CN108689882A - The synthetic method of t-butylisocyanate - Google Patents
The synthetic method of t-butylisocyanate Download PDFInfo
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- CN108689882A CN108689882A CN201810374093.2A CN201810374093A CN108689882A CN 108689882 A CN108689882 A CN 108689882A CN 201810374093 A CN201810374093 A CN 201810374093A CN 108689882 A CN108689882 A CN 108689882A
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- Prior art keywords
- butylisocyanate
- synthetic method
- reaction
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- added dropwise
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
This case is related to a kind of synthetic method of t-butylisocyanate, and the synthetic method of t-butylisocyanate includes the following steps:(1) premixed liquid is uniformly mixed to obtain at 90-180 DEG C by the 9/10 of suitable catalyst and theoretical amount solvent quality, stream liquid feeding is gradually added dropwise into the premixed liquid, it is added dropwise and reaction solution is maintained 90-180 DEG C, maintain the reflux for state, be stirred to react 15~25h;(2) mixed liquor of step 1) after reaction is sent into rotary evaporating device, rotary evaporation washs, and drying obtains t-butylisocyanate product.The present invention, which is reacted with tert-butylamine base formyl chloride directly in atent solvent, is made t-butylisocyanate, the synthetic method eliminates security risk from technique source, for a rational technology, production safety, reaction yield is high, production cost is low, the t-butylisocyanate preparation method of three wastes.
Description
Technical field
The present invention relates to chemical industry synthesis field more particularly to a kind of synthetic methods of t-butylisocyanate.
Background technology
T-butylisocyanate is important organic synthesis intermediate, the chemical synthesis of prior art t-butylisocyanate
Method is obtained for Material synthesis by the phosgene or surpalite of tert-butylamine and severe toxicity.Since phosgene is hypertoxic gas, either exist
There is larger security risk in laboratory or experiment or industrialized production.Though and surpalite is liquid, encounters activity
Charcoal, iron or organic amine etc. are easily broken down into phosgene, and transport and storage process are more difficult, and there is also larger during use
Security risk.Therefore, how a kind of method of safe and reliable synthesizing tertiary butyl isocyanates is provided, is current urgent need to resolve
Problem.
Invention content
For the technical problems in the prior art, a kind of synthetic route of this case offer is simple, securely and reliably, is more suitable for
The synthetic method of the t-butylisocyanate of industrialized production.
To achieve the above object, this case is achieved through the following technical solutions:
A kind of synthetic method of t-butylisocyanate, wherein the synthetic method of the t-butylisocyanate includes such as
Lower step:
(1) the 9/10 of suitable catalyst and theoretical amount solvent quality is uniformly mixed to obtain premixed liquid at 90-180 DEG C, to
Stream liquid feeding is gradually added dropwise in the premixed liquid, starts synthetic reaction, time for adding is 2~4h, is added dropwise and maintains reaction solution
At 90-180 DEG C, state is maintained the reflux for, is stirred to react 15~25h;
(2) mixed liquor of step 1) after reaction is sent into rotary evaporating device, rotary evaporation washs, and drying obtains uncle
Butyl isocyanate product, reaction equation are:
Preferably, the synthetic method of the t-butylisocyanate, wherein the catalyst includes 30~35wt%
Triethylamine, 40~45wt% pyridines and 25~30wt%N- methylpyrroles.
Preferably, the synthetic method of the t-butylisocyanate, wherein the solvent be selected from toluene, dimethylbenzene,
One kind in chlorobenzene and dichloro-benzenes.
Preferably, the synthetic method of the t-butylisocyanate, wherein the stream liquid feeding includes tert-butylamine Ji Jia
Acyl chlorides, the 1/10 of theoretical amount solvent quality and stabilizer.
Preferably, the synthetic method of the t-butylisocyanate, wherein the stabilizer includes 30~40wt%
Citric acid and 60~70wt% p-methyl benzenesulfonic acid;The molar ratio of the stabilizer and tert-butylamine base formyl chloride is 0.003~
0.006:1。
Preferably, the synthetic method of the t-butylisocyanate, wherein the tert-butylamine base formyl chloride and catalysis
The molar ratio of agent is 1:0.03~0.1.
Preferably, the synthetic method of the t-butylisocyanate, wherein the solvent and tert-butylamine base formyl chloride
Molar ratio be 3~20:1.
Preferably, the synthetic method of the t-butylisocyanate, wherein the premix mixing speed be 300~
500 revs/min, the mixing speed of the synthetic reaction is 200~400 revs/min.
Preferably, the synthetic method of the t-butylisocyanate, wherein the pressure when rotary evaporation is
0.04~0.08Mpa, temperature are 80 DEG C~90 DEG C.
Preferably, the synthetic method of the t-butylisocyanate, wherein the drying mode is dry for reduced vacuum
Dry, drying temperature is 70-90 DEG C, and drying time is 6~9h.
The beneficial effects of the invention are as follows:
(1) present invention tert-butylamine base formyl chloride reacts directly in atent solvent is made t-butylisocyanate, the conjunction
Security risk is eliminated from technique source at method, for a rational technology, production safety, reaction yield is high, production cost is low,
The t-butylisocyanate preparation method of three wastes.
(2) present invention process route is advanced, avoids the phosgene and surpalite of severe toxicity, safety easy to operate, reaction yield
Height, production cost is low, basic three wastes, has larger implementary value and economic results in society.
(3) present invention improves the yield of product using triethylamine, pyridine and N- methylpyrroles as catalyst;To include
The stream liquid feeding of tert-butylamine base formyl chloride, solvent and stabilizer is gradually added dropwise into premixed liquid, improves the conversion ratio of reactant,
To improve the yield of product;Stabilizer citric acid and p-methyl benzenesulfonic acid collaboration use, and effectively increase the steady of reaction system
It is qualitative, reduce the generation of by-product.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, to enable those skilled in the art with reference to specification
Word can be implemented according to this.
Embodiment 1
In the 1000ml four-hole bottles equipped with mechanical agitation, constant pressure funnel, reflux condensing tube and thermometer, it is added
2.4g triethylamines, 3.3 pyridines, 2.6g N- methylpyrroles and 249g toluene to four-hole boiling flask, start and stir and be kept stirring speed
Degree is warming up to 90 DEG C, by 135.5g tert-butylamine bases formyl chloride, 27g toluene, 0.3g citric acids and 0.67g to first at 300 revs/min
Constant pressure funnel is added, in 90 DEG C of titration 3h of temperature in benzene sulfonic acid, is added dropwise and maintains the reflux for state at 90 DEG C, it is anti-to continue stirring
15h is answered, speed is kept stirring at 400 revs/min, after reaction, mixed liquor is sent into rotary evaporating device, rotary evaporation pressure
For 0.05Mpa, temperature is 80 DEG C~90 DEG C, is washed with water 3 times, 80 DEG C of dry 9h, obtain product in reduced vacuum drying box
T-butylisocyanate 134.3g, yield 92%, content 99.2%.
Embodiment 2
In the 1000ml four-hole bottles equipped with mechanical agitation, constant pressure funnel, reflux condensing tube and thermometer, it is added
The dichloro-benzenes of 2.2g triethylamines, 3.5 pyridines, 2.8g N- methylpyrroles and 2646g starts and stirs and be kept stirring speed 400
Rev/min, 160 DEG C are warming up to, by 135.5g tert-butylamine bases formyl chloride, 294g dichloro-benzenes, 0.54g citric acids and 0.98g to toluene
Constant pressure funnel is added, in 160 DEG C of titration 2h of temperature in sulfonic acid, is added dropwise and maintains the reflux for state at 160 DEG C, it is anti-to continue stirring
4h is answered, speed is kept stirring at 300 revs/min, after reaction, mixed liquor is sent into rotary evaporating device, rotary evaporation, rotation
Evaporating pressure is 0.06Mpa, and temperature is 85 DEG C, is washed with water 3 times, and 90 DEG C of dry 6h in depressurizing hollow drying box are produced
Product t-butylisocyanate 135.8g, yield 93%, content 99.5%.
Embodiment 3
In the 1000ml four-hole bottles equipped with mechanical agitation, constant pressure funnel, reflux condensing tube and thermometer, it is added
The chlorobenzene of the triethylamine and 3.2g pyridines, 2.3g N- methylpyrroles and 1622g of 2.9g starts and stirs and be kept stirring speed and exist
500 revs/min, 110 DEG C are warming up to, by 135.5g tert-butylamine bases formyl chloride, 180g chlorobenzenes, 0.76g citric acids and 1.14g to toluene
Sulfonic acid is added constant pressure funnel and 2h is added dropwise at 110 DEG C, and maintaining the reflux for state at 110 DEG C after being added dropwise continues to be stirred to react
11h is kept stirring speed at 300 revs/min, after reaction, mixed liquor is sent into rotary evaporating device, rotary evaporation, rotation
Evaporating pressure is 0.06Mpa, and temperature is 90 DEG C, is washed with water three times, and 70 DEG C of dry 9h in depressurizing hollow drying box are produced
Product t-butylisocyanate 137.2g, yield 94%, content 99.6%.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.
Claims (10)
1. a kind of synthetic method of t-butylisocyanate, which is characterized in that the synthetic method packet of the t-butylisocyanate
Include following steps:
(1) the 9/10 of suitable catalyst and theoretical amount solvent quality is uniformly mixed to obtain premixed liquid at 90-180 DEG C, to described
Stream liquid feeding is gradually added dropwise in premixed liquid, starts synthetic reaction, time for adding is 2~4h, is added dropwise reaction solution maintaining 90-
180 DEG C, state is maintained the reflux for, is stirred to react 15~25h;
(2) mixed liquor of step 1) after reaction is sent into rotary evaporating device, rotary evaporation washs, and drying obtains tertiary butyl
Isocyanate products, reaction equation are:
。
2. the synthetic method of t-butylisocyanate as described in claim 1, which is characterized in that the catalyst include 30~
35wt% triethylamines, 40~45wt% pyridines and 25~30wt%N- methylpyrroles.
3. the synthetic method of t-butylisocyanate as described in claim 1, which is characterized in that the solvent be selected from toluene,
One kind in dimethylbenzene, chlorobenzene and dichloro-benzenes.
4. the synthetic method of t-butylisocyanate as described in claim 1, which is characterized in that the stream liquid feeding includes tertiary fourth
Carbamoyl chlorine, the 1/10 of theoretical amount solvent quality and stabilizer.
5. the synthetic method of t-butylisocyanate as claimed in claim 4, which is characterized in that the stabilizer include 30~
40wt% citric acids and 60~70wt% p-methyl benzenesulfonic acid;The molar ratio of the stabilizer and tert-butylamine base formyl chloride is 0.005
~0.01:1.
6. the synthetic method of t-butylisocyanate according to any one of claims 1-4, which is characterized in that the tert-butylamine
The molar ratio of base formyl chloride and catalyst is 1:0.03~0.1.
7. the synthetic method of t-butylisocyanate according to any one of claims 1-4, which is characterized in that the solvent with
The molar ratio of tert-butylamine base formyl chloride is 3~20:1.
8. the synthetic method of t-butylisocyanate as described in claim 1, which is characterized in that the premix mixing speed is
300~500 revs/min, the mixing speed of the synthetic reaction is 200~400 revs/min.
9. the synthetic method of t-butylisocyanate as described in claim 1, which is characterized in that the pressure when rotary evaporation
Power is 0.04~0.08Mpa, and temperature is 80 DEG C~90 DEG C.
10. the synthetic method of t-butylisocyanate as described in claim 1, which is characterized in that the drying mode is to subtract
Pressure vacuum drying, drying temperature are 70-90 DEG C, and drying time is 6~9h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810374093.2A CN108689882A (en) | 2018-04-24 | 2018-04-24 | The synthetic method of t-butylisocyanate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810374093.2A CN108689882A (en) | 2018-04-24 | 2018-04-24 | The synthetic method of t-butylisocyanate |
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| CN108689882A true CN108689882A (en) | 2018-10-23 |
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| CN201810374093.2A Pending CN108689882A (en) | 2018-04-24 | 2018-04-24 | The synthetic method of t-butylisocyanate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218163A (en) * | 2019-05-20 | 2019-09-10 | 江苏蓝丰生物化工股份有限公司 | The synthetic method of n-butyl isocyanate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852317A (en) * | 1971-11-16 | 1974-12-03 | Basf Ag | Production of isocyanates |
| US3860623A (en) * | 1972-03-03 | 1975-01-14 | Basf Ag | Production of isocyanates |
| CN86100286A (en) * | 1986-01-15 | 1986-07-16 | 湖南化工研究所 | Method for preparing methyl isocyanate |
| CN1844091A (en) * | 2006-05-08 | 2006-10-11 | 江苏安邦电化有限公司 | Process for preparing butyl isocyanate |
| CN102976976A (en) * | 2012-11-29 | 2013-03-20 | 湖南化工研究院 | Preparation method for methyl isocyanate |
| CN105418459A (en) * | 2015-12-09 | 2016-03-23 | 海利贵溪化工农药有限公司 | Process for producing high yield methyl isocyanate |
| CN107162934A (en) * | 2017-06-07 | 2017-09-15 | 江苏蓝丰生物化工股份有限公司 | The synthetic method of isopropyl isocyanate |
-
2018
- 2018-04-24 CN CN201810374093.2A patent/CN108689882A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852317A (en) * | 1971-11-16 | 1974-12-03 | Basf Ag | Production of isocyanates |
| US3860623A (en) * | 1972-03-03 | 1975-01-14 | Basf Ag | Production of isocyanates |
| CN86100286A (en) * | 1986-01-15 | 1986-07-16 | 湖南化工研究所 | Method for preparing methyl isocyanate |
| CN1844091A (en) * | 2006-05-08 | 2006-10-11 | 江苏安邦电化有限公司 | Process for preparing butyl isocyanate |
| CN102976976A (en) * | 2012-11-29 | 2013-03-20 | 湖南化工研究院 | Preparation method for methyl isocyanate |
| CN105418459A (en) * | 2015-12-09 | 2016-03-23 | 海利贵溪化工农药有限公司 | Process for producing high yield methyl isocyanate |
| CN107162934A (en) * | 2017-06-07 | 2017-09-15 | 江苏蓝丰生物化工股份有限公司 | The synthetic method of isopropyl isocyanate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218163A (en) * | 2019-05-20 | 2019-09-10 | 江苏蓝丰生物化工股份有限公司 | The synthetic method of n-butyl isocyanate |
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Application publication date: 20181023 |
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