CN106748627A - A kind of method that one kettle way prepares 3,5 dimethyl bromobenzenes - Google Patents

A kind of method that one kettle way prepares 3,5 dimethyl bromobenzenes Download PDF

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Publication number
CN106748627A
CN106748627A CN201610999079.2A CN201610999079A CN106748627A CN 106748627 A CN106748627 A CN 106748627A CN 201610999079 A CN201610999079 A CN 201610999079A CN 106748627 A CN106748627 A CN 106748627A
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added dropwise
kettle way
prepares
reaction
reaction vessel
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徐新连
苗余
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SUZHOU LUOSEN ADDITIVE CO Ltd
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SUZHOU LUOSEN ADDITIVE CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/093Preparation of halogenated hydrocarbons by replacement by halogens
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00Preparation of compounds containing amino groups bound to a carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/20Diazonium compounds

Abstract

The present invention relates to a kind of method that one kettle way prepares 3,5 dimethyl bromobenzenes, it is comprised the following steps:(a)To glacial acetic acid, dimethylaniline is sequentially added in reaction vessel, sulfuric acid solution is then added dropwise, keeping temperature is 30 ~ 40 DEG C and continues that bromine is added dropwise, and continues stirring reaction 0.5 ~ 1 hour;(b)The reaction vessel is placed in ice bath, sodium nitrite solution is added dropwise thereto and keeping temperature is less than 5 DEG C, be incubated after dripping off and placed;(c)Take hypophosphorous acid to be cooled to less than 5 DEG C, add copper sulphate to form mixture, then drop to step(b)The reaction vessel in, be warming up to after dripping off 15 ~ 30 DEG C reaction overnight, stratification;(d)Take organic layer and enter water-filling, saturated sodium bicarbonate solution washing successively.Greatly save equipment investment cumbersome with what operation brought, greatly reduce the yield of waste water, it is more environmentally friendly.

Description

A kind of method that one kettle way prepares 3,5- dimethyl bromobenzenes
Technical field
The invention belongs to chemical assistant field, and in particular to a kind of method that one kettle way prepares 3,5- dimethyl bromobenzenes.
Background technology
3,5- dimethyl bromobenzenes are a kind of important chemical intermediates.The 3.5- dimethyl bromobenzenes of high-purity can be used for electricity Sub- chemical field, wide market.It is industrial at present to be mainly by adding raw material 2,6- diformazans in the presence of glacial acetic acid Base aniline, is then slowly added dropwise certain density sulfuric acid, is allowed to generate 2,6- dimethylaniline sulfate, and continuing stirring makes 2,6- Dimethylaniline all dissolves, and then at a temperature of 40 DEG C or so, bromine is slowly added dropwise, and after drop finishes, ice bath is cooled to 0 degree. Bromo-derivative sulfate solid is separated out, centrifugation obtains white crystal(2,6- dimethyl -4- bromanilines), then in diazotising kettle In, by above-mentioned bromo-derivative sulfuric acid dissolution, natrium nitrosum is added dropwise and is allowed to diazotising, then recycle deaminizing for diazol anti- Should, product is reduced to product 3,5- dimethyl bromobenzenes.It is a production workshop section that the technique often walks reaction, and equipment is huge, technique It is cumbersome, and just put into next technique as raw material after needing to be purified, cause target product yield low, wastewater flow rate Greatly.
The content of the invention
A kind of one kettle way is provided and prepares 3,5- dimethyl bromobenzenes the invention aims to overcome the deficiencies in the prior art Method.
To reach above-mentioned purpose, the technical solution adopted by the present invention is:A kind of one kettle way prepares 3,5- dimethyl bromobenzenes Method, it is comprised the following steps:
(a)To glacial acetic acid, dimethylaniline is sequentially added in reaction vessel, sulfuric acid solution is then added dropwise, keeping temperature is 30 ~ 40 DEG C continue that bromine is added dropwise, continue stirring reaction 0.5 ~ 1 hour;
(b)The reaction vessel is placed in ice bath, sodium nitrite solution is added dropwise thereto and keeping temperature is less than 5 DEG C, drop Insulation is placed after complete;
(c)Take hypophosphorous acid to be cooled to less than 5 DEG C, add copper sulphate to form mixture, then drop to step(b)The reaction In container, 15 ~ 30 DEG C of reactions are warming up to after dripping off overnight, stratification;
(d)Take organic layer and enter water-filling, saturated sodium bicarbonate solution washing successively.
Optimally, step(d)In, rectifying is also carried out after being washed with the saturated sodium bicarbonate solution.
Further, step(c)In, the mixture to step is added dropwise(b)Reaction vessel in when, control programming rate Ensure the nitrogen not slug that produces with deflation speed.
Further, step(c)In, the mass concentration of copper sulphate is 0.1 ~ 0.2% in the mixture.
Further, step(a)In, the mass ratio of the dimethylaniline, glacial acetic acid, sulfuric acid and bromine is 1:2.5~4: 1~1.5:1~1.5;The mass ratio of the dimethylaniline, natrium nitrosum and hypophosphorous acid is 1:0.5~0.8:4~6.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art:One kettle way system of the present invention The method of standby 3,5- dimethyl bromobenzenes, carries out the reaction of each step successively in a reaction vessel, and centre does not need extra carrying The operating procedures such as pure, mother liquid recycle, greatly save cumbersome, the process is simple that equipment investment and operation bring;More meaningful It is by the control of material rate and be that one kettle way is produced, while product yield is substantially increased, to greatly reduce useless The yield of water, it is more environmentally friendly.
Specific embodiment
The present invention is further described below in conjunction with embodiment.
Embodiment 1
The present embodiment provides a kind of method that one kettle way prepares 3,5- dimethyl bromobenzenes, and it is comprised the following steps:
(a)To sequentially adding 120g glacial acetic acid, 36g 2,6- dimethylanilines in 500ml there-necked flasks(0.3mol), then it is added dropwise Sulfuric acid solution(Include the concentrated sulfuric acids of 40g 98% and 100ml water), keeping temperature is that 40 DEG C of continuation are added dropwise 48g bromines(0.3mol), Continue stirring reaction and cause within 0.5 hour that reaction is complete;The rate of addition of above-mentioned sulfuric acid solution and bromine is also existing conventional ginseng Number, as long as not causing reaction too many fierce and slug;
(b)There-necked flask is placed in ice bath, down to 0 DEG C or so;Sodium nitrite solution is added dropwise thereto(It is sub- containing 20.6g Sodium nitrate and 60ml water), keep it in less than 5 DEG C(Note the nitrogen for controlling programming rate and deflation speed to ensure generation not Slug), drip off(Ibid)Insulation placement afterwards forms diazonium salt solution;
(c)Take 182g hypophosphorous acid to be cooled to 0 DEG C, add 0.3g copper sulphate to form mixture, then drop to step(b)Reaction In container(It is added dropwise in diazonium salt solution, state modulator requirement is added dropwise ibid), 20 DEG C of reactions are warming up to after dripping off overnight, There is the transparent organic layer of rufous to separate out;Stratification;
(d)Take organic layer and enter water-filling, saturated sodium bicarbonate solution washing successively(Can repeatedly wash respectively)Obtain final product crude product(Measure Purity is more than 99%);Then carrying out rectifying obtains colourless transparent liquid, and weight is 52.3g(Yield is 95.13%), purity is 99.9%。
Embodiment 2
The present embodiment provides a kind of method that one kettle way prepares 3,5- dimethyl bromobenzenes, and it is comprised the following steps:
(a)To sequentially adding 90g glacial acetic acid, 36g 2,6- dimethylanilines in 500ml there-necked flasks(0.3mol), sulphur is then added dropwise Acid solution(Include the concentrated sulfuric acids of 36g 98% and 100ml water), keeping temperature is 30 DEG C and continues dropwise addition 36g bromines, and continuation is stirred anti- Answer and cause within 1 hour that reaction is complete;The rate of addition of above-mentioned sulfuric acid solution and bromine is also existing conventional parameter, as long as not causing Reaction is too many fierce and slug;
(b)There-necked flask is placed in ice bath, down to 0 DEG C or so;Sodium nitrite solution is added dropwise thereto(Contain 18g nitrous Sour sodium and 60ml water), keep it in less than 5 DEG C(Notice that the nitrogen for controlling programming rate and deflation speed to ensure generation is not rushed Material), drip off(Ibid)Insulation placement afterwards forms diazonium salt solution;
(c)Take 144g hypophosphorous acid to be cooled to 5 DEG C, add 0.28g copper sulphate to form mixture, then drop to step(b)It is anti- In answering container(It is added dropwise in diazonium salt solution, state modulator requirement is added dropwise ibid), 30 DEG C are warming up to after dripping off and were reacted At night, there is the transparent organic layer of rufous to separate out;Stratification;
(d)Take organic layer and enter water-filling, saturated sodium bicarbonate solution washing successively(Can repeatedly wash respectively)Obtain final product crude product(Measure Purity is more than 99%);Then carrying out rectifying obtains colourless transparent liquid, and weight is 50.3g(Yield is 91.6%), purity is 99.9%.
Embodiment 3
The present embodiment provides a kind of method that one kettle way prepares 3,5- dimethyl bromobenzenes, and it is comprised the following steps:
(a)To sequentially adding 144g glacial acetic acid, 36g 2,6- dimethylanilines in 500ml there-necked flasks(0.3mol), then it is added dropwise Sulfuric acid solution(Include the concentrated sulfuric acids of 54g 98% and 100ml water), keeping temperature is 30 DEG C and continues dropwise addition 54g bromines, and continuation is stirred Reaction causes that reaction is complete for 40 minutes;The rate of addition of above-mentioned sulfuric acid solution and bromine is also existing conventional parameter, as long as not So that reacting too many fierceness and slug;
(b)There-necked flask is placed in ice bath, down to 0 DEG C or so;Sodium nitrite solution is added dropwise thereto(It is sub- containing 28.8g Sodium nitrate and 60ml water), keep it in less than 5 DEG C(Note the nitrogen for controlling programming rate and deflation speed to ensure generation not Slug), drip off(Ibid)Insulation placement afterwards forms diazonium salt solution;
(c)Take 216g hypophosphorous acid to be cooled to 0 DEG C, add 0.216g copper sulphate to form mixture, then drop to step(b)It is anti- In answering container(It is added dropwise in diazonium salt solution, state modulator requirement is added dropwise ibid), 15 DEG C are warming up to after dripping off and were reacted At night, there is the transparent organic layer of rufous to separate out;Stratification;
(d)Take organic layer and enter water-filling, saturated sodium bicarbonate solution washing successively(Can repeatedly wash respectively)Obtain final product crude product(Measure Purity is more than 99%);Then carrying out rectifying obtains colourless transparent liquid, and weight is 51.5g(Yield is 93.8%), purity is 99.9%.
Comparative example 1
The present embodiment provides the method that one kind prepares 3,5- dimethyl bromobenzenes, and it is comprised the following steps:
(a)To 120 grams of glacial acetic acid, 36 grams of 36 grams of 2,6- dimethylanilines of addition in 500ml there-necked flasks(0.3mol), then it is added dropwise Sulfuric acid solution(Include the concentrated sulfuric acids of 40g 98% and 100ml water;It is kept stirring for so that raw material is completely dissolved, in above-described embodiment 1 It is also such), keeping temperature is that 40 DEG C of continuation are added dropwise 48g bromines(0.3mol), continue stirring reaction and cause within 0.5 hour to have reacted Entirely;
(b)There-necked flask is placed in ice bath, down to 0 DEG C or so;Product is fully separated out, be centrifugally separating to obtain white crystal The mother liquid recycle for bottom reaction;
(c)By step(b)During the white crystal that obtains adds second 500ml there-necked flask, add a small amount of dilute sulfuric acid to cause Congored test paper becomes blue, and sodium nitrite solution is then added dropwise thereto(Contain 20.6g natrium nitrosums and 60ml water), keep it Below 5 DEG C(Noting controlling programming rate and deflation speed ensures the nitrogen that produces not slug), drip off(Ibid)Insulation afterwards is put Put to form diazonium salt solution;
(d)Take 182g hypophosphorous acid to be cooled to 0 DEG C, add 0.3g copper sulphate to form mixture, then drop to step(c)Reaction In container(It is added dropwise in diazonium salt solution, state modulator requirement is added dropwise ibid), 20 DEG C of reactions are warming up to after dripping off overnight, There is the transparent organic layer of rufous to separate out;Stratification;
(d)Take organic layer and enter water-filling, saturated sodium bicarbonate solution washing successively(Can repeatedly wash respectively)Obtain final product crude product(Measure Purity is more than 99%);Then carrying out rectifying obtains colourless transparent liquid, and weight is 49.67g(Yield is 90.44%), purity is 99.5%。
The above embodiments merely illustrate the technical concept and features of the present invention, its object is to allow person skilled in the art Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention, all according to the present invention The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.

Claims (5)

1. a kind of method that one kettle way prepares 3,5- dimethyl bromobenzenes, it is characterised in that it is comprised the following steps:
(a)To glacial acetic acid, dimethylaniline is sequentially added in reaction vessel, sulfuric acid solution is then added dropwise, keeping temperature is 30 ~ 40 DEG C continue that bromine is added dropwise, continue stirring reaction 0.5 ~ 1 hour;
(b)The reaction vessel is placed in ice bath, sodium nitrite solution is added dropwise thereto and keeping temperature is less than 5 DEG C, drop Insulation is placed after complete;
(c)Take hypophosphorous acid to be cooled to less than 5 DEG C, add copper sulphate to form mixture, then drop to step(b)The reaction In container, 15 ~ 30 DEG C of reactions are warming up to after dripping off overnight, stratification;
(d)Take organic layer and enter water-filling, saturated sodium bicarbonate solution washing successively.
2. the method that one kettle way according to claim 1 prepares 3,5- dimethyl bromobenzenes, it is characterised in that:Step(d)In, Rectifying is also carried out after being washed with the saturated sodium bicarbonate solution.
3. the method that one kettle way according to claim 1 and 2 prepares 3,5- dimethyl bromobenzenes, it is characterised in that:Step(c) In, the mixture to step is added dropwise(b)Reaction vessel in when, control programming rate and deflation speed ensure produce nitrogen Not slug.
4. the method that one kettle way according to claim 1 and 2 prepares 3,5- dimethyl bromobenzenes, it is characterised in that:Step(c) In, the mass concentration of copper sulphate is 0.1 ~ 0.2% in the mixture.
5. the method that one kettle way according to claim 4 prepares 3,5- dimethyl bromobenzenes, it is characterised in that:Step(a)In, The mass ratio of the dimethylaniline, glacial acetic acid, sulfuric acid and bromine is 1:2.5~4:1~1.5:1~1.5;The dimethylaniline, The mass ratio of natrium nitrosum and hypophosphorous acid is 1:0.5~0.8:4~6.
CN201610999079.2A 2016-11-14 2016-11-14 A kind of method that one kettle way prepares 3,5 dimethyl bromobenzenes Pending CN106748627A (en)

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CN111908998A (en) * 2020-08-12 2020-11-10 中国科学院化学研究所 Preparation method of monobromoaromatic compound

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Application publication date: 20170531