid catalyst that synthesizing guaiacol is used, cheap, environmental friendliness, can be recycled.Feature of the present invention is that preparation technology is simple, and reaction conditions is gentle, and the reaction times is short, and the methyl catechol obtaining is faint yellow clear liquid, good product quality, and productive rate is high, and selectivity is high, and by product is few, and all by products in reaction solution can be recycled.
Summary of the invention
Object of the present invention is exactly in view of the foregoing defects the prior art has, a kind of chemical synthesis and preparation method of methyl catechol is provided, adopt pyrocatechol to react with sodium carbonate and can generate two kinds of free radicals, be bis-phenol free radical and single phenol free radical, because bis-phenol free radical absorption electronic capability is stronger, more easily be combined with methyl and first generate single phenol free radical (methyl catechol), rear generation veratrole, therefore control the amount of methyl in raw material (methylcarbonate), can reduce the generation of by product veratrole, controllability and the selectivity of reaction are better, and product yield is high.
A chemical synthesis and preparation method for methyl catechol, mainly by the raw material of following weight part, made:
A) pyrocatechol is 450-550 parts; B) methyl-sulfate is 450-500 parts; C) sodium carbonate is 420-480 parts; D) toluene is 95-115 parts; E) sodium hydroxide is 100-120 parts; F) sulfuric acid is 50-100 parts;
Its preparation technology comprises following making step:
(1) reaction process
In normal temperature downhill reaction still, add 95-115 parts of toluene, 420-480 parts, sodium carbonate, add while stirring 450-550 parts of pyrocatechols, feed intake and finish the rear steam heating of opening, 450-500 parts of methyl-sulfates are squeezed in header tank standby simultaneously; After insulation finishes, start to drip methyl-sulfate, and maintain the temperature between 95～100 ℃, be added dropwise to complete rear insulation reaction; Insulation finishes to add water for cooling to 80 ℃ in backward still,, then to adding 100-120 parts, sodium hydroxide to carry out alkali cleaning, the thick methanol solution of the institute's tail gas that produces generation byproduct; After insulation finishes, stop stirring, within standing 20 minutes, carry out layering, water layer is put into geosyncline, organic phase is put into 1# precipitation still storage tank;
(2) extraction process
Water layer is sucked in extraction kettle from geosyncline, add toluene, insulated and stirred at 30～40 ℃, carries out single extraction; After extraction finishes, stop stirring stratification, water layer is put into geosyncline, organic phase enters 1# precipitation still storage tank; And then water layer is sucked in extraction kettle from geosyncline, add toluene, in scale tank, squeeze into 50-100 parts, sulfuric acid, control temperature between 30～40 ℃, sulfuric acid is dropped in extraction kettle; Dropwise rear continuation and stir, stratification, oil reservoir enters 2# precipitation still storage tank, and water layer is sent to multiple-effect evaporator and makes byproduct saltcake through concentrated, crystallization, and water vapor is through condensation recovery;
(3) precipitation operation
Organic phase in precipitation still storage tank is squeezed in precipitation still and is heated to 110 ℃ of left and right, solvent toluene is steamed, through condenser condenses recovery; Remaining methyl catechol crude product is squeezed into still kettle and is carried out rectifying;
(4) distillation process
Methyl catechol crude product after precipitation is squeezed in still kettle, open steam and vacuum pump and carry out underpressure distillation, more than 120 ℃ cuts will put into product receiving tank, 120 ℃ of following fractions are squeezed into column distillation in distillation tower again, product is put into product receiving tank, and barrelling is sold.
Preferably, the raw materials of above-mentioned methyl catechol is mainly made by the following preferably raw material of weight part:
A) pyrocatechol is 500 parts; B) methyl-sulfate is 480 parts; C) sodium carbonate is 460 parts; D) toluene is 105 parts; E) sodium hydroxide is 110 parts; F) sulfuric acid is 60 parts.
The invention has the beneficial effects as follows:
Novel process of the present invention adopts anhydrous free radical reaction, free radical reaction is to utilize the skin of free radical Elektronenschale to have an azygous electronics, to increasing by second electronics, there is very strong avidity, thereby the reaction that forms stable structure and carry out, this technique is used sodium carbonate to replace original sodium hydroxide solution as reaction raw materials, generate the free radical of alkyl, unstable due to free radical, easily absorb electronics and form rock steady structure, itself has affinity, can attract each other with other free radical methyl on one's own initiative, therefore the initiative of reaction is higher, speed of response is very fast.Pyrocatechol reacts with sodium carbonate and can generate two kinds of free radicals, be bis-phenol free radical and single phenol free radical, because bis-phenol free radical absorption electronic capability is stronger, more easily be combined with methyl and first generate single phenol free radical (methyl catechol), therefore rear generation veratrole, controls the amount of methyl in raw material (methylcarbonate), can reduce the generation of by product veratrole, controllability and the selectivity of reaction are better, and product yield is high;
(2) comparing another advantage with traditional technology is exactly that subsequent reactions product separation ratio is easier to.Because novel process is swift in response, the reaction times shortens greatly, and by product is less, the probability that generates tar reduces greatly, and easily separated and thorough, organic phase (product) content is high, impurity is few, reduces separation costs, and the tar in water is fewer, after multi-effect distilling, saltcake is purer, has utility value, can offset separation costs, the water reclaiming is purer, recycle is few on subsequent reactions impact, the equal recoverable of byproduct, and environmental pollution is few.Experiment finds that the transformation efficiency of novel process raw material pyrocatechol is up to 99%, methyl catechol selectivity 89%, veratrole selectivity 98%, the ratio of methyl catechol and veratrole is 8:1, the byproduct methanol concentration generating reaches 47.1%, can be directly outer selling, saltcake purity, colourity are better, water circulation use on subsequent reactions without impact;
(3) make the production cycle shorten nearly 3 hours, the yield of product reaches 99%, and product purity is reached more than 99.5%;
(4) adopt novel composite catalyst, improved significantly reactivity and the product yield of pyrocatechol.
Accompanying drawing explanation
Accompanying drawing 1 is structural representation of the present invention.
Embodiment
By reference to the accompanying drawings 1, the invention will be further described:
Embodiment 1, and the present invention is mainly made by the following preferably raw material of weight part:
A) pyrocatechol technical grade > 99.5% 500kg;
B) methyl-sulfate technical grade > 99.5% 480 kg;
C) sodium carbonate technical grade >=99% 460kg;
D) toluene technical grade 99.9% 105 kg;
E) sodium hydroxide technical grade 99% 110 kg.
F) sulfuric acid industry level 60% 60kg
The chemical synthesis process of methyl catechol of the present invention, comprises following making step:
(1) reaction process
The toluene, the 460kg sodium carbonate solution that in normal temperature downhill reaction still, add 85kg, the pyrocatechol that adds while stirring 500kg, feed intake and finish the rear steam heating of opening, temperature is controlled at about 95 ℃ insulation 0.5h, 480kg methyl-sulfate is squeezed in header tank standby simultaneously.After insulation finishes, start to drip methyl-sulfate, and maintain the temperature between 95～100 ℃, about 1.5h completes dropping, is added dropwise to complete rear insulation reaction 2 hours.Insulation finishes to add the process water of specified amount to be cooled to 80 ℃ in backward still, stir 0.5h, then to adding the sodium hydroxide solution of 110kg to carry out alkali cleaning, about 50 ℃ insulations 7 hours, the tail gas that produces passed in device for absorbing tail gas and absorbs and produce the thick methanol solution of byproduct.After insulation finishes, stop stirring, within standing 20 minutes, carry out layering, water layer is put into geosyncline, organic phase is put into 1# precipitation still storage tank.
(2) extraction process
Water layer is sucked in extraction kettle from geosyncline, add the toluene of 10kg, insulated and stirred 0.5h at 30～40 ℃, carries out single extraction.After extraction finishes, stop stirring standing 1O minute layering, water layer is put into geosyncline, organic phase enters 1# precipitation still storage tank.And then water layer is sucked in extraction kettle from geosyncline, add the toluene of 10kg, to the sulfuric acid of squeezing into 60kg in scale tank, control temperature between 30～40 ℃, sulfuric acid is dropped in extraction kettle.Dropwise rear continuation and stir 1O minute, then stop stirring, standing 2O minute layering, oil reservoir enters 2# precipitation still storage tank, and water layer is sent to multiple-effect evaporator and makes byproduct saltcake through concentrated, crystallization, and water vapor is through condensation recovery.
(3) precipitation operation
Organic phase in precipitation still storage tank is squeezed in precipitation still and is heated to llO ℃ of left and right, solvent toluene is steamed, through condenser condenses recovery.Remaining methyl catechol crude product is squeezed into still kettle and is carried out rectifying.
(4) distillation process
Methyl catechol crude product after precipitation is squeezed in still kettle, open steam and vacuum pump and carry out underpressure distillation, more than 120 ℃ cuts will put into product receiving tank, 120 ℃ of following fractions are squeezed into column distillation in distillation tower again, product is put into product receiving tank, and barrelling is sold.
Embodiment 2: a kind of chemosynthesis formula of methyl catechol, mainly contains following raw material and make:
A) pyrocatechol technical grade > 99.5% 450kg;
B) methyl-sulfate technical grade > 99.5% 450 kg;
C) sodium carbonate technical grade >=99% 420kg;
D) toluene technical grade 99.9% 95 kg;
E) sodium hydroxide technical grade 99% 100 kg.
F) sulfuric acid industry level 60% 50kg
The chemical synthesis process of methyl catechol of the present invention, comprises following making step:
(1) reaction process
The toluene, the 420kg sodium carbonate solution that in normal temperature downhill reaction still, add 75kg, the pyrocatechol that adds while stirring 450kg, feed intake and finish the rear steam heating of opening, temperature is controlled at about 95 ℃ insulation 0.5h, 450kg methyl-sulfate is squeezed in header tank standby simultaneously.After insulation finishes, start to drip methyl-sulfate, and maintain the temperature between 95～100 ℃, about 1.5h completes dropping, is added dropwise to complete rear insulation reaction 2 hours.Insulation finishes to add the process water of specified amount to be cooled to 80 ℃ in backward still, stir 0.5h, then to adding the sodium hydroxide solution of 100kg to carry out alkali cleaning, about 50 ℃ insulations 7 hours, the tail gas that produces passed in device for absorbing tail gas and absorbs and produce the thick methanol solution of byproduct.After insulation finishes, stop stirring, within standing 20 minutes, carry out layering, water layer is put into geosyncline, organic phase is put into 1# precipitation still storage tank.
(2) extraction process
Water layer is sucked in extraction kettle from geosyncline, add the toluene of 10kg, insulated and stirred 0.5h at 30～40 ℃, carries out single extraction.After extraction finishes, stop stirring standing 1O minute layering, water layer is put into geosyncline, organic phase enters 1# precipitation still storage tank.And then water layer is sucked in extraction kettle from geosyncline, add the toluene of 10kg, to the sulfuric acid of squeezing into 50kg in scale tank, control temperature between 30～40 ℃, sulfuric acid is dropped in extraction kettle.Dropwise rear continuation and stir 1O minute, then stop stirring, standing 2O minute layering, oil reservoir enters 2# precipitation still storage tank, and water layer is sent to multiple-effect evaporator and makes byproduct saltcake through concentrated, crystallization, and water vapor is through condensation recovery.
(3) precipitation operation
Organic phase in precipitation still storage tank is squeezed in precipitation still and is heated to llO ℃ of left and right, solvent toluene is steamed, through condenser condenses recovery.Remaining methyl catechol crude product is squeezed into still kettle and is carried out rectifying.
(4) distillation process
Methyl catechol crude product after precipitation is squeezed in still kettle, open steam and vacuum pump and carry out underpressure distillation, more than 120 ℃ cuts will put into product receiving tank, 120 ℃ of following fractions are squeezed into column distillation in distillation tower again, product is put into product receiving tank, and barrelling is sold.
Embodiment 3: a kind of chemosynthesis formula of methyl catechol, mainly contains following raw material and make:
A) pyrocatechol technical grade > 99.5% 550kg;
B) methyl-sulfate technical grade > 99.5% 500 kg;
C) sodium carbonate technical grade >=99% 480kg;
D) toluene technical grade 99.9% 115 kg;
E) sodium hydroxide technical grade 99% 120 kg.
F) sulfuric acid industry level 60% 100kg
The chemical synthesis process of methyl catechol of the present invention, comprises following making step:
(1) reaction process
The toluene, the 480kg sodium carbonate solution that in normal temperature downhill reaction still, add 95kg, the pyrocatechol that adds while stirring 550kg, feed intake and finish the rear steam heating of opening, temperature is controlled at about 95 ℃ insulation 0.5h, 500kg methyl-sulfate is squeezed in header tank standby simultaneously.After insulation finishes, start to drip methyl-sulfate, and maintain the temperature between 95～100 ℃, about 1.5h completes dropping, is added dropwise to complete rear insulation reaction 2 hours.Insulation finishes to add the process water of specified amount to be cooled to 80 ℃ in backward still, stir 0.5h, then to adding the sodium hydroxide solution of 120kg to carry out alkali cleaning, about 50 ℃ insulations 7 hours, the tail gas that produces passed in device for absorbing tail gas and absorbs and produce the thick methanol solution of byproduct.After insulation finishes, stop stirring, within standing 20 minutes, carry out layering, water layer is put into geosyncline, organic phase is put into 1# precipitation still storage tank.
(2) extraction process
Water layer is sucked in extraction kettle from geosyncline, add the toluene of 10kg, insulated and stirred 0.5h at 30～40 ℃, carries out single extraction.After extraction finishes, stop stirring standing 1O minute layering, water layer is put into geosyncline, organic phase enters 1# precipitation still storage tank.And then water layer is sucked in extraction kettle from geosyncline, add the toluene of 10kg, to the sulfuric acid of squeezing into 100kg in scale tank, control temperature between 30～40 ℃, sulfuric acid is dropped in extraction kettle.Dropwise rear continuation and stir 1O minute, then stop stirring, standing 2O minute layering, oil reservoir enters 2# precipitation still storage tank, and water layer is sent to multiple-effect evaporator and makes byproduct saltcake through concentrated, crystallization, and water vapor is through condensation recovery.
(3) precipitation operation
Organic phase in precipitation still storage tank is squeezed in precipitation still and is heated to llO ℃ of left and right, solvent toluene is steamed, through condenser condenses recovery.Remaining methyl catechol crude product is squeezed into still kettle and is carried out rectifying.
(4) distillation process
Methyl catechol crude product after precipitation is squeezed in still kettle, open steam and vacuum pump and carry out underpressure distillation, more than 120 ℃ cuts will put into product receiving tank, 120 ℃ of following fractions are squeezed into column distillation in distillation tower again, product is put into product receiving tank, and barrelling is sold.
Claims (2)
1. a chemical synthesis and preparation method for methyl catechol, is characterized in that mainly by the raw material of following weight part, being made:
A) pyrocatechol is 450-550 parts; B) methyl-sulfate is 450-500 parts; C) sodium carbonate is 420-480 parts; D) toluene is 95-115 parts; E) sodium hydroxide is 100-120 parts; F) sulfuric acid is 50-100 parts;
Its preparation technology comprises following making step:
(1) reaction process
In normal temperature downhill reaction still, add 95-115 parts of toluene, 420-480 parts, sodium carbonate, add while stirring 450-550 parts of pyrocatechols, feed intake and finish the rear steam heating of opening, 450-500 parts of methyl-sulfates are squeezed in header tank standby simultaneously; After insulation finishes, start to drip methyl-sulfate, and maintain the temperature between 95～100 ℃, be added dropwise to complete rear insulation reaction; Insulation finishes to add water for cooling to 80 ℃ in backward still,, then to adding 100-120 parts, sodium hydroxide to carry out alkali cleaning, the thick methanol solution of the institute's tail gas that produces generation byproduct; After insulation finishes, stop stirring, within standing 20 minutes, carry out layering, water layer is put into geosyncline, organic phase is put into 1# precipitation still storage tank;
(2) extraction process
Water layer is sucked in extraction kettle from geosyncline, add toluene, insulated and stirred at 30～40 ℃, carries out single extraction; After extraction finishes, stop stirring stratification, water layer is put into geosyncline, organic phase enters 1# precipitation still storage tank; And then water layer is sucked in extraction kettle from geosyncline, add toluene, in scale tank, squeeze into 50-100 parts, sulfuric acid, control temperature between 30～40 ℃, sulfuric acid is dropped in extraction kettle; Dropwise rear continuation and stir, stratification, oil reservoir enters 2# precipitation still storage tank, and water layer is sent to multiple-effect evaporator and makes byproduct saltcake through concentrated, crystallization, and water vapor is through condensation recovery;
(3) precipitation operation
Organic phase in precipitation still storage tank is squeezed in precipitation still and is heated to 110 ℃ of left and right, solvent toluene is steamed, through condenser condenses recovery; Remaining methyl catechol crude product is squeezed into still kettle and is carried out rectifying;
(4) distillation process
Methyl catechol crude product after precipitation is squeezed in still kettle, open steam and vacuum pump and carry out underpressure distillation, more than 120 ℃ cuts will put into product receiving tank, 120 ℃ of following fractions are squeezed into column distillation in distillation tower again, product is put into product receiving tank, and barrelling is sold.
2. the chemical synthesis and preparation method of methyl catechol according to claim 1, is characterized in that: mainly by the following preferably raw material of weight part, made:
A) pyrocatechol is 500 parts; B) methyl-sulfate is 480 parts; C) sodium carbonate is 460 parts; D) toluene is 105 parts; E) sodium hydroxide is 110 parts; F) sulfuric acid is 60 parts.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341304A (en) * | 2020-12-24 | 2021-02-09 | 江苏新瑞药业有限公司 | Method for recovering solvent in valsartan preparation process mother liquor |
| CN115850033A (en) * | 2022-11-30 | 2023-03-28 | 重庆欣欣向荣精细化工有限公司 | Synthetic method of guaiacol |
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| CN101219938A (en) * | 2008-01-18 | 2008-07-16 | 青岛亿明翔精细化工科技有限公司 | Guaiacol synthesizing method |
| CN101492353A (en) * | 2009-03-13 | 2009-07-29 | 北京化工大学 | Method for producing guaiacol with methanol method |
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| JPS4857935A (en) * | 1971-11-24 | 1973-08-14 | ||
| JPH0857935A (en) * | 1994-08-24 | 1996-03-05 | Tomy Kikai Kogyo Kk | Die of extrusion molding apparatus |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341304A (en) * | 2020-12-24 | 2021-02-09 | 江苏新瑞药业有限公司 | Method for recovering solvent in valsartan preparation process mother liquor |
| CN112341304B (en) * | 2020-12-24 | 2024-05-24 | 江苏新瑞药业有限公司 | Recovery method of solvent in valsartan preparation process mother liquor |
| CN115850033A (en) * | 2022-11-30 | 2023-03-28 | 重庆欣欣向荣精细化工有限公司 | Synthetic method of guaiacol |
| CN115850033B (en) * | 2022-11-30 | 2024-04-02 | 重庆欣欣向荣精细化工有限公司 | Synthesis method of guaiacol |
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Application publication date: 20141015 |