CN102234218A - Preparation method of 2,4-dichlorotoluene - Google Patents
Preparation method of 2,4-dichlorotoluene Download PDFInfo
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- CN102234218A CN102234218A CN2010101540456A CN201010154045A CN102234218A CN 102234218 A CN102234218 A CN 102234218A CN 2010101540456 A CN2010101540456 A CN 2010101540456A CN 201010154045 A CN201010154045 A CN 201010154045A CN 102234218 A CN102234218 A CN 102234218A
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Abstract
The invention discloses a preparation method of 2,4-dichlorotoluene, which comprises the following steps: mixing 5-chloro-2-methylaniline with an acid, stirring, cooling to -10-15 DEG C, adding nitrites, controlling the adding speed of the nitrites to allow the temperature to be no more than 15 DEG C, stirring, controlling the temperature to be 15-60 DEG C, and performing a thermal decomposition reaction; after the thermal decomposition reaction, separating an organic phase at the lower layer, and recovering unreacted acids by a graphite absorption tower; washing the organic phase with water to neutrality, performing distillation, removing o-chlorotoluene generated during the reaction at 180-198 DEG C, performing rectification, collecting fractions at 198-201 DEG C to obtain 2,4-dichlorotoluene. The preparation method of 2,4-dichlorotoluene of the invention has high product yield, and low production cost.
Description
Technical field
The present invention relates to a kind of 2, the preparation method of 4-toluene dichloride.
Background technology
2, the 4-toluene dichloride is used to produce 2,4 dichloro benzene formaldehyde, 2,4 dichloro benzene nitrile, and the intermediate of system weedicide and dyestuff.In the prior art, 2, in the main prior art of the preparation of 4-toluene dichloride, mainly be with; Toluene is that raw material gets through chlorination reaction, is 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 4-toluene dichloride.
Provided by the present invention 2, the preparation method of 4-toluene dichloride comprises the steps:
5-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 is controlled at 5～60 ℃ and carries out pyrolysis;
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 180～198 ℃, carries out rectifying then, collects 196～201 ℃ of fractions, obtains 2, the preparation of 4-toluene dichloride.
Of the present invention 2, the preparation method of 4-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, acetate, the oxalic acid any or appoint several.
Of the present invention 2, the preparation method of 4-toluene dichloride, wherein, described nitrite is potassium nitrite, Sodium Nitrite, ammonium nitrite or calcium nitrite.
Of the present invention 2, the preparation method of 4-toluene dichloride do not use the X catalyst series, safe, production cost is low, product yield height, and help cleaner production control in the commercial run, the acid in the reaction absorbs in absorbing still, helps 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 5-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 a 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 is with absorbing 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 180～198 ℃, carry out rectifying then, collect 198～201 ℃ of fractions, obtain fraction 152 grams.
With 2, the 4-toluene dichloride is standard substance, gas chromatographic analysis.Analytical results as shown in Table 1 and Table 2.
Table 1.2,4-toluene dichloride standard stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 4.573 | 271.778 |
| 2 | 8.705 | 140716.984 |
| 3 | 9.148 | 1017.089 |
| 4 | 9.397 | 375.987 |
| 5 | 13.942 | 674.289 |
Table 2. fraction stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 8.673 | 1333781.828 |
| 2 | 9.128 | 282.140 |
| 3 | 9.382 | 35.824 |
| 4 | 9.397 | 375.987 |
| 5 | 13.942 | 674.289 |
In the fraction 2,6-toluene dichloride purity is 99.92%, calculates yield 94.41% with 5-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 5-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 a 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 180～198 ℃, carry out rectifying then, collect 196～201 ℃ of fractions, obtain fraction 227 grams.
With 2, the 4-toluene dichloride is standard substance, gas chromatographic analysis.Analytical results is shown in table 3 and table 4.
Table 3.2,4-toluene dichloride standard stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 4.573 | 271.778 |
| 2 | 8.705 | 140716.984 |
| 3 | 9.148 | 1017.089 |
| 4 | 9.397 | 375.987 |
| 5 | 13.942 | 674.289 |
Table 4. fraction stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 8.683 | 132901.258 |
| 2 | 9.138 | 281.140 |
| 3 | 9.352 | 35.924 |
| 4 | 9.407 | 374.667 |
| 5 | 13.912 | 669.381 |
In the fraction 2,6-toluene dichloride purity is 99.92%, calculates yield 94.00% with 5-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 5-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 a 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 is with absorbing 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 180～198 ℃, carry out rectifying then, collect 198～201 ℃ of fractions, obtain fraction 303.5 grams.
Table 4.2,4-toluene dichloride standard stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 4.573 | 271.778 |
| 2 | 8.705 | 140716.984 |
| 3 | 9.148 | 1017.089 |
| 4 | 9.397 | 375.987 |
| 5 | 13.942 | 674.289 |
Table 5. fraction stratographic analysis result
| Peak number | Retention time (min) | Peak height |
| 1 | 8.694 | 133001.247 |
| 2 | 9.129 | 284.150 |
| 3 | 9.385 | 35.924 |
| 4 | 9.407 | 368.667 |
| 5 | 13.912 | 657.271 |
In the fraction 2,6-toluene dichloride purity is 99.92%, calculates yield 94.25% with 5-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 (4)
1.2 the preparation method of 4-toluene dichloride comprises the steps:
5-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 is controlled at 15～60 ℃ and carries out pyrolysis;
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 180～198 ℃, carries out rectifying then, collects 198～201 ℃ of fractions, obtains 2, the 4-toluene dichloride.
2. preparation method according to claim 1 is characterized in that: described acid be in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, fluoroboric acid, hydrofluoric acid, silicofluoric acid, formic acid, acetate, the oxalic acid any or appoint several.
3. preparation method according to claim 1 and 2 is characterized in that: described nitrite is potassium nitrite, Sodium Nitrite, ammonium nitrite or calcium nitrite.
4. preparation method according to claim 3 is characterized in that: the mol ratio of described 5-chloro-2-aminotoluene, described acid and described nitrite is (1～2): (1～3): (1～2).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786387A (en) * | 2012-08-27 | 2012-11-21 | 山东福尔股份有限公司 | Preparation method for p-fluorotoluene |
| CN102786385A (en) * | 2012-08-27 | 2012-11-21 | 山东福尔股份有限公司 | Preparation method of m-fluorotoluene |
| CN102786386A (en) * | 2012-08-27 | 2012-11-21 | 山东福尔股份有限公司 | Preparation method of 4-chloro-2-fluorotoluene |
| CN107673951A (en) * | 2017-08-18 | 2018-02-09 | 河南师范大学 | A kind of high efficiency preparation method of 2,4,5 trifluoro benzene acetic acid |
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 201010154045 patent/CN102234218B/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 (1)
| Title |
|---|
| 梁诚: "芳香族含氟中间体合成技术进展", 《有机氟工业》, no. 1, 31 December 2007 (2007-12-31), pages 26 - 34 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786387A (en) * | 2012-08-27 | 2012-11-21 | 山东福尔股份有限公司 | Preparation method for p-fluorotoluene |
| CN102786385A (en) * | 2012-08-27 | 2012-11-21 | 山东福尔股份有限公司 | Preparation method of m-fluorotoluene |
| CN102786386A (en) * | 2012-08-27 | 2012-11-21 | 山东福尔股份有限公司 | Preparation method of 4-chloro-2-fluorotoluene |
| CN102786386B (en) * | 2012-08-27 | 2015-01-21 | 山东福尔有限公司 | Preparation method of 4-chloro-2-fluorotoluene |
| CN107673951A (en) * | 2017-08-18 | 2018-02-09 | 河南师范大学 | A kind of high efficiency preparation method of 2,4,5 trifluoro benzene acetic acid |
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| CN102234218B (en) | 2013-07-24 |
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