CN107473973A - A kind of nitrotoleune preparation method of 6 chlorine 2 - Google Patents
A kind of nitrotoleune preparation method of 6 chlorine 2 Download PDFInfo
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- CN107473973A CN107473973A CN201710639330.9A CN201710639330A CN107473973A CN 107473973 A CN107473973 A CN 107473973A CN 201710639330 A CN201710639330 A CN 201710639330A CN 107473973 A CN107473973 A CN 107473973A
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- chloro
- chlorine
- nitrobenzene
- nitrobenzenes
- nitrotoleune
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of nitrotoleune preparation method of 6 chlorine 2, comprise the following steps：（1）, ortho-methylnitrobenzene, thionyl chloride are added into chlorination tank, stir, heating, be passed through chlorine, reacted under conditions of 65 ~ 75oC and the nitrotoleune first product of 6 chlorine 2 is made；（2）, by step（1）The nitrotoleune first product of 6 chlorine of product 2 be transferred to washing kettle, thionyl chloride is washed out, material after washing carries out dewater treatment, and the nitrotoleune crude product of 6 chlorine 2 is made；（3）, by step（2）The obtained nitrotoleune crude product of 6 chlorine 2, is transferred to rectifying column and is purified, and obtains the nitrotoleune sterling of 6 chlorine 2；（4）, by step（3）The obtained nitrotoleune sterling of 6 chlorine 2 is crystallized, and crystallization temperature is controlled in 40 50oC, obtains the nitrotoleune high sterling of 6 chlorine 2.Beneficial effects of the present invention：Using thionyl chloride as catalyst, solve the problem of chlorination production cycle length, low content, good basis has been established to prepare the nitro of 6 chlorine 2 of high-purity.
Description
Technical field
The invention belongs to the preparing technical field of chlorine-containing compound, more particularly to a kind of 6- Chloro-2-Nitrobenzene systems
Preparation Method.
Background technology
6- Chloro-2-Nitrobenzenes are a kind of important medicine, agricultural chemicals, dyestuff intermediate, belong to becoming more meticulous for high added value
Chemical product, current preparation technology synthesizes 6- Chloro-2-Nitrobenzenes mainly using ortho-methylnitrobenzene as raw material, by chlorination, with three
Iron chloride makees catalyst, and reaction synthesis 6- Chloro-2-Nitrobenzene crude products are carried out with chlorine.Entering washing, then carry out pickling,
Alkali cleaning, stratification.6- Chloro-2-Nitrobenzenes are separated to be dehydrated.By distillation, crystallization and purification, the chloro- 2- nitros of 6- are made
Toluene.The shortcomings that preparation method：1st, the chlorination reaction cycle is grown.2nd, reaction yield is low, and production cost is high.
The content of the invention
According to existing process technical deficiency, the present invention provides a kind of 6- Chloro-2-Nitrobenzenes preparation method, including following step
Suddenly：
（1）, chlorination：Ortho-methylnitrobenzene, thionyl chloride are added into chlorination tank, 63r/min stirrings, heating, is passed through chlorine, 65
Reacted under conditions of ~ 75oC and 6- Chloro-2-Nitrobenzene first products are made, chemical equation is：
（2）, by step（1）Product 6- Chloro-2-Nitrobenzene first products be transferred to washing kettle, thionyl chloride is washed out, after washing
Material is dehydrated into dehydrating kettle, and 6- Chloro-2-Nitrobenzene crude products are made at 100 ~ 110 DEG C in temperature control.
（3）, by step（2）Obtained 6- Chloro-2-Nitrobenzene crude products, are transferred to rectifying column and are purified, and control rectifying
150 ~ 160 DEG C of column bottom temperature, 85 ~ 95 DEG C of tower top temperature, backflow, obtain 6- Chloro-2-Nitrobenzene sterlings.
（4）, by step（3）Obtained 6- Chloro-2-Nitrobenzenes sterling carries out crystallization and purification, crystallization temperature control 40 ~
50 oC, obtain 6- Chloro-2-Nitrobenzene high sterlings.
Wherein, 1 ~ 5 part of thionyl chloride, 150 ~ 170 parts of chlorine, 95 ~ 105 parts of ortho-methylnitrobenzene.
As optimization, the step（2）6- Chloro-2-Nitrobenzenes first product carries out washing-pickling-washing-alkali cleaning-water
Wash-be dehydrated into next step.
As optimization, step（2）The water：6- Chloro-2-Nitrobenzene first products mass ratio is 1：1.5~2.
As optimization, step（3）6- Chloro-2-Nitrobenzene content >=92% in the 6- Chloro-2-Nitrobenzenes sterling.
As optimization, step（4）6- Chloro-2-Nitrobenzenes content in the 6- Chloro-2-Nitrobenzenes high sterling >=
99%。
The preparation method of 6- Chloro-2-Nitrobenzenes of the present invention using thionyl chloride as catalyst, using ortho-methylnitrobenzene and
Chlorine reaction generates 6- Chloro-2-Nitrobenzene first products, by a series of purge processes, finally gives product, this method can show
Write and reduce side reaction, improve yield.The 6- Chloro-2-Nitrobenzene purity prepared by the present invention can reach more than 99%, have energy
Low, the features such as automaticity is high, and byproduct of reaction is few, and reaction time is short is consumed, there is preferable economic benefit and social benefit.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments.It is general based on the embodiment in the present invention, this area
The every other embodiment that logical technical staff is obtained under the premise of creative work is not made, belongs to protection of the present invention
Scope.The experimental method of unreceipted actual conditions in the following example, generally according to normal condition, or according to manufacturer
Proposed condition, unless stated otherwise, ratio and percentage are based on weight.
The raw materials used embodiment of the present invention is commercially available.
Embodiment 1
1st, chlorinating step：3300kg ortho-methylnitrobenzenes and 32kg thionyl chlorides are added into chlorination tank, opens device for absorbing tail gas,
63r/min is stirred.It is passed into 85kg/h flow by chlorine is vaporized in chlorination tank, controlling reaction temperature 65oC, reaction 27
Hour, sampling analysis, when ortho-methylnitrobenzene content is 10%, after chlorination reaction terminates, blowing compressed air about two into chlorination tank
Hour, chlorine content in chlorination tank is reduced, obtains 6- Chloro-2-Nitrobenzene first products.During subsequent operation, new thing is added by ormal weight
Material, start the chlorination reaction of next batch.
2nd, washing step：The 6- Chloro-2-Nitrobenzenes first product measured is added into washing kettle, opens washing kettle stirring, will
Hydrochloric acid is added in washing kettle in measuring tank, stirring, is stood 20min, layering, lower floor's material is washed, stirred, is stood
20min, layering, material after washing is subjected to alkali cleaning, it is 8 that liquid caustic soda, which is added dropwise, to pH, is stirred, stratification；Washing, layering, is obtained
The mass ratio of 6- Chloro-2-Nitrobenzene crude products, this step reclaimed water and 6- Chloro-2-Nitrobenzene first products is 1:1.5.
3rd, dehydration：6- Chloro-2-Nitrobenzene crude products are transferred to dehydrating kettle, distilled using vacuum, temperature control
In 100C, small part water is steamed to water receiving tank system, and after measure pH is 7,6- Chloro-2-Nitrobenzenes are put into storage tank.
4th, washing tail gas step：Absorb through falling-film absorber from the tail gas that chlorinating step comes and sold outside hydrochloric acid, through Alkali absorption
Into sodium hypochlorite, the tail gas after two-level absorption tower absorbs carries out high altitude discharge.
5th, rectification step：First start vavuum pump, vacuum, start to feed to trourelle.Open chuck and be warming up to 150 DEG C, part
Material is vaporized, and bottom of towe is flowed back to again in uphill process is vaporized, and by continuous ramp cycle, the material of vaporization rises to tower top,
Tower top temperature control is at 90 DEG C or so, and after material injects overhead condenser by evaporation tube, liquefaction to the cold is back in return tank
Formed in tower and circulated.Temperature carries out sampling analysis with after backflow two hours of normal table before opening big tower transfering material pump.
Observe liquid level in big tower, to big tower in after specified location open the circulation pump, bottom of towe be warming up to 160 DEG C, it is cold to open tower
Condenser water-circulating pump, material are vaporized to tower top by heater, are flowed into overhead condenser by evaporation tube, are liquefied to the cold, flow
Enter return tank.Oil temperature and vacuum are controlled, after a period of stabilisation, sampling analysis, big tower top 6- Chloro-2-Nitrobenzenes content liter
During to 92%, open and receive valve reception, the size of reception amount can be controlled according to the height of 6- Chloro-2-Nitrobenzene contents, content be
More than 92% 6- Chloro-2-Nitrobenzenes are stored in chlordene tank.
1st, crystallisation step：After opening vacuum, check chlordene tank liquid level completes material addition crystallizer, charging after whether normal
Stop charging afterwards.
Hot and cold water tank's priming valve is opened, after controlling water temperature, by material fast cooling to 50 DEG C, then with 2~3 DEG C/h's
After speed is cooled to 35 DEG C or so, temperature recovery occurs in the material in crystallizer, observes the temperature of good each crystallizer, waits thing
Material crystallize, and after temperature does not rise, rise terminates, then after being cooled to 30 DEG C with 1~2 DEG C/h speed, one hour of standing, takes out
Mother liquor, mother liquor are evacuated in mother liquor tank.
Mother liquor tank is vacuumized, opens and prepares to lead sweat tank after hot and cold water tank is warming up to 35 DEG C with 3~4 DEG C/h speed,
With 1 DEG C/h heating, after being raised to 35 DEG C or so, then with 0.5 DEG C/h speed 38 DEG C or so are warming up to, sampling analysis.At this moment again
Slowly heated up with 0.2~0.3 DEG C/h speed, observe the situation and quantity of perspiration of material in crystallizer, control the speed of heating fast
Slowly, sampling detection 6- Chloro-2-Nitrobenzenes content more than 99.5 is qualified.After reaction terminates, stop vaccum pump motor, open water tank
Steam valve, be rapidly heated to 50 DEG C of steam off valves and circulating pump of cutting off the water, obtain the purity of 6- Chloro-2-Nitrobenzenes >=
99.5%。
Embodiment 2
Prepared according to 6- Chloro-2-Nitrobenzene preparation methods in embodiment 1, only change the following of the following steps of embodiment 1
Parameter：
1st, chlorinating step：3300kg ortho-methylnitrobenzenes and 85kg thionyl chlorides are added into chlorination tank, opens device for absorbing tail gas,
63r/min is stirred.It is passed into 85kg/h flow by chlorine is vaporized in chlorination tank, controlling reaction temperature 70oC, reaction 27
Hour, sampling analysis, when ortho-methylnitrobenzene content is 10%, after chlorination reaction terminates, blowing compressed air about two into chlorination tank
Hour, chlorine content in chlorination tank is reduced, obtains 6- Chloro-2-Nitrobenzene first products.During subsequent operation, new thing is added by ormal weight
Material, start the chlorination reaction of next batch.
2nd, washing step：The 6- Chloro-2-Nitrobenzenes first product measured is added into washing kettle, opens washing kettle stirring, will
Hydrochloric acid is added in washing kettle in measuring tank, stirring, is stood 20min, layering, lower floor's material is washed, stir, stand
20min, layering, material after washing is subjected to alkali cleaning, it is 8 that liquid caustic soda, which is added dropwise, to pH, is stirred, stratification；Washing, layering, is obtained
The mass ratio of 6- Chloro-2-Nitrobenzene crude products, this step reclaimed water and 6- Chloro-2-Nitrobenzene first products is 1:1.8.
3rd, dehydration：6- Chloro-2-Nitrobenzene crude products are transferred to dehydrating kettle, distilled using vacuum, temperature control
In 105oC, small part water is steamed to water receiving tank system, and after measure pH is 7,6- Chloro-2-Nitrobenzenes are put into storage tank.
Test result indicates that purity >=99.5% of the 6- Chloro-2-Nitrobenzenes finally given.
Embodiment 3
Prepared according to 6- Chloro-2-Nitrobenzene preparation methods in embodiment 1, only change the following of the following steps of embodiment 1
Parameter：
1st, chlorinating step：3300kg ortho-methylnitrobenzenes and 155kg thionyl chlorides are added into chlorination tank, opens tail gas absorption dress
Put, 63r/min stirrings.It is passed into 85kg/h flow by chlorine is vaporized in chlorination tank, controlling reaction temperature 75oC, reaction
27 hours, sampling analysis, when ortho-methylnitrobenzene content is 10%, after chlorination reaction terminates, into chlorination tank, blowing compressed air was about
Two hours, chlorine content in chlorination tank is reduced, obtains 6- Chloro-2-Nitrobenzene first products.During subsequent operation, added by ormal weight new
Material, start the chlorination reaction of next batch.
2nd, washing step：The 6- Chloro-2-Nitrobenzenes first product measured is added into washing kettle, opens washing kettle stirring, will
Hydrochloric acid is added in washing kettle in measuring tank, stirring, is stood 20min, layering, lower floor's material is washed, stirred, is stood
20min, layering, material after washing is subjected to alkali cleaning, it is 8 that liquid caustic soda, which is added dropwise, to pH, is stirred, stratification；Washing, layering, is obtained
The mass ratio of 6- Chloro-2-Nitrobenzene crude products, this step reclaimed water and 6- Chloro-2-Nitrobenzene first products is 1:2.
3rd, dehydration：6- Chloro-2-Nitrobenzene crude products are transferred to dehydrating kettle, distilled using vacuum, temperature control
In 110oC, small part water is steamed to water receiving tank system, and after measure pH is 7,6- Chloro-2-Nitrobenzenes are put into storage tank.
Test result indicates that purity >=99.5% of the 6- Chloro-2-Nitrobenzenes finally given.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (5)
1. the present invention provides a kind of 6- Chloro-2-Nitrobenzenes preparation method, comprise the following steps：
（1）, chlorination：Ortho-methylnitrobenzene, thionyl chloride are added into chlorination tank, is stirred, heating, is passed through chlorine, 65 ~ 75oC's
Under the conditions of react 6- Chloro-2-Nitrobenzene first products be made；
（2）, by step（1）Product 6- Chloro-2-Nitrobenzene first products be transferred to washing kettle, thionyl chloride is washed out, after washing
Material is dehydrated into dehydrating kettle, and 6- Chloro-2-Nitrobenzene crude products are made at 100 ~ 110 DEG C in temperature control；
（3）, by step（2）Obtained 6- Chloro-2-Nitrobenzene crude products, are transferred to rectifying column and are purified, control rectifying column bottom
150 ~ 160 DEG C of temperature, 85 ~ 95 DEG C of tower top temperature, backflow obtain 6- Chloro-2-Nitrobenzene sterlings；
（4）, by step（3）The 6- Chloro-2-Nitrobenzenes of 92% obtained carry out crystallization and purification, and crystallization temperature is controlled in 40 ~ 50 o
C, obtain 6- Chloro-2-Nitrobenzene high sterlings；
Wherein, 1 ~ 5 part of thionyl chloride, 150 ~ 170 parts of chlorine, 95 ~ 105 parts of ortho-methylnitrobenzene.
A kind of 2. 6- Chloro-2-Nitrobenzenes preparation method according to claim 1, it is characterised in that：The step（2）6-
Chloro-2-Nitrobenzene first product wash-and pickling-washing-alkali cleaning-washing-dehydration enters next step.
3. any 6- Chloro-2-Nitrobenzenes preparation method according to claim 1 and 2, it is characterised in that：Step
（2）The water：6- Chloro-2-Nitrobenzenes mass ratio is 1：1.5~2.
A kind of 4. 6- Chloro-2-Nitrobenzenes preparation method according to claim 1, it is characterised in that：Step（3）The 6-
6- Chloro-2-Nitrobenzenes content >=92% in Chloro-2-Nitrobenzene sterling.
A kind of 5. 6- Chloro-2-Nitrobenzenes preparation method according to claim 1, it is characterised in that：Step（4）The 6-
6- Chloro-2-Nitrobenzenes content >=99.5% in Chloro-2-Nitrobenzene high sterling.
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| CN201710639330.9A CN107473973A (en) | 2017-07-31 | 2017-07-31 | A kind of nitrotoleune preparation method of 6 chlorine 2 |
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| CN201710639330.9A CN107473973A (en) | 2017-07-31 | 2017-07-31 | A kind of nitrotoleune preparation method of 6 chlorine 2 |
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