26/4/2018 CN104447433A - Method for synthesizing 3,5-dibromoparatoluensulfonyl chloride - Google Patents

 Patents CN 104447433

Method for synthesizing 3,5-dibromoparatoluensulfonyl chloride

Abstract
CN104447433A
The invention discloses a method for synthesizing 3,5-dibromoparatoluensulfonyl chloride. A
CN Application
treatment method comprises the following steps: adding nitric acid and concentrated sulfuric acid
into methylbenzene in an ice-water bath state; reacting for a certain time, adding iron powder and
hydrochloric acid, slowly stirring, and then adding a bromine elementary substance to react; carrying Download PDF Find Prior Art Similar
out diazotization treatment on the solution, adding new hydrochloric acid, and heating to the
temperature of 110 DEG C; adding hypophosphorous acid, and re uxing at a high temperature to Other languages: Chinese
obtain 3,5-dibromomethylbenzene; adding prepared dibromomethylbenzene into a four-mouth ask
Inventor: 董燕敏
which is provided with a constant-pressure funnel, a stirrer, a condenser and a thermometer, heating
to the temperature of 100 DEG C, slowly dropwise adding concentrated sulfuric acid and then Original Assignee: 常州大学
continuing to react at a boiling point temperature; after the reaction is ended, pouring reactants in Priority date : 2014-11-11
water, separating out crystals, ltering and drying to obtain 3,5-dibromopara-toluenesulfonic acid;
nally reacting by using carbon tetrachloride, sulfur powder and chlorine gas, ltering and drying to
obtain 8.29g of 3,5-dibromoparatoluensulfonyl chloride of which the yield is 78.95%. The method Family: CN (1)
disclosed by the invention can be used for solving lots of problems existing in the prior art,
Date App/Pub Number Status
increasing the yield of the product and lowering the cost.
2014-11-11 CN 201410632890
Classi cations
2015-03-25 CN104447433A Application

Y02P20/582 Recycling of unreacted starting or intermediate materials

Info: Patent citations (3), Non-patent citations (3), Cited by (1),
Legal events, Similar documents, Priority and Related
Applications

External links: Espacenet, Global Dossier, Discuss

Claims (2) translated from Chinese

1. A synthesis of 3,5-dibromo-toluenesulfonyl chloride method, wherein the synthesis method 3, 5-dibromo toluene is: (1) 20g toluene was added to the reaction ask in an
ice-water bath state . dropwise 14ml0 62mol / L nitric acid and 8ml0 98mol / L of concentrated sulfuric acid, for 40 minutes to obtain a toluene group present; (2) iron
powder and then placed 5g (catalytic) reaction ask, and then quickly added dropwise 10ml0. 19mol / L hydrochloric acid was slowly stirred for 3 minutes, heated to 80 °
C for 20 minutes to obtain p-toluidine; (3) was added 3g elemental bromine in solution, maintained 80 ° C 10 min the reaction was stopped. Until the solution was cooled
to room temperature, the solution was slowly added dropwise 16mL0. 66m〇L / L aqueous solution of sodium nitrite (diazotization process) and 5ml0. 19mol / L
hydrochloric acid, warmed to ll〇 ° C, su cient reaction to give chloro diazo-4-carbaldehyde-2,6-dibromobenzene. (4) addition of hypophosphorous acid (H3P02) in the
reaction solution was complete, the re ux temperature, after 2 hours, extracted, evaporated to dryness to give 3, 5-dibromo standby 18. 22g of toluene.

2. 1 according to the claim one synthetic 2- uoro-5-bromo terephthalic acid, wherein: (1) equipped with a constant pressure funnel, a stirrer, a condenser, a
thermometer, four-necked ask in the course of the reaction (2); prepared was added 15g3, 5-dibromo toluene, warmed to 100-1KTC, concentrated sulfuric acid
was slowly added dropwise concentrated sulfuric acid 30ml0 5mol / L, the dropwise addition, the reaction was continued at the boiling temperature. and water
produced 3,5-dibromo toluene is distilled off continuously, condensed into the water separator, dehydration again into the reactor, after completion of the reaction,

the excess steam 3, 5-dibromo toluene, cooling the reaction was poured into 200ml of water, the obtained 3,5-dibromo-toluenesulfonic crystallization, ltration and
drying to give 10. 98g3, 5- dibromo-toluenesulfonic acid. (3) in four reaction ask was added 40ml of carbon tetrachloride, 10. 5g3, 5-dibromo-p-toluenesulfonic
acid, 0. 8g sulfur powder, stirring was warmed to 60 ° C, and chlorine gas started 5 hours chlorine gas was stopped, after stirring for 1 hour, 2 hours and then
passed chlorine gas, after the reaction, recovery of the solvent, the reaction was poured into ice water, ltered and dried to obtain 8. 55g3, 5- dibromo-p-
toluenesulfonyl.

Description translated from Chinese

A 3-3,5-dibromo p-toluenesulfonyl chloride synthesized

FIELD

[0001] The present invention belongs to the eld of organic reactions, to a 3, for the synthesis of 3,5-dibromo-toluenesulfonyl chloride.

Background technique

[0002] 3, 5-dibromo p-toluenesulfonyl chloride, white crystals or columnar crystals Ling, irritating odor. Insoluble in water, soluble in alcohol, ether. Skin, eye irritation. 3, 5-
dibromo p-toluenesulfonyl chloride as a catalyst widely used for various chemical reactions. It can be used as an additive other aspects of plastics, furniture varnishes
and adhesives. Widely used, it will de nitely rise to concern. Today, some of the conventional processes in two ways: 1 toluene with an excess of chlorosulfonic acid at
low temperature direct reaction of elemental bromine was added, this produces a large number of by-products, di cult to separate, energy-consuming. 2. toluene with
chlorosulfonic acid in the presence of certain salts and a temperature toluenesulfonic acid chloride with an excess, although this method of energy but higher reaction
temperature is low, the use of low value product. The present invention overcomes the high energy consumption, higher reaction temperatures a series of problems, a raw
material was synthesized in three steps as toluene, a small consumption of raw materials, high recovery and high utility value.

SUMMARY

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26/4/2018 CN104447433A - Method for synthesizing 3,5-dibromoparatoluensulfonyl chloride - Google Patents
[0003] In order to solve the prior art present many problems, the present invention provides a synthesis of 3,5-dibromo-toluenesulfonyl chloride in a simple way to solve
the problem of the conventional method of synthesis. While increasing product yield cost savings.

[0004] A novel method for the synthesis of 3, 5-dibromo p-toluenesulfonyl chloride.

[0005] The synthetic routes of the present invention are:

Figure CN104447433AD00031

[0007] The present invention relates to 3,5-dibromo-toluenesulfonyl chloride synthesis process comprises the steps of:

[0008] 1.3 3,5-dibromo toluene Synthesis:

[0009] (1) A reaction ask was added 20g of toluene was added dropwise under ice-water bath 14ml0 state 62mol / L nitric acid and 8ml0 98mol / L of concentrated
sulfuric acid, for 40 minutes to obtain the present toluene.;

[0010] ⑵ reaction ask was then placed in 5g iron powder (catalytic), and then quickly added dropwise slowly IOmlO 19mol / L hydrochloric acid was stirred for 3
minutes, heated to 80 ° C for 20 minutes to obtain p-toluidine.;

[0011] (3) was added to a solution of 3g elemental bromine, maintaining 80 ° C 10 min the reaction was stopped. Until the solution was cooled to room temperature, the
solution was slowly added dropwise 16mL0. 66m〇L / L aqueous solution of sodium nitrite (diazotization process) and 5ml0. 19mol / L hydrochloric acid, warmed to ll〇
° C, su cient reaction to give chloro diazo-4-carbaldehyde-2,6-dibromobenzene.

[0012] (4) adding hypophosphorous acid (H3PO2) solution in a complete reaction, at re ux temperature, after 2 hours, extracted, evaporated to dryness to give 3, 5-
dibromo standby 18. 22g of toluene.

[0013] 2.3, 5-dibromo-toluene sulfonated:

[0014] (1) equipped with a constant pressure funnel, a stirrer, a cooler, and a thermometer was charged prepared 15g3, 5-dibromo toluene, warmed to l〇〇-ll〇 ° C, slowly
added dropwise . concentrated sulfuric acid 30ml0 5mol / L concentrated sulfuric acid, dropwise addition, the reaction was continued at the boiling temperature;

[0015] (2) generated during the reaction of water and 3,5-dibromo toluene is distilled off continuously, condensed into the water separator, dehydration again into the
reactor, after completion of the reaction, the excess was distilled 3, 5-dibromo toluene, cooling, the reaction was poured into 200ml of water, the obtained 3,5-dibromo-
toluenesulfonic crystallization, ltration and drying to give 10. 98g3, 5- dibromo-p-toluenesulfonic acid;

[0016] 3. Synthesis of 3,5-dibromo-p-toluenesulfonyl:

[0017] (1) a four-neck reaction ask was added 40ml of carbon tetrachloride, 10. 5g3, 5-dibromo-p-toluenesulfonic acid, 0 · 8g sulfur powder, stirring was warmed to 60 °
C, chlorine gas started, after 5 hours the chlorine gas was stopped. After stirring for 1 hour, 2 hours and then passed chlorine gas. After completion of the reaction, the
solvent is recovered, the reaction was poured into ice water, ltered and dried to obtain 8. 55g3, 5- dibromo p-toluenesulfonyl chloride, in a yield of 81.42%. Speci c
embodiments

[0018] A reaction ask was added 20g of toluene was added dropwise 14ml0. 62mol / L nitric acid and 8ml0. 98mol / L of concentrated sulfuric acid under ice-cooling
condition for 40 minutes to give toluene present pairs. Then into the reaction ask 5g iron powder (catalytic), and then quickly added dropwise IOmlO. Slow 19mol / L
hydrochloric acid was stirred for 3 minutes, heated to 80 ° C for 20 minutes to obtain p-toluidine. 3g added to the solution of elemental bromine, maintaining 80 ° C 10
min the reaction was stopped. Until the solution was cooled to room temperature, the solution was slowly added dropwise 16mL0. 66m〇L / L aqueous solution of
sodium nitrite (diazotization process) and 5ml0. 19mol / L hydrochloric acid, warmed to IKTC, su cient reaction to give a diazonium chloride 4-carboxaldehyde-2,6-
dibromobenzene. Addition of hypophosphorous acid (H3PO2) solution in a complete reaction, at re ux temperature, after 2 hours, extracted, evaporated to dryness to
give 3, 5-dibromo standby 18. 22g of toluene. Equipped with a constant pressure funnel, a stirrer, a cooler, and a thermometer was charged prepared 15g3, 5-dibromo
toluene, warmed to 100-1KTC, concentrated sulfuric acid was slowly added dropwise 30ml0. 5mol / L of concentrated sulfuric acid after nishing the dropping, the
reaction was continued at the boiling temperature. Generated during the reaction of water and 3,5-dibromo toluene is distilled off continuously, condensed into the water
separator, dehydration again into the reactor, after completion of the reaction, the excess steam 3, 5-dibromo toluene, cooling, the reaction was poured into 200ml of
water, the obtained 3,5-dibromo-toluenesulfonic crystallization, ltration and drying to give 10. 98g3, 5- dibromo-toluenesulfonic acid. In the four reaction ask was added
40ml of carbon tetrachloride, 10. 5g3, 5-dibromo-p-toluenesulfonic acid, 0. 8g sulfur powder, stirring was warmed to 60 ° C, and chlorine gas started, stopped after 5
hours into chlorine. After stirring for 1 hour, 2 hours and then passed chlorine gas. After completion of the reaction, the solvent is recovered, the reaction was poured into
ice water, ltered and dried to obtain 8. 55g3, 5- dibromo p-toluenesulfonyl chloride, in a yield of 81.42%.

[0019] Example 1

[0020] A reaction ask was added 20g of toluene was added dropwise under ice-water bath 14ml0 state. 62mol / L nitric acid and 8ml0. 98mol / L of concentrated
sulfuric acid, the reaction after 40 minutes into the iron powder 5g, and then quickly added dropwise IOmlO. 19mol / L hydrochloric acid was slowly stirring for 3 minutes,
heated to 80 ° C for 20 min. 3g then added to the solution of elemental bromine, maintaining 80 ° C 10 min the reaction was stopped. Until the solution was cooled to
room temperature, the solution was slowly added dropwise 16mL0. 66m〇L / L aqueous solution of sodium nitrite and 5ml0. 19mol / L hydrochloric acid, warmed to 110
° C. Added to the complete reaction of hypophosphorous acid solution, at re ux temperature, after 2 hours, extracted, evaporated to dryness to give 3, 5-dibromo standby
18. 22g of toluene. Equipped with a constant pressure funnel, a stirrer, a cooler, and a thermometer was charged prepared 15g3, 5-dibromo toluene, heated to 100 ° C,
was slowly added concentrated sulfuric acid 30ml0. 5mol / L of concentrated sulfuric acid after nishing the dropping, the reaction was continued at the boiling
temperature. After completion of the reaction, the reaction was poured into 200ml of water, to obtain crystallization, ltration and drying to give 10. 65g3, 5- dibromo-p-
toluenesulfonic acid standby. In the four reaction ask was added 40ml of carbon tetrachloride, 10. 5g3, 5-dibromo-p-toluenesulfonic acid, 0. 8g sulfur powder, stirring
was warmed to 60 ° C, and chlorine gas started, stopped after 5 hours into chlorine. After stirring for 1 hour, 2 hours and then passed chlorine gas. After completion of
the reaction, the solvent is recovered, the reaction was poured into ice water, ltered and dried to obtain 8. 29g3, 5- dibromo p-toluenesulfonyl chloride, in a yield of
78.95%.

[0021] Example 2

[0022] A reaction ask was added 20g of toluene was added dropwise under ice-water bath 14ml0 state. 62mol / L nitric acid and 8ml0. 98mol / L of concentrated
sulfuric acid, the reaction after 40 minutes into the iron powder 5g, and then quickly added dropwise IOmlO. 19mol / L hydrochloric acid was slowly stirring for 3 minutes,
heated to 80 ° C for 20 min. 3g then added to the solution of elemental bromine, maintaining 80 ° C 10 min the reaction was stopped. Until the solution was cooled to
room temperature, the solution was slowly added dropwise 16mL0. 66m〇L / L aqueous solution of sodium nitrite and 5ml0. 19mol / L hydrochloric acid, warmed to 110
° C. Added to the complete reaction of hypophosphorous acid solution, at re ux temperature, after 2 hours, extracted, evaporated to dryness to give 3, 5-dibromo standby
18. 22g of toluene. Equipped with a constant pressure funnel, a stirrer, a cooler, and a thermometer was charged prepared 15g3, 5-dibromo toluene, heated to 105 ° C,

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was slowly added concentrated sulfuric acid 30ml0. 5mol / L of concentrated sulfuric acid after nishing the dropping, the reaction was continued at the boiling
temperature. After completion of the reaction, the reaction was poured into 200ml of water, to obtain crystallization, ltration and drying to give 10. 98g3, 5- dibromo-p-
toluenesulfonic acid standby. In the four reaction ask was added 40ml of carbon tetrachloride, 10. 5g3, 5-dibromo-p-toluenesulfonic acid, 0. 8g sulfur powder, stirring
was warmed to 60 ° C, and chlorine gas started, stopped after 5 hours into chlorine. After stirring for 1 hour, 2 hours and then passed chlorine gas. After completion of
the reaction, the solvent is recovered, the reaction was poured into ice water, ltered and dried to obtain 8. 41g3, 5- dibromo p-toluenesulfonyl chloride, in a yield of
80.09%.

[0023] Example 3

[0024] A reaction ask was added 20g of toluene was added dropwise under ice-water bath 14ml0 state. 62mol / L nitric acid and 8ml0. 98mol / L of concentrated
sulfuric acid, the reaction after 40 minutes into the iron powder 5g, and then quickly added dropwise IOmlO. 19mol / L hydrochloric acid was slowly stirring for 3 minutes,
heated to 80 ° C for 20 min. 3g then added to the solution of elemental bromine, maintaining 80 ° C 10 min the reaction was stopped. Until the solution was cooled to
room temperature, the solution was slowly added dropwise 16mL0. 66m〇L / L aqueous solution of sodium nitrite and 5ml0. 19mol / L hydrochloric acid, warmed to 110
° C. Added to the complete reaction of hypophosphorous acid solution, at re ux temperature, after 2 hours, extracted, evaporated to dryness to give 3, 5-dibromo standby
18. 22g of toluene. Equipped with a constant pressure funnel, a stirrer, a cooler, and a thermometer was charged prepared 15g3, 5-dibromo toluene, heated to 110 ° C,
was slowly added concentrated sulfuric acid 30ml0. 5mol / L of concentrated sulfuric acid after nishing the dropping, the reaction was continued at the boiling
temperature. After completion of the reaction, the reaction was poured into 200ml of water, to obtain crystallization, ltration and drying to give 10. 96g3, 5- dibromo-p-
toluenesulfonic acid standby. In the four reaction ask was added 40ml of carbon tetrachloride, 10. 5g3, 5-dibromo-p-toluenesulfonic acid, 0. 8g sulfur powder, stirring
was warmed to 60 ° C, and chlorine gas started, stopped after 5 hours into chlorine. After stirring for 1 hour, 2 hours and then passed chlorine gas. After completion of
the reaction, the solvent is recovered, the reaction was poured into ice water, ltered and dried to obtain 8. 38g3, 5- dibromo p-toluenesulfonyl chloride, in a yield of
79.80%.

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