CN100336804C - Water phase high pressure method for preparing N,N'-di (m-tolyl) urea - Google Patents
Water phase high pressure method for preparing N,N'-di (m-tolyl) urea Download PDFInfo
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- CN100336804C CN100336804C CNB200610051603XA CN200610051603A CN100336804C CN 100336804 C CN100336804 C CN 100336804C CN B200610051603X A CNB200610051603X A CN B200610051603XA CN 200610051603 A CN200610051603 A CN 200610051603A CN 100336804 C CN100336804 C CN 100336804C
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- Prior art keywords
- urea
- tolyl
- aminotoluene
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- preparing
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 15
- UPUMJVLEADOLKF-UHFFFAOYSA-N 1,3-bis(3-methylphenyl)urea Chemical compound CC1=CC=CC(NC(=O)NC=2C=C(C)C=CC=2)=C1 UPUMJVLEADOLKF-UHFFFAOYSA-N 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 8
- 239000011707 mineral Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 3
- BLSVCHHBHKGCSQ-UHFFFAOYSA-N (2-methylphenyl)urea Chemical compound CC1=CC=CC=C1NC(N)=O BLSVCHHBHKGCSQ-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 abstract 8
- 239000000463 material Substances 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960005081 diclofenamide Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a water-phase high-pressure preparation method for N, N'-di (m-tolyl) urea. The method comprises the following steps: 1) dropping mineral acid for a salt forming reaction after mixing m-toluidine and water, adding urea after dropping and then stirring: the equivalent ratio of the m-toluidine to the inorganic acid is 1:0.95 to 1.05, the molar ratio of the m-toluidine to urea is 1:0.5 to 1, and the temperature of the salt forming reaction is from 0 to 80 DEG C; 2) adding the reaction liquid into a high-pressure reaction vessel for 1 to 5 hours by ranging the pressure of the high-pressure reaction vessel from 2 to 10 atm, relieving pressure, discharging, centrifuging and washing with water. The method has the advantages of cheap material price, extensive material source, simple reaction, high total yield, low production cost, etc., and the method is suitable for industrial production. The mol yield coefficient measured by m-toluidine can reach more than 90% of a theoretical quantity, and the mol yield coefficient of the mother liquid used repeatedly after reaction can reach more than 95 %.
Description
Technical field
The present invention relates to the preparation method of symmetrical diphenyl urea, relate in particular to a kind of N, the water phase high pressure method for preparing of N '-two (tolyl) urea.
Background technology
N, N '-two (tolyl) urea is a kind of rocket fuel stablizer, also is a kind of polymeric additive.Its another purposes is through oversulfonate, chlorination, and hydrolysis generates 3-methyl-2 at last, the 6-dichlorphenamide bulk powder; This substituting group aniline is a kind of important pesticide intermediate, so research N, N '-two (tolyl) urea synthetic has industrial meaning.
N, N '-two (tolyl) urea only has one piece of indian patent report (IN 161612) by meta-aminotoluene and urea condensation preparation, wherein uses amylalcohol and makes solvent, 110 °～145 ℃ reactions down; The amylalcohol price is more expensive, and the trouble of recovery is arranged again.Other N, N '-two (tolyl) urea synthetic method relates to isocyanic ester etc., and synthetic cost is all very high, and is industrial all inadvisable.
Summary of the invention
The objective of the invention is provides a kind of easy N in order to overcome the deficiencies in the prior art, the water phase high pressure method for preparing of N '-two (tolyl) urea.
Method steps is as follows
1) with meta-aminotoluene with after water mixes, the dropping inorganic acid salt-forming reaction drips off the back and adds urea, stirs; The equivalence ratio of meta-aminotoluene and mineral acid is 1: 0.95～1.05, and the mol ratio of meta-aminotoluene and urea is 1: 0.5～1, and the salt-forming reaction temperature is 0～80 ℃;
2) above-mentioned reaction solution is joined in the autoclave, autoclave pressure to 2～10atm keeps pressure release after 1-5 hour, discharging, and centrifugal, water washing gets final product.
Described centrifugal, water washing mother liquor mixes with meta-aminotoluene in the step 1) and continues salt-forming reaction.
The equivalence ratio of meta-aminotoluene and mineral acid is 1: 1.Mineral acid is sulfuric acid, hydrochloric acid or phosphoric acid.The mol ratio of meta-aminotoluene and urea is 1: 0.5～0.55.Autoclave pressure is 3～6atm.
Advantage of the present invention is:
1) raw material is cheap and easy to get, meta-aminotoluene, and these several raw materials of mineral acid and urea all compare cheaply;
2) yield is higher, and the reaction molar yield can reach more than 90%; Reaction back mother liquor is through applying mechanically, and molar yield can reach more than 95%;
3) reaction is simple, is suitable for suitability for industrialized production.
Embodiment
Reaction formula of the present invention is as follows:
Embodiment 1
1) with meta-aminotoluene with after water mixes, drip the sulfuric acid salt-forming reaction, drip off the back and add urea, stir; Meta-aminotoluene and vitriolic equivalence ratio are 1: 0.95, and the mol ratio of meta-aminotoluene and urea is 1: 0.5, and the salt-forming reaction temperature is 0 ℃;
2) above-mentioned reaction solution is joined in the autoclave, autoclave pressure keeps pressure release after 5 hours to 2atm, and discharging is centrifugal, and hot wash gets finished product N, N '-two (tolyl) urea, and molar yield is 90%, in meta-aminotoluene.
Embodiment 2
1) with meta-aminotoluene with after water mixes, the dripping hydrochloric acid salt-forming reaction drips off the back and adds urea, stirs; The equivalence ratio of meta-aminotoluene and hydrochloric acid is 1: 1.05, and the mol ratio of meta-aminotoluene and urea is 1: 1, and the salt-forming reaction temperature is 80 ℃;
2) above-mentioned reaction solution is joined in the autoclave, autoclave pressure keeps pressure release after 1 hour to 10atm, and discharging is centrifugal, and hot wash gets finished product N, N '-two (tolyl) urea, and molar yield is 91%, in meta-aminotoluene.
Embodiment 3
1) with meta-aminotoluene with after water mixes, drip the phosphoric acid salt-forming reaction, drip off the back and add urea, stir; The equivalence ratio of meta-aminotoluene and phosphoric acid is 1: 1, and the mol ratio of meta-aminotoluene and urea is 1: 0.5, and the salt-forming reaction temperature is 0 ℃;
2) above-mentioned reaction solution is joined in the autoclave, autoclave pressure keeps pressure release after 2 hours to 4atm, and discharging is centrifugal, and hot wash gets finished product N, N '-two (tolyl) urea, and molar yield is 92%, in meta-aminotoluene.
Embodiment 4
1) with meta-aminotoluene with after water mixes, the dripping hydrochloric acid salt-forming reaction drips off the back and adds urea, stirs; The equivalence ratio of meta-aminotoluene and hydrochloric acid is 1: 1, and the mol ratio of meta-aminotoluene and urea is 1: 0.55, and the salt-forming reaction temperature is 40 ℃;
2) above-mentioned reaction solution is joined in the autoclave, autoclave pressure keeps pressure release after 1 hour to 6atm, and discharging is centrifugal, and hot wash gets finished product N, N '-two (tolyl) urea, and molar yield is 93%, in meta-aminotoluene.
Embodiment 5
1) with reacted centrifugal and water that washing is come out among the embodiment 1 with after meta-aminotoluene mixes, drip the sulfuric acid salt-forming reaction, drip off back adding urea, stirring; Meta-aminotoluene and vitriolic equivalence ratio are 1: 0.95, and the mol ratio of meta-aminotoluene and urea is 1: 0.5, and the salt-forming reaction temperature is 0 ℃;
2) above-mentioned reaction solution is joined in the autoclave, autoclave pressure keeps pressure release after 5 hours to 5atm, and discharging is centrifugal, and hot wash gets finished product N, N '-two (tolyl) urea, and molar yield is 95.5%, in meta-aminotoluene.
Claims (6)
1. N, the water phase high pressure method for preparing of N '-two (tolyl) urea, it is characterized in that: method steps is as follows
1) with meta-aminotoluene with after water mixes, the dropping inorganic acid salt-forming reaction drips off the back and adds urea, stirs; The equivalence ratio of meta-aminotoluene and mineral acid is 1: 0.95～1.05, and the mol ratio of meta-aminotoluene and urea is 1: 0.5～1, and the salt-forming reaction temperature is 0～80 ℃;
2) above-mentioned reaction solution is joined in the autoclave, autoclave pressure to 2～10atm keeps pressure release after 1-5 hour, discharging, and centrifugal, water washing gets final product.
2. a kind of N according to claim 1, the water phase high pressure method for preparing of N '-two (tolyl) urea is characterized in that: described centrifugal, water washing mother liquor mixes with meta-aminotoluene in the step 1) and continues salt-forming reaction.
3. a kind of N according to claim 1, the water phase high pressure method for preparing of N '-two (tolyl) urea, it is characterized in that: the equivalence ratio of described meta-aminotoluene and mineral acid is 1: 1.
4. a kind of N according to claim 1, the water phase high pressure method for preparing of N '-two (tolyl) urea, it is characterized in that: described mineral acid is sulfuric acid, hydrochloric acid or phosphoric acid.
5. a kind of N according to claim 1, the water phase high pressure method for preparing of N '-two (tolyl) urea, it is characterized in that: the mol ratio of described meta-aminotoluene and urea is 1: 0.5～0.55.
6. a kind of N according to claim 1, the water phase high pressure method for preparing of N '-two (tolyl) urea, it is characterized in that: autoclave pressure is 3～6atm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610051603XA CN100336804C (en) | 2006-05-24 | 2006-05-24 | Water phase high pressure method for preparing N,N'-di (m-tolyl) urea |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610051603XA CN100336804C (en) | 2006-05-24 | 2006-05-24 | Water phase high pressure method for preparing N,N'-di (m-tolyl) urea |
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| CN1850793A CN1850793A (en) | 2006-10-25 |
| CN100336804C true CN100336804C (en) | 2007-09-12 |
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| CNB200610051603XA Expired - Fee Related CN100336804C (en) | 2006-05-24 | 2006-05-24 | Water phase high pressure method for preparing N,N'-di (m-tolyl) urea |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250139B (en) * | 2008-03-25 | 2010-09-15 | 浙江大学 | Method for synthesizing 3,3'-dimethoxy diphenylurea |
| CN101628882B (en) * | 2009-08-05 | 2013-07-03 | 池州万维化工有限公司 | Production process of N, N'-2 (2,6-2-phenyl-isopropyl) carbodiimide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN161612B (en) * | 1984-07-04 | 1988-01-02 | Council Scient Ind Res | |
| CN1033179A (en) * | 1988-09-23 | 1989-05-31 | 北京农业大学 | Directly synthetic 4,4 '-method of dinitro diphenyl urea |
| EP0437258A1 (en) * | 1990-01-12 | 1991-07-17 | Nkk Corporation | Method of manufacturing aromatic urethane |
| SU1736140A1 (en) * | 1990-04-04 | 1996-04-20 | Государственный научно-исследовательский и проектный институт карбамида и продуктов органического синтеза с опытным заводом | Process for preparing phenylurea |
-
2006
- 2006-05-24 CN CNB200610051603XA patent/CN100336804C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN161612B (en) * | 1984-07-04 | 1988-01-02 | Council Scient Ind Res | |
| CN1033179A (en) * | 1988-09-23 | 1989-05-31 | 北京农业大学 | Directly synthetic 4,4 '-method of dinitro diphenyl urea |
| EP0437258A1 (en) * | 1990-01-12 | 1991-07-17 | Nkk Corporation | Method of manufacturing aromatic urethane |
| SU1736140A1 (en) * | 1990-04-04 | 1996-04-20 | Государственный научно-исследовательский и проектный институт карбамида и продуктов органического синтеза с опытным заводом | Process for preparing phenylurea |
Non-Patent Citations (1)
| Title |
|---|
| CeCl3.7H2O-KI-catalyzed, environmentally friendly synthesisof N,N'-disubstituted ureas in water under microwaveirradiation Li Zheng等人,SYNTHETIC COMMUNICATIONS,Vol.vol.35 No.no.17 2005 * |
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