CN1962630A - N'-dicyclohexyl thiourea preparation method - Google Patents
N'-dicyclohexyl thiourea preparation method Download PDFInfo
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- CN1962630A CN1962630A CN 200610154719 CN200610154719A CN1962630A CN 1962630 A CN1962630 A CN 1962630A CN 200610154719 CN200610154719 CN 200610154719 CN 200610154719 A CN200610154719 A CN 200610154719A CN 1962630 A CN1962630 A CN 1962630A
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- CN
- China
- Prior art keywords
- dicyclohexyl thiourea
- thiocarbamide
- hexahydroaniline
- preparation
- dicyclohexyl
- 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.)
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- 238000002360 preparation method Methods 0.000 title claims description 13
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 34
- KAJICSGLHKRDLN-UHFFFAOYSA-N 1,3-dicyclohexylthiourea Chemical compound C1CCCCC1NC(=S)NC1CCCCC1 KAJICSGLHKRDLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 19
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 abstract 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 229940043279 diisopropylamine Drugs 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- GRHBQAYDJPGGLF-UHFFFAOYSA-N isothiocyanic acid Chemical compound N=C=S GRHBQAYDJPGGLF-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparing method of N, N'-dicyclohexyl thiourea, which comprises the following steps: adopting water as reacting solvent and 1-10% PEG-400 as catalyst; reacting thiourea and diisopropylamine with molar rate at 0.4-0.6: 1 under normal pressure to reflux for 16-36h; filtering; washing; separating to obtain the product.
Description
Technical field
The present invention relates to the thiocarbamide synthetic method, relate in particular to a kind of N, the preparation method of N '-dicyclohexyl thiourea.
Background technology
N, N '-dicyclohexyl thiourea are preparation N, a kind of important intermediate of N '-dicyclohexylcarbodiimide (DCC).N, N '-dicyclohexylcarbodiimide (DCC) are the low temperature dewatering agent of compounds such as industry and laboratory synthetic aldehyde commonly used, ketone, amino acid, acid anhydrides, ester, are widely used in fine chemistry industry industries such as medicine, agricultural chemicals; Industrial general by aqueous sodium hypochlorite solution oxidation N, N '-dicyclohexyl thiourea obtains.Therefore how more efficiently and greenly to synthesize N, N '-dicyclohexyl thiourea receives people's huge concern.Many methods have been reported N, the preparation method of N '-dicyclohexyl thiourea.Wherein, a kind of directly preparation N of present industrial use, the method for N '-dicyclohexyl thiourea is the synthetic method of alkali or acid catalysis hexahydroaniline and dithiocarbonic anhydride.For example, (1) document Synthetic Communications, 27 (13), 2255-2260; 1997 have reported trolamine catalysis hexahydroaniline and carbon disulphide manufacture N, the method for N '-dicyclohexyl thiourea; (2) document Journal of Organic Chemistry, 64 (3), 1029-1032; 1999 have described zinc oxide and alchlor concerted catalysis hexahydroaniline and carbon disulphide manufacture N, the reaction of N '-dicyclohexyl thiourea; (3) document Synthesis, (11), 1569-1574; 2000 have reported that hexahydroaniline and isothiocyanic acid nak response prepare N, the another kind of method of N '-dicyclohexyl thiourea.Yet catalysis hexahydroaniline and dithiocarbonic anhydride prepared in reaction N, N '-dicyclohexyl thiourea often need the adding of careful control dithiocarbonic anhydride, take place to dash material to prevent lower boiling, incendive dithiocarbonic anhydride, even combustion explosion etc.In addition, use this method and also can produce by product-hypertoxic gas vulcanization hydrogen, this is in the laboratory or abnormally dangerous in industrial enforcement, easily toxic gas leakage takes place and produces very big potential safety hazard.Moreover, in the preparation method who has reported, have many experimentations to relate to strong acid or highly basic condition, expensive variety of problems such as reagent, low-yield, aftertreatment complexity and long reaction time.Thereby, under condition gentleness, eco-friendly, solving N efficiently, the synthetic of N '-dicyclohexyl thiourea is very important and urgent.
Summary of the invention
The purpose of this invention is to provide a kind of N, the preparation method of N '-dicyclohexyl thiourea.
It is to be reaction solvent with water, is catalyzer with PEG-400, and thiocarbamide and hexahydroaniline be atmospheric pressure reflux reaction 16～36 hours, after filtration, washing, separates obtaining N, N '-dicyclohexyl thiourea, and the molar equivalent ratio of thiocarbamide and hexahydroaniline is 0.4～0.6: 1; The consumption of catalyst P EG-400 is 1～10% molar equivalent of thiocarbamide, and reaction formula is:
The described reaction times is preferably 20～30 hours.The molar equivalent ratio of thiocarbamide and hexahydroaniline is preferably 0.45～0.55: 1; The consumption of catalyst P EG-400 is preferably 3～8% molar equivalents of thiocarbamide.
The present invention compares with existing synthetic method, has the following advantages:
1) reaction conditions gentleness;
2) use cheap PEG-400 to make catalyzer, reaction solvent and catalyzer can recycle;
3) feed intake and aftertreatment all very simple, pollute for a short time, be easy to realize industrialized production.
Embodiment
N, the molecular formula of N '-dicyclohexyl thiourea is:
N, the novel preparation method's of N '-dicyclohexyl thiourea concrete reactions steps is as follows:
With water is reaction solvent, is catalyzer with PEG-400, and thiocarbamide and hexahydroaniline be atmospheric pressure reflux reaction 16～36 hours, after filtration, washing, separates obtaining high yield, highly purified N, N '-dicyclohexyl thiourea; Reaction solvent and catalyzer can recycle.Wherein the molar equivalent ratio of thiocarbamide and hexahydroaniline is 0.4～0.6: 1; The consumption of catalyst P EG-400 is 1～10% molar equivalent of thiocarbamide.20～30 hours recommendation response time; Recommending the molar equivalent ratio of thiocarbamide and hexahydroaniline is 0.45～0.55: 1, and the override ratio is 0.5: 1; Recommending the consumption of catalyst P EG-400 is 3～8% molar equivalents of thiocarbamide, and override is 4% molar equivalent.
Following examples will help to understand the present invention, but be not limited to content of the present invention:
Embodiment 1
10 mmole thiocarbamides, 20 mmole hexahydroaniline and 0.4 mmole PEG-400 are blended in 20 ml waters, normal pressure heating reflux reaction 16 hours, finish reaction, product is separated out in cooling, filters (filtrate recovery), washes with water, drying obtains N, N '-dicyclohexyl thiourea is 2.1 grams, productive rate 80%, 181～182 ℃ of fusing points.
Embodiment 2
10 mmole thiocarbamides and 20 mmole hexahydroaniline are blended in the filtrate that recovery obtains among the embodiment 1, normal pressure heating reflux reaction 36 hours, finish reaction, product is separated out in cooling, filters (filtrate recovery), washes with water, drying obtains N, N '-dicyclohexyl thiourea is 2.2 grams, productive rate 83%, 180～182 ℃ of fusing points.
Embodiment 3
12 mmole thiocarbamides, 20 mmole hexahydroaniline and 0.12 mmole PEG-400 are blended in 18 ml waters, normal pressure heating reflux reaction 24 hours, finish reaction, product is separated out in cooling, filters (filtrate recovery), washes with water, drying obtains N, N '-dicyclohexyl thiourea is 2.3 grams, productive rate 86%, 178～181 ℃ of fusing points.
Embodiment 4
12 mmole thiocarbamides, 20 mmole hexahydroaniline and 1.2 mmole PEG-400 are blended in 18 ml waters, normal pressure heating reflux reaction 24 hours, finish reaction, product is separated out in cooling, filters (filtrate recovery), washes with water, drying obtains N, N '-dicyclohexyl thiourea is 2.2 grams, productive rate 82%, 178～181 ℃ of fusing points.
Embodiment 5
8 mmole thiocarbamides, 20 mmole hexahydroaniline and 0.12 mmole PEG-400 are blended in 18 ml waters, normal pressure heating reflux reaction 28 hours, finish reaction, product is separated out in cooling, filters (filtrate recovery), washes with water, drying obtains N, N '-dicyclohexyl thiourea is 2.05 grams, productive rate 85%, 178～181 ℃ of fusing points.
Claims (4)
1. N, the preparation method of N '-dicyclohexyl thiourea, it is characterized in that it is is reaction solvent with water, with PEG-400 is catalyzer, thiocarbamide and hexahydroaniline be atmospheric pressure reflux reaction 16～36 hours, after filtration, washing, separates obtaining N, N '-dicyclohexyl thiourea, the molar equivalent ratio of thiocarbamide and hexahydroaniline is 0.4～0.6: 1; The consumption of catalyst P EG-400 is 1～10% molar equivalent of thiocarbamide, and reaction formula is:
2. a kind of N according to claim 1, the preparation method of N '-dicyclohexyl thiourea is characterized in that the described reaction times is 20～30 hours.
3. a kind of N according to claim 1, the preparation method of N '-dicyclohexyl thiourea, the molar equivalent ratio that it is characterized in that described thiocarbamide and hexahydroaniline is 0.45～0.55: 1.
4. a kind of N according to claim 1, the preparation method of N '-dicyclohexyl thiourea, the consumption that it is characterized in that described catalyst P EG-400 is 3～8% molar equivalents of thiocarbamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610154719 CN1962630A (en) | 2006-11-21 | 2006-11-21 | N'-dicyclohexyl thiourea preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610154719 CN1962630A (en) | 2006-11-21 | 2006-11-21 | N'-dicyclohexyl thiourea preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1962630A true CN1962630A (en) | 2007-05-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610154719 Pending CN1962630A (en) | 2006-11-21 | 2006-11-21 | N'-dicyclohexyl thiourea preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1962630A (en) |
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2006
- 2006-11-21 CN CN 200610154719 patent/CN1962630A/en active Pending
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