CN105384595A - 1, 4-bis(chloromethyl)benzene synthesis technology - Google Patents
1, 4-bis(chloromethyl)benzene synthesis technology Download PDFInfo
- Publication number
- CN105384595A CN105384595A CN201510932940.9A CN201510932940A CN105384595A CN 105384595 A CN105384595 A CN 105384595A CN 201510932940 A CN201510932940 A CN 201510932940A CN 105384595 A CN105384595 A CN 105384595A
- Authority
- CN
- China
- Prior art keywords
- benzyl dichloride
- chloromethyl
- bis
- synthesis technique
- benzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 18
- 238000005516 engineering process Methods 0.000 title abstract description 5
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 title abstract 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012043 crude product Substances 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002608 ionic liquid Substances 0.000 claims abstract description 6
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- DVNFMHWKXQEEAH-UHFFFAOYSA-N 1-dodecyl-3-methyl-2h-imidazole Chemical group CCCCCCCCCCCCN1CN(C)C=C1 DVNFMHWKXQEEAH-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- GTLWADFFABIGAE-UHFFFAOYSA-N 1-chloroethylbenzene Chemical compound CC(Cl)C1=CC=CC=C1 GTLWADFFABIGAE-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a 1, 4-bis(chloromethyl)benzene synthesis technology and belongs to the technical field of organic chemical synthesis. The technology comprises that under LED light source irradiation, p-xylene and chlorine undergo a reaction in the presence of an ionic liquid catalyst to produce a 1, 4-bis(chloromethyl)benzene reaction solution, the 1, 4-bis(chloromethyl)benzene reaction solution is cooled and separated so that a 1, 4-bis(chloromethyl)benzene crude product is obtained, and the 1, 4-bis(chloromethyl)benzene crude product is subjected to vacuum rectification so that 1, 4-bis(chloromethyl)benzene is obtained. The 1, 4-bis(chloromethyl)benzene has a melting point of 98-101 DEG C and purity of 99% or more. The 1, 4-bis(chloromethyl)benzene synthesis technology is free of any solvent, guarantees high product purity, has the characteristics of high conversion rate, fast reaction rate and low cost and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of synthesis technique to benzyl dichloride, belong to organic chemical synthesis technical field.
Background technology
Be a kind of important chemical feedstocks to benzyl dichloride, outward appearance is white flaky crystals, as the intermediate of organic synthesis, mainly for the manufacture of terephthalyl alcohol, terephthaldehyde's ether, terephthalaldehyde and other dyestuff, and can also as medicine intermediate.CN104230653A discloses and at 80 DEG C, carries out chlorination with p-Xylol, when in sample 35wt% reaches to benzyl dichloride content time stop logical chlorine, then by carrying out flash distillation and rectifying obtains benzyl dichloride, this technique just carries out flash distillation and underpressure distillation when reaching 35% to benzyl dichloride transformation efficiency, also exists that conversion rate of products is low, high in cost of production problem.
Summary of the invention
The object of this invention is to provide a kind of synthesis technique to benzyl dichloride, have the advantages that speed of response is fast, yield is high, cost is low.
Synthesis technique to benzyl dichloride of the present invention, comprises the following steps:
(1) react:
P-Xylol and ionic-liquid catalyst are joined in retort, under LED light source irradiates, passes into chlorine wherein react, obtain benzyl dichloride reaction solution;
Described ionic-liquid catalyst is 1-dodecyl-3-Methylimidazole villaumite or 1-butyl-2,3-Methylimidazole villaumite;
(2) be separated:
To join in separating tank benzyl dichloride reaction solution and carry out cooling separation, upper solution enters in retort and proceeds reaction, and lower floor's solution is to benzyl dichloride crude product;
(3) refining:
To join in rectifying tower benzyl dichloride crude product and carry out rectification under vacuum, and collect cut and obtain benzyl dichloride.
Wherein, preferred technical scheme is as follows:
Step (1) intermediate ion liquid catalyst consumption is 1 ‰-5 ‰ of p-Xylol quality.
In step (1), temperature of reaction is 110-120 DEG C, and the reaction times is 3-10h.
Step (1) to being 70-80wt% to the content of benzyl dichloride in benzyl dichloride reaction solution.
In step (1), the mol ratio of p-Xylol and chlorine is 1:1.3-2.0.
In step (2), cooling temperature is 85-90 DEG C, and the number of separating tank is two or more.
Vacuum tightness in step (3) during underpressure distillation is 8mmHg, and the cut temperature of collection is 150-155 DEG C.
Ionic liquid in the present invention is named again " high-temperature fusion salt ", it has wider liquid temperature scope and good physics and chemistry character, non-volatile, nonflammable explosive, be not oxidized, there is higher thermostability, all stable to water and air, there is the advantageous characteristic of good dissolving power, larger polarity and controllability and approximate zero toxicity simultaneously.
Reaction equation of the present invention is as follows:
Of the present invention to main containing p-Xylol in benzyl dichloride reaction solution, to benzyl dichloride with to methyl benzyl chloride, the fusing point of p-Xylol is-48 DEG C, be 98-101 DEG C to the fusing point of benzyl dichloride, it is 4 DEG C to the fusing point of methyl benzyl chloride, utilize the fusing point of each material in reaction solution different, adopt the mode that cooling is separated, make to be separated with to methyl benzyl chloride with p-Xylol benzyl dichloride, p-Xylol after separation and reactor is entered from separating tank upper strata to methyl benzyl chloride continue reaction, between lower floor, benzyl dichloride enters treating tower and refines, thus minimizing is reacted the continuation of benzyl dichloride and chlorine, the object reducing by product and generate and improve yield can be played.
Beneficial effect of the present invention is as follows:
The present invention obtain to benzyl dichloride, fusing point is 98-101 DEG C, and purity reaches more than 99%; The present invention is mixed into without any solvent, ensure that the high purity of product, has the advantages that yield is high, reaction is fast, cost is low, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
As follows to the synthesis technique of benzyl dichloride:
(1) react:
100g p-Xylol and 0.1g1-dodecyl-3-Methylimidazole villaumite are joined in retort, LED light source irradiate under pass into 173.9g chlorine, react 10h at 110 DEG C, obtain to benzyl dichloride content be 70wt% to benzyl dichloride reaction solution;
(2) be separated:
To join in separating tank to benzyl dichloride reaction solution, at 90 DEG C, carry out layered shaping, upper solution returns in retort and proceeds reaction, and lower floor's solution is to benzyl dichloride crude product;
(3) refining:
To join in rectifying tower to benzyl dichloride crude product, under 8mmHg, carry out rectification under vacuum, collect 150-155 DEG C of cut, obtain 116.60g to benzyl dichloride, content is 99%, and fusing point is 98.5-100.9 DEG C.
Embodiment 2
As follows to the synthesis technique of benzyl dichloride:
(1) react:
100g p-Xylol and 0.2g1-dodecyl-3-Methylimidazole villaumite are joined in retort, LED light source irradiate under pass into 200.6g chlorine, react 6h at 115 DEG C, obtain to benzyl dichloride content be 75wt% to benzyl dichloride reaction solution;
(2) be separated:
To join in separating tank to benzyl dichloride reaction solution, at 85 DEG C, carry out layered shaping, upper solution returns in retort and proceeds reaction, and lower floor's solution is to benzyl dichloride crude product;
(3) refining:
To join in rectifying tower to benzyl dichloride crude product, under 8mmHg, carry out rectification under vacuum, collect 150-155 DEG C of cut, obtain 124.86g to benzyl dichloride, content is 99.05%, and fusing point is 99.1-100.6 DEG C.
Embodiment 3
As follows to the synthesis technique of benzyl dichloride:
(1) react:
100g p-Xylol and 0.5g1-butyl-2,3-Methylimidazole villaumite are joined in retort, LED light source irradiate under pass into 267.5g chlorine, react 3h at 120 DEG C, obtain to benzyl dichloride content be 80wt% to benzyl dichloride reaction solution;
(2) be separated:
To join in separating tank by the overflow port of retort to benzyl dichloride reaction solution, at 80 DEG C, carry out layered shaping, upper solution returns in retort and proceeds reaction, and lower floor's solution is to benzyl dichloride crude product;
(3) refining:
To join in rectifying tower to benzyl dichloride crude product, under 8mmHg pressure, carry out rectification under vacuum, collect 150-155 DEG C of cut, obtain 133.12g to benzyl dichloride, content is 99.1%, and fusing point is 99.5-100.6 DEG C.
Claims (9)
1. to a synthesis technique for benzyl dichloride, it is characterized in that: comprise the following steps:
(1) react:
P-Xylol and ionic-liquid catalyst are mixed, then under LED light source irradiates, passes into chlorine to it and react, obtain benzyl dichloride reaction solution;
Described ionic-liquid catalyst is 1-dodecyl-3-Methylimidazole villaumite or 1-butyl-2,3-Methylimidazole villaumite;
(2) be separated:
To join in separating tank benzyl dichloride reaction solution and carry out cooling separation, obtain benzyl dichloride crude product;
(3) refining:
To join in rectifying tower benzyl dichloride crude product and carry out rectification under vacuum, and collect cut and obtain a benzyl dichloride.
2. the synthesis technique to benzyl dichloride according to claim 1, is characterized in that: step (1) intermediate ion liquid catalyst consumption is 1 ‰-5 ‰ of p-Xylol quality.
3. the synthesis technique to benzyl dichloride according to claim 1, is characterized in that: in step (1), temperature of reaction is 110-120 DEG C.
4. the synthesis technique to benzyl dichloride according to claim 1, is characterized in that: in step (1), the reaction times is 3-10h.
5. the synthesis technique to benzyl dichloride according to claim 1, is characterized in that: between step (1), in the middle of benzyl dichloride reaction solution, the content of benzyl dichloride is 70-80wt%.
6. the synthesis technique to benzyl dichloride according to claim 1, is characterized in that: in step (1), the mol ratio of p-Xylol and chlorine is 1:1.3-2.0.
7. the synthesis technique to benzyl dichloride according to claim 1, is characterized in that: in step (2), cooling temperature is 85-90 DEG C.
8. the synthesis technique to benzyl dichloride according to claim 1, is characterized in that: the vacuum tightness in step (3) during underpressure distillation is 8mmHg.
9. the preparation method of according to claim 1 benzyl dichloride, is characterized in that: the cut temperature of collecting during underpressure distillation in step (3) is 150-155 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510932940.9A CN105384595B (en) | 2015-12-14 | 2015-12-14 | To the synthesis technique of benzyl dichloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510932940.9A CN105384595B (en) | 2015-12-14 | 2015-12-14 | To the synthesis technique of benzyl dichloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105384595A true CN105384595A (en) | 2016-03-09 |
| CN105384595B CN105384595B (en) | 2017-06-20 |
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| CN201510932940.9A Active CN105384595B (en) | 2015-12-14 | 2015-12-14 | To the synthesis technique of benzyl dichloride |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409528A (en) * | 2018-01-31 | 2018-08-17 | 青岛和兴精细化学有限公司 | A kind of new process prepared using novel reaction equipment to benzyl dichloride |
| CN110734357A (en) * | 2019-12-10 | 2020-01-31 | 江苏环保产业技术研究院股份公司 | benzyl chloride and its derivative preparing process |
| CN112142552A (en) * | 2019-06-26 | 2020-12-29 | 张家港九力新材料科技有限公司 | Method for preparing p-dichlorobenzyl through ultraviolet light induced catalysis |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415700C (en) * | 2006-04-14 | 2008-09-03 | 浙江巍华化工有限公司 | Method of producing chlorobenzyl by photochlorination |
| CN104230653A (en) * | 2014-09-22 | 2014-12-24 | 潜江新亿宏有机化工有限公司 | Manufacturing technology of p-xylylene dichloride |
| CN104402698B (en) * | 2014-10-29 | 2016-01-20 | 柳州丰康泰科技有限公司 | 2-(4-aminomethyl phenyl) propionic acid synthesize method |
-
2015
- 2015-12-14 CN CN201510932940.9A patent/CN105384595B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 施沈一等: "氯化烷基咪唑: 一种氯气吸收及氯化反应的媒介", 《有机化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409528A (en) * | 2018-01-31 | 2018-08-17 | 青岛和兴精细化学有限公司 | A kind of new process prepared using novel reaction equipment to benzyl dichloride |
| CN112142552A (en) * | 2019-06-26 | 2020-12-29 | 张家港九力新材料科技有限公司 | Method for preparing p-dichlorobenzyl through ultraviolet light induced catalysis |
| CN110734357A (en) * | 2019-12-10 | 2020-01-31 | 江苏环保产业技术研究院股份公司 | benzyl chloride and its derivative preparing process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105384595B (en) | 2017-06-20 |
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Address after: Double Yang Zichuan District 255190 Shandong city of Zibo Province Applicant after: Shandong Kaisheng New Materials Co.,Ltd. Address before: Double Yang Zichuan District 255190 Shandong city of Zibo Province Applicant before: SHANDONG KAISHENG NEW MATERIALS CO., LTD. |
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Inventor after: Xue Juqiang Inventor after: Zhang Liang Inventor after: Han Nannan Inventor after: Shi Yufei Inventor after: Sun Fengchun Inventor after: Zhang Shanmin Inventor after: Bi Yixia Inventor after: Zhang Taiming Inventor after: Xie Shengbin Inventor after: Sun Qingmin Inventor after: Wang Ronghai Inventor after: Li Guanghui Inventor before: Xue Juqiang Inventor before: Sun Fengchun Inventor before: Zhang Shanmin Inventor before: Bi Yixia Inventor before: Zhang Taiming Inventor before: Xie Shengbin |
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