CN104829418B - Method for preparing benzyl chloride compound - Google Patents
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Abstract
The invention discloses a method for preparing a benzyl chloride compound through a pressurization reaction of aromatic hydrocarbon in a pressure reactor at 100-140DEG C under 1-4bar for 8-12h with an aqueous formaldehyde solution or trioxymethylene or paraformaldehyde and concentrated hydrochloric acid as a chloromethyl reagent. The product content is greater than 99.0%, and the product yield is greater than 90%. The pressurization reaction is adopted in the invention, so the activity of the chloromethyl reagent is enhanced, escape of HCl is avoided, and the disadvantages of high cost, large amount of three wastes, and difficult treatment brought by continuous introduction of HCl, greatly excess use of concentrated hydrochloric acid, and use of protonic acids, Lewis acids, phase transfer catalysts and ionic liquid catalysts are changed. A molar ratio of aldehyde to the aromatic hydrocarbon is 1:2-4, so the molecular concentration of the aromatic hydrocarbon in a system is greatly improved, and the proportion of a monochloromethylation product of the aromatic hydrocarbon is effectively improved. The method has the advantages of low cost of the raw material, simple process operation, small amount of the three wastes, high yield and good quality of the target compound, and suitableness for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of benzyl chloride class compound.
Background technology
Benzyl chloride class compound is very important fine-chemical intermediate, can be used to synthesize various very important parasite killing
Agent.General structure is as follows：
Such as R in general structure1、R2、R4For CH3, R3Benzyl chloride class compound 2,4,6- trimethyl benzyl chlorides for H are insecticide spiral shells
First demodicid mite ester (spiromesifen) important intermediate (Li Hui, Xu Xi it, the synthesis of Zhao Dongjiang .2,4,6- trimethylbenzene acetic acid
Research [J]. fine-chemical intermediate, 2010,40 (1):15~17；Liu Yu, Zhao Dongjiang, Yang Bin .2,4,6- trimethylbenzene acetic acid
Improvement in synthesis studies [J]. fine-chemical intermediate, 2014,44 (1):4-6)；R1、R3For CH3, R2、R4For the benzyl chloride class of H
Compound 2,5- dimethyl benzyl chlorides are the important intermediate (CN102140062B of insecticide spiral shell worm ethyl ester (spirotetramat)；
WO2012122747A1)。
The synthesis of benzyl chloride class compound belongs to the chloromethylation of aromatic hydrocarbons, and synthetic method can according to chloromethyl source reagent difference
It is divided into four class (CN1918103B；WO2012122747A1)：1) with MeOCH2Cl or (CH2Cl)2O be chloromethyl reagent, such chlorine
Methyl source agent of activity is higher, but stability is poor, and volatile, zest is big, corrosivity are big, have severe toxicity, be known carcinogenic
Thing, stores transport difficult, and document report is less.2) with chloromethyl alkyl ether as chloromethyl reagent, such as Cl formalins (CH2)
nCH3(Cl formalins)2(CH2) n (n=1~7), such chloromethyl source reagent has that boiling point is high, toxicity is low, without carcinogenic
Etc. characteristic, as chloromethylation reagents safely and effectively, but it is relatively costly, range of application is little, is mainly used in ion exchange resin
Preparation.3) with metal chloromethyl source reagent as chloromethyl reagent, such as ClCH2SiMe3And ClSiMe2- HCHO, typically by organic
Compound Me3SiCH2Li is transformed, it is the features such as with nontoxic, high selectivity, high yield but relatively costly, prepare it is difficult.4)
Using formalin or metaformaldehyde or paraformaldehyde with hydrochloric acid or HCl as chloromethyl reagent, such agent of activity is relatively
Weak, the response time is longer, but reaction is related to the low prices of raw materials, small toxicity, applied range, storage convenient transportation, document report
Road is most.
Using formalin or metaformaldehyde or paraformaldehyde with hydrochloric acid or HCl as chloromethyl reagent, current way
It is by raw material aromatic hydrocarbons, chloromethyl reagent formalin or metaformaldehyde or paraformaldehyde, catalyst (Bronsted acid or road under normal pressure
Lewis acid, phase transfer catalyst, ionic liquid one or more) and atent solvent when liquid (substrate be can be without solvent) put
In entering reactor, then heating up logical HCl reactions or adds temperature reaction after concentrated hydrochloric acid, reaction to finish, and is layered, extracts, rectification
Obtain target, the most not high, (CN102140062B between 48~92% of document report yield；WO2012122747A1；
Takezawa T,Kusano T.Nippon Kagaku Kaishi.1989,(6),1047；Wei Wei. the chloromethylation of aromatic hydrocarbons and
The oxidation reaction research of benzyl chloride. Institutes Of Technology Of Nanjing's Master's thesis, 2009；Hu Yulin. aromatic hydrocarbons chloromethylation new method is ground
Study carefully. University Of Xiangtan's Master's thesis, 2008；Zhang Haiqun. the synthesis [J] of chloromethylation-dibenzo-14-crown-4. synthesis chemistry,
2011,19(6)：794-795；The .2 of Li Hui, Xu Xi, the study on the synthesis [J] of 4,6- trimethylbenzene acetic acid. in the middle of fine chemistry industry
Body, 2010,40 (1)：15~17；Liu Yu, Zhao Dongjiang, Yang Bin .2,4,6- trimethylbenzene acetic acid improvement in synthesis studies [J].
Fine-chemical intermediate, 2014,44 (1):4-6).
Reaction expression is as follows：
The process recovery ratio is not high, main cause：One is formalin or metaformaldehyde or paraformaldehyde and hydrochloric acid or HCl
The chloromethyl agent of activity of composition is relatively weak, reacts more difficult complete；Two is with the concentration for carrying out aromatic hydrocarbons in system of reaction
Reduce, on the contrary the concentration of benzyl chloride increases so that and the chloromethyl reagent that formaldehyde is formed with HCl increases with benzyl chloride touch opportunity, causes
Two replacement impurity increase.
Document report (CN102140062B；The .2 of Li Hui, Xu Xi, the study on the synthesis [J] of 4,6- trimethylbenzene acetic acid. essence
Thin chemical intermediate, 2010,40 (1)：15~17；Liu Yu, Zhao Dongjiang, Yang Bin .2,4,6- trimethylbenzene acetic acid synthesis techniques change
Enter research [J]. fine-chemical intermediate, 2014,44 (1):4-6), HCl gases are persistently led between 50~100 DEG C or is used
Substantial amounts of concentrated hydrochloric acid (6~15 times of primary response material mole) is reacted, and can strengthen the activity of chloromethyl reagent, improves anti-
Answer yield.But HCl constantly escapes under high temperature, system HCl concentration is constantly reduced, and later stage chloromethyl agent of activity strengthens not substantially,
Reaction is incomplete, and yield is undesirable.And persistently lead to HCl gases or the method using a large amount of concentrated hydrochloric acid under high temperature, can bring
The problems such as substantial amounts of acid waste gas, residual highly acid kettle, high-salt wastewater, big for environment pollution, three-protection design is more difficult.
Document report (Li Hui, Xu Xi it, Zhao Dongjiang, the study on the synthesis of 2,4,6- trimethylbenzene acetic acid,《In fine chemistry industry
Mesosome》, Vol.40.No.1, P15-17 (2010)；Liu Yu, Zhao Dongjiang, Yang Bin, 2,4,6- trimethylbenzene acetic acid synthesis techniques change
Enter research,《Fine-chemical intermediate》, Vol.44.No.1, P4-6 (2014)), by the mol ratio for increasing aromatic hydrocarbons and aldehyde, suppression
Make the generation of two replacement impurity, but because formalin or metaformaldehyde or paraformaldehyde and hydrochloric acid or the chloromethane of HCl compositions
Base agent of activity is relatively weak, reacts more difficult complete, causes yield still not ideal；And concentrated hydrochloric acid consumption reaches in document
7.2 times (mol ratio), post processing produces substantial amounts of high-salt wastewater.
The content of the invention
The invention provides the preparation method of benzyl chloride class compound is to adopt compressive reaction, with aromatic hydrocarbons as raw material, with formaldehyde
Aqueous solution or metaformaldehyde or paraformaldehyde and concentrated hydrochloric acid are used as chloromethyl reagent, in pressure reactor, controlling reaction temperature
100~140 DEG C, 1~4bar of reaction pressure, 8~12h of response time, after reaction terminates, layering, extraction, rectification obtain target product
Thing benzyl chloride class compound.Gained benzyl chloride kind compound content is more than 99.0%, and yield is 90.6~93.4%.
Reaction equation is：
Benzyl chloride class compound of the present invention refers to R in reaction equation1It is CH3；R2It is H, CH3；R3It is H, CH3；R4It is H, CH3
2,4,6- trimethyls benzyl chloride and 2,5- dimethyl benzyl chlorides；The concentrated hydrochloric acid refers to the hydrochloric acid that mass percentage concentration is 36%；Virtue
Hydrocarbon refers to xylol or sym-trimethylbenzene.；Formalin or metaformaldehyde or paraformaldehyde are referred to as into aldehyde, wherein trimerization first
The amount of the material of aldehyde and paraformaldehyde is in terms of formaldehyde monomers；The mol ratio of Quan ︰ Fang Ting ︰ concentrated hydrochloric acid is the ︰ 1.3~1.5 of 1 ︰ 2~4.
Concrete operation step：Aromatic hydrocarbons, formalin or metaformaldehyde or paraformaldehyde and concentrated hydrochloric acid are all added into pressure
After power kettle, closed reactor opens stirring, and between 100~140 DEG C of controlling reaction temperature, 1~4bar of reaction pressure, insulation is anti-
8~12h between seasonable.After reaction terminates, system is cooled to into room temperature, separates organic faciess, water mutually with substrate aromatic hydrocarbons extraction 2 times afterwards
Merge organic faciess, with saturated aqueous sodium carbonate neutrality is washed till, separate oil reservoir rectification and obtain benzyl chloride class compound.
The present invention adopts compressive reaction, strengthens chloromethyl agent of activity, while avoiding the escape of HCl, changes and continues
Logical HCl, be excessively used concentrated hydrochloric acid significantly, using this kind of catalyst of Bronsted acid, lewis acid, phase transfer catalyst and ionic liquid
The drawback such as the high cost brought, quantity of three wastes be big, difficult.Aldehyde is 1 with the mol ratio of aromatic hydrocarbons:2~4, substantially increase system
The molecular concentration of middle aromatic hydrocarbons, effectively raises the monochloro methylate ratio of aromatic hydrocarbons, and the cost of raw material is cheap, technological operation
Simply, quantity of three wastes is few, target compound high income, quality better, and product content is more than 99.0%, and yield is more than 90%, is suitable to work
Industry metaplasia is produced.
Specific embodiment
Following % refers both to percetage by weight, and the monochloro methylate yield of aromatic hydrocarbons is with formalin or metaformaldehyde
Or paraformaldehyde meter.
Embodiment 1：The synthesis of 2,5- dimethyl benzyl chlorides
127.2g xylol (1.2mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to
100 DEG C, pressure rises to 1bar, insulation reaction 8h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer is used
50ml xylol is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
85.3g2,5- dimethyl benzyl chloride, content 99.2%, yield 91.3%.
Embodiment 2：The synthesis of 2,4,6- trimethyl benzyl chlorides
144.0g sym-trimethylbenzene. (1.2mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to
100 DEG C, pressure rises to 1bar, insulation reaction 8h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer is used
50ml sym-trimethylbenzene. is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
93.4g2,4,6- trimethyl benzyl chlorides, content 99.3%, yield 91.7%.
Embodiment 3：The synthesis of 2,5- dimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde),
99%], the other the same as in Example 1, obtains object 85.2g, content 99.2%, yield 91.2%.
Embodiment 4：The synthesis of 2,5- dimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], the other the same as in Example 1, obtains object 84.7g, content 99.3%, yield 90.7%
Embodiment 5：The synthesis of 2,5- dimethyl benzyl chlorides
79.1g concentrated hydrochloric acid (0.78mol, 36%) is changed to into 91.3g concentrated hydrochloric acid (0.9mol, 36%), other same embodiments
1, obtain object 86.5g, content 99.2%, yield 92.6%.
Embodiment 6：The synthesis of 2,5- dimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, the other the same as in Example 1 obtains object 86.4g, and content 99.2% is received
Rate 92.5%.
Embodiment 7：The synthesis of 2,5- dimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 1 is applied, object 86.4g, content 99.2%, yield 92.5% is obtained.
Embodiment 8：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde),
99%], the other the same as in Example 2, obtains object 92.8g, content 99.1%, yield 91.0%.
Embodiment 9：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], the other the same as in Example 2, obtains object 92.3g, content 99.2%, yield 90.6%
Embodiment 10：The synthesis of 2,4,6- trimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, the other the same as in Example 2 obtains object 94.0g, and content 99.3% is received
Rate 92.3%.
Embodiment 11：The synthesis of 2,4,6- trimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 2 is applied, object 94.0g, content 99.3%, yield 92.3% is obtained.
Embodiment 12：The synthesis of 2,4,6- trimethyl benzyl chlorides
79.1g concentrated hydrochloric acid (0.78mol, 36%) is changed to into 91.3g concentrated hydrochloric acid (0.9mol, 36%), other same embodiments
2, obtain object 93.9g, content 99.3%, yield 92.2%.
Embodiment 13：The synthesis of 2,5- dimethyl benzyl chlorides
127.2g xylol (1.2mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 100 DEG C, pressure rises to 1bar, insulation reaction 8h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer, water
Layer is extracted 2 times with 50ml xylol, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower rectification on oil reservoir
Obtain 86.3g 2,5- dimethyl benzyl chlorides, content 99.2%, yield 92.4%.
Embodiment 14：The synthesis of 2,4,6- trimethyl benzyl chlorides
144.0g sym-trimethylbenzene. (1.2mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 100 DEG C, pressure rises to 1bar, insulation reaction 8h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer, water
Layer is extracted 2 times with 50ml sym-trimethylbenzene., and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower rectification on oil reservoir
Obtain the trimethyl benzyl chlorides of 93.8g 2,4,6-, content 99.4%, yield 92.2%.
Embodiment 15：The synthesis of 2,5- dimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], the other the same as in Example 13 obtains object 85.6g, content 99.3%, yield 91.7%.
Embodiment 16：The synthesis of 2,5- dimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, the other the same as in Example 13 obtains object 86.5g, content 99.2%,
Yield 92.6%.
Embodiment 17：The synthesis of 2,5- dimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 13 is applied, object 85.7g, content 99.2%, yield 91.7% is obtained.
Embodiment 18：The synthesis of 2,4,6- trimethyl benzyl chlorides
18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%] are changed to into 19.6g (CHO)n[0.6mol is (with formaldehyde
Meter), 92%], the other the same as in Example 14 obtains object 93.1g, content 99.1%, yield 91.3%.
Embodiment 19：The synthesis of 2,4,6- trimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, the other the same as in Example 14 obtains object 93.9g, content 99.4%,
Yield 92.3%.
Embodiment 20：The synthesis of 2,4,6- trimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 14 is applied, object 94.2g, content 99.4%, yield 92.6% is obtained.
Embodiment 21：The synthesis of 2,5- dimethyl benzyl chlorides
127.2g xylol (1.2mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 100 DEG C, pressure rises to 1bar, insulation reaction 12h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer,
Water layer is extracted 2 times with 50ml xylol, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower essence on oil reservoir
Evaporate and obtain 86.0g 2,5- dimethyl benzyl chlorides, content 99.2%, yield 92.0%.
Embodiment 22：The synthesis of 2,4,6- trimethyl benzyl chlorides
144.0g sym-trimethylbenzene. (1.2mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 100 DEG C, pressure rises to 1bar, insulation reaction 12h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer,
Water layer is extracted 2 times with 50ml sym-trimethylbenzene., and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower essence on oil reservoir
Evaporate and obtain the trimethyl benzyl chlorides of 93.8g 2,4,6-, content 99.4%, yield 92.2%.
Embodiment 23：The synthesis of 2,5- dimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], the other the same as in Example 21 obtains object 85.5g, content 99.3%, yield 91.6%.
Embodiment 24：The synthesis of 2,5- dimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 21 is applied, object 85.9g, content 99.2%, yield 91.9% is obtained.
Embodiment 25：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], the other the same as in Example 22 obtains object 93.0g, content 99.1%, yield 91.2%.
Embodiment 26：The synthesis of 2,4,6- trimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 22 is applied, object 93.6g, content 99.4%, yield 92.0% is obtained.
Embodiment 27：The synthesis of 2,5- dimethyl benzyl chlorides
127.2g xylol (1.2mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to into 100
DEG C, pressure rises to 1bar, insulation reaction 12h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer 50ml
Xylol is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
86.7g2,5- dimethyl benzyl chloride, content 99.2%, yield 92.8%.
Embodiment 28：The synthesis of 2,4,6- trimethyl benzyl chlorides
144.0g sym-trimethylbenzene. (1.2mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to into 100
DEG C, pressure rises to 1bar, insulation reaction 12h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer 50ml
Sym-trimethylbenzene. is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
94.2g2,4,6- trimethyl benzyl chlorides, content 99.3%, yield 92.5%.
Embodiment 29：The synthesis of 2,5- dimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], the other the same as in Example 27, obtain object 85.9g, content 99.3%, yield 92.0%
Embodiment 30：The synthesis of 2,5- dimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 27 is applied, object 86.6g, content 99.3%, yield 92.8% is obtained.
Embodiment 31：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], the other the same as in Example 28, obtain object 93.8g, content 99.1%, yield 91.9%
Embodiment 32：The synthesis of 2,4,6- trimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 28 is applied, object 94.8g, content 99.3%, yield 93.1% is obtained.
Embodiment 33：The synthesis of 2,4,6- trimethyl benzyl chlorides
144.0g sym-trimethylbenzene. (1.2mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 140 DEG C, pressure rises to 3.7bar, insulation reaction 8h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer,
Water layer is extracted 2 times with 50ml sym-trimethylbenzene., and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower essence on oil reservoir
Evaporate and obtain the trimethyl benzyl chlorides of 93.7g 2,4,6-, content 99.4%, yield 92.1%.
Embodiment 34：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], the other the same as in Example 33 obtains object 93.6g, content 99.1%, yield 91.7%.
Embodiment 35：The synthesis of 2,5- dimethyl benzyl chlorides
127.2g xylol (1.2mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde), 92%], closed reactor opens stirring, by kettle
To 140 DEG C, pressure rises to 3.7bar, insulation reaction 8h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer,
Water layer is extracted 2 times with 50ml xylol, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower essence on oil reservoir
Evaporate and obtain 85.2g 2,5- dimethyl benzyl chlorides, content 99.3%, yield 91.3%.
Embodiment 36：The synthesis of 2,5- dimethyl benzyl chlorides
79.1g concentrated hydrochloric acid (0.78mol, 36%) is changed to into 91.3g concentrated hydrochloric acid (0.9mol, 36%), other same embodiments
35, obtain object 86.1g, content 99.3%, yield 92.2%.
Embodiment 37：The synthesis of 2,5- dimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, the other the same as in Example 35 obtains object 85.2g, content 99.3%,
Yield 91.3%.
Embodiment 38：The synthesis of 2,5- dimethyl benzyl chlorides
127.2g xylol (1.2mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to into 140
DEG C, pressure rises to 3.7bar, insulation reaction 8h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer is used
50ml xylol is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
86.8g 2,5- dimethyl benzyl chloride, content 99.2%, yield 92.9%.
Embodiment 39：The synthesis of 2,5- dimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde),
99%], the other the same as in Example 38, obtain object 86.6g, content 99.2%, yield 92.7%.
Embodiment 40：The synthesis of 2,5- dimethyl benzyl chlorides
127.2g xylol (1.2mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to
140 DEG C, pressure rises to 3.7bar, insulation reaction 12h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer
Extracted 2 times with 50ml xylol, organic layer is merged afterwards, with saturated sodium carbonate neutrality is washed till, separated tower rectification on oil reservoir and obtain
To 86.3g 2,5- dimethyl benzyl chlorides, content 99.2%, yield 92.4%.
Embodiment 41：The synthesis of 2,5- dimethyl benzyl chlorides
127.2g xylol (1.2mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 140 DEG C, pressure rises to 3.7bar, insulation reaction 12h for temperature rise.After reaction terminates, system is cooled to into room temperature, is separated organic
Layer, water layer is extracted 2 times with 50ml xylol, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower on oil reservoir
Rectification obtains 86.4g 2,5- dimethyl benzyl chlorides, content 99.2%, yield 92.5%
Embodiment 42：The synthesis of 2,5- dimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], the other the same as in Example 41 obtains object 85.9g, content 99.3%, yield 92.0%.
Embodiment 43：The synthesis of 2,4,6- trimethyl benzyl chlorides
144.0g sym-trimethylbenzene. (1.2mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to into 140
DEG C, pressure rises to 3.7bar, insulation reaction 8h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer is used
50ml sym-trimethylbenzene. is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
94.7g 2,4,6- trimethyl benzyl chloride, content 99.3%, yield 93.0%.
Embodiment 44：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], the other the same as in Example 43, obtain object 94.2g, content 99.1%, yield 92.3%
Embodiment 45：The synthesis of 2,4,6- trimethyl benzyl chlorides
144.0g sym-trimethylbenzene. (1.2mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to
140 DEG C, pressure rises to 3.7bar, insulation reaction 12h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer
Extracted 2 times with 50ml sym-trimethylbenzene., organic layer is merged afterwards, with saturated sodium carbonate neutrality is washed till, separated tower rectification on oil reservoir and obtain
To the trimethyl benzyl chlorides of 94.0g 2,4,6-, content 99.3%, yield 92.3%.
Embodiment 46：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], the other the same as in Example 45, obtain object 93.7g, content 99.1%, yield 91.8%
Embodiment 47：The synthesis of 2,4,6- trimethyl benzyl chlorides
144.0g sym-trimethylbenzene. (1.2mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 140 DEG C, pressure rises to 3.7bar, insulation reaction 12h for temperature rise.After reaction terminates, system is cooled to into room temperature, is separated organic
Layer, water layer is extracted 2 times with 50ml sym-trimethylbenzene., and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower on oil reservoir
Rectification obtains the trimethyl benzyl chlorides of 94.2g 2,4,6-, content 99.4%, yield 92.6%.
Embodiment 48：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], the other the same as in Example 47 obtains object 94.1g, content 99.1%, yield 92.2%.
Embodiment 49：The synthesis of 2,5- dimethyl benzyl chlorides
254.4g xylol (2.4mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to
100 DEG C, pressure rises to 1bar, insulation reaction 8h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer is used
50ml xylol is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
86.3g2,5- dimethyl benzyl chloride, content 99.2%, yield 92.3%.
Embodiment 50：The synthesis of 2,4,6- trimethyl benzyl chlorides
288.0g sym-trimethylbenzene. (2.4mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to
100 DEG C, pressure rises to 1bar, insulation reaction 8h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer is used
50ml sym-trimethylbenzene. is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
93.8g2,4,6- trimethyl benzyl chlorides, content 99.3%, yield 92.1%.
Embodiment 51：The synthesis of 2,5- dimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde),
99%], the other the same as in Example 49, obtain object 85.8g, content 99.2%, yield 91.8%.
Embodiment 52：The synthesis of 2,5- dimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], the other the same as in Example 49, obtain object 85.1g, content 99.3%, yield 91.1%
Embodiment 53：The synthesis of 2,5- dimethyl benzyl chlorides
79.1g concentrated hydrochloric acid (0.78mol, 36%) is changed to into 91.3g concentrated hydrochloric acid (0.9mol, 36%), other same embodiments
49, obtain object 86.6g, content 99.2%, yield 92.7%.
Embodiment 54：The synthesis of 2,5- dimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, the other the same as in Example 49 obtains object 86.6g, content 99.2%,
Yield 92.7%.
Embodiment 55：The synthesis of 2,5- dimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 49 is applied, object 86.4g, content 99.2%, yield 92.4% is obtained.
Embodiment 56：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde),
99%], the other the same as in Example 50, obtains object 93.3g, content 99.4%, yield 91.7%.
Embodiment 57：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], the other the same as in Example 50, obtains object 92.8g, content 99.1%, yield 91.0%
Embodiment 58：The synthesis of 2,4,6- trimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, the other the same as in Example 50 obtains object 94.2g, content 99.3%,
Yield 92.5%.
Embodiment 59：The synthesis of 2,4,6- trimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 50 is applied, object 94.2g, content 99.3%, yield 92.5% is obtained.
Embodiment 60：The synthesis of 2,4,6- trimethyl benzyl chlorides
79.1g concentrated hydrochloric acid (0.78mol, 36%) is changed to into 91.3g concentrated hydrochloric acid (0.9mol, 36%), other same embodiments
50, obtain object 94.3g, content 99.3%, yield 92.6%.
Embodiment 61：The synthesis of 2,5- dimethyl benzyl chlorides
254.4g xylol (2.4mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 100 DEG C, pressure rises to 1bar, insulation reaction 8h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer, water
Layer is extracted 2 times with 50ml xylol, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower rectification on oil reservoir
Obtain 86.5g 2,5- dimethyl benzyl chlorides, content 99.2%, yield 92.6%.
Embodiment 62：The synthesis of 2,4,6- trimethyl benzyl chlorides
288.0g sym-trimethylbenzene. (2.4mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 100 DEG C, pressure rises to 1bar, insulation reaction 8h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer, water
Layer is extracted 2 times with 50ml sym-trimethylbenzene., and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower rectification on oil reservoir
Obtain the trimethyl benzyl chlorides of 94.1g 2,4,6-, content 99.4%, yield 92.5%.
Embodiment 63：The synthesis of 2,5- dimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], other obtain object 85.9g, content 99.3%, yield 92.0% with embodiment 61.
Embodiment 64：The synthesis of 2,5- dimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, other obtain object 87.0g with embodiment 61, content 99.2%,
Yield 93.1%.
Embodiment 65：The synthesis of 2,5- dimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 61 is applied, object 87.0g, content 99.2%, yield 93.1% is obtained.
Embodiment 66：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], other obtain object 93.8g, content 99.1%, yield 91.9% with embodiment 62.
Embodiment 67：The synthesis of 2,4,6- trimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, other obtain object 94.9g with embodiment 62, content 99.4%,
Yield 93.3%.
Embodiment 68：The synthesis of 2,4,6- trimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 62 is applied, object 94.9g, content 99.4%, yield 93.3% is obtained.
Embodiment 69：The synthesis of 2,5- dimethyl benzyl chlorides
254.4g xylol (2.4mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 100 DEG C, pressure rises to 1bar, insulation reaction 12h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer,
Water layer is extracted 2 times with 50ml xylol, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower essence on oil reservoir
Evaporate and obtain 86.4g 2,5- dimethyl benzyl chlorides, content 99.2%, yield 92.4%.
Embodiment 70：The synthesis of 2,4,6- trimethyl benzyl chlorides
288.0g sym-trimethylbenzene. (2.4mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 100 DEG C, pressure rises to 1bar, insulation reaction 12h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer,
Water layer is extracted 2 times with 50ml sym-trimethylbenzene., and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower essence on oil reservoir
Evaporate and obtain the trimethyl benzyl chlorides of 93.7g 2,4,6-, content 99.4%, yield 92.1%.
Embodiment 71：The synthesis of 2,5- dimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], other obtain object 85.6g, content 99.3%, yield 91.9% with embodiment 69.
Embodiment 72：The synthesis of 2,5- dimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 69 is applied, object 86.4g, content 99.2%, yield 92.5% is obtained.
Embodiment 73：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], other obtain object 93.7g, content 99.1%, yield 91.8% with embodiment 70.
Embodiment 74：The synthesis of 2,4,6- trimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 70 is applied, object 93.7g, content 99.4%, yield 92.1% is obtained.
Embodiment 75：The synthesis of 2,5- dimethyl benzyl chlorides
254.4g xylol (2.4mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to into 100
DEG C, pressure rises to 1bar, insulation reaction 12h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer 50ml
Xylol is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
87.3g2,5- dimethyl benzyl chloride, content 99.2%, yield 93.4%.
Embodiment 76：The synthesis of 2,4,6- trimethyl benzyl chlorides
288.0g sym-trimethylbenzene. (2.4mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to into 100
DEG C, pressure rises to 1bar, insulation reaction 12h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer 50ml
Sym-trimethylbenzene. is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
94.9g2,4,6- trimethyl benzyl chlorides, content 99.3%, yield 93.2%.
Embodiment 77：The synthesis of 2,5- dimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], other obtain object 86.7g, content 99.3%, yield 92.9% with embodiment 75
Embodiment 78：The synthesis of 2,5- dimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 75 is applied, object 87.0g, content 99.4%, yield 93.3% is obtained.
Embodiment 79：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], other obtain object 94.6g, content 99.1%, yield 92.7% with embodiment 76
Embodiment 80：The synthesis of 2,4,6- trimethyl benzyl chlorides
By reaction temperature, 100 DEG C are changed to 140 DEG C of reaction temperature, and pressure rises to 1bar and is changed to rise to 3.7bar, and other are with real
Example 76 is applied, object 94.9g, content 99.3%, yield 93.2% is obtained.
Embodiment 81：The synthesis of 2,4,6- trimethyl benzyl chlorides
288.0g sym-trimethylbenzene. (2.4mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 140 DEG C, pressure rises to 3.7bar, insulation reaction 8h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer,
Water layer is extracted 2 times with 50ml sym-trimethylbenzene., and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower essence on oil reservoir
Evaporate and obtain the trimethyl benzyl chlorides of 93.7g 2,4,6-, content 99.4%, yield 92.1%.
Embodiment 82：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], other obtain object 93.5g, content 99.1%, yield 91.6% with embodiment 81.
Embodiment 83：The synthesis of 2,5- dimethyl benzyl chlorides
254.4g xylol (2.4mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde), 92%], closed reactor opens stirring, by kettle
To 140 DEG C, pressure rises to 3.7bar, insulation reaction 8h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer,
Water layer is extracted 2 times with 50ml xylol, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower essence on oil reservoir
Evaporate and obtain 85.6g 2,5- dimethyl benzyl chlorides, content 99.3%, yield 91.9%.
Embodiment 84：The synthesis of 2,5- dimethyl benzyl chlorides
79.1g concentrated hydrochloric acid (0.78mol, 36%) is changed to into 91.3g concentrated hydrochloric acid (0.9mol, 36%), other same embodiments
83, obtain object 86.6g, content 99.3%, yield 92.8%.
Embodiment 85：The synthesis of 2,5- dimethyl benzyl chlorides
Insulation reaction 8h is changed to into insulation reaction 12h, other obtain object 85.7g with embodiment 83, content 99.3%,
Yield 91.8%.
Embodiment 86：The synthesis of 2,5- dimethyl benzyl chlorides
254.4g xylol (2.4mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 140 DEG C, pressure rises to 3.7bar, insulation reaction 8h for temperature rise.After reaction terminates, system is cooled to into room temperature, separates organic layer,
Water layer is extracted 2 times with 50ml xylol, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower essence on oil reservoir
Evaporate and obtain 86.5g 2,5- dimethyl benzyl chlorides, content 99.2%, yield 92.6%.
Embodiment 87：The synthesis of 2,5- dimethyl benzyl chlorides
254.4g xylol (2.4mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to into 140
DEG C, pressure rises to 3.7bar, insulation reaction 8h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer is used
50ml xylol is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
87.3g 2,5- dimethyl benzyl chloride, content 99.2%, yield 93.4%.
Embodiment 88：The synthesis of 2,5- dimethyl benzyl chlorides
254.4g xylol (2.4mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to
140 DEG C, pressure rises to 3.7bar, insulation reaction 12h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer
Extracted 2 times with 50ml xylol, organic layer is merged afterwards, with saturated sodium carbonate neutrality is washed till, separated tower rectification on oil reservoir and obtain
To 86.5g 2,5- dimethyl benzyl chlorides, content 99.2%, yield 92.6%.
Embodiment 89：The synthesis of 2,5- dimethyl benzyl chlorides
254.4g xylol (2.4mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 140 DEG C, pressure rises to 3.7bar, insulation reaction 12h for temperature rise.After reaction terminates, system is cooled to into room temperature, is separated organic
Layer, water layer is extracted 2 times with 50ml xylol, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower on oil reservoir
Rectification obtains 86.9g 2,5- dimethyl benzyl chlorides, content 99.2%, yield 93.0%
Embodiment 90：The synthesis of 2,5- dimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], other obtain object 86.5g, content 99.3%, yield 92.7% with embodiment 89.
Embodiment 91：The synthesis of 2,4,6- trimethyl benzyl chlorides
288.0g sym-trimethylbenzene. (2.4mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to into 140
DEG C, pressure rises to 3.7bar, insulation reaction 8h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer is used
50ml sym-trimethylbenzene. is extracted 2 times, and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and is separated tower rectification on oil reservoir and is obtained
95.0g 2,4,6- trimethyl benzyl chloride, content 99.3%, yield 93.3%.
Embodiment 92：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], other obtain object 94.8g, content 99.1%, yield 92.9% with embodiment 91
Embodiment 93：The synthesis of 2,4,6- trimethyl benzyl chlorides
288.0g sym-trimethylbenzene. (2.4mol, 99%), 79.1g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.78mol, 36%) and 48.6g formalins (0.6mol, 37%), closed reactor opens stirring, and kettle temperature is risen to
140 DEG C, pressure rises to 3.7bar, insulation reaction 12h.After reaction terminates, system is cooled to into room temperature, separates organic layer, water layer
Extracted 2 times with 50ml sym-trimethylbenzene., organic layer is merged afterwards, with saturated sodium carbonate neutrality is washed till, separated tower rectification on oil reservoir and obtain
To the trimethyl benzyl chlorides of 94.0g 2,4,6-, content 99.5%, yield 92.5%.
Embodiment 94：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 48.6g formalins (0.6mol, 37%) be changed to 19.6g paraformaldehydes [0.6mol (in terms of formaldehyde),
92%], other obtain object 93.8g, content 99.1%, yield 91.9% with embodiment 93
Embodiment 95：The synthesis of 2,4,6- trimethyl benzyl chlorides
288.0g sym-trimethylbenzene. (2.4mol, 99%), 91.3g concentrated hydrochloric acid are sequentially added in the autoclave pressure of 500ml
(0.9mol, 36%) and 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], closed reactor opens stirring, by kettle
To 140 DEG C, pressure rises to 3.7bar, insulation reaction 12h for temperature rise.After reaction terminates, system is cooled to into room temperature, is separated organic
Layer, water layer is extracted 2 times with 50ml sym-trimethylbenzene., and organic layer is merged afterwards, and with saturated sodium carbonate neutrality is washed till, and separates tower on oil reservoir
Rectification obtains the trimethyl benzyl chlorides of 94.8g 2,4,6-, content 99.4%, yield 93.2%.
Embodiment 96：The synthesis of 2,4,6- trimethyl benzyl chlorides
By 18.2g metaformaldehydes [0.6mol (in terms of formaldehyde), 99%], [0.6mol is (with formaldehyde to be changed to 19.6g paraformaldehydes
Meter), 92%], other obtain object 94.8g, content 99.1%, yield 92.9% with embodiment 95.
Claims (1)
1. a kind of preparation method of benzyl chloride class compound, it is characterised in that compressive reaction is adopted, with aromatic hydrocarbons as raw material, with formalin
Solution or metaformaldehyde or paraformaldehyde and concentrated hydrochloric acid as chloromethyl reagent, in pressure reactor, controlling reaction temperature 100
~140 DEG C, 1~4bar of reaction pressure, 8~12h of response time, after reaction terminates, layering, extraction, rectification obtain target product
Benzyl chloride class compound,
Reaction equation is：
The benzyl chloride class compound refers to R in reaction equation1It is CH3；R2It is H, CH3；R3It is H, CH3；R4It is H, CH32,4,6- tri-
Methyl benzyl chloride and 2,5- dimethyl benzyl chlorides；The concentrated hydrochloric acid refers to the hydrochloric acid that mass percentage concentration is 36%；Aromatic hydrocarbons is referred to two
Toluene or sym-trimethylbenzene.；Formalin or metaformaldehyde or paraformaldehyde are referred to as into aldehyde, wherein metaformaldehyde and poly first
The amount of the material of aldehyde is in terms of formaldehyde monomers；The mol ratio of Quan ︰ Fang Ting ︰ concentrated hydrochloric acid is the ︰ 1.3~1.5 of 1 ︰ 2~4.
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| CN109111340A (en) * | 2018-10-26 | 2019-01-01 | 浙江众成包装材料股份有限公司 | Serialization prepares the high pressure reaction assembly of 1- (1- bromoethyl) -4- chloromethylbenzene |
| CN111072470A (en) * | 2019-12-18 | 2020-04-28 | 大连奇凯医药科技有限公司 | Method for preparing 2, 5-dimethyl phenylacetyl chloride |
| CN111362776A (en) * | 2020-04-25 | 2020-07-03 | 河北兰升生物科技有限公司 | Improved preparation method of 2, 5-disubstituted benzyl chloride |
| CN112552182B (en) * | 2020-11-20 | 2022-10-11 | 杭州新桂实业有限公司 | New synthesis process of naftifine drug intermediate N-methyl-1-naphthylmethylamine |
| CN112723986A (en) * | 2020-12-24 | 2021-04-30 | 衢州康鹏化学有限公司 | Preparation method of p-chloromethyl styrene |
| CN113149808A (en) * | 2021-04-21 | 2021-07-23 | 浦拉司科技（上海）有限责任公司 | Preparation method of ethyl benzyl chloride |
| CN114057540B (en) * | 2021-12-10 | 2023-11-10 | 西安凯立新材料股份有限公司 | Method for preparing 2, 5-dimethyl benzyl chloride |
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