CN109369459A - Thiourea-uv Method produces N, the method for N '-di-t-butyl carbodiimide - Google Patents
Thiourea-uv Method produces N, the method for N '-di-t-butyl carbodiimide Download PDFInfo
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- CN109369459A CN109369459A CN201811180633.XA CN201811180633A CN109369459A CN 109369459 A CN109369459 A CN 109369459A CN 201811180633 A CN201811180633 A CN 201811180633A CN 109369459 A CN109369459 A CN 109369459A
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- thiourea
- butyl
- tert
- carbodiimide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C267/00—Carbodiimides
Abstract
The invention belongs to technical field of organic synthesis, are specifically related to a kind of Thiourea-uv Method production N, the method for N '-di-t-butyl carbodiimide.First N, N '-di-tert-butyl thiourea are synthesized in an aqueous medium with tert-butylamine and carbon disulfide；By N, N '-di-tert-butyl thiourea carries out once oxidation after being filtered, being dried, and sequentially adds in reaction kettle together with piece alkali, solvent, catalyst, it is warming up to 60-65 DEG C, oxidant is added, is reacted 2 hours under the conditions of 60~65 DEG C, static 20-25min discards lower layer's water phase；Secondary oxidation reaction is carried out, quantitative oxidant and catalyst is added dropwise, is reacted 1 hour at 65 DEG C；Alkali neutralization is added to wash, branch vibration layer steams solvent, and rectification under vacuum obtains N, N '-di-t-butyl carbodiimide.Thiourea-uv Method of the present invention produces N, and the method for N '-di-t-butyl carbodiimide, reaction condition is mild, high income, and purity is high, post-processing is simple, and process water can be recycled.
Description
Technical field
The invention belongs to technical field of organic synthesis, are specifically related to a kind of Thiourea-uv Method production N, N '-di-t-butyl carbon two
The method of imines.
Background technique
N, N '-di-t-butyl carbodiimide are a kind of chemical substances, and molecular formula is C9H18N2.N, N '-di-t-butyl carbon two
Imines, molecular weight 154.25；Main content >=99.0%；Boiling point: 48-50 DEG C；Density: 20 DEG C of 0.800g/mL at；Flash-point
95°F；Purposes；Chemical formula is as follows:
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of Thiourea-uv Method production N, N '-di-t-butyl carbon two
The method of imines.The production method reaction condition is mild, high income, and purity is high, post-processing is simple, and process water, which can recycle, to be made
With.
Thiourea-uv Method production N of the present invention, the method for N '-di-t-butyl carbodiimide, specifically includes the following steps:
(1) N is first synthesized in an aqueous medium with tert-butylamine and carbon disulfide, hydrogen peroxide is added dropwise in N '-di-tert-butyl thiourea respectively
And liquid alkaline, remove by-product hydrogen sulfide；
(2) N for preparing step (1), N '-di-tert-butyl thiourea filtered, dry after carry out once oxidation, together with piece
Alkali, solvent, catalyst sequentially add in reaction kettle, are warming up to 60-65 DEG C, and oxidant is added, and reaction 2 is small under the conditions of 60~65 DEG C
When, static 20-25min discards lower layer's water phase；
(3) secondary oxidation reaction is carried out, quantitative oxidant and catalyst is added dropwise, is reacted 1 hour at 65 DEG C；
(4) plus alkali neutralization washing, branch vibration layer steam solvent, and rectification under vacuum obtains N, N '-di-t-butyl carbodiimide.
Wherein:
The mass ratio of tert-butylamine described in step (1) and carbon disulfide is 1:0.5-0.9.
Catalyst described in step (2) is one or both of polyethylene glycol or benzyltriethylammoinium chloride；Solvent
It is one of benzene, toluene or methylene chloride；The quality that catalyst is added is N, the 3%-8% of N '-di-tert-butyl thiourea quality；
The quality of the solvent of addition is N, 3-6 times of N '-di-tert-butyl thiourea quality.
Oxidant described in step (2) and step (3) is the liquor natrii hypochloritis of 8~10% concentration, and oxidant is to drip
The mode added is added, and controls and drip off in 1 hour.
Once oxidation described in step (2), the quality of the oxidant of addition are N, the 4- of N '-di-tert-butyl thiourea quality
5.5 again.
Secondary oxidation described in step (3), the quality of the oxidant of addition are N, the 1- of N '-di-tert-butyl thiourea quality
3 times.
Catalyst described in step (3) is one or both of polyethylene glycol or benzyltriethylammoinium chloride.
As a preferred technical solution, Thiourea-uv Method described in present aspect produces N, N '-di-t-butyl carbodiimide
Method, specifically includes the following steps:
(1) N is first synthesized in an aqueous medium with tert-butylamine and carbon disulfide, hydrogen peroxide is added dropwise in N '-di-tert-butyl thiourea respectively
And liquid alkaline, remove by-product hydrogen sulfide；
(2) by the N after filtering, being dry, N '-di-tert-butyl thiourea carries out once oxidation, together with piece alkali, catalyst, solvent
It sequentially adds in reaction kettle, is warming up to 60 DEG C, the hypochlorous acid of pre-configured 8~10% concentration of oxidant was dripped off with 1 hour
Sodium solution reacts 2 hours under the conditions of 60~65 DEG C, static 20 minutes, discards lower layer's water phase；
(3) secondary oxidation reaction is carried out, quantitative liquor natrii hypochloritis and catalyst is added dropwise, is reacted 1 hour at 65 DEG C；
(4) plus alkali neutralization washing, branch vibration layer steam solvent, and rectification under vacuum obtains N, N '-di-t-butyl carbodiimide.
Compared with the prior art, the present invention has the following beneficial effects:
Thiourea-uv Method of the present invention produces N, the method for N '-di-t-butyl carbodiimide, production method reaction condition temperature
With, high income, purity is high, post-processing is simple, and process water can be recycled.
Detailed description of the invention
Fig. 1 is Thiourea-uv Method production N of the present invention, the process flow chart of N '-di-t-butyl carbodiimide.
Specific embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
1000Kg water, 135Kg tert-butylamine are added in reaction solution, 85Kg carbon disulfide, temperature control is added dropwise in starting stirring
Between 25 DEG C, insulation reaction 1 hour, 60 DEG C are warming up to, liquid alkaline 120L, hydrogen peroxide 80L, temperature control is added dropwise respectively several times
Between 55 DEG C, insulation reaction 2 hours, cools down, filter, drying obtains N, N '-di-tert-butyl thiourea.
By 100KgN, N '-di-tert-butyl thiourea, 400Kg benzene is added in another reaction kettle, adds 5Kg piece alkali, 6Kg catalysis
Kettle temperature is raised to 60 DEG C by agent polyethylene glycol, and 450Kg sodium hypochlorite is added dropwise, and sodium hypochlorite is the solution of 8~10% mass concentrations,
Oxidant is added in a manner of being added dropwise, and is controlled and dripped off in 1 hour.It is reacted 2 hours under the conditions of 63 DEG C, stands 20 minutes,
Discard lower layer's water phase.
The complete oxidation solution of once oxidation is transferred to secondary oxidation kettle, adds 1Kg catalyst polyethylene glycol, 150Kg chlorine is added dropwise
Sour sodium reacts 1 hour under the conditions of 60-65 DEG C of temperature.
Add 5Kg soda ash, 300Kg water, stir 1 hour, stand, branch vibration layer steams solvent, and rectification under vacuum obtains N, N '-
Di-t-butyl carbodiimide；Yield 93%, 99.4% or more purity.
Embodiment 2
1000Kg water, 135Kg tert-butylamine are added in a kettle, 68Kg carbon disulfide, temperature control is added dropwise in starting stirring
Between 30 DEG C, insulation reaction 1 hour, 60 DEG C are warming up to, liquid alkaline 120L, hydrogen peroxide 80L, temperature control is added dropwise respectively several times
Between 60 DEG C, 2 hours are kept the temperature, is cooled down, is filtered, drying obtains N, N '-di-tert-butyl thiourea.
By 100Kg N, N '-di-tert-butyl thiourea, 400Kg benzene is added in another reaction kettle, adds 5Kg piece alkali, 6Kg catalysis
Kettle temperature is raised to 60 DEG C by agent benzyltriethylammoinium chloride, and 450Kg sodium hypochlorite is added dropwise, and sodium hypochlorite is 8~10% mass concentrations
Solution, oxidant is added in a manner of being added dropwise, and controls and drip off in 1 hour.It reacts 2 hours, stands under the conditions of 65 DEG C
20 minutes, discard lower layer's water phase.
The complete oxidation solution of once oxidation is transferred to secondary oxidation kettle, adds 1Kg catalyst benzyltriethylammoinium chloride, is added dropwise
150Kg sodium hypochlorite reacts 1 hour under the conditions of 60-65 DEG C of temperature.
Add 5Kg soda ash, 300Kg water, stir 1 hour, stand, branch vibration layer steams solvent, and rectification under vacuum obtains N, N '-
Di-t-butyl carbodiimide；Yield 92%, 99.3% or more purity.
Embodiment 3
1000Kg water, 135Kg tert-butylamine are added in reaction solution, 85Kg carbon disulfide, temperature control is added dropwise in starting stirring
Between 35 DEG C, insulation reaction 1 hour, 60 DEG C are warming up to, liquid alkaline 120L, hydrogen peroxide 80L, temperature control is added dropwise respectively several times
Between 65 DEG C, insulation reaction 2 hours, cools down, filter, drying obtains N, N '-di-tert-butyl thiourea.
By 110KgN, N '-di-tert-butyl thiourea, 400Kg benzene is added in another reaction kettle, adds 5Kg piece alkali, 8Kg catalysis
Kettle temperature is raised to 60 DEG C by agent polyethylene glycol, and 450Kg sodium hypochlorite is added dropwise, and sodium hypochlorite is the solution of 8~10% mass concentrations,
Oxidant is added in a manner of being added dropwise, and is controlled and dripped off in 1 hour.It is reacted 2 hours under the conditions of 65 DEG C, stands 20 minutes,
Discard lower layer's water phase.
The complete oxidation solution of once oxidation is transferred to secondary oxidation kettle, adds 1Kg catalyst polyethylene glycol, 150Kg chlorine is added dropwise
Sour sodium reacts 1 hour under the conditions of 60-65 DEG C of temperature.
Add 5Kg soda ash, 300Kg water, stir 1 hour, stand, branch vibration layer steams solvent, and rectification under vacuum obtains N, N '-
Di-t-butyl carbodiimide；Yield 94%, 99.5% or more purity.
Claims (8)
1. a kind of Thiourea-uv Method produces N, the method for N '-di-t-butyl carbodiimide, it is characterised in that: specifically includes the following steps:
(1) N is first synthesized in an aqueous medium with tert-butylamine and carbon disulfide, hydrogen peroxide and liquid is added dropwise in N '-di-tert-butyl thiourea respectively
Alkali removes by-product hydrogen sulfide；
(2) N for preparing step (1), N '-di-tert-butyl thiourea filtered, dry after carry out once oxidation, together with piece alkali,
Catalyst, solvent sequentially add in reaction kettle, are warming up to 60-65 DEG C, and oxidant is added, reacts 2 hours under the conditions of 60~65 DEG C,
Static 20-25min discards lower layer's water phase；
(3) secondary oxidation reaction is carried out, quantitative oxidant and catalyst is added dropwise, is reacted 1 hour at 65 DEG C；
(4) plus alkali neutralization washing, branch vibration layer steam solvent, and rectification under vacuum obtains N, N '-di-t-butyl carbodiimide.
2. Thiourea-uv Method according to claim 1 produces N, the method for N '-di-t-butyl carbodiimide, it is characterised in that: step
Suddenly the mass ratio of tert-butylamine described in (1) and carbon disulfide is 1:0.5-0.9.
3. Thiourea-uv Method according to claim 1 produces N, the method for N '-di-t-butyl carbodiimide, it is characterised in that: step
Suddenly catalyst described in (2) is one or both of polyethylene glycol or benzyltriethylammoinium chloride；Solvent be benzene, toluene or
One of methylene chloride.
4. Thiourea-uv Method according to claim 1 produces N, the method for N '-di-t-butyl carbodiimide, it is characterised in that: step
Suddenly the quality that catalyst described in (2) is added is N, the 3%-8% of N '-di-tert-butyl thiourea quality；The matter of the solvent of addition
Amount is N, 3-6 times of N '-di-tert-butyl thiourea quality.
5. Thiourea-uv Method according to claim 1 produces N, the method for N '-di-t-butyl carbodiimide, it is characterised in that: step
Suddenly oxidant described in (2) and step (3) is the liquor natrii hypochloritis of 8~10% concentration, and oxidant is added in a manner of being added dropwise
Enter, and controls and dripped off in 1 hour.
6. Thiourea-uv Method according to claim 1 produces N, the method for N '-di-t-butyl carbodiimide, it is characterised in that: step
Suddenly once oxidation described in (2), the quality of the oxidant of addition are N, 4-5.5 times of N '-di-tert-butyl thiourea quality.
7. Thiourea-uv Method according to claim 1 produces N, the method for N '-di-t-butyl carbodiimide, it is characterised in that: step
Suddenly secondary oxidation described in (3), the quality of the oxidant of addition are N, 1-3 times of N '-di-tert-butyl thiourea quality.
8. Thiourea-uv Method according to claim 1 produces N, the method for N '-di-t-butyl carbodiimide, it is characterised in that: step
Suddenly catalyst described in (3) is one or both of polyethylene glycol or benzyltriethylammoinium chloride.
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| CN201811180633.XA CN109369459A (en) | 2018-10-09 | 2018-10-09 | Thiourea-uv Method produces N, the method for N '-di-t-butyl carbodiimide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702421A (en) * | 2022-04-15 | 2022-07-05 | 鹤壁中昊新材料科技有限公司 | Preparation method for synthesizing 1, 3-disubstituted symmetric thiourea by taking primary amine as raw material |
Citations (3)
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|---|---|---|---|---|
| JPH08198836A (en) * | 1995-01-26 | 1996-08-06 | Sanshin Chem Ind Co Ltd | Production of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide |
| CN101096349A (en) * | 2006-06-26 | 2008-01-02 | 山东金城医药化工有限公司 | Production technique of N,N'-dicyclo hexylcar bodiimide |
| CN103382168A (en) * | 2013-07-31 | 2013-11-06 | 浙江普康化工有限公司 | Synthetic method for N,N'-diisopropyl carbodiimide |
-
2018
- 2018-10-09 CN CN201811180633.XA patent/CN109369459A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08198836A (en) * | 1995-01-26 | 1996-08-06 | Sanshin Chem Ind Co Ltd | Production of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide |
| CN101096349A (en) * | 2006-06-26 | 2008-01-02 | 山东金城医药化工有限公司 | Production technique of N,N'-dicyclo hexylcar bodiimide |
| CN103382168A (en) * | 2013-07-31 | 2013-11-06 | 浙江普康化工有限公司 | Synthetic method for N,N'-diisopropyl carbodiimide |
Non-Patent Citations (3)
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| 赵丽华: "N,N’-二异丙基碳二亚胺的合成", 《山东化工》 * |
| 连经社等: "《油田化学应用技术》", 30 April 2007, 中国石油大学出版社 * |
| 镇江市农药厂等: "螟铃畏原粉及中间体分析", 《农药》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702421A (en) * | 2022-04-15 | 2022-07-05 | 鹤壁中昊新材料科技有限公司 | Preparation method for synthesizing 1, 3-disubstituted symmetric thiourea by taking primary amine as raw material |
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