CN105085202A - Synthetic method for trichloromethoxybenzene - Google Patents
Synthetic method for trichloromethoxybenzene Download PDFInfo
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Abstract
The invention discloses a synthetic method for trichloromethoxybenzene. According to the invention, anisole is used as a raw material and undergoes photochlorination with chlorine in a solvent under the action of a catalyst, and trichloromethoxybenzene is obtained after separation of the solvent. Compared with reported methods in the prior art, the method provided by the invention has the characteristics of simple operation, mild reaction conditions, no emission of three wastes (i.e., waste gas, waste water and industrial residue), no usage of chemicals forbidden by international and domestic environmental protection organizations, easiness in separation of the product from the solvent, etc.
Description
Technical field
The invention discloses a kind of method of synthesizing trichlorine metoxybenzene.Take methyl-phenoxide as raw material, carry out optical chlorinating reaction with chlorine in a solvent with under catalyst action, after being separated solvent, obtain trichlorine metoxybenzene.Compared with the production method reported, the present invention has easy and simple to handle, the feature such as reaction conditions is gentle, product is easily separated, solvent easily reclaims, product isomer-free, environmental protection.
Background technology
Along with the progress of science, product innovation, the novel material of the high-performance in each field, high quality, high technology content constantly come out, and organic compound is the important intermediate of the industry product innovations such as medicine, agricultural chemicals, electronics, dyestuff, novel material development and production always.
Fluorine in fluorine-containing organic intermediate due to atomic radius little, there is again larger electronegativity, C-F key bond energy that it is formed is more much bigger than C-H key bond energy, significantly increase stability and the physiologically active of organic compound, fluorinated organic compound also has higher fat-soluble and hydrophobicity in addition, promote its absorption in vivo and transmission speed, physiological action is changed.Thus a lot of fluorine-containing medicines is relative in performance with agricultural chemicals has the features such as consumption is few, toxicity is low, drug effect is high, metabolic capacity is strong, produces great impact to the pharmacodynamics of medicine and pharmacokinetics.Because the performance of Drugs Containing Fluorine is superior, therefore, the application of fluorine-containing organic intermediate domestic and international market has been promoted to the research and development of Drugs Containing Fluorine.
In the novel pesticide synthesized in recent years, with fastest developing speed with the environmentally friendly fluoro-containing pesticide of efficient, low toxicity, low residue.Existing nearly 100 these type of fluoro-containing pesticide new variety occur at present, and wherein more than 60% commercialization, has more than 20 kind to occupy the dominant position of pesticide market.
As the representative that the thifluzamide of crop bactericide and the indoxacarb of sterilant are the fluoro-containing pesticides of up-to-date research and development, above-mentioned two kinds of distinctive advantages of fluoro-containing pesticide such as agricultural chemicals is few with consumption, toxicity is low, drug effect is high, metabolic capacity is strong, are extensively promoted the use of by the whole world in recent years.
Trichlorine metoxybenzene is irreplaceable important intermediate in synthetic pesticide thifluzamide, indoxacarb, flucarbazonesodium process, and the solvent that trichloromethoxy chlorobenzene synthesis in the past uses is tetracol phenixin, p-chloro benzo trifluoride-99 series, hexanaphthene, tetrahydrofuran (THF) etc.Tetracol phenixin is as solvent, because it is special structural, ozone generation chain reaction easily and in air, destroy the ozonosphere in air, harm humans is healthy, so State Environmental Protection Administration issued bulletin in 2003, determine from 1 day June in 2003, prohibit the use tetracol phenixin as clean-out system and chemical reaction solvent in China." bulletin " requirement simultaneously, the departments concerned actively will be supervised and be assisted enterprise to carry out in real earnest, conscientiously carries out forbidding work.Violate the enterprise of this regulation, the punishment that local environment protection administrative responsibile institution carries out together with relevant department in accordance with the law will be subject to.There is separation difficulty in other above-mentioned solvent; Industrial cost rises; By product is many, degradation problem under reaction yield.The present invention in optical chlorinating reaction with simple and easy to get, free of contamination dual-trifluoromethyl benzene for solvent, add that azo compound is as initiator, polychloride is as catalyzer, and target product content is high, and reaction yield is high.Product and solvent easily separated, easily reclaim.Improve the purity of target product, improve production efficiency.Compared with technique in the past, be have more economy, the novel green technique of the feature of environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of reaction conditions gentleness, wide adaptability, raw material to be easy to get, pollute little, environmental protection, can synthesize the method for trichlorine metoxybenzene simply and easily.
To achieve these goals, technical scheme of the present invention is as follows:
A synthetic method for trichlorine metoxybenzene, described trichlorine metoxybenzene 1, its characteristic molecular formula is: C
7h
5cl
3o;
With methyl-phenoxide 2 for starting raw material, with chlorination reagent 3 and initiator 4, catalyzer 5 at solvent dual-trifluoromethyl benzene (C
8h
4f
6) carry out optical chlorinating reaction in 6, obtain compound 1 after being separated solvent;
Synthetic route is as shown in following reaction formula:
Be specially:
The first step: with azo compound 4 for initiator, with polychloride 5 for catalyzer, raw material 2 is at solvent dual-trifluoromethyl benzene 6 (C
8h
4f
6) in carry out optical chlorinating reaction with chlorination reagent 3 and generate trichloromethoxy chlorobenzene 1.Through being separated solvent after reaction terminates, obtain trichlorine metoxybenzene 1.
In technical scheme:
1. product 1 is trichlorine metoxybenzene.
2. azo-initiator 4 is preferably one or two or more kinds in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl.Usually also azo-initiator can be substituted as Light chlorimation initiator, as adopted benzoyl peroxide or dilauroyl peroxide etc. with superoxide.In above-mentioned azo-initiator, with Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile) catalytic effect relatively good, but best by azo-bis-iso-dimethyl effect.Usage quantity is generally the 0.1-10% of raw material (methyl-phenoxide) weight, consumption be raw material weight 1-7% within the scope of effect better, consumption is that the 2-4% effect of raw material weight is best.
3. polychloride 5 is one or two or more kinds in phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride.Usual usage quantity is the 0.5-15% of raw material (methyl-phenoxide) weight, consumption be raw material weight 2-5% within the scope of effect better, consumption is that the 3-4% effect of raw material weight is best.
4. chlorination reagent 3 is chlorine.Reaction end GC method tracing detection, when benzyl dichloride content is reaction end lower than 0.5%.The speed that passes into of chlorine also has impact to reaction.Every 100 liters of reaction solutions, control logical chlorine speed and usually control to be 3 ~ 20L/s, and control is that 5 ~ 15L/s effect is better, and control is that 8 ~ 12L/s effect is best.
In reaction process, logical chlorine speed determines the reaction times, and the logical chlorine speed fast then reaction times is short, on the contrary then long reaction time.The optical chlorinating reaction time that described logical chlorine speed is corresponding is above generally 3-120 hour.Wherein, the reaction times is that 5-96 hour effect is better, and the reaction times is that 12-40 hour effect is best.
When proceeding to 7 ~ 15 hours when reacted: in every 100L reaction solution, when logical chlorine speed control is 3 ~ 5L/s, benzyl dichloride content is high, and reaction is not carried out completely; When logical chlorine speed control is 13 ~ 18L/s, now react for the excessive mistake end reaction of chlorine, in system, ring muriate increases.
Control logical chlorine speed constant (every 100L solvent, logical chlorine speed control is 8 ~ 10L/s), the logical chlorine time short (3 hours), benzyl dichloride content is high and three benzyl chloride content are low, and reaction is not carried out completely, reaction yield being caused low.Logical chlorine overlong time (after 18 hours), can cause ring muriate to increase, and the selectivity of impact reaction, increases the content of by product.
5. raw material 2 is methyl-phenoxide.The main content of ingredient requirement is greater than 99.5% (GC), and not metal ion in raw material, moisture is less than 20ppm, appearance requirement water white transparency.
6. chlorinated solvent 6 is dual-trifluoromethyl benzene (adjacent two phenylfluoroforms, two phenylfluoroform, to one or two or more kinds in two phenylfluoroform series).Light chlorimation solvent is in the past all tetracol phenixin, phenylfluoroform, adjacent, the series such as p-chloro benzo trifluoride-99, but tetracol phenixin makees solvent, the destructiveness special because of it is prohibited use by country, and adjacent, p-chloro benzo trifluoride-99 series makees solvent, with product separation difficulty, in sepn process, energy consumption is high.Therefore all there is the problem that pollution is large, energy consumption is high in Light chlorimation solvent in the past.And bis trifluoromethyl benzene-series (adjacent two phenylfluoroforms, two phenylfluoroform, to two phenylfluoroforms) is as Light chlorimation solvent, successfully avoid above-mentioned Problems existing, pollution-free and be easy to be separated, and after solvent recuperation, dual-trifluoromethyl benzene also can be used as important medicine, pesticide intermediate, is widely used in chemical industry.Dual-trifluoromethyl benzene is as the Light chlorimation solvent of present method, and usual usage quantity is raw material 1-50 times (w/w), and when 2-20 times, (w/w) reaction effect is better, and when 3-10 times, (w/w) reaction effect is best.
7. optical chlorinating reaction temperature is generally 40-150 DEG C.Wherein, optimal reaction temperature is 60-100 DEG C.Temperature of reaction is too low, and increase by-product ring muriate, temperature is too high, and initiator 4 can be caused sharply to decompose, and increases the uncontrollable Hazard Factor of reaction.
8. when described in, product 1 is separated with solvent 6, with non-metallic fillers (such as drawing western porcelain ring, Bauer magnet ring, ceramic corrugated filler, glass filler etc.) in distillation tower, avoid during recycling design 6, metal object being brought in solvent, affect the selectivity of optical chlorinating reaction.
Initiator usage quantity, polychloride usage quantity, logical chlorine speed, Light chlorimation solvent load, the optical chlorinating reaction temperature usual use numerical value between them, better use between numerical value, best (the best) use numerical value and can distinguish cross-matched, such as: optical chlorinating reaction temperature optimal reaction temperature is 60-100 DEG C, can respectively with the usual usage quantity of azo-initiator, better consumption or best consumption one_to_one corresponding.
The present invention has the following advantages:
1. chlorination reagent 3 is cheaply easy to get.
2. optical chlorinating reaction mild condition, is easy to control.
3. optical chlorinating reaction solvent for use is easy to get, pollution-free, easily separated, belongs to environment-friendly type solvent; Adopt the solvent in present method, reactant content is high, almost 100% is converted into target product, and no coupling product produces; Reaction yield is high, close to the theoretical yield of reaction, has high industrial value; And solvent inherently medicine, pesticide intermediate, recycle value high.
In a word, the present invention adopts aforesaid method to synthesize trichlorine metoxybenzene, and technique is environmental protection more, and product yield is high, and the trichlorine metoxybenzene crude product purity of gained reaches more than 98%, and yield reaches 99%, far above prior art.Its beneficial effect is: by product is few, and productive rate is high, good economy performance, and the good and steady quality of product purity, whole technological process reaches zero release, achieves friendly process, is suitable for suitability for industrialized production.
Embodiment
Contribute to understanding the present invention further by following embodiment.
The various raw material that following examples adopt and reagent are commercially available, repeat no more.
The first step: prepare trichlorine metoxybenzene.This step reaction equation is as follows:
Embodiment 1
In 500mL reaction flask, add two trifluoromethylbenzene (200g successively, 145ml), azo-bis-iso-dimethyl 2 grams and phosphorus trichloride 2 grams, be warming up to 60 DEG C, open mercury lamp and carry out illumination to reaction solution, start to pass into chlorine in bottle, logical chlorine speed control is at 20ml/s, start to drip methyl-phenoxide 80g (0.56mol) simultaneously, within 1 hour, drip off.Dropwise, continue to maintain 70-80 DEG C of reaction, reaction end is by GC tracing detection, benzyl dichloride mass content <0.5% is reaction end, and this reaction time is 5 hours, stops passing into chlorine, then air purge is carried out, target product (trichlorine metoxybenzene) 149 grams is obtained, content 95.1%, yield 90.4% removed the solvent in reaction solution by distillation after.
The confirmation of product: with analytically pure trichlorine metoxybenzene for standard substance, by gas chromatographic detection, confirm that the product in the present embodiment is trichlorine metoxybenzene, purity is 95.1%.
And by nuclear-magnetism qualitative detection: the chemical shift determination product of carbon spectrum and hydrogen spectrum is trichlorine metoxybenzene.
Embodiment 2
In 500mL reaction flask, add two trifluoromethylbenzenes (400g, 285ml), azo-bis-iso-dimethyl 2 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 150 grams will be obtained, content 95.4%, yield 91.3% after reaction solution desolvation.
Embodiment 3
In 500mL reaction flask, add two trifluoromethylbenzenes (480g, 345ml), azo-bis-iso-dimethyl 2 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 150 grams will be obtained, content 95.5%, yield 91.43% after reaction solution desolvation.
Embodiment 4
In 500mL reaction flask, add two trifluoromethylbenzenes (560g, 400ml), azo-bis-iso-dimethyl 2 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 151 grams will be obtained, content 95.7%, yield 92.2% after reaction solution desolvation.
Embodiment 5
In 500mL reaction flask, add two trifluoromethylbenzenes (640g, 460ml), azo-bis-iso-dimethyl 2 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 151 grams will be obtained, content 95.9%, yield 92.4% after reaction solution desolvation.
Embodiment 6
In 500mL reaction flask, add two trifluoromethylbenzenes (720g, 518ml), azo-bis-iso-dimethyl 2 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 152 grams will be obtained, content 96%, yield 93.1% after reaction solution desolvation.
Embodiment 7
In 500mL reaction flask, add two trifluoromethylbenzenes (800g, 575ml), azo-bis-iso-dimethyl 2 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 152 grams will be obtained, content 96.3%, yield 93.43% after reaction solution desolvation.
Embodiment 8
In 500mL reaction flask, add two trifluoromethylbenzenes (800g, 575ml), azo-bis-iso-dimethyl 0.8 gram and phosphorus trichloride 1 gram successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 153 grams will be obtained, content 94.4%, yield 92.2% after reaction solution desolvation.
Embodiment 9
In 500mL reaction flask, add two trifluoromethylbenzenes (800g, 575ml), azo-bis-iso-dimethyl 1 gram and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Reaction solution precipitation is obtained target product (trichlorine metoxybenzene) 153 grams, content 94.6%, yield 92.3% except after agent.
Embodiment 10
In 500mL reaction flask, add two trifluoromethylbenzenes (800g, 575ml), azo-bis-iso-dimethyl 1.2 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 155 grams will be obtained, content 94.2%, yield 93.2% after reaction solution desolvation.
Embodiment 11
In 500mL reaction flask, add two trifluoromethylbenzenes (800g, 575ml), azo-bis-iso-dimethyl 1.5 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 154 grams will be obtained, content 95%, yield 93.3% after reaction solution desolvation.
Embodiment 12
In 500mL reaction flask, add two trifluoromethylbenzenes (800g, 575ml), azo-bis-iso-dimethyl 1.8 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 154 grams will be obtained, content 95.3%, yield 93.6% after reaction solution desolvation.
Embodiment 13
In 500mL reaction flask, add two trifluoromethylbenzenes (800g, 575ml), azo-bis-iso-dimethyl 2.2 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 157 grams will be obtained, content 97.3%, yield 97.5% after reaction solution desolvation.
Embodiment 14
In 500mL reaction flask, add two dual-trifluoromethyl benzenes (800g, 575ml), azo-bis-iso-dimethyl 2.5 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Target product (trichlorine metoxybenzene) 157 grams will be obtained, content 97.5%, yield 97.7% after reaction solution desolvation.
Embodiment 15
In 500mL reaction flask, add two trifluoromethylbenzenes (800g, 575ml), azo-bis-iso-dimethyl 3 grams and phosphorus trichloride 2 grams successively, all the other operations are with embodiment 1.Reaction solution precipitation is obtained target product (trichlorine metoxybenzene) 157 grams, content 97.9%, yield 98.1% except after agent.
Embodiment 16
In 500mL reaction flask, all the other operations, with embodiment 15, dropwise, continue to maintain 130-140 DEG C of reaction 5 hours, then purge, target product (trichlorine metoxybenzene) 158 grams will be obtained after reaction solution desolvation, content 93.7%, yield 94.5%.
Embodiment 17
In 500mL reaction flask, operate same embodiment 15, dropwise, continue to maintain 110-120 DEG C of reaction 5 hours, then purge, target product (trichlorine metoxybenzene) 158 grams will be obtained after reaction solution desolvation, content 94.9%, yield 95.7%.
Embodiment 18
In 500mL reaction flask, operate same embodiment 15, dropwise, continue to maintain 80-100 DEG C of reaction 5 hours, then purge, target product (trichlorine metoxybenzene) 158 grams will be obtained after reaction solution desolvation, content 98.4%, yield 99.2%.
Embodiment 19
In 500mL reaction flask, operate same embodiment 15, dropwise, continue to maintain 80-100 DEG C of reaction 3 hours, then purge, target product (trichlorine metoxybenzene) 155 grams will be obtained after reaction solution desolvation, content 98.9%, yield 97.6%.
Embodiment 20
In 500mL reaction flask, operate same embodiment 15, dropwise, continue to maintain 80-100 DEG C of reaction 7 hours, then purge, target product (trichlorine metoxybenzene) 157 grams will be obtained after reaction solution desolvation, content 98.9%, yield 99.1%.
Embodiment 21
In 500mL reaction flask, operate same embodiment 15, dropwise, continue to maintain 80-100 DEG C of reaction 10 hours, then purge, target product (trichlorine metoxybenzene) 157 grams will be obtained after reaction solution desolvation, content 99.4%, yield 99.6%.
Embodiment 22
In 500mL reaction flask, operate same embodiment 15, dropwise, continue to maintain 80-100 DEG C of reaction 13 hours, then purge, target product (trichlorine metoxybenzene) 157 grams will be obtained after reaction solution desolventizing, content 99.3%, yield 99.5%.
Embodiment 23
In 500mL reaction flask, operate same embodiment 15, dropwise, continue to maintain 80-100 DEG C of reaction 15 hours, then purge, target product (trichlorine metoxybenzene) 158 grams will be obtained after reaction solution desolventizing, content 98.3%, yield 99.1%.
In embodiment 2-23, when constant to chloroneb charging capacity, change solvent input amount successively, initiator input amount, catalyzer input amount, temperature of reaction and reaction times, do in the following table to contrast (table one) on the impact of must the measuring of reaction target product, content, yield:
Table one
Embodiment 24
Repeat embodiment 21 operate, will wherein chlorinated solvent change between two phenylfluoroforms, obtain target product (trichlorine metoxybenzene) 157 grams, content 99.3%, yield 99.5%.
Embodiment 25
Repeat embodiment 22 to operate, wherein will change adjacent two phenylfluoroforms into by chlorinated solvent, and obtain target product (trichlorine metoxybenzene) 157 grams, content 99.4%, yield 99.6%.
Embodiment 26
Repeat embodiment 22 to operate, will wherein change into two phenylfluoroforms and a two phenylfluoroform mixture (volume ratio is 1:1) by chlorinated solvent, and obtain target product (trichlorine metoxybenzene) 158 grams, content 98.8%, yield 99.64%.
Embodiment 27
Repeat embodiment 22 to operate, will wherein change into two phenylfluoroforms and adjacent two phenylfluoroform mixtures (volume ratio is 1:1) by chlorinated solvent, and obtain target product (trichlorine metoxybenzene) 157 grams, content 98.9%, yield 99.1%.
Embodiment 28
Repeat embodiment 22 to operate, wherein will change adjacent two phenylfluoroforms and a two phenylfluoroform mixture (volume ratio is 1:1) into by chlorinated solvent, and obtain target product (trichlorine metoxybenzene) 158 grams, content 98.4%, yield 99.2%.
Table two
| Sequence number | Solvent | Output (g) | Content (%) | Yield (%) |
| 24 | Between two phenylfluoroforms | 157 | 99.3 | 99.5 |
| 25 | Adjacent two phenylfluoroforms | 157 | 99.4 | 99.6 |
| 26 | To two phenylfluoroforms+two phenylfluoroform | 158 | 98.8 | 99.64 |
| 27 | To two phenylfluoroforms+adjacent two phenylfluoroforms | 157 | 98.9 | 99.1 |
| 28 | Adjacent two phenylfluoroforms+two phenylfluoroform | 158 | 98.4 | 99.2 |
Comparative example 1
In 500mL reaction flask, reference (take chlorobenzene as the method that trichlorine metoxybenzene produced by solvent; C07C43/225 (2006.01) I), add chlorobenzene (400g successively, 365ml), Diisopropyl azodicarboxylate 3 grams and phosphorus trichloride 2 grams, be warming up to 60 DEG C, open mercury lamp and illumination is carried out to reaction solution, start to pass into chlorine in bottle, logical chlorine speed control is at 20ml/s, start to drip methyl-phenoxide 80g (0.56mol) simultaneously, dropwise, continue to maintain 80-100 DEG C of reaction 10 hours, then air purge is carried out, chlorination material 158g will be obtained, target product (trichlorine metoxybenzene) content 32%, yield 32.3% after reaction solution desolvation.
Comparative example 2
Reference (take chlorobenzene as the method that trichlorine metoxybenzene produced by solvent; C07C43/225 (2006.01) I), according to the embodiment operation in document, when carrying out embodiment 2 and operating, to be raised to after temperature of reaction reaction solution in container full, cannot chlorine to be passed into.And when operating according to embodiment in document 3, the solvent that cannot obtain in embodiment must be measured.Only drop into 832.5 grams of solvents in this embodiment, but write and obtain 1138 grams (chlorobenzene rate of recovery 94.83%) when chlorobenzene reclaims, obviously do not square with the fact.803 grams of solvents are had to during operation.
Comparative example 3
In 500mL reaction flask, add fluorobenzene (400g successively, 400ml), azo-bis-iso-dimethyl 3 grams and phosphorus trichloride 2 grams, be warming up to 60 DEG C, open mercury lamp and illumination is carried out to reaction solution, start to pass into chlorine in bottle, logical chlorine speed control is at 20ml/s, start to drip methyl-phenoxide 80g (0.56mol) simultaneously, dropwise, continue to maintain 80-100 DEG C of reaction 10 hours, then air purge is carried out, chlorination material 152g will be obtained, target product (trichlorine metoxybenzene) content 56%, yield 54.3% after reaction solution desolvation.
Comparative example 4
In 500mL reaction flask, add ethylene dichloride (400g successively, 320ml), azo-bis-iso-dimethyl 3 grams and phosphorus trichloride 2 grams, be warming up to 60 DEG C, open mercury lamp and illumination is carried out to reaction solution, start to pass into chlorine in bottle, logical chlorine speed control is at 20ml/s, start to drip benzene 80g (0.56mol) simultaneously, dropwise, continue to maintain 80-100 DEG C of reaction 10 hours, then air purge is carried out, chlorination material 155g will be obtained, target product (trichlorine metoxybenzene) content 53.9%, yield 53.3% after reaction solution desolvation.
Comparative example 5
In 500mL reaction flask, with reference to ((1) METHODOFMAKINGTRICHLOROMETHOXYBENZENE; US005773668A; ) add p-chloro benzo trifluoride-99 (400g successively, 295ml), azo-bis-iso-dimethyl 3 grams and phosphorus trichloride 2 grams, be warming up to 60 DEG C, open mercury lamp and illumination is carried out to reaction solution, start to pass into chlorine in bottle, logical chlorine speed control is at 20ml/s, start to drip methyl-phenoxide 80g (0.56mol) simultaneously, dropwise, continue to maintain 80-100 DEG C of reaction 10 hours, then carry out air purge, chlorination material 154g will be obtained after reaction solution desolvation, target product (trichlorine metoxybenzene) content 95.3%.Yield 93.6%.But need carry out under a reduced pressure during this reaction precipitation, energy consumption is high, and production efficiency is low, and solvent recovering rate is low, is not suitable for suitability for industrialized production.
In comparative example 1-5, only solvent is changed, other conditions all perform according to top condition in embodiment, are listed as follows (table three) by reaction result, are convenient to same the first step embodiment and are contrasted.
Table three
Conclusion:
1. as can be seen from table one: when the input amount of benzene feedstock methyl ether is constant, the input amount of solvent is only in 10 times (weight ratios) of raw material, catalyzer input amount is 2.5% (weight ratio) of material quantity, temperature of reaction is 80 ~ 100 DEG C, reaction times is 10 hours, and reaction conditions is optimum.Wherein by the logical chlorine speed control reaction times, speed then long reaction time slowly, otherwise then the time short.In synthetic method one, embodiment 21 is optimum reaction condition.
2. as can be seen from table one, table two and table three: Light chlorimation solvent of the present invention be uniquely can make target compound content, Light chlorimation yield reaches the highest solvent; In reaction process, no coupling product produces, and the reaction three wastes are few, are beneficial to environmental protection; Easily be separated with reaction product under normal pressure, reaction process and sepn process are easy to control and operation; Optical chlorinating reaction mild condition, is content with very little.The chemical that the Light chlorimation solvent that present method adopts not is country or forbids in the world, and solvent inherently medicine, pesticide intermediate, after reclaiming, utility value is high.So for synthesis trichlorine metoxybenzene, the Light chlorimation solvent adopted in the present invention is optimum solvent.
Claims (7)
1. synthesize the method for trichlorine metoxybenzene, it is characterized in that:
In chlorinated solvent, be that raw material and chlorine carry out optical chlorinating reaction with methyl-phenoxide, resultant of reaction is trichlorine metoxybenzene;
Described chlorinated solvent is adjacent two phenylfluoroforms, two phenylfluoroform, mixture to one or two or more kinds in two phenylfluoroforms.
2. method according to claim 1, is characterized in that:
Detailed process is, adds catalyzer, initiator in chlorinated solvent, and start to pass into chlorine and drip benzene feedstock methyl ether simultaneously, under illumination condition, raw material and chlorine carry out optical chlorinating reaction, and after being reacted to terminal, desolvation obtains target product.
3. method according to claim 1 and 2, it is characterized in that: dual-trifluoromethyl benzene is as Light chlorimation solvent, usual usage quantity is 1-50 times (w/w) of raw material, when 2-20 times, (w/w) reaction effect is better, and when 3-10 times, (w/w) reaction effect is best.
4. the method according to claim 1,2 or 3, is characterized in that:
When benzyl dichloride mass content is reaction end lower than 0.5%; Meanwhile, every 100 liters of reaction solutions, control logical chlorine speed and are generally 3 ~ 20L/s, and control is that 5 ~ 15L/s effect is better, and control is that 8 ~ 12L/s effect is best.
5. the method according to claim 2,3 or 4, is characterized in that: described initiator is one or two or more kinds in azo-bis-iso-dimethyl, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, dilauroyl peroxide; Described initiator add-on is 0.1 ~ 10% (w/w) of raw material; Consumption be raw material weight 1-7% within the scope of effect better, consumption is that the 2-4% effect of raw material weight is best;
Catalyzer is one or two or more kinds in phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride; Usual usage quantity is the 0.5-15% of benzene feedstock methyl ether weight, consumption be raw material weight 2-8% within the scope of effect better, consumption is that the 3-4% effect of raw material weight is best.
6. the method according to claim 1,2,3,4 or 5, is characterized in that: described chlorination reaction temperature is 40-150 DEG C; Wherein, optimal reaction temperature is 60-100 DEG C.
7. the method according to claim 1,2,3,4,5 or 6, is characterized in that:
The input amount of all reaction solutions in conversion unit of reaction system is 30 ~ 80% of conversion unit volume.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008175A (en) * | 2016-05-19 | 2016-10-12 | 山东道可化学有限公司 | Production method of trifluoromethoxybenzene |
| CN110937983A (en) * | 2019-12-27 | 2020-03-31 | 大连奇凯医药科技有限公司 | Method for producing trichloromethoxybenzene by using hexafluorobenzene as solvent |
| CN111004095A (en) * | 2019-12-27 | 2020-04-14 | 大连奇凯医药科技有限公司 | Method for continuously/semi-continuously preparing trichloromethoxybenzene compounds |
| CN114539036A (en) * | 2022-01-26 | 2022-05-27 | 金凯(辽宁)生命科技股份有限公司 | Method for efficiently synthesizing trichloromethoxybenzene by controlling chlorination depth |
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| CN103553884A (en) * | 2013-11-15 | 2014-02-05 | 金凯(辽宁)化工有限公司 | Method for preparing trifluoromethoxybenzene |
| CN103772160A (en) * | 2013-12-20 | 2014-05-07 | 刘世伟 | Method for synthesizing trichlorine methoxyl chlorobenzene and trichlorine methoxyl phenylamine |
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| WO2000012456A1 (en) * | 1998-08-31 | 2000-03-09 | Occidental Chemical Corporation | Method of reducing ring chlorination in the manufacture of a trichloromethoxybenzene |
| CN102557895A (en) * | 2010-12-28 | 2012-07-11 | 北京金源化学集团有限公司 | Method for preparing trichlorine metoxybenzene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008175A (en) * | 2016-05-19 | 2016-10-12 | 山东道可化学有限公司 | Production method of trifluoromethoxybenzene |
| CN110937983A (en) * | 2019-12-27 | 2020-03-31 | 大连奇凯医药科技有限公司 | Method for producing trichloromethoxybenzene by using hexafluorobenzene as solvent |
| CN111004095A (en) * | 2019-12-27 | 2020-04-14 | 大连奇凯医药科技有限公司 | Method for continuously/semi-continuously preparing trichloromethoxybenzene compounds |
| CN114539036A (en) * | 2022-01-26 | 2022-05-27 | 金凯(辽宁)生命科技股份有限公司 | Method for efficiently synthesizing trichloromethoxybenzene by controlling chlorination depth |
| CN114539036B (en) * | 2022-01-26 | 2023-12-08 | 金凯(辽宁)生命科技股份有限公司 | Method for efficiently synthesizing trichloromethoxybenzene by controlling chlorination depth |
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