阅读说明：本技术 一种α,γ,γ,γ-四氯丁酸酯的合成方法 (Synthetic method of alpha, gamma-tetrachlorobutyrate ) 是由 肖自胜 尹笃林 兰支利 蔡果 张超 钟文周 毛丽秋 于 2021-02-20 设计创作，主要内容包括：一种α,γ,γ,γ-四氯丁酸酯的合成方法,将四氯化碳和丙烯酸酯,与铜盐和/或亚铜盐主催化剂、有机胺类或咪唑类助催化剂和极性的惰性有机溶剂,先在室温下搅拌混合后,密闭反应釜,升温进行加成反应,再冷却至室温,过滤,滤液先常压蒸馏回收四氯化碳,再减压精馏,得α,γ,γ,γ-四氯丁酸酯。本发明方法所得产品α,γ,γ,γ-四氯丁酸酯的纯度高达99.5%,单程反应收率高达96.1%,且产物易于分离,反应副产物少,催化剂与配体催化效果优异,原料和催化剂廉价易得,溶剂和催化剂易于回收利用；本发明方法反应条件温和,工艺操作简单,生产成本低,经济效益好,适宜于工业化生产。(A process for synthesizing alpha, gamma-tetrachlorobutyrate includes such steps as mixing carbon tetrachloride and acrylate with copper salt and/or cuprous salt as primary catalyst, organic amine or imidazole as cocatalyst and polar inertial organic solvent, stirring at room temp, sealing reactor, heating for addition reaction, cooling to room temp, filtering, distilling filtrate at ordinary pressure to recover carbon tetrachloride, and vacuum rectifying to obtain alpha, gamma-tetrachlorobutyrate. The purity of the product alpha, gamma-tetrachlorobutyrate obtained by the method is up to 99.5 percent, the one-way reaction yield is up to 96.1 percent, the product is easy to separate, reaction byproducts are few, the catalytic effect of the catalyst and the ligand is excellent, the raw materials and the catalyst are cheap and easy to obtain, and the solvent and the catalyst are easy to recycle; the method has the advantages of mild reaction conditions, simple process operation, low production cost and good economic benefit, and is suitable for industrial production.)

1. A method for synthesizing alpha, gamma-tetrachlorobutyrate is characterized by comprising the following steps: stirring and mixing carbon tetrachloride and acrylic ester with a copper salt and/or cuprous salt main catalyst, an organic amine or imidazole cocatalyst and a polar inert organic solvent at room temperature, then sealing the reaction kettle, heating to perform addition reaction, cooling to room temperature, filtering, distilling the filtrate at normal pressure to recover carbon tetrachloride, and then performing reduced pressure rectification to obtain alpha, gamma and gamma-tetrachlorobutyrate.

2. The method for synthesizing α, γ, γ, γ -tetrachlorobutyrate according to claim 1, wherein: the molar ratio of the carbon tetrachloride to the acrylate is 0.1-10.0: 1; taking a raw material with a small mole number in carbon tetrachloride and acrylic ester as a reference raw material, wherein the mole ratio of a main catalyst to the reference raw material is 0.010-0.200: 1; the molar ratio of the main catalyst to the cocatalyst is 1: 0.2-5.0; the volume mass ratio of the polar inert organic solvent to the reference raw material is 0.5-20.0: 1.

3. The method for synthesizing α, γ, γ, γ -tetrachlorobutyrate according to claim 1 or 2, characterized by: the stirring and mixing time at room temperature is 20-40 min; heating to 40-140 ℃, and carrying out addition reaction for 5-20 h; the temperature of the atmospheric distillation is 50-90 ℃, and the time is 1-3 h; the temperature of the vacuum rectification is 90-120 ℃, the pressure is 10-30 kPa, and the time is 1-3 h.

4. The method for synthesizing α, γ, γ, γ -tetrachlorobutyrate according to any one of claims 1 to 3, characterized by: firstly, carrying out reflux reaction on a main catalyst and a cocatalyst in an organic solvent, carrying out reduced pressure distillation, washing and dispersing, filtering, and carrying out vacuum drying to obtain a catalyst complex; the mass volume ratio of the main catalyst to the organic solvent is 1: 5.0-40.0; the organic solvent is one or more of methanol, ethanol, acetone or acetonitrile; the temperature of the reflux reaction is 10-80 ℃, and the time is 1-10 h; the temperature of the vacuum rectification is 40-80 ℃, the pressure is 10-30 kPa, and the time is 1-3 h; the organic solvent used for washing and dispersing is diethyl ether; the temperature of the vacuum drying is 40-80 ℃, the pressure is 10-30 kPa, and the time is 8-20 h.

5. The method for synthesizing α, γ, γ, γ -tetrachlorobutyrate according to any one of claims 1 to 4, characterized by: the structural formula of the acrylate is as follows:wherein R is₁、R₂Identical or different, R₁Is H or-CH₃，R₂Is C₁～C₆Linear or branched alkyl or benzyl; the copper salt or cuprous salt is one or more of chloride, oxide, nitrate, acetate or sulfate of copper or cuprous and hydrate thereof; the organic amine cocatalyst is one or more of primary amine, secondary amine, tertiary amine, aliphatic amine, aromatic amine or alcohol amine(ii) a The imidazole cocatalyst has a structural formula as follows:wherein R is₁、R₂Identical or different, R₁Is a hydrogen atom or a methyl group, R₂Is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms; the polar inert organic solvent is alkyl nitrile or benzonitrile with 2-4 carbons.

Technical Field

The invention relates to a synthetic method of alpha, gamma-tetrachlorobutyrate, in particular to a synthetic method of (alpha-methyl) -alpha, gamma-tetrachlorobutyrate.

Background

The (alpha-methyl) -alpha, gamma-tetrachlorobutyrate is an important organic synthetic raw material, is an important initiator in acrylic resin synthesis, and has important application in the field of fine chemical synthesis; has wide application prospect in the field of pesticide synthesis, in particular to the synthesis of chlorine-containing pyrethroid compounds. It is known that chlorine is one of the commonly used non-metallic elements with strong activity, and has strong reaction advantages in electronegativity and bond energy based on the nuclear structure characteristics, and materials treated by chlorination have enhanced properties in service life, weather resistance, corrosion resistance and the like. Therefore, (alpha-methyl) -alpha, gamma-tetrachlorobutyrate has great development potential in the novel material industry.

One of the synthesis methods of (alpha-methyl) -alpha, gamma-tetrachlorobutyrate is as follows: with (alpha-meth) acrylate and CCl₄The raw material is obtained by free radical Addition Reaction (ATRA), namely Karaxi Addition Reaction (Kharasch Addition Reaction) under the action of a catalyst, and the chemical equation of the Reaction is shown as the following formula.

The common catalyst is chloride or oxide of copper, iron, cobalt, ruthenium, nickel and other elements, and as the catalyst is inorganic salt or metal oxide, the solubility of the catalyst in an organic solvent is poor. Therefore, in order to smoothly perform the synthesis reaction, a suitable metal catalyst should be selected on the one hand, and a suitable ligand should be selected on the other hand, and the selection of the suitable ligand is the most important reason for smoothly performing the reaction.

Perez et al disclose a method for the trace synthesis of alpha-methyl-alpha, gamma-tetrachlorobutyric acid methyl ester, a scorpion-like complex of copper Tp^tBu,MeCuCl is used as a catalyst, deuterated benzene is used as a solvent, and the yield of the alpha-methyl-alpha, gamma-tetrachlorobutyric acid methyl ester is 95 percent by adopting nuclear magnetic spectrum method detection. Although the conversion rate of the raw material of the method can reach 95%, the preparation of the boron salt ligand used for preparing the catalyst is difficult, the amplification cost of the experimental scheme is expensive, and the industrialization is difficult to realize (Inorganic Chemistry, Vol.46, number 19, 2007, 7725-.

Pintauer et al disclose a trace preparation of methyl alpha, gamma-tetrachlorobutyrate using tris [2- (dimethylamino) ethyl group]Amine-copper complexes [ Cu^II(Me₆TREN)Cl][Cl]As catalyst, AIBN as free radical initiator, CCl₄With methyl acrylate in acetonitrile solvent. However, the yield of the product alpha, gamma-tetrachlorobutyric acid methyl ester detected by nuclear magnetic spectroscopy is only 67%, and the multidentate amine ligand used for preparing the catalyst has many synthesis byproducts, low yield and high ligand synthesis cost, and the addition of the initiator AIBN makes the reaction process difficult to control, easily causes the system to implode, increases the byproducts of tar high polymer generated by the reaction, and is difficult to realize industrialization (Dalton trans., 2011,40, 4909-4. 4917).

Nicole et al disclose a method for synthesizing alpha-methyl-alpha, gamma-tetrachlorobutyric acid methyl ester and alpha, gamma-tetrachlorobutyric acid methyl ester using bis (2-pyridylmethyl) amine-copper complex as catalyst, using tris (2-pyridylmethyl) amine-copper complex [ Cu^II(TPMA)Cl][Cl]The catalyst takes AIBN or V-70 as an initiator. However, the yield of alpha, gamma-tetrachloro methyl butyrate synthesized by using methyl acrylate as a basic raw material is only 47 percent; the yield of alpha-methyl-alpha, gamma-tetrachlorobutyric acid methyl ester synthesized by taking methyl methacrylate as a basic raw material is only 66 percent, and the preparation method of the catalyst tris (2-picolyl) amine-copper complex is complex, the reaction operation is complex, the components of reaction byproducts are complex, high-boiling-point polymerized tar is more, the post-treatment is difficult, and the catalyst is not suitable for industrial application (Dalton trans., 2011,40, 3060-one-material 3066).

In summary, a synthesis method of alpha, gamma-tetrachlorobutyrate, which has high product purity and yield, easy product separation, few reaction byproducts, excellent catalytic effect of catalyst and ligand, cheap and easily available raw materials and catalyst, easy solvent and catalyst recycling, mild reaction conditions, simple process operation and low production cost, and is suitable for industrial production, is urgently needed to be found.

Disclosure of Invention

The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a synthesis method of alpha, gamma-tetrachlorobutyrate, which has the advantages of high product purity and yield, easy product separation, few reaction byproducts, excellent catalytic effect of the catalyst and the ligand, cheap and easily available raw materials and catalysts, easy recycling of the solvent and the catalyst, mild reaction conditions, simple process operation, low production cost and suitability for industrial production.

The technical scheme adopted by the invention for solving the technical problems is as follows: a process for synthesizing alpha, gamma-tetrachlorobutyrate includes such steps as mixing carbon tetrachloride and acrylate with copper salt and/or cuprous salt as primary catalyst, organic amine or imidazole as cocatalyst and polar inertial organic solvent, stirring at room temp, sealing reactor, heating for addition reaction, cooling to room temp, filtering, distilling filtrate at ordinary pressure to recover carbon tetrachloride, and vacuum rectifying to obtain alpha, gamma-tetrachlorobutyrate. The present inventors have studied and found that, if only inorganic copper salts such as copper chloride salts and/or cuprous salts are used as catalysts, the reaction hardly proceeds at the same temperature; however, the addition of an appropriate ligand to the reaction system helps to increase the solubility of the copper salt and/or cuprous salt catalyst in the organic solvent, thereby increasing the catalytic efficiency. Further research shows that copper salt and/or cuprous salt is compounded with organic amine or imidazole compound to form Cu-N structure containing complex, and the relatively stable complex structure can combine with CCl in the reaction system effectively₄Inducing homolytic cleavage of its C-Cl bond to produce. CCl₃Free radicals can release chlorine atom free radicals under certain conditions, thereby further accelerating the synthesis process.

The synthetic route of the one-pot method of the method is shown as follows.

Preferably, the molar ratio of carbon tetrachloride to acrylate is 0.1 to 10.0:1 (more preferably 0.2 to 9.0:1, and still more preferably 1.5 to 8.0: 1). Acrylates with CCl₄As the reaction raw materials, the two are theoretically reacted in a molar ratio of 1:1 to obtain a product, but in order to complete the reaction, increase the utilization rate of the basic raw materials and suppress the occurrence of the side reactions, it is more preferable that one of the raw materials is used in an amount larger than the other raw material. At the same time, because CCl₄Is a byproduct inevitably generated in the industrial production process of methane chlorination, is a second type of controlled substance in annex B of Montreal protocol on ozone layer depletion substances, and the use of CCl is prohibited nationwide from 6.1.6.2003₄As a cleaning agent, CCl has been used in the laboratory starting and stopping at 1 month and 1 day in 2019₄Annual CCl is applied to enterprises meeting the requirements₄The raw materials are used and put on record, and annual CCl is given to dealers meeting the requirements₄Method of marketing documentation severely limits CCl₄The use of (a); however, CCl₄The use as a chemical raw material for producing non-ODS substances is not limited. At present, about 5 percent of by-product CCl is inevitably generated in the process of producing dichloromethane and chloroform by chlorination of methane₄Balancing excess CCl for environmental protection₄Capacity, development CCl₄The method of the invention preferably improves CCl₄The feed ratio of (a); after the reaction is finished, the method of atmospheric distillation is adopted, so that the excessive raw materials can be recovered and used for the next batch of reaction, and waste or pollution discharge cannot be caused.

Preferably, the raw material with small mole number in carbon tetrachloride and acrylic ester is used as a reference raw material, and the molar ratio of the main catalyst to the reference raw material is 0.010-0.200: 1 (more preferably 0.010-0.100: 1). The theoretical yield of product in the process of the invention is also converted by moles of the reference starting material. If the dosage of the catalyst is too much, the concentration of free radicals generated in the reaction process is too high, so that dimerization and polymerization phenomena of products are generated, the color of a system becomes dark, byproducts are increased, and the cost of energy sources and the like for recovering the catalyst is increased; if the amount of the catalyst used is too small, the concentration of the radicals in the whole reaction system becomes too low, the reaction proceeds slowly, and the yield of the product becomes low.

Preferably, the molar ratio of the main catalyst to the cocatalyst is 1: 0.2-5.0 (more preferably 1: 1-4). If the ratio is too large, the cocatalyst ligand is bonded too sufficiently with the copper ions in the main catalyst, and the copper ions are difficult to bond with CCl in the system₄Binding, making it difficult to effectively control the concentration of free radicals in the system; if the ratio is too low, it is difficult to effectively disperse copper ions in an organic system, resulting in slow reaction and low product yield.

Preferably, the volume-to-mass ratio (mL/g) of the polar inert organic solvent to the reference raw material is 0.5 to 20.0:1 (more preferably 0.7 to 16.0: 1). If the amount of the organic solvent is too small, the reaction raw materials and the catalyst are not sufficiently dissolved, coking occurs in the reaction process, and if the amount of the organic solvent is too large, energy waste is caused.

Preferably, the stirring and mixing time at room temperature is 20-40 min. If the stirring time is too short, the complexing degree of the main catalyst and the cocatalyst is not enough or part of the main catalyst and the cocatalyst cannot form a catalytic system with a single structure, so that the reaction selectivity is reduced; if the stirring time is too long, although the main catalyst and the cocatalyst can form a catalytic system with a single structure, unnecessary energy waste can be caused.

Preferably, the temperature is increased to 40-140 ℃ (more preferably 80-120 ℃), and the addition reaction is carried out for 5-20 h (more preferably 10-20 h). If the reaction temperature is too high, side reactions increase, the tar content increases, the product quality decreases, the reaction yield decreases, and CCl₄And the vapor pressure of the acrylic ester is too large, thereby enabling the reaction processThe pressure born by the middle reaction kettle is too high, so that the performance requirement on equipment is increased; if the reaction temperature is too low, the reaction time is prolonged, and the production efficiency is lowered.

Preferably, the temperature of the atmospheric distillation is 50-90 ℃ and the time is 1-3 h.

Preferably, the temperature of the vacuum rectification is 90-120 ℃, the pressure is 10-30 kPa, and the time is 1-3 h.

Preferably, the main catalyst and the cocatalyst are subjected to reflux reaction in an organic solvent, and after reduced pressure distillation, the main catalyst and the cocatalyst are washed, dispersed, filtered and dried in vacuum to obtain the catalyst complex. As the copper salt and/or cuprous salt of the main catalyst is inorganic salt and has low solubility in an organic solvent, the dispersion of the catalyst in an organic phase can be influenced, and the copper ion pair CCl can be partially inhibited₄The inducing activity of the medium C-Cl bond homolytic cracking is that the main catalyst and the cocatalyst are prepared into a crystal complex, so that the solubility of the main catalyst in an organic solvent is greatly improved.

The inventor researches and discovers that the CCl is directly converted into the CCl₄The one-pot method of adding copper salt and/or cuprous salt and cocatalyst ligand into the mixed system of acrylic ester can only obtain the yield on the medium or moderate level, mainly because the structure and appearance of the complex formed in the one-pot method are mostly in amorphous state, so that the structure of the addition product is lack of uniform and stable controllability, the side products of dimerization and polymerization are increased, and the tar content of high polymer is increased. Further research shows that after the main catalyst and the cocatalyst are synthesized into the catalyst complex in advance, the coordination number of copper salt and/or cuprous salt and a cocatalyst ligand in the catalyst complex is controllable, the spatial structure and the composition are highly consistent, the appearance is neat, the crystal form is single, the catalytic activity and the selectivity are high, the catalytic performance is single, complex molecules for catalyzing dimerization or polymerization reaction do not exist, reaction byproducts are few, and the production safety is high.

The synthesis route for synthesizing the catalyst complex (1) and using it as the catalyst (2) in the process of the present invention in advance is shown below.

From the above, in the reaction (1), by controlling the amount of the cocatalyst ligand, it is possible to obtain complex crystals with uniform composition and structure, and the complex crystals have higher catalytic performance for the reaction system.

Preferably, the mass-to-volume ratio (g/mL) of the main catalyst to the organic solvent is 1: 5.0-40.0 (more preferably 1: 10.0-39.0). If the amount of the organic solvent is too low, the reaction raw materials and the catalyst are not sufficiently dissolved, coking occurs in the reaction process, and if the amount of the organic solvent is too much, a larger amount of energy is wasted.

Preferably, the organic solvent is one or more of methanol, ethanol, acetone or acetonitrile. The solvent is helpful for the main catalyst and the cocatalyst to be fully dissolved and complexed, so that a catalytic reaction system with a single structure is formed.

Preferably, the temperature of the reflux reaction is 10-80 ℃ (more preferably 50-80 ℃), and the time is 1-10 h (more preferably 2-6 h). In the reflux reaction process, the main catalyst and the cocatalyst are fully complexed to form a complex with a single structure, and the obtained catalyst complex has complex components and unstable or obviously inactivated catalytic performance due to too low reflux temperature or too short reflux time.

Preferably, the temperature of the vacuum rectification is 40-80 ℃, the pressure is 10-30 kPa, and the time is 1-3 h.

Preferably, the organic solvent used for washing the dispersion is diethyl ether.

Preferably, the temperature of the vacuum drying is 40-80 ℃, the pressure is 10-30 kPa, and the time is 8-20 h.

Preferably, the acrylate has the formula:wherein R is₁、R₂Identical or different, R₁Is H or-CH₃，R₂Is C₁～C₆Straight chain or beltBranched alkyl or benzyl. More preferably, the acrylate is one or more of methyl acrylate, ethyl acrylate, alpha-butyl methacrylate, alpha-benzyl methacrylate, alpha-ethyl methacrylate, butyl acrylate and the like.

Preferably, the cupric salt or cuprous salt is one or more of chloride, oxide, nitrate, acetate or sulfate of copper or cuprous, hydrate thereof and the like.

Preferably, the organic amine cocatalyst is one or more of primary amine, secondary amine, tertiary amine, aliphatic amine, aromatic amine or alcohol amine. More preferably, the organic amine cocatalyst is one or more of ethanolamine, diethanolamine, triethylamine, triethanolamine, N '-tetramethylethylenediamine, N' -tetramethylpropylenediamine, N-dimethylaniline, or the like. N, N, N ', N' -tetramethylethylenediamine is more preferable.

Preferably, the imidazole based cocatalyst has the formula:wherein R is₁、R₂Identical or different, R₁Is a hydrogen atom or a methyl group, R₂Is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms. More preferably, the imidazole cocatalyst is one or more of imidazole, N-methylimidazole, chlorinated-1-ethyl-3-methylimidazole, chlorinated-1-butyl-3-methylimidazole, chlorinated-1-dodecyl-3-methylimidazole or chlorinated-1-hexadecyl-3-methylimidazole. N-methylimidazole or 1-dodecyl-3-methylimidazole chloride is more preferable. The imidazole cocatalyst has better cocatalyst activity for activating a copper salt and/or cuprous salt main catalyst, and has better capability of complexing copper ions because nitrogen atoms on an imidazole ring have higher electronegativity, and a ligand with long-chain alkyl has certain emulsification effect on a complex formed by the imidazole ring and a copper salt and/or cuprous salt, so that the dissolution of the complex in an organic phase is promoted.

Preferably, the polar inert organic solvent is alkyl nitrile or benzonitrile with 2-4 carbons. More preferably, the polar inert organic solvent is one or more of acetonitrile, propionitrile, butyronitrile or benzonitrile.

The method for calculating the one-way reaction yield of the method comprises the following steps:

w% = m (tca)% W%/[ n (ACA or CTC)% m (tca)]100%, wherein m (TCA) is the mass of the actually obtained product alpha, gamma-tetrachlorobutyrate, w% is the product purity, n (ACA) is the mole number of acrylate, and n (CTC) is CCl₄M (TCA) is the molar mass of alpha, gamma-tetrachlorobutyrate), and CCl₄The raw material with the small mole number in the acrylic ester is taken as a reference raw material, and the mole number is substituted into the calculation.

The method has the following beneficial effects:

(1) the purity of the product alpha, gamma-tetrachlorobutyrate obtained by the method is up to 99.5 percent, the one-way reaction yield is up to 96.1 percent, the product is easy to separate, reaction byproducts are few, the catalytic effect of the catalyst and the ligand is excellent, the raw materials and the catalyst are cheap and easy to obtain, and the solvent and the catalyst are easy to recycle;

(2) the method has mild reaction conditions, does not need initiators such as a photoinitiator AIBN, and other catalytic means such as ultraviolet illumination, and the like, has simple process operation, low production cost and good economic benefit, and is suitable for industrial production.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of methyl α, γ, γ, γ -tetrachlorobutyrate obtained in example 1 of the present invention;

FIG. 2 is a nuclear magnetic carbon spectrum of alpha, gamma-tetrachlorobutyric acid methyl ester obtained in example 1 of the present invention;

FIG. 3 is a mass spectrum of α, γ, γ, γ -tetrachlorobutyric acid methyl ester obtained in example 2 of the present invention;

FIG. 4 is an XRD spectrum of the copper chloride and N-methylimidazole (1/2 molar ratio) complex and its standard card (PDF # 32-1608) obtained in example 3 of the present invention;

FIG. 5 is a nuclear magnetic hydrogen spectrum of ethyl α, γ, γ, γ -tetrachlorobutyrate obtained in example 4 of the present invention;

FIG. 6 is a nuclear magnetic carbon spectrum of ethyl α, γ, γ, γ -tetrachlorobutyrate obtained in example 4 of the present invention;

FIG. 7 is a mass spectrum of ethyl α, γ, γ, γ -tetrachlorobutyrate obtained in example 4 of the present invention.

Detailed Description

The invention is further illustrated by the following examples and figures.

The raw materials or chemical agents used in the examples of the present invention are obtained by conventional commercial methods unless otherwise specified.

Dissolving the alpha, gamma-tetrachlorobutyrate obtained in the embodiment of the invention in a deuterated chloroform solution for nuclear magnetic detection.

Example 1

13.0g (84.5 mmol) of carbon tetrachloride and 6.54g (76.0 mmol) of methyl acrylate are mixed with 0.13g (0.76 mmol) of CuCl₂•2H₂The preparation method comprises the steps of putting an O main catalyst, 0.088g (0.76 mmol) of N, N, N ', N' -tetramethylethylenediamine cocatalyst and 10mL of acetonitrile into a stainless steel reaction kettle with a polytetrafluoroethylene liner, stirring at room temperature for 20min, sealing the reaction kettle, heating to 110 ℃, carrying out addition reaction for 12h, cooling to room temperature, filtering, distilling the filtrate at 70 ℃ under normal pressure for 2h, recovering carbon tetrachloride, and carrying out reduced pressure rectification at 90 ℃ and 20kPa for 2h to obtain 14.87g of alpha, gamma-tetrachloro methyl butyrate.

Through GC analysis, the purity of the alpha, gamma-tetrachloro methyl butyrate obtained in the embodiment of the invention is 95.6 percent, and the one-way reaction yield calculated by taking methyl acrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (aca)% m (tca) ] = 100% = 14.87g × 95.6%/(76 mmol × 239.93g/mol) = 100% = 78.0%.

As shown in fig. 1, it can be seen from analysis and attribution of each signal peak that the nuclear magnetic hydrogen spectrum characterization result of the α, γ, γ, γ -tetrachlorobutyric acid methyl ester obtained in the embodiment of the present invention is consistent with the structure of the target product α, γ, γ, γ -tetrachlorobutyric acid methyl ester.

As shown in fig. 2, it can be seen from analysis and attribution of each signal peak that the nuclear magnetic carbon spectrum characterization result of the α, γ, γ, γ -tetrachlorobutyric acid methyl ester obtained in the example of the present invention is consistent with the structure of the target product α, γ, γ, γ -tetrachlorobutyric acid methyl ester.

Example 2

23.4g (152.1 mmol) of carbon tetrachloride and 6.54g (76.0 mmol)Methyl acrylate, with 0.95g (3.8 mmol) of CuSO₄•5H₂Placing an O main catalyst, 0.93g (15.2 mmol) ethanolamine cocatalyst and 100mL propionitrile in a stainless steel reaction kettle with a polytetrafluoroethylene liner, stirring at room temperature for 40min, sealing the reaction kettle, heating to 100 ℃, carrying out addition reaction for 10h, cooling to room temperature, filtering, distilling the filtrate at 80 ℃ under normal pressure for 2h, recovering carbon tetrachloride, and carrying out reduced pressure rectification at 90 ℃ and 15kPa for 3h to obtain 15.49g of alpha, gamma-tetrachlorobutyric acid methyl ester.

Through GC analysis, the purity of the alpha, gamma-tetrachloro methyl butyrate obtained in the embodiment of the invention is 96.5 percent, and the one-way reaction yield calculated by taking methyl acrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (aca)% m (tca) ] = 100% = 15.49g × 96.5%/(76mmol × 239.93g/mol) = 100% = 82.0%.

As shown in FIG. 3, the mass spectrum has no obvious molecular and ion peaks, but has an obvious M +2 isotope peak, which accords with the characteristics of organic matters containing ester groups and chlorine elements, namely M/z205 and 169; m/z117, 83 indicate that the product contains a plurality of chlorine atoms; the product obtained in the embodiment of the invention can be determined to be the target product alpha, gamma-tetrachlorobutyric acid methyl ester by combining nuclear magnetic detection.

Example 3

2.59g (15.20 mmol) of CuCl are added₂•2H₂The O main catalyst and 2.50g (30.40 mmol) of N-methylimidazole cocatalyst are subjected to reflux reaction for 2h at 70 ℃ in 100mL of methanol, and after rectification under reduced pressure for 1.5h at 50 ℃ and 10kPa, the product is washed and dispersed by ether, filtered and dried under 50 ℃ and 10kPa for 8h in vacuum to obtain 4.08g of catalyst complex 1.

As shown in FIG. 4, XRD spectra of copper chloride and N-methylimidazole of the catalyst complex obtained in the example of the present invention were analyzed at 2θThe catalyst complex obtained in the embodiment of the invention is a single crystal formed by copper chloride and N-methylimidazole according to the molar ratio of 1:2, as compared with the XRD (X-ray diffraction) spectrum of a standard card (PDF # 32-1608) of the series of absorption peaks which generate stronger absorption peaks at 14.25 degrees, 15.81 degrees, 17.58 degrees, 20.90 degrees, 24.22 degrees, 26.47 degrees and 26.67 degrees.

46.8g (304.2 mmol) of carbon tetrachloride and 6.54g (76.0 mmol) of methyl acrylate were introduced,with 0.23g of catalyst complex 1 (containing CuCl)₂0.76mmol, 1.52mmol of N-methylimidazole) and 10mL of acetonitrile, placing the mixture in a stainless steel reaction kettle with a polytetrafluoroethylene inner container, stirring the mixture at room temperature for 30min, then sealing the reaction kettle, heating the mixture to 110 ℃, carrying out addition reaction for 12h, cooling the mixture to room temperature, filtering the mixture, distilling the filtrate at 90 ℃ under normal pressure for 2h, recovering carbon tetrachloride, and then carrying out reduced pressure rectification at 90 ℃ and 10kPa for 2.5h to obtain 16.67g of alpha, gamma and gamma-tetrachlorobutyric acid methyl ester.

Through GC analysis, the purity of the alpha, gamma-tetrachloro methyl butyrate obtained in the embodiment of the invention is 99.5 percent, and the one-way reaction yield calculated by taking methyl acrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (aca)% m (tca) ] = 100% = 16.67g × 99.5%/(76mmol × 239.93g/mol) = 100% = 91.0%.

The nuclear magnetism and GC-MS detection can confirm that the product obtained by the embodiment of the invention has the same structure with the target product alpha, gamma-tetrachloro methyl butyrate.

Example 4

First 3.67g (15.20 mmol) of Cu (NO)₃)₂•3H₂Carrying out reflux reaction on an O main catalyst and 2.50g (30.4 mmol) of an N-methylimidazole cocatalyst in 60mL of acetone at 60 ℃ for 3h, carrying out reduced pressure rectification at 60 ℃ and 30kPa for 2h, washing and dispersing with diethyl ether, filtering, and carrying out vacuum drying at 60 ℃ and 30kPa for 12h to obtain 3.94g of catalyst complex 2.

Through detection, the catalyst complex obtained in the embodiment of the invention is a single crystal formed by copper nitrate and N-methylimidazole according to a molar ratio of 1: 2.

93.5g (608.0 mmol) of carbon tetrachloride and 7.61g (76.0 mmol) of ethyl acrylate are reacted with 0.53g of catalyst complex 2 (containing Cu (NO)₃)₂1.52mmol, 3.04mmol of N-methylimidazole) and 80mL of butyronitrile, placing the mixture in a stainless steel reaction kettle with a polytetrafluoroethylene inner container, stirring the mixture at room temperature for 30min, then sealing the reaction kettle, heating the mixture to 90 ℃, carrying out addition reaction for 20h, cooling the mixture to room temperature, filtering the mixture, distilling the filtrate at 90 ℃ under normal pressure for 3h, recovering carbon tetrachloride, and then carrying out reduced pressure rectification for 3h at 100 ℃ and 10kPa to obtain 19.42g of alpha, gamma and gamma-tetrachlorobutyric acid ethyl ester.

Through GC analysis, the purity of the alpha, gamma-tetrachloro ethyl butyrate obtained in the embodiment of the invention is 95.5 percent, and the one-way reaction yield calculated by taking the ethyl acrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (aca)% m (tca) ] = 100% = 19.42g × 95.5%/(76.0mmol × 253.96g/mol) = 100% = 96.1%.

As shown in fig. 5, 6 and 7, it can be determined through nuclear magnetic resonance and GC-MS detection that the product obtained in the embodiment of the present invention has a structure consistent with that of the target product, ethyl α, γ, γ -tetrachlorobutyrate.

Example 5

First 3.03g (15.20 mmol) of Cu (CH)₃COO)₂•H₂The O main catalyst and 4.99g (60.80 mmol) of N-methylimidazole cocatalyst are subjected to reflux reaction for 4h at 80 ℃ in 80mL of acetone, the mixture is subjected to reduced pressure rectification for 2.5h at 70 ℃ and 20kPa, then the mixture is washed and dispersed by ether, filtered, and dried in vacuum for 16h at 70 ℃ and 20kPa to obtain 4.38g of catalyst complex 3.

Through detection, the catalyst complex obtained in the embodiment of the invention is a single crystal formed by copper acetate and N-methylimidazole according to a molar ratio of 1: 4.

13.0g (84.5 mmol) of carbon tetrachloride and 10.8g (76 mmol) of alpha-butyl methacrylate are reacted with 0.39g of catalyst complex 3 containing Cu (CH)₃COO)₂0.76mmol, 3.04mmol of N-methylimidazole) and 10mL of acetonitrile, placing the mixture in a stainless steel reaction kettle with a polytetrafluoroethylene inner container, stirring the mixture at room temperature for 30min, then sealing the reaction kettle, heating the mixture to 140 ℃, carrying out addition reaction for 6h, cooling the mixture to room temperature, filtering the mixture, distilling the filtrate at 70 ℃ under normal pressure for 1h, recovering carbon tetrachloride, and then carrying out reduced pressure rectification at 90 ℃ and 15kPa for 1.5h to obtain 19.46g of alpha-methyl-alpha, gamma-tetrachlorobutyric acid butyl ester.

Through GC analysis, the purity of the alpha-methyl-alpha, gamma-tetrachlorobutyl butyrate obtained in the embodiment of the invention is 92.5 percent, and the one-way reaction yield calculated by taking the alpha-butyl methacrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (aca)% m (tca) ] = 100% = 19.46g × 92.5%/(76mmol × 296.04g/mol) = 100% = 80.0%.

The nuclear magnetism and GC-MS detection can confirm that the product obtained in the embodiment of the invention has the same structure with the target product, namely the butyl alpha-methyl-alpha, gamma-tetrachlorobutyrate.

Example 6

17.54g (114.0 mmol) of carbon tetrachloride and 13.39g (76.0 mmol) of benzyl alpha-methacrylate are reacted with 0.30g (1.50 mmol) of Cu (CH)₃COO)₂•H₂Placing an O main catalyst, 0.32g (3.04 mmol) of diethanolamine cocatalyst and 60mL of benzonitrile in a stainless steel reaction kettle with a polytetrafluoroethylene liner, stirring for 20min at room temperature, sealing the reaction kettle, heating to 60 ℃, carrying out addition reaction for 18h, cooling to room temperature, filtering, distilling the filtrate at 80 ℃ under normal pressure for 1.5h, recovering carbon tetrachloride, and carrying out reduced pressure rectification for 3h at 110 ℃ and 10kPa to obtain 21.23g of alpha-methyl-alpha, gamma-tetrachlorobutyric acid benzyl ester.

Through GC analysis, the purity of the alpha-methyl-alpha, gamma-tetrachloro benzyl butyrate obtained in the embodiment of the invention is 94.5%, and the one-way reaction yield calculated by taking the alpha-benzyl methacrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (aca)% m (tca) ] = 100% = 21.23g × 94.5%/(76mmol × 330.06g/mol) = 100% = 80.0%.

The nuclear magnetism and GC-MS detection can confirm that the structures of the products obtained in the embodiment of the invention are consistent with the structures of the target products, namely the alpha-methyl-alpha, gamma-tetrachloro benzyl butyrate.

Example 7

9.23g (60.0 mmol) of carbon tetrachloride and 20.55g (180.0 mmol) of ethyl alpha-methacrylate are reacted with 0.29g (1.20 mmol) of Cu (NO)₃)₂•3H₂Placing an O main catalyst, 0.29g (2.41 mmol) of N, N-dimethylaniline cocatalyst and 10mL of acetonitrile in a stainless steel reaction kettle with a polytetrafluoroethylene inner container, stirring for 30min at room temperature, then sealing the reaction kettle, heating to 100 ℃, carrying out addition reaction for 15h, cooling to room temperature, filtering, distilling the filtrate at 90 ℃ under normal pressure for 2h, recovering carbon tetrachloride, and then carrying out reduced pressure rectification for 3h at 100 ℃ and 10kPa to obtain 15.38g of alpha-methyl-alpha, gamma-tetrachlorobutyric acid ethyl ester.

Through GC analysis, the purity of the alpha-methyl-alpha, gamma-tetrachlorobutyric acid ethyl ester obtained in the embodiment of the invention is 92%, and the one-way reaction yield calculated by taking the alpha-methyl methacrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (ctc) × m (tca) ] = 100% = 15.38g × 92%/(60mmol × 267.98g/mol) = 100% = 88%.

The nuclear magnetism and GC-MS detection can confirm that the product obtained in the embodiment of the invention has the same structure with the target product of the alpha-methyl-alpha, gamma-tetrachloro ethyl butyrate.

Example 8

17.54g (114.0 mmol) of carbon tetrachloride, 13.39g (76.0 mmol) of alpha-benzyl methacrylate, 0.15g (1.52 mmol) of CuCl main catalyst, 0.87g (3.03 mmol) of chlorinated 1-dodecyl-3-methylimidazole cocatalyst and 10mL of acetonitrile are placed in a stainless steel reaction kettle with a polytetrafluoroethylene liner, the mixture is stirred at room temperature for 30min, the reaction kettle is sealed, the temperature is increased to 50 ℃, an addition reaction is carried out for 10h, then the reaction kettle is cooled to the room temperature, filtration is carried out, filtrate is distilled at 80 ℃ under normal pressure for 1.5h, carbon tetrachloride is recovered, and then the distillation is carried out under reduced pressure at 110 ℃ and 10kPa for 2h to obtain 24.81g of alpha-methyl-alpha, gamma and gamma-tetrachlorobenzyl butyrate.

Through GC analysis, the purity of the alpha-methyl-alpha, gamma-tetrachlorobutyric acid benzyl ester obtained in the embodiment of the invention is 93%, and the one-way reaction yield calculated by taking the alpha-methyl-acrylic acid benzyl ester as a reference raw material is as follows: w% = m (tca)% W%/[ n (aca)% m (tca) ] = 100% = 24.81g × 93%/(76mmol × 330.06g/mol) = 100% = 92.0%.

The nuclear magnetism and GC-MS detection can confirm that the structures of the products obtained in the embodiment of the invention are consistent with the structures of the target products, namely the alpha-methyl-alpha, gamma-tetrachloro benzyl butyrate.

Example 9

11.69g (76.0 mmol) of carbon tetrachloride and 19.48g (152.0 mmol) of butyl acrylate were mixed with 0.22g (1.54 mmol) of Cu₂Placing an O main catalyst, 0.45g (3.02 mmol) triethanolamine cocatalyst and 10mL acetonitrile in a stainless steel reaction kettle with a polytetrafluoroethylene liner, stirring at room temperature for 40min, sealing the reaction kettle, heating to 100 ℃, carrying out addition reaction for 10h, cooling to room temperature, filtering, distilling the filtrate at 80 ℃ under normal pressure for 2h, recovering carbon tetrachloride, and carrying out reduced pressure rectification at 100 ℃ and 20kPa for 3h to obtain 17.70g of alpha, gamma-butyl tetrachlorobutyrate.

Through GC analysis, the purity of the alpha, gamma-tetrachlorobutyl butyrate obtained in the embodiment of the invention is 91.5 percent, and the one-way reaction yield calculated by taking butyl acrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (ctc) × m (tca) ] = 100% = 17.70g × 91.5%/(76mmol × 282.01g/mol) = 100% = 75.6%.

The nuclear magnetism and GC-MS detection can confirm that the product obtained in the embodiment of the invention has the same structure with the target product alpha, gamma-butyl tetrachlorobutyrate.

Comparative example 1

Putting 13.0g (84.5 mmol) of carbon tetrachloride and 6.54g (76.0 mmol) of methyl acrylate, 0.125g (1.52 mmol) of N-methylimidazole and 10mL of acetonitrile into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, firstly stirring for 30min at room temperature, then sealing the reaction kettle, heating to 110 ℃ for addition reaction for 12h, cooling to room temperature, and filtering.

No product was formed in the filtrate obtained in this comparative example by GC analysis.

From this fact, it was found that the reaction hardly proceeded under the same conditions except the conditions without adding the main catalyst to the reaction system.

Comparative example 2

13.0g (84.5 mmol) of carbon tetrachloride and 6.54g (76.0 mmol) of methyl acrylate, 0.13g (0.76 mmol) of CuCl₂•2H₂And placing O and 10mL of acetonitrile in a stainless steel reaction kettle with a polytetrafluoroethylene inner container, stirring at room temperature for 30min, mixing, sealing the reaction kettle, heating to 110 ℃, performing addition reaction for 12h, cooling to room temperature, filtering, distilling the filtrate at 80 ℃ under normal pressure for 2h, recovering carbon tetrachloride, and performing reduced pressure rectification for 3h at 100 ℃ and 30kPa to obtain 6.91g of alpha, gamma-tetrachlorobutyric acid methyl ester.

After GC analysis, the purity of the alpha, gamma-tetrachlorobutyric acid methyl ester obtained in the comparative example is 83.5%, and the one-way reaction yield calculated by taking methyl acrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (aca)% m (tca) ] = 100% = 6.91g × 83.5%/(76mmol × 239.93g/mol) = 100% = 31.6%, and a large amount of tarry polymer exists in the reaction solution.

It is understood that, under otherwise identical conditions, the reaction product is of little value if no cocatalyst is added to the reaction system.

Comparative example 3

13.0g (84.5 mmol) of carbon tetrachloride and 7.61g (76.0 mmol) of alpha-methyl are introducedMethyl methacrylate with 0.26g of catalyst complex 1 obtained in example 3 (containing CuCl)₂0.76mmol, 1.52mmol of N-methylimidazole) and 10mL of acetonitrile, placing the mixture in a stainless steel reaction kettle with a polytetrafluoroethylene inner container, stirring the mixture for 30min at room temperature, sealing the reaction kettle, heating the mixture to 180 ℃, carrying out addition reaction for 12h, cooling the mixture to room temperature, filtering the mixture, distilling the filtrate at 80 ℃ under normal pressure for 2h, recovering carbon tetrachloride, and carrying out reduced pressure rectification for 2h at 105 ℃ and 10kPa to obtain 10.24g of alpha-methyl-alpha, gamma-tetrachlorobutyric acid methyl ester.

After GC analysis, the purity of the alpha-methyl-alpha, gamma-tetrachlorobutyric acid methyl ester obtained in the comparative example is 90.5%, and the one-way reaction yield calculated by taking the alpha-methyl methacrylate as a reference raw material is as follows: w% = m (tca)% W%/[ n (aca)% m (tca) ] = 100% =10.24g × 90.5%/(76mmol × 253.96g/mol) = 100% =48.0%, and a large amount of tar is produced in the reaction solution, and the main component thereof is a polymer produced by the addition polymerization reaction.

From this, it is found that the reaction temperature has a large influence on the product yield under the same conditions, and that if the reaction temperature is too high, not only the product yield is greatly reduced, but also the product appearance and purity are poor.