CN102234219B - 2,6-dichlorotoluene preparation method - Google Patents
2,6-dichlorotoluene preparation method Download PDFInfo
- Publication number
- CN102234219B CN102234219B CN 201010154152 CN201010154152A CN102234219B CN 102234219 B CN102234219 B CN 102234219B CN 201010154152 CN201010154152 CN 201010154152 CN 201010154152 A CN201010154152 A CN 201010154152A CN 102234219 B CN102234219 B CN 102234219B
- Authority
- CN
- China
- Prior art keywords
- organic phase
- reaction
- chloro
- temperature
- aminotoluene
- 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.)
- Active
Links
- 0 C[C@@]1C(*)=C(C)C(Cl)=CC=C1 Chemical compound C[C@@]1C(*)=C(C)C(Cl)=CC=C1 0.000 description 2
- DMEDNTFWIHCBRK-UHFFFAOYSA-N Cc(c(Cl)ccc1)c1Cl Chemical compound Cc(c(Cl)ccc1)c1Cl DMEDNTFWIHCBRK-UHFFFAOYSA-N 0.000 description 1
- ZUVPLKVDZNDZCM-UHFFFAOYSA-N Cc(c(N)ccc1)c1Cl Chemical compound Cc(c(N)ccc1)c1Cl ZUVPLKVDZNDZCM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a 2,6-dichlorotoluene preparation method which comprises the following steps: mixing and stirring 3-chloro-2-toluidine and acid, cooling the above mixture to a temperature of -10-15 DEG C, adding nitrite, wherein a speed of adding the nitrite is controlled that the temperature of the mixture is not higher than 15 DEG C, followed by stirring, and carrying out a thermal decomposition reaction, wherein the temperature of the mixture is controlled at 15-60 DEG C; after finish of the thermal decomposition reaction, separating lower organic phase, and recycling unreacted acid with a graphite absorbing tower; washing the organic phase with water to a neutral state, carrying out distillation, in a temperature of 180-196 DEG C removing o-chlorotoluene generated in the reaction, carrying out rectification and collecting distillate of 196-200.5 DEG C to obtain the 2,6-dichlorotoluene. The 2,6-dichlorotoluene preparation method in the invention has the advantages of high product yield and low production cost.
Description
Technical field
The present invention relates to a kind of 2, the preparation method of 6-toluene dichloride.
Background technology
2,6-toluene dichloride is for the production of 2,6-dichlorobenzaldehyde, 2,6-dichlorobenzonitrile, and the intermediate of weedicide processed and dyestuff.In the prior art, in the main prior art of the preparation of 2,6-toluene dichloride, mainly be to be that raw material gets through chlorination reaction with toluene, be expressed as follows with chemical equation:
Wherein X is a kind of among Cu, Fe, Sb and the Al, and Solvent is chloroform, methylene dichloride, water etc. or does not have solvent.And this method yield only can reach 40%, and product cost is relatively also than higher.
Summary of the invention
The purpose of this invention is to provide a kind of product yield height, production cost low 2, the preparation method of 6-toluene dichloride.
Provided by the present invention 2, the preparation method of 6-toluene dichloride comprises the steps:
3-chloro-2-aminotoluene and acid are mixed, stir, be cooled to-10～15 ℃ and add nitrite, the speed that control adds nitrite makes temperature not be higher than 15 ℃, stirs then, and temperature of reaction control is carried out pyrolysis at 15～50 ℃;
After described pyrolysis is finished, tell the organic phase of lower floor earlier, unreacted acid is reclaimed with the graphite absorption tower;
Described organic phase is washed to neutrality, distills then, removes the ortho-chlorotolu'ene that produces in the reaction for 180～196 ℃, carries out rectifying then, collects 196～200.5 ℃ of fractions, obtains the preparation of 2,6-toluene dichloride.
Of the present invention 2, the preparation method of 6-toluene dichloride, wherein, described acid be in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, fluoroboric acid, hydrofluoric acid, silicofluoric acid, formic acid, acetic acid, the oxalic acid any or appoint several.
Of the present invention 2, the preparation method of 6-toluene dichloride, wherein, described nitrite is potassium nitrite, Sodium Nitrite, ammonium nitrite or calcium nitrite.
Of the present invention 2, the preparation method of 6-toluene dichloride do not use the X catalyst series, safe, production cost is low, product yield height, and be conducive to cleaner production control in the commercial run, the acid in the reaction absorbs in absorbing still, is conducive to resource circulation utilization.
Embodiment
Embodiment 1
The adding of 3mol hydrogenchloride is equipped with in 1000 milliliters the there-necked flask of mechanical stirring, reflux condensing tube, thermometer, then 1mol 3-chloro-2-aminotoluene is added dropwise in the there-necked flask, stir into the off-white color particle, slowly add Sodium Nitrite 1mol after being cooled to-10 ℃, the control feed rate makes temperature not be higher than 10 ℃, after adding, the system of being stirred to is red-brown.Carry out thermolysis then, temperature is controlled at 15 ℃, and following chemical reaction takes place system:
After reaction is finished, tell the organic phase of lower floor earlier, unreacted hydrogen chloride absorbs with the graphite absorption tower, reclaim, organic phase is washed to neutrality, removes a spot of ortho-chlorotolu'ene that produces in the reaction for 180～196 ℃, carry out rectifying then, collect 196～200.5 ℃ of fractions, obtain fraction 151.5 grams.
Be standard substance with 2,6-toluene dichloride, gas chromatographic analysis.Analytical results as shown in Table 1 and Table 2.
Table 1.2,6-toluene dichloride standard stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 4.415 | 349.431 |
| 2 | 7.963 | 171940.109 |
| 3 | 8.325 | 1283.241 |
| 4 | 8.512 | 486.467 |
| 5 | 12.187 | 860.515 |
Table 2. fraction stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 7.828 | 151871.250 |
| 2 | 8.218 | 314.432 |
| 3 | 8.407 | 48.279 |
In the fraction 2,6-toluene dichloride purity is 99.92%, calculates yield 94.10% with 3-chloro-2-aminotoluene.
Embodiment 2
The adding of 2mol hydrogenchloride is equipped with in 1000 milliliters the there-necked flask of mechanical stirring, reflux condensing tube, thermometer, then 1.5mol 3-chloro-2-aminotoluene is added dropwise in the there-necked flask, stir into the off-white color particle, slowly add potassium nitrite 2mol after being cooled to-10 ℃, the control feed rate makes temperature not be higher than 10 ℃, after adding, the system of being stirred to is red-brown.Carry out thermolysis then, temperature is controlled at 40 ℃, and following chemical reaction takes place system:
After reaction is finished, tell the organic phase of lower floor earlier, unreacted hydrogen chloride absorbs with the graphite absorption tower, reclaim, organic phase is washed to neutrality, removes a spot of ortho-chlorotolu'ene that produces in the reaction for 180～196 ℃, carry out rectifying then, collect 196～200.5 ℃ of fractions, obtain fraction 227.5 grams.
Be standard substance with 2,6-toluene dichloride, gas chromatographic analysis.Analytical results as shown in Table 1 and Table 2.
Table 3.2,6-toluene dichloride standard stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 4.415 | 349.431 |
| 2 | 7.963 | 171940.109 |
| 3 | 8.325 | 1283.241 |
| 4 | 8.512 | 486.467 |
| 5 | 12.187 | 860.515 |
Table 4. fraction stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 7.849 | 151869.140 |
| 2 | 8.261 | 316.522 |
| 3 | 8.442 | 47.975 |
In the fraction 2,6-toluene dichloride purity is 99.92%, calculates yield 94.20% with 3-chloro-2-aminotoluene.
Embodiment 3
The adding of 1mol hydrogenchloride is equipped with in 1000 milliliters the there-necked flask of mechanical stirring, reflux condensing tube, thermometer, then 2mol 3-chloro-2-aminotoluene is added dropwise in the there-necked flask, stir into the off-white color particle, slowly add ammonium nitrite 2mol after being cooled to-10 ℃, the control feed rate makes temperature not be higher than 10 ℃, after adding, the system of being stirred to is red-brown.Carry out thermolysis then, temperature is controlled at 60 ℃, and following chemical reaction takes place system:
After reaction is finished, tell the organic phase of lower floor earlier, unreacted hydrogen chloride absorbs with the graphite absorption tower, reclaim, organic phase is washed to neutrality, removes a spot of ortho-chlorotolu'ene that produces in the reaction for 180～196 ℃, carry out rectifying then, collect 196～200.5 ℃ of fractions, obtain fraction 304.5 grams.
Be standard substance with 2,6-toluene dichloride, gas chromatographic analysis.Analytical results as shown in Table 1 and Table 2.
Table 5.2,6-toluene dichloride standard stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 4.415 | 349.431 |
| 2 | 7.963 | 171940.109 |
| 3 | 8.325 | 1283.241 |
| 4 | 8.512 | 486.467 |
| 5 | 12.187 | 860.515 |
Table 6. fraction stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 7.835 | 151872.350 |
| 2 | 8.273 | 316.832 |
| 3 | 8.442 | 48.864 |
In the fraction 2,6-toluene dichloride purity is 99.92%, calculates yield 94.57% with 3-chloro-2-aminotoluene.
Above embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (3)
1. one kind 2, the preparation method of 6-toluene dichloride comprises the steps:
The adding of 3mol hydrogenchloride is equipped with in 1000 milliliters the there-necked flask of mechanical stirring, reflux condensing tube, thermometer, then 1mol3-chloro-2-aminotoluene is added dropwise in the there-necked flask, stir into the off-white color particle, slowly add Sodium Nitrite 1mol after being cooled to-10 ℃, the control feed rate makes temperature not be higher than 10 ℃, and after adding, the system of being stirred to is red-brown, carry out thermolysis then, temperature is controlled at 15 ℃;
After reaction is finished, tell the organic phase of lower floor earlier, unreacted hydrogen chloride absorbs with the graphite absorption tower, reclaim, organic phase is washed to neutrality, removes a spot of ortho-chlorotolu'ene that produces in the reaction, carries out rectifying then for 180～196 ℃, collect 196～200.5 ℃ of fractions, obtain fraction 151.5 gram, in the described fraction 2,6-toluene dichloride purity is 99.92%, calculate yield 94.10% with 3-chloro-2-aminotoluene.
2. the preparation method of a 6-toluene dichloride comprises the steps:
The adding of 2mol hydrogenchloride is equipped with in 1000 milliliters the there-necked flask of mechanical stirring, reflux condensing tube, thermometer, then 1.5mol3-chloro-2-aminotoluene is added dropwise in the there-necked flask, stir into the off-white color particle, slowly add potassium nitrite 2mol after being cooled to-10 ℃, the control feed rate makes temperature not be higher than 10 ℃, and after adding, the system of being stirred to is red-brown, carry out thermolysis then, temperature is controlled at 40 ℃;
After reaction is finished, tell the organic phase of lower floor earlier, unreacted hydrogen chloride absorbs with the graphite absorption tower, reclaim, organic phase is washed to neutrality, removes a spot of ortho-chlorotolu'ene that produces in the reaction, carries out rectifying then for 180～196 ℃, collect 196～200.5 ℃ of fractions, obtain fraction 227.5 gram, in the described fraction 2,6-toluene dichloride purity is 99.92%, calculate yield 94.20% with 3-chloro-2-aminotoluene.
3. one kind 2, the preparation method of 6-toluene dichloride comprises the steps:
The adding of 1mol hydrogenchloride is equipped with in 1000 milliliters the there-necked flask of mechanical stirring, reflux condensing tube, thermometer, then 2mol3-chloro-2-aminotoluene is added dropwise in the there-necked flask, stir into the off-white color particle, slowly add ammonium nitrite 2mol after being cooled to-10 ℃, the control feed rate makes temperature not be higher than 10 ℃, and after adding, the system of being stirred to is red-brown, carry out thermolysis then, temperature is controlled at 60 ℃;
After reaction is finished, tell the organic phase of lower floor earlier, unreacted hydrogen chloride absorbs with the graphite absorption tower, reclaim, organic phase is washed to neutrality, removes a spot of ortho-chlorotolu'ene that produces in the reaction, carries out rectifying then for 180～196 ℃, collect 196～200.5 ℃ of fractions, obtain fraction 304.5 gram, in the described fraction 2,6-toluene dichloride purity is 99.92%, calculate yield 94.57% with 3-chloro-2-aminotoluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010154152 CN102234219B (en) | 2010-04-23 | 2010-04-23 | 2,6-dichlorotoluene preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010154152 CN102234219B (en) | 2010-04-23 | 2010-04-23 | 2,6-dichlorotoluene preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102234219A CN102234219A (en) | 2011-11-09 |
| CN102234219B true CN102234219B (en) | 2013-09-18 |
Family
ID=44885397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010154152 Active CN102234219B (en) | 2010-04-23 | 2010-04-23 | 2,6-dichlorotoluene preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102234219B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1490677A (en) * | 1975-05-24 | 1977-11-02 | Bayer Ag | Process for the preparation of 2,5-dichlorotoluene |
| CN1080279A (en) * | 1992-06-16 | 1994-01-05 | 化学工业部沈阳化工研究院 | 2, the preparation of 4-toluene dichloride |
-
2010
- 2010-04-23 CN CN 201010154152 patent/CN102234219B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1490677A (en) * | 1975-05-24 | 1977-11-02 | Bayer Ag | Process for the preparation of 2,5-dichlorotoluene |
| CN1080279A (en) * | 1992-06-16 | 1994-01-05 | 化学工业部沈阳化工研究院 | 2, the preparation of 4-toluene dichloride |
Non-Patent Citations (4)
| Title |
|---|
| 2, 6 一二氯甲苯合成路线的探讨;倪祥根等;《染料工业》;19941231;第31卷(第4期);22-25 * |
| 倪祥根等.2 6 一二氯甲苯合成路线的探讨.《染料工业》.1994 |
| 梁诚.芳香族含氟中间体合成技术进展.《有机氟工业》.2007,(第1期),26-34. |
| 芳香族含氟中间体合成技术进展;梁诚;《有机氟工业》;20071231(第1期);26-34 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102234219A (en) | 2011-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1930105B (en) | Method for preparation of a fluoroaromatic compound from an aminoaromatic amine compound | |
| JP6272878B2 (en) | Cough quench and method incorporating it | |
| CN102234218B (en) | Preparation method of 2,4-dichlorotoluene | |
| CN105622369B (en) | A kind of preparation method of cyclopropyl methyl ketone | |
| CN111004100A (en) | Method for synthesizing perfluorohexanone | |
| CN105037151A (en) | Preparation method of 3-alkoxy alkyl propionate | |
| CN101810984B (en) | Method for recycling organic chlorsilane process tail gas | |
| CN104844411A (en) | Method for synthesizing hexafluoro-1,3-butadiene | |
| CN102234221B (en) | Preparation method of fluorobenzene | |
| CN103641780B (en) | A kind of method of purifying isoquinoline from coal tar crude product | |
| CA2933285C (en) | A method for separating the mixture of zirconium oxide and hafnium oxide by pyrometallurgy | |
| CN101613286A (en) | The separation of nitrobenzene chlorides and method of comprehensive utilization | |
| CN102234219B (en) | 2,6-dichlorotoluene preparation method | |
| CN101838197A (en) | Method for preparing 2,2,4-trimethyl-1,3-pentanediol single-isobutyrate | |
| CN104262081B (en) | A kind ofly full chloro-1,3-butadiene gas phase is utilized to prepare the method for perchloro-ethane | |
| CN103333143B (en) | Preparation method of high-purity benzbromarone | |
| CN104418752B (en) | Method for synthesizing single nitro-o-xylene employing catalytic nitration in micro-reactor | |
| CN109593099A (en) | Preparation method of high-purity tricresyl phosphate | |
| CN105061330A (en) | Preparing method for 4, 6-dichloropyrimidine | |
| CN101885657A (en) | Method for recovering symmetrical straight-chain even normal paraffin from waste liquor | |
| CN214634110U (en) | Hydrochloric acid desorption device using sulfuric acid as extractant | |
| CN108499592A (en) | One kind being used for CO2Catalyst of cycloaddition reaction and preparation method thereof | |
| CN103664713B (en) | A kind of method and device preparing fluorine sulfimidic acid | |
| CN103848768A (en) | Application method of methylamino formyl chloride decomposition tail gas hydrogen chloride in cartap synthesis | |
| CN102134258B (en) | Method for preparing neutral ethyoxyl high-boiling-point silicone oil by using organosilicon high-boiling-point material as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANDONG FU ER CO., LTD. Free format text: FORMER OWNER: LONGKOU FU ER BIOCHEMICAL TECHNOLOGY CO., LTD. Effective date: 20120314 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20120314 Address after: 265713, Yantai City, Shandong province Longkou City Xu Fu Street, Ru Lin Zhuang Applicant after: Shandong Fuer Co., Ltd. Address before: Longkou City Xu town south of Shandong Province in 265713 coal mine in Yantai City Applicant before: Longkou Fuer Biochemical Technology Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHANDONG FUER CO., LTD. Free format text: FORMER NAME: SHANDONG FU ER CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 265713, Yantai City, Shandong province Longkou City Xu Fu Street, Ru Lin Zhuang Patentee after: SHANDONG FUER CO., LTD. Address before: 265713, Yantai City, Shandong province Longkou City Xu Fu Street, Ru Lin Zhuang Patentee before: Shandong Fuer Co., Ltd. |