CN101284768B - Preparation method for intermediate epichlorophdrin of herbicide pretilachlor - Google Patents
Preparation method for intermediate epichlorophdrin of herbicide pretilachlor Download PDFInfo
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- CN101284768B CN101284768B CN2008100618780A CN200810061878A CN101284768B CN 101284768 B CN101284768 B CN 101284768B CN 2008100618780 A CN2008100618780 A CN 2008100618780A CN 200810061878 A CN200810061878 A CN 200810061878A CN 101284768 B CN101284768 B CN 101284768B
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Abstract
The invention relates to a method for preparing a herbicide pretilachlor intermediate chloride ether, which comprises: under the action of an organic amine catalyst, the chloride ether can be obtained by reacting ethylene glycol monopropyl ether with bis (trichloromethyl) hydroxyphenyl in the organic solvent according to the following chemical equation: HOC2H4OC3H7+Cl3COCOOCCl3 - ClC2H4OC3H7+CO2+HCl. The method substitutes bis(trichloromethyl) hydroxyphenyl for traditional chlorination reagents, such as thionly chloride, phosphorus oxychloride and hydrogen chloride, etc., and the potential safety hazard can be eliminated from the process source by using the novel chlorination reagent. Simultaneously, the emissions of pollutants are greatly reduced; the method is a cleaning process with mild reaction conditions, safe and reliable operating process and high product yield, and has good industrialization implementation value and social economic benefits.
Description
Technical field
The present invention relates to the preparation method of compound, particularly a kind of preparation method of herbicide pretilachlor intermediate chlorine ether.
Background technology
Chloroethyl propyl ether (2-positive propoxy monochloroethane) is called for short chlorine ether, it is an important intermediate of the synthetic herbicide third careless amine, this weedicide is a kind of efficient, low toxicity, the special-purpose selectivity bud phase weedicide in early stage wide spectrum rice field, succeed in developing by Switzerland Ciba-Geigy company, use extensively at present, be subjected to the high evaluation of agricultural plant protection department.Chlorine ether is as its important intermediate, how to adopt the preparation method of clean and effective to receive people's very big concern.Present stage chlorine ether the preparation method, mainly contain: 1. in the presence of a large amount of acid binding agent DMF, use the sulfur oxychloride chlorination, yield is about 90%, 2. in the presence of Zinc Chloride Anhydrous, prepares yield about 50% with the acidifying of exsiccant hydrogen chloride gas; 3. at K
2CO
3In the acid binding agent, use the phosphorus oxychloride chlorination, yield about 85%.Though method 1. yield is higher, reaction process discharges a large amount of SO 2 tail gas, and DMF is difficult to reclaim, and produces a large amount of waste gas waste water, the processing cost height; Method 2. yield is low, and ethylene glycol ether is unstable under strong acidic condition, and exsiccant hydrogenchloride source is difficult in addition, and there is potential safety hazard in use.Contain a large amount of by product phosphoric acid in the product that 3. method obtains, and phosphorus oxychloride is as the seriously corroded of chlorinating agent to equipment, a large amount of phosphorated waste water intractable, pollution problem is serious.Above-mentioned several method all is not suitable for chlorine ether sunlight suitability for industrialized production owing to exist different defectives.
Summary of the invention
The objective of the invention is provides a kind of reaction conditions gentleness for the deficiency that solves above-mentioned technology, and safe operation process is reliable, product yield height, the preparation method of the herbicide pretilachlor intermediate chlorine ether that the generation pollutent is few.
In order to achieve the above object, the preparation method of the herbicide pretilachlor intermediate chlorine ether that this usefulness invention is designed be ethylene glycol ether with two (trichloromethyl) carbonic ethers under the effect of organic amine catalyzer, in organic solvent through following chemical equation: 3HOC
2H
4OC
3H
7+ Cl
3COCOOCCl
3→ 3ClC
2H
4OC
3H
7+ 3CO
2+ 3HCl obtains described chlorine ether.Operating process be earlier with the organic amine catalyst dissolution in organic solvent, add ethylene glycol ether again, with this solution heat temperature raising to 50 ℃ between 150 ℃, slowly drip the organic solvent solution that is dissolved with two (trichloromethyl) carbonic ethers, drip off back insulation reaction 3-5 hour, reaction solution is cooled to room temperature, collects product chlorine ether after diluted alkaline is neutralized to neutrality, washing, layering, organic layer drying, underpressure distillation supervisor.
Ethylene glycol ether: two (trichloromethyl) carbonic ether: the molar weight ratio that feeds intake of organic amine catalyzer be 1: 0.3 to 0.6: 0.1 to 0.5, consumption of organic solvent be the ethylene glycol ether quality 1-5 doubly.The organic amine catalyzer is pyridine, triethylamine, N, dinethylformamide, N, accelerine, N-methylpyrrole, 1, the mixture of 3-dimethyl-2-imidazolidone, tetramethyl guanidine one of them or more than one arbitrary proportions.Organic solvent can be chloroform, tetracol phenixin, ethylene dichloride, tetrahydrofuran (THF), hexanaphthene, benzene,toluene,xylene, chlorobenzene, dichlorobenzene one of them.Slowly drip the time of the organic solvent solution that is dissolved with two (trichloromethyl) carbonic ethers simultaneously, be controlled at about 1-2 hour to best.
The present invention replaces chlorination reagents such as traditional sulfur oxychloride, phosphorus oxychloride, hydrogenchloride with two (trichloromethyl) carbonic ether, by using novel chlorination reagent, eliminated potential safety hazard from the technology source.Greatly reducing the discharging of pollutent simultaneously, is a kind of reaction conditions gentleness, and safe operation process is reliable, and the cleaning procedure that product yield is high has favorable industrial implementary value and economic results in society.
Embodiment
Below by embodiment patent of the present invention is further described.
Embodiment 1
The preparation method of the described herbicide pretilachlor intermediate of present embodiment chlorine ether be ethylene glycol ether with two (trichloromethyl) carbonic ethers under the effect of organic amine catalyzer, in organic solvent through following chemical equation: 3HOC
2H
4OC
3H
7+ Cl
3COCOOCCl
3→ 3ClC
2H
4OC
3H
7+ 3CO
2+ 3HCl obtains described chlorine ether.Operating process is: earlier with the organic amine catalyst dissolution in organic solvent, add ethylene glycol ether again, with this solution heat temperature raising to 50 ℃ between 150 ℃, slowly drip the organic solvent solution that is dissolved with two (trichloromethyl) carbonic ethers, drip off back insulation reaction 3-5 hour, reaction solution is cooled to room temperature, is neutralized to neutrality, collects product chlorine ether with twice washing of 200ml moisture, standing demix, organic layer with dryings such as Calcium Chloride Powder Anhydrous, underpressure distillation through diluted alkaline.
Feed intake amount of substance than ethylene glycol ether: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.35: 0.1, the charging capacity of ethylene glycol ether is 10.5g (0.1mol), two (trichloromethyl) carbonic ether charging capacity is 10.5g (0.035mol), catalyzer is a pyridine, consumption is 0.8g (0.01lmol), organic solvent is a chloroform, and consumption is 30ml, is 4.3 times of ethylene glycol ether quality.
Temperature of reaction is 50-60 ℃, gets product 10.2g, product yield 83.5%, purity (GC) 98.9%, boiling point 129-131 ℃.
Embodiment 2
The preparation method of the described herbicide pretilachlor intermediate of present embodiment chlorine ether, it is described to feed intake amount of substance than ethylene glycol ether: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.4: 0.2, the charging capacity of ethylene glycol ether is 10.5g (0.1mol), two (trichloromethyl) carbonic ether charging capacity is 12g (0.04mol), catalyzer is a pyridine, and consumption is 1.6g (0.02mol), and organic solvent is a toluene, consumption is 40ml, is 3.3 times of ethylene glycol ether quality.
Temperature of reaction is 100～110 ℃, and other is operated with embodiment 1, gets product 10.8g, product yield 88.5%, purity (GC) 98.5%, 130～132 ℃ of boiling points.
Embodiment 3
The preparation method of the described herbicide pretilachlor intermediate of present embodiment chlorine ether, it is described to feed intake amount of substance than ethylene glycol ether: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.35: 0.1, the charging capacity of ethylene glycol ether is 10.5g (0.1mol), two (trichloromethyl) carbonic ether charging capacity is 10.5g (0.035mol), catalyzer is a triethylamine, and consumption is 1g (0.01mol), and organic solvent is an ethylene dichloride, consumption is 35ml, is 4.2 times of ethylene glycol ether quality.
Temperature of reaction is 70～80 ℃, and other is operated with embodiment 1, gets product 10.5g, product yield 86%, purity (GC) 98.9%, 128～131 ℃ of boiling points.
Embodiment 4
The preparation method of the described herbicide pretilachlor intermediate of present embodiment chlorine ether, it is described to feed intake amount of substance than ethylene glycol ether: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.4: 0.2, the charging capacity of ethylene glycol ether is 10.5g (0.1mol), two (trichloromethyl) carbonic ether charging capacity is 12g (0.04mol), catalyzer is a triethylamine, and consumption is 2g (0.02mol), and organic solvent is a chlorobenzene, consumption is 40ml, is 4.2 times of ethylene glycol ether quality.
Temperature of reaction is 120～130 ℃, and other is operated with embodiment 1, gets product 10.7g, product yield 87.5%, purity (GC) 99.2%, 130～131 ℃ of boiling points.
Embodiment 5
The preparation method of the described herbicide pretilachlor intermediate of present embodiment chlorine ether, it is described to feed intake amount of substance than ethylene glycol ether: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.4: 0.3, the charging capacity of ethylene glycol ether is 10.5g (0.1mol), two (trichloromethyl) carbonic ether charging capacity is 12g (0.04mol), catalyzer is the N-methylpyrrole, consumption is 2.5g (0.03mol), organic solvent is a tetrahydrofuran (THF), consumption is 35ml, is 3.0 times of ethylene glycol ether quality.
Temperature of reaction is 60～70 ℃, and other is operated with embodiment 1, gets product 11.2g, product yield 91.5%, purity (GC) 98.8%, 129～132 ℃ of boiling points.
Embodiment 6
The preparation method of the described herbicide pretilachlor intermediate of present embodiment chlorine ether, it is described to feed intake amount of substance than ethylene glycol ether: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.3: 0.1, the charging capacity of ethylene glycol ether is 10.5g (0.1mol), two (trichloromethyl) carbonic ether charging capacity is 9g (0.03mol), catalyzer is a pyridine, and consumption is 0.8g (0.01mol), and organic solvent is a toluene, consumption is 40ml, is 3.3 times of ethylene glycol ether quality.
Temperature of reaction is 100～110 ℃, and other is operated with embodiment 1, gets product 10.4g, product yield 85%, purity (GC) 99.0%, 129～131 ℃ of boiling points.
Embodiment 7
The preparation method of the described herbicide pretilachlor intermediate of present embodiment chlorine ether, it is described to feed intake amount of substance than ethylene glycol ether: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.6: 0.5, the charging capacity of ethylene glycol ether is 10.5g (0.1mol), two (trichloromethyl) carbonic ether charging capacity is 18g (0.06mol), catalyzer is N, dinethylformamide, consumption is 3.75g (0.05mol), organic solvent is a toluene, consumption is 40ml, is 3.3 times of ethylene glycol ether quality.
Temperature of reaction is 100～110 ℃, and other is operated with embodiment 1, gets product 11.5g, product yield 94%, purity (GC) 98.8%, 128～130 ℃ of boiling points.
Embodiment 8
The preparation method of the described herbicide pretilachlor intermediate of present embodiment chlorine ether, it is described to feed intake amount of substance than ethylene glycol ether: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.6: 0.5, the charging capacity of ethylene glycol ether is 10.5g (0.1mol), two (trichloromethyl) carbonic ether charging capacity is 18g (0.06mol), catalyzer is N, dinethylformamide, consumption is 3.75g (0.05mol), organic solvent is an orthodichlorobenzene, consumption is 35ml, is 4.6 times of ethylene glycol ether quality.
Temperature of reaction is 140～150 ℃, and other is operated with embodiment 1, gets product 11.3g, product yield 92.2%, purity (GC) 99%, 129～131 ℃ of boiling points.
Claims (6)
1. the preparation method of a herbicide pretilachlor intermediate chlorine ether is characterized in that at ethylene glycol ether and two (trichloromethyl) carbonic ethers under the effect of organic amine catalyzer, in organic solvent through following chemical equation: 3HOC
2H
4OC
3H
7+ Cl
3COCOOCCl → 3ClC
2H
4OC
3H
7+ 3CO
2+ 3HCl obtains described chlorine ether.
2. the preparation method of herbicide pretilachlor intermediate chlorine ether according to claim 1, it is characterized in that earlier the organic amine catalyst dissolution in organic solvent, add ethylene glycol ether again, with this solution heat temperature raising to 50 ℃ between 150 ℃, slowly drip the organic solvent solution that is dissolved with two (trichloromethyl) carbonic ethers, drip off back insulation reaction 3 to 5 hours, then reaction solution is cooled to room temperature, after diluted alkaline is neutralized to neutrality, washing, layering, organic layer drying, underpressure distillation program, collects product chlorine ether.
3. the preparation method of herbicide pretilachlor intermediate chlorine ether according to claim 1 and 2, its feature is stored in described ethylene glycol ether: two (trichloromethyl) carbonic ether: the molar weight ratio that feeds intake of organic amine catalyzer be 1: 0.3 to 0.6: 0.1 to 0.5, consumption of organic solvent be the ethylene glycol ether quality 1-5 doubly.
4. the preparation method of herbicide pretilachlor intermediate chlorine ether according to claim 1 and 2, its feature is pyridine, triethylamine, N at the described organic amine catalyzer of fourth, dinethylformamide, N, accelerine, N-methylpyrrole, 1, the mixture of 3-dimethyl-2 imidazolidone, tetramethyl guanidine one of them or more than one arbitrary proportions; Described organic solvent be chloroform, tetracol phenixin, ethylene dichloride, tetrahydrofuran (THF), hexanaphthene,, stupid, the dimethylbenzene of first, chlorobenzene, dichlorobenzene one of them.
5. the preparation method of herbicide pretilachlor intermediate chlorine ether according to claim 3, it is characterized in that described organic amine catalyzer is pyridine, triethylamine, N, dinethylformamide, N, accelerine, N-methylpyrrole, 1, the mixture of 3-dimethyl-2-imidazolidone, tetramethyl guanidine one of them or more than one arbitrary proportions; Described organic solvent be chloroform, tetracol phenixin, ethylene dichloride, tetrahydrofuran (THF), hexanaphthene, benzene,toluene,xylene, chlorobenzene, dichlorobenzene one of them.
6. the preparation method of herbicide pretilachlor intermediate chlorine ether according to claim 1 and 2 is characterized in that slowly dropping is dissolved with the time of the organic solvent solution of two (trichloromethyl) carbonic ethers, is controlled in 1-2 hour.
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| CN101284768B true CN101284768B (en) | 2011-08-17 |
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| CN105541563B (en) * | 2015-12-14 | 2018-02-02 | 山东凯盛新材料股份有限公司 | The preparation method of 2 propoxyl group chloroethanes |
| CN105461520A (en) * | 2015-12-14 | 2016-04-06 | 山东凯盛新材料有限公司 | Synthetic method for 2-propoxyethyl chloride |
| CN105523901B (en) * | 2015-12-14 | 2018-02-06 | 山东凯盛新材料股份有限公司 | The synthetic method of 2 propoxyl group chloroethanes |
| CN105348052B (en) * | 2015-12-14 | 2018-06-19 | 山东凯盛新材料股份有限公司 | The synthesis technology of 2- propoxyl group chloroethanes |
| CN105348050A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Production process of 2-propoxy-chloroethane |
| CN105348051B (en) * | 2015-12-14 | 2018-04-24 | 山东凯盛新材料股份有限公司 | The synthesis technique of chloroethyl positive propyl ether |
| CN105523902B (en) * | 2015-12-14 | 2018-01-30 | 山东凯盛新材料股份有限公司 | The preparation method of 2 chloroethyl propyl ethers |
| CN105461521B (en) * | 2015-12-14 | 2018-08-31 | 山东凯盛新材料股份有限公司 | The synthetic method of 2- chloroethyl propyl ethers |
| CN105348049B (en) * | 2015-12-14 | 2018-01-12 | 山东凯盛新材料股份有限公司 | The method for synthesizing 2 propoxyl group chloroethanes |
| CN107216239B (en) * | 2017-07-25 | 2021-08-06 | 利尔化学股份有限公司 | Preparation method of chlorinated aliphatic ether |
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