CN103274944A - Preparation method of methylchloroformate - Google Patents
Preparation method of methylchloroformate Download PDFInfo
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- CN103274944A CN103274944A CN2013101868252A CN201310186825A CN103274944A CN 103274944 A CN103274944 A CN 103274944A CN 2013101868252 A CN2013101868252 A CN 2013101868252A CN 201310186825 A CN201310186825 A CN 201310186825A CN 103274944 A CN103274944 A CN 103274944A
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Abstract
The invention discloses a preparation method of methylchloroformate. The preparation method comprises the following steps of: with solid phosgene and methanol as raw materials, adding an acid binding agent to the raw materials, stirring the obtained mixture at low temperature to obtain a mixed solution, carrying out acid-washing, alkali-washing, and saturated brine washing on the mixed solution, carrying out reduced-pressure distillation on the washed product and collecting the methylchloroformate fraction. Compared with the prior art, the preparation method has the following obvious advantages that (1) the solid phosgene method, which is mild in reaction conditions, safe and convenient to operate, and high in yield, replaces a traditional phosgene method for the synthesis of the methylchloroformate; (2) the preparation method can be applied to industrialized production and is conductive to the transportation and use of the raw materials; and (3) as the current synthesis method of the methylchloroformate uses a phosgene method or a double phosgene method, and the solid phosgene which replaces a reaction for preparing the methylchloroformate meets environment-friendly chemical requirements and opens up a wider application prospect in the application fields of using the solid phosgene to replace the phosgene.
Description
Technical field
The invention belongs to the organic synthesis field, particularly a kind of preparation method of compound methyl-chloroformate.
Background technology
Solid phosgene is triphosgene again, is a kind of broad-spectrum green chemical industry product, has important prospect in fine chemistry industry and organic synthesis field.Dissolve in organic solvents such as methylene dichloride, chloroform, ether, ethanol, tetrahydrofuran (THF), toluene.Relatively with hypertoxic phosgene boiling point height, surface vapor pressure is low, thermostability is high, only handles as general poisonous substance, can replace phosgene to carry out various organic reactions.
Methyl-chloroformate has application very widely as the intermediate of Insecticides (tech) ﹠ Herbicides (tech) on the agricultural chemicals in organic synthesis, contain multiple functional groups such as methyl, methoxyl group, carbonyl, acyl chlorides in its molecular structure, thereby have good reaction activity, can carry out carbonylation, methylate, organic synthesis such as methoxylation, carbonyl methoxylation and transesterify.In pesticide producing, can be used for carbamate insecticides, also for the production of sterilant and multiple weedicide; In national defense industry for the production of centralite with as war gas.Traditional technology is to be made by the reaction of methyl alcohol photoreactive gas both at home and abroad at present, because security considerations such as the hypertoxicity of phosgene and transportation preparations, adopting additive method to replace is the inevitable demand of new millennium.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who adopts green chemical industry product solid phosgene to replace the synthetic methyl-chloroformate of phosgene.
The technical solution that realizes the object of the invention is:
A kind of preparation method of methyl-chloroformate is characterized in that may further comprise the steps:
The first step adds methyl alcohol and organic solvent and acid binding agent in reactor, low temperature stirs;
Second step was dissolved in solid phosgene in the organic solvent, and slowly dripped in reactor, and reaction finishes back nitrogen purging reaction system, and tail gas feeds alkali lye and absorbs;
In the 3rd step, through overpickling, alkali cleaning, saturated common salt water washing, the organic phase drying obtains containing the mixed solution of methyl-chloroformate with second mixed solution that obtain of step;
In the 4th step, with the mixed solution underpressure distillation that contains methyl-chloroformate that the 3rd step obtained, collect the methyl-chloroformate cut.
Wherein, organic solvent was selected methylene dichloride, trichloromethane, tetrachloro formic acid, ethanol or ethyl acetate for use during the first step, second went on foot.
Acid binding agent is selected triethylamine, pyridine, N for use in the first step, dinethylformamide or N, N-diisopropyl aniline.
The first step low temperature stirs the control temperature at-5 ~ 0 ℃, and temperature of reaction is-30 ~ 25 ℃ in second step, and the reaction times is 0.5 ~ 5 h.
Alkali lye is selected NaOH solution for use in second step.
KHSO is selected in pickling for use in the 3rd step
4Solution, NaHCO is selected in alkali cleaning for use
3Solution.
The present invention compared with prior art, its remarkable advantage: (1) adopts the solid phosgene method to replace traditional phosgenation to synthesize methyl-chloroformate, reaction conditions gentleness, easy-to-operate, yield are higher; (2) this technology can be applied in suitability for industrialized production, is conducive to transportation and the use of raw material; (3) synthetic phosgene or the trichloromethylchloroformate method of still adopting of present methyl-chloroformate replaces the reaction of preparation methyl-chloroformate to meet the requirement of Green Chemistry with solid phosgene, and more solid phosgene replaces the Application Areas of phosgene to open up more wide application prospect.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Description of drawings
The preparation method's of Fig. 1 methyl-chloroformate of the present invention schema.
Embodiment
A kind of preparation method of methyl-chloroformate is characterized in that may further comprise the steps:
The first step adds methyl alcohol and organic solvent and acid binding agent in reactor, low temperature stirs;
Second step was dissolved in solid phosgene in the organic solvent, and slowly dripped in reactor, and reaction finishes back nitrogen purging reaction system, and tail gas feeds alkali lye and absorbs;
In the 3rd step, through overpickling, alkali cleaning, saturated common salt water washing, the organic phase drying obtains containing the mixed solution of methyl-chloroformate with second mixed solution that obtain of step;
In the 4th step, with the mixed solution underpressure distillation that contains methyl-chloroformate that the 3rd step obtained, collect the methyl-chloroformate cut.
In order to determine the optimum reaction condition of methyl-chloroformate preparation, factors such as temperature, time and acid binding agent have been discussed respectively.The experimental technique of each influence factor is as follows:
(1) influence of temperature to reacting:
Fixedly acid binding agent is triethylamine, and the reaction times is that 3h is constant, and temperature of reaction is respectively-30 ℃ ,-20 ℃ ,-10 ℃, 0 ℃, 10 ℃, 25 ℃ in second step of control, and product yield is as follows:
| Temperature of reaction/℃ | -30℃ | -20℃ | -10℃ | 0℃ | 10℃ | 25℃ |
| Methyl-chloroformate yield/% | 72.42 | 72.81 | 72.08 | 67.28 | 64.62 | 50.95 |
(2) influence in reaction times:
Fixedly acid binding agent is triethylamine, and temperature of reaction-20 is ℃ constant, and the reaction times is respectively 0.5h, 1h, 2h, 3h, 4h, 5h in second step of control, and product yield is as follows:
| Reaction times/h | 0.5 | 1 | 2 | 3 | 4 | 5 |
| Methyl-chloroformate yield/% | 60.44 | 72.86 | 72.62 | 72.08 | 65.84 | 61.95 |
(3) influence of acid binding agent:
The fixation reaction temperature is-20 ℃, and the reaction times, 3h was constant, control the first step acid binding agent be respectively triethylamine, pyridine,
N, dinethylformamide, N, the N-diisopropyl aniline, product yield is as follows:
| Acid binding agent | Triethylamine | Pyridine | N, dinethylformamide | N, the N-diisopropyl aniline |
| Methyl-chloroformate yield/% | 67.31 | 69.61 | 65.48 | 77.28 |
Embodiment 1
In the there-necked flask of 100 mL, add 50 mL methylene dichloride and 10 mL methyl alcohol and 3mL triethylamine successively,-5 ℃ are stirred down, the 5g solid phosgene is dissolved in the 20 mL methylene dichloride, and in reactor, slowly drip, exothermic heat of reaction also generates a large amount of gases, and 30 min dropwise, and continues-30 ℃ of following reaction 0.5 h and stops, reaction finishes back nitrogen purging reaction system, and tail gas absorbs with sodium hydroxide solution.The gained mixed solution is through 5% aqueous potassium hydrogen sulfate (50 mL * 2), 5% sodium bicarbonate aqueous solution (50 mL * 2), saturated aqueous common salt (100 mL) washing extraction, organic phase obtains the mixed solution that transparent liquid is methyl-chloroformate with anhydrous magnesium sulfate drying, underpressure distillation under 15mmHg again, collect 30 ~ 35 ℃ of methyl-chloroformate cuts, yield 72.4%, nuclear-magnetism, gas chromatographic analysis are target product.
Embodiment 2
In the there-necked flask of 100 mL, add 50 mL ethanol and 10 mL methyl alcohol and 3mL pyridine successively,-5 ℃ are stirred down, the 5g solid phosgene is dissolved in the 20 mL ethanol, and in reactor, slowly drip, exothermic heat of reaction also generates a large amount of gases, and 30 min dropwise, and continues-10 ℃ of following reaction 5 h and stops, reaction finishes back nitrogen purging reaction system, and tail gas absorbs with sodium hydroxide solution.The gained mixed solution is through 5% aqueous potassium hydrogen sulfate (50 mL * 2), 5% sodium bicarbonate aqueous solution (50 mL * 2), saturated aqueous common salt (100 mL) washing extraction, organic phase obtains the mixed solution that transparent liquid is methyl-chloroformate with anhydrous magnesium sulfate drying, underpressure distillation under 15mmHg again, collect 30 ~ 35 ℃ of methyl-chloroformate cuts, yield, 69.6%, nuclear-magnetism, gas chromatographic analysis are target product.
Embodiment 3
In the there-necked flask of 100 mL, add 50 mL trichloromethanes and 10 mL methyl alcohol and 3mLN successively, dinethylformamide,-5 ℃ are stirred down, the 5g solid phosgene is dissolved in the 20 mL trichloromethanes, and slowly drips in reactor, exothermic heat of reaction also generates a large amount of gases, 30 min dropwise, continue to react under the room temperature 2 h and stop, reaction finishes back nitrogen purging reaction system, and tail gas absorbs with sodium hydroxide solution.The gained mixed solution is through 5% aqueous potassium hydrogen sulfate (50 mL * 2), 5% sodium bicarbonate aqueous solution (50 mL * 2), saturated aqueous common salt (100 mL) washing extraction, organic phase obtains the mixed solution that transparent liquid is methyl-chloroformate with anhydrous magnesium sulfate drying, underpressure distillation under 15mmHg again, collect 30 ~ 35 ℃ of methyl-chloroformate cuts, yield 64.8%, nuclear-magnetism, gas chromatographic analysis are target product.
Embodiment 4
In the there-necked flask of 100 mL, add 50 mL tetrachloromethanes and 10 mL methyl alcohol and 3mL triethylamine successively,-5 ℃ are stirred down, the 5g solid phosgene is dissolved in the 20 mL tetrachloromethanes, and in reactor, slowly drip, exothermic heat of reaction also generates a large amount of gases, and 30 min dropwise, and continues to react under the room temperature 2 h and stops, reaction finishes back nitrogen purging reaction system, and tail gas absorbs with sodium hydroxide solution.The gained mixed solution is through 5% aqueous potassium hydrogen sulfate (50 mL * 2), 5% sodium bicarbonate aqueous solution (50 mL * 2), saturated aqueous common salt (100 mL) washing extraction, organic phase obtains the mixed solution that transparent liquid is methyl-chloroformate with anhydrous magnesium sulfate drying, underpressure distillation under 15mmHg again, collect 30 ~ 35 ℃ of methyl-chloroformate cuts, yield 68.6%, yield nuclear-magnetism, gas chromatographic analysis are target product.
Embodiment 5
In the there-necked flask of 100 mL, add 50 mL ethyl acetate and 10 mL methyl alcohol and 3mLN successively, the N-diisopropyl aniline,-5 ℃ are stirred down, the 5g solid phosgene is dissolved in the 20 mL ethyl acetate, and slowly drips in reactor, exothermic heat of reaction also generates a large amount of gases, 30 min dropwise, reaction 3 h stop under continuing 10 ℃, and reaction finishes back nitrogen purging reaction system, and tail gas absorbs with sodium hydroxide solution.The gained mixed solution is through 5% aqueous potassium hydrogen sulfate (50 mL * 2), 5% sodium bicarbonate aqueous solution (50 mL * 2), saturated aqueous common salt (100 mL) washing extraction, organic phase obtains the mixed solution that transparent liquid is methyl-chloroformate with anhydrous magnesium sulfate drying, underpressure distillation under 15mmHg again, collect 30 ~ 35 ℃ of methyl-chloroformate cuts, yield 77.2%, nuclear-magnetism, gas chromatographic analysis are target product.
Claims (8)
1. the preparation method of a methyl-chloroformate is characterized in that may further comprise the steps:
The first step adds methyl alcohol and organic solvent and acid binding agent in reactor, low temperature stirs;
Second step was dissolved in solid phosgene in the organic solvent, and slowly dripped in reactor, and reaction finishes back nitrogen purging reaction system, and tail gas feeds alkali lye and absorbs;
In the 3rd step, through overpickling, alkali cleaning, saturated common salt water washing, the organic phase drying obtains containing the mixed solution of methyl-chloroformate with second mixed solution that obtain of step;
In the 4th step, with the mixed solution underpressure distillation that contains methyl-chloroformate that the 3rd step obtained, collect the methyl-chloroformate cut.
2. the preparation method of methyl-chloroformate according to claim 1 is characterized in that, organic solvent was selected methylene dichloride, trichloromethane, tetrachloro formic acid, ethanol or ethyl acetate for use during the first step, second went on foot.
3. the preparation method of methyl-chloroformate according to claim 1 is characterized in that, acid binding agent is selected triethylamine, pyridine, N for use in the first step, dinethylformamide or N, N-diisopropyl aniline.
4. the preparation method of methyl-chloroformate according to claim 1 is characterized in that, the first step low temperature stirs the control temperature at-5 ~ 0 ℃.
5. the preparation method of methyl-chloroformate according to claim 1 is characterized in that, temperature of reaction is-30 ~ 25 ℃ in second step, and the reaction times is 0.5 ~ 5 h.
6. the preparation method of methyl-chloroformate according to claim 1 is characterized in that, alkali lye is selected NaOH solution for use in second step.
7. the preparation method of methyl-chloroformate according to claim 1 is characterized in that, KHSO is selected in pickling for use in the 3rd step
4Solution.
8. the preparation method of methyl-chloroformate according to claim 1 is characterized in that, NaHCO is selected in alkali cleaning for use in the 3rd step
3Solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001086A (en) * | 2015-06-29 | 2015-10-28 | 安徽广信农化股份有限公司 | Synthetic method of methylclhlorofonmate |
| CN109663477A (en) * | 2018-12-30 | 2019-04-23 | 安徽广信农化股份有限公司 | A kind of method for treatment of waste material preparing ethyl chloroformate |
| CN113402389A (en) * | 2020-03-17 | 2021-09-17 | 上海祖玥新材料科技有限公司 | Preparation method for synthesizing isopropyl chloride by reacting isopropanol with phosgene |
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| CN1644579A (en) * | 2004-12-21 | 2005-07-27 | 浙江工业大学 | N-alkoxide oxo-2-triazolidone derivative, its preparation and use |
| CN101245001A (en) * | 2007-02-16 | 2008-08-20 | 宝山钢铁股份有限公司 | Process for synthesizing carbonochloridic acid 9-fluorene methyl ester |
-
2013
- 2013-05-20 CN CN2013101868252A patent/CN103274944A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644579A (en) * | 2004-12-21 | 2005-07-27 | 浙江工业大学 | N-alkoxide oxo-2-triazolidone derivative, its preparation and use |
| CN101245001A (en) * | 2007-02-16 | 2008-08-20 | 宝山钢铁股份有限公司 | Process for synthesizing carbonochloridic acid 9-fluorene methyl ester |
Non-Patent Citations (3)
| Title |
|---|
| LUCIA PASQUATO，ET AL.: ""Conversion of Bis(trichloromethyl) Carbonate to Phosgene and Reactivity of Triphosgene, Diphosgene, and Phosgene with Methanol"", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| 张广才等: ""1-吡唑酰基-2-烷氧基羰基肼类化合物的合成及其生物活性"", 《合成化学》 * |
| 翁建全等: ""N-烃氧羰基-2-噻唑烷酮衍生物的合成及其杀菌活性"", 《农药学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001086A (en) * | 2015-06-29 | 2015-10-28 | 安徽广信农化股份有限公司 | Synthetic method of methylclhlorofonmate |
| CN109663477A (en) * | 2018-12-30 | 2019-04-23 | 安徽广信农化股份有限公司 | A kind of method for treatment of waste material preparing ethyl chloroformate |
| CN113402389A (en) * | 2020-03-17 | 2021-09-17 | 上海祖玥新材料科技有限公司 | Preparation method for synthesizing isopropyl chloride by reacting isopropanol with phosgene |
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Application publication date: 20130904 |