CN106242967B - The new technique for synthesizing of methyl benzoylformate - Google Patents
The new technique for synthesizing of methyl benzoylformate Download PDFInfo
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- CN106242967B CN106242967B CN201610548031.XA CN201610548031A CN106242967B CN 106242967 B CN106242967 B CN 106242967B CN 201610548031 A CN201610548031 A CN 201610548031A CN 106242967 B CN106242967 B CN 106242967B
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- methyl
- acetophenones
- dimethoxy
- methyl benzoylformate
- benzoylformate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The present invention relates to the brand-new technique of synthesis of light trigger and herbicide metamitron intermediate methyl benzoylformate, from having no document report.Using acetophenone as initiation material, react with methyl nitrite to obtain 2 in the presence of hydrogen chloride, 2 dimethoxy-acetophenones, 2,2 dimethoxy-acetophenones obtain methyl benzoylformate after further sloughing a molecule alkyl halide after chlorine chloro (or bromine bromo) under the catalytic action of the DI-tert-butylphenol compounds of 4 methyl of catalyst 2,6.Investigated reaction in hydrogen chloride to 2, the influence that the influence of 2 dimethoxy-acetophenones production and the DI-tert-butylphenol compounds of 4 methyl of catalyst 2,6 produce to methyl benzoylformate, it is determined that the optimal condition of methyl benzoylformate production, provide a new technology simple to operate, economical and practical.
Description
Technical field
The invention belongs to a kind of system of light trigger and pesticide intermediate methyl benzoylformate in compound synthesis field
Standby new method, has no document report.
Background technology
Photocuring technology is 20th century new technique that comes out of mid-term, and it using ultraviolet light (visible ray) is the energy that it, which is, is drawn
Hair is with the process that chemical reactivity liquid fast transition is solid.Compared with traditional heat curing techniques, it has
Curing rate is fast, high efficiency, small, excellent performance and expense are low pollution the advantages of, be a kind of fast-developing " green " new technology.
Nineteen forty-six U.S. Inmot, company obtained the patent in terms of first ultraviolet light solidifies (UV).1967, German Bayer AG will
UV curing technologies industrialize, and start to be applied to woodenware processing, so as to draw the concept of light trigger.1970, vapour Ba-Jia Ji
Company has invented I -651, is laid the foundation for the fast development of light trigger, while also established vapour Ba-Jia Ji companies in light
Initiator is studied and the leadership of production field.In the past 10 years, external light trigger dosage annual growth is 8.1%, China
UV cured articles annual growth rate is up to 35%.
Methyl benzoylformate is a kind of new light trigger to grow up in recent years, have efficiency of initiation it is high,
The advantages that heat endurance is good, low-yellowing, low smell, the status in photocuring opaque products is especially prominent.
Metamitron is low toxicity, the low-residual triazine herbicide of Bayer A.G's exploitation the 1970s, can be prevented
Except a variety of single, double cotyledon weeds.Metamitron is widely used in Sugarbeet Fields weeding abroad, is the agricultural chemicals product of a large-tonnage
Kind, industrialized production is also had begun at home.
The production method of methyl benzoylformate is anti-using the king-sized chlorobenzoyl chloride of excitant and solid sodium cyanide at present
Benzoyl nitrile should be obtained, then further acidolysis, esterification obtains methyl benzoylformate.The process route uses hypertoxic cyaniding
Sodium powder end, production process risk is big, and substantial amounts of sour water is produced during acidolysis, and the pollution to environment is heavier,
Production cost is also high.
The content of the invention
It is an object of the invention to overcome the shortcomings that raw material excitant is greatly in the prior art and toxicity is big, there is provided a kind of brand-new
Methyl benzoylformate preparation method.The invention provides new reaction scheme, catalyst, reaction temperature, reaction mass
Than thus providing a kind of production technology of methyl benzoylformate more practical, cost is lower.
The present invention solves its technical problem and takes following technical scheme to realize：
A kind of production new technique of light trigger and metamitron intermediate methyl benzoylformate.It is related to intermediate and production
The structural formula of thing is：
Preferably, acetophenone is used as initiation material, reacts with methyl nitrite to obtain intermediate under hydrogen chloride effect
2,2- dimethoxy-acetophenones；2,2- dimethoxy-acetophenones are in the presence of catalyst 4- methyl -2,6 di t butyl phenol
An one's share of expenses for a joint undertaking alkyl halide, which is taken off, after chlorinated with chlorine (or bromine bromo) obtains methyl benzoylformate.
Preferably, the catalyst hydrogen chloride gas used in the production of 2,2- dimethoxy-acetophenones, methyl benzoylformate
Production in the catalyst that uses be 4- methyl -2,6 di t butyl phenol.
Preferably, the solvent used in the production process of 2,2- dimethoxy-acetophenones is methanol, toluene and hexamethylene etc.,
The solvent used in the production process of methyl benzoylformate is chlorobenzene, 1,2- dichloroethanes and hexamethylene etc..
Preferably, the raw material that 2,2- dimethoxy-acetophenones carry out halo elimination reaction is chlorine or bromine.
Preferably, material ratio is (weight ratio) in the production of 2,2- dimethoxy-acetophenones：Acetophenone：Hydrogen chloride：Nitrous
Sour methyl esters=1:0.3：1.1.
Preferably, material ratio is (weight ratio) in the production process of methyl benzoylformate：2,2- dimethoxy-acetophenones：
4- methyl -2,6 di t butyl phenol：Halogen=1：0.1:1.
Preferably, the reaction temperature of the production of 2,2- dimethoxy-acetophenones is 35-40 DEG C.
Preferably, reaction temperature is 110-120 DEG C in the production process of methyl benzoylformate.
The advantages and positive effects of the present invention are：
1st, the present invention is initiation material using acetophenone, and hydrogen chloride gas reacts as catalyst with methyl nitrite
To 2,2- dimethoxy-acetophenones, further halo elimination reaction obtains methyl benzoylformate.
2nd, the present invention proposes new reaction scheme, and compared with traditional technique, the methyl benzoylformate of synthesis has valency
Lattice are cheap, and the advantages of non-environmental-pollution, more economical environmentally friendly technique is provided for the industrialized production of methyl benzoylformate.
Embodiment
With reference to specific embodiment, the invention will be further described.The present invention prepares the synthesis of methyl benzoylformate
Chemical formula is as follows：
The present invention is described in further detail with reference to embodiment.
Comparative example 1
(1) in 2000 liters of reactor, 600kg methanol and 240kg acetophenones are added, being passed through 72kg under frozen water cooling does
Dry hydrogen chloride gas, it is maintained at 30-35 DEG C and is passed through 264kg methyl nitrites, continues after having led in this thermotonus 2 hours,
Stop reaction, steam methanol, obtain crude product, add 400kg toluene, neutralized with 10% sodium hydroxide solution, liquid separation obtains
The toluene solution on upper strata, steam toluene and obtain crude product, crude product progress rectification under vacuum is obtained into 2,2- dimethoxy-acetophenones
260kg, yield 72.2%.
(2) in 1000 liters of reactor, 180kg2,2- dimethoxy-acetophenones, the uncle of 9kg4- methyl -2,6- bis- are added
Butylphenol and 400kg chlorobenzenes, are heated to 110 DEG C, are passed through chlorine 71kg, there is hydrogen chloride and methyl chloride gas during the course of the reaction
Release, gas-chromatography tracking reaction process, stop being passed through chlorine after the completion of reaction, cool down, be passed through nitrogen to drive mistake in solution away
The chlorine and hydrogen chloride gas of amount, then washed once, liquid separation with the sodium carbonate liquor of saturation, remove the chlorobenzene solution decompression of layer
Chlorobenzene is steamed, obtains crude product, rectification under vacuum obtains methyl benzoylformate 142kg, yield 86.6%.
Embodiment 2
(1) in 2000 liters of reactor, 600kg methanol and 240kg acetophenones are added, being passed through 64kg under frozen water cooling does
Dry hydrogen chloride gas, it is maintained at 30-35 DEG C and is passed through 260kg methyl nitrites, continues after having led in this thermotonus 2 hours,
Stop reaction, steam methanol, obtain crude product, add 400kg toluene, neutralized with 10% sodium hydroxide solution, liquid separation obtains
The toluene solution on upper strata, steam toluene and obtain crude product, crude product progress rectification under vacuum is obtained into 2,2- dimethoxy-acetophenones
248kg, yield 68.9%.
(2) in 1000 liters of reactor, 180kg2,2- dimethoxy-acetophenones, the uncle of 18kg4- methyl -2,6- bis- are added
Butylphenol and 400kg chlorobenzenes, are heated to 110 DEG C, are passed through chlorine 71kg, there is hydrogen chloride and methyl chloride gas during the course of the reaction
Release, gas-chromatography tracking reaction process, stop being passed through chlorine after the completion of reaction, cool down, be passed through nitrogen to drive mistake in solution away
The chlorine and hydrogen chloride gas of amount, then washed once, liquid separation with the sodium carbonate liquor of saturation, remove the chlorobenzene solution decompression of layer
Chlorobenzene is steamed, obtains crude product, rectification under vacuum obtains methyl benzoylformate 148kg, yield 90.2%.
Embodiment 3
In 1000 milliliters of reaction bulb, add 400g hexamethylenes, 18g4- methyl -2,6- DI-tert-butylphenol compounds and
180g2,2- dimethoxy-acetophenone, 60-70 DEG C is heated to, 158g bromines are added dropwise, produce bromomethane and bromine during the course of the reaction
Change hydrogen, continue stirring reaction after dripping off 1 hour, stop reaction, cooling, be passed through nitrogen to drive excessive bromine and bromination away
Hydrogen, washed with the sodium carbonate liquor of saturation, liquid separation, steam hexamethylene, obtain crude product, rectification under vacuum obtains benzoyl first
Sour methyl esters 152g, yield 92.7%.
Embodiment 4
In 1000 milliliters of reaction bulb, 400g chlorobenzenes, 18g4- methyl -2,6- DI-tert-butylphenol compounds and 180g2 are added,
2- dimethoxy-acetophenones, 110-120 DEG C is heated to, 158g bromines are added dropwise, produce bromomethane and hydrogen bromide during the course of the reaction
Gas, continues stirring reaction 1 hour after dripping off, stop reaction, cooling, be passed through nitrogen to drive excessive bromine and bromination hydrogen away
Body, washed with the sodium carbonate liquor of saturation, liquid separation, lower floor's chlorobenzene solution decompression steams chlorobenzene, obtains crude product, rectification under vacuum obtains
To methyl benzoylformate 148g, yield 90.2%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (2)
- A kind of 1. production new technique of light trigger methyl benzoylformate, it is characterised in that acetophenone is used as initiation material, React with methyl nitrite to obtain intermediate 2,2- dimethoxy-acetophenones under hydrogen chloride effect；2,2- dimethoxy-acetophenones A molecule bromomethane is taken off with bromine reaction obtain benzoyl first in the presence of catalyst 4- methyl -2,6 di t butyl phenol Sour methyl esters, in the step of preparing methyl benzoylformate, reaction dissolvent is hexamethylene, and reaction temperature is 60-70 DEG C.
- 2. the production new technique of light trigger methyl benzoylformate according to claim 1, it is characterised in that 2,2- bis- In the synthetic method of methoxyacetophenone, acetophenone is used as initiation material, is reacted under hydrogen chloride effect with methyl nitrite, Reaction dissolvent is methanol, and reaction temperature is 30-35 DEG C.
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| TW201922682A (en) * | 2017-10-27 | 2019-06-16 | 日商住友化學股份有限公司 | Process for benzoyl formic acid compound and pyridazine compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5159117A (en) * | 1990-08-24 | 1992-10-27 | Basf Aktiengesellschaft | Preparation of α,α-dialkoxy ketones |
| CN103787886A (en) * | 2013-07-15 | 2014-05-14 | 天津久日化学股份有限公司 | Preparation method of methyl phenylglyoxylate |
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2016
- 2016-07-12 CN CN201610548031.XA patent/CN106242967B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5159117A (en) * | 1990-08-24 | 1992-10-27 | Basf Aktiengesellschaft | Preparation of α,α-dialkoxy ketones |
| CN103787886A (en) * | 2013-07-15 | 2014-05-14 | 天津久日化学股份有限公司 | Preparation method of methyl phenylglyoxylate |
Non-Patent Citations (2)
| Title |
|---|
| Photoinduced alcoholysis of α,α,α-tribromoacetophenone to benzoylformate;Yasuji Izawa et al;《Bull. Chem. Soc. Jpn.》;1983;第56卷(第5期);全文 * |
| α,α-二烷氧基苯乙酮类光敏剂的合成;宋俊林等;《化学通报》;1991(第1期);全文 * |
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