CN104447356A - Synthesis method of 3-fluoro-N-dimethyl o-phenylenediamine - Google Patents
Synthesis method of 3-fluoro-N-dimethyl o-phenylenediamine Download PDFInfo
- Publication number
- CN104447356A CN104447356A CN201410633366.2A CN201410633366A CN104447356A CN 104447356 A CN104447356 A CN 104447356A CN 201410633366 A CN201410633366 A CN 201410633366A CN 104447356 A CN104447356 A CN 104447356A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- phenylene diamine
- add
- fluoro
- phenylenediamine
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of 3-fluoro-N-dimethyl o-phenylenediamine. The method comprises the following steps: with ortho-nitroaniline as a raw material, carrying out base catalysis on o-phenylenediamine and diethyl sulfate at the molar ratio of 1 to 2 by virtue of sodium bicarbonate for 2 hours at the pH value of 8 and the reaction temperature of 20-22 DEG C, so as to prepare N-dimethyl o-phenylenediamine; enabling N-dimethyl o-phenylenediamine to fully react with a fluoride solution under the action of a Pt/C catalyst; and washing, carrying out phase splitting and reduced pressure desolventizing, and drying to obtain 3-fluoro-N-dimethyl o-phenylenediamine, wherein the yield reaches over 87%.
Description
Technical field
The present invention relates to a kind of synthetic method of compound, the synthetic method of a kind of 3-fluoro-N-dimethyl O-Phenylene Diamine.
Background technology
O-Phenylene Diamine is as medicine intermediate, and dyestuff intermediate, for the preparation of vat dyes and cationic dyestuff, for the production of the yellowish-brown M of fur, vat scarlet GG, also can be used for manufacturing polymeric amide, urethane and levelling agent.Agricultural chemicals for the synthesis of systemic fungicide, as derosal, thiophanate and thiophanate methyl etc.It is the intermediate of synthesis multiple heterocycles, for oxidation inhibitor processed.O-Phenylene Diamine and derivative thereof can as starting raw materials, form the polynary nitrogen heterocyclic aromatic compound of benzo by thermal response and microwave radiation means and carbonyl compound reaction, and such as benzimidazoles and benzo are mixed nitrogen class etc.
Summary of the invention
The invention provides the synthetic method of the 3-fluoro-N-dimethyl O-Phenylene Diamine that a kind of reaction conditions is simple, non-secondary pollution, by product are few.
For achieving the above object, the synthetic route of 3-of the present invention fluoro-N-dimethyl O-Phenylene Diamine is:
The building-up process of the 3-that the present invention relates to fluoro-N-dimethyl O-Phenylene Diamine comprises the following steps:
1, the synthesis of O-Phenylene Diamine
(1) under the protection of nitrogen and under nickel katalysis, in reactor, add sodium sulfide solution and 197g o-Nitraniline that 78.5g massfraction is 21%, sealing is warming up to 105-110 DEG C, and pressure is upgraded to 1.5-2MPa, stir reduction 4h, be cooled to less than 40 DEG C filtrations;
(2) by filter cake heating and melting, underpressure distillation, collects 150-200 DEG C of cut and is O-Phenylene Diamine.
2, N-dimethyl O-Phenylene Diamine
(1) difference device agitator, prolong, dropping funnel and thermometer on four-hole bottle is, add 202g O-Phenylene Diamine, 30mL ethanol, add 3.6g sodium bicarbonate after stirring and dissolving in batches, make pH remain on about 8 in reaction process;
(2) stir lower control temperature at 6-8 DEG C, slowly add 302g methyl-sulfate, maintain the temperature at 20-22 DEG C after adding and continue reacting by heating 2h, extract with benzene after reacting completely;
(3) be the sodium bicarbonate aqueous solution of 5% and the water washing extraction liquid of 200mL with 150mL massfraction, Anhydrous potassium carbonate is dry, removes extraction agent under reduced pressure, obtains white crystal with sherwood oil recrystallization.
3,3-fluoro-N-dimethyl O-Phenylene Diamine
(1) in the 500mL three-necked bottle that thermometer, electric mixer and dropping funnel are housed, add 78.5gN-dimethyl O-Phenylene Diamine, 20mL fluorine solution, 0.6g massfraction be 0.35 Pt/C make its abundant stirring and dissolving;
(2) control temperature of reaction below 10 DEG C, slowly add 20mL ethanol and pass into nitrogen, at maintaining the temperature at 20-25 DEG C, continue reflection 1-2h;
(3) after reaction terminates, 150g water and 150mL ethyl acetate is added in reaction flask, stir 20-25min, rear phase-splitting, upper organic phase 150g and 150g15% salt acid elution, the organic phase 40g anhydrous sodium sulphate obtained and 15g activated carbon treatment, filter, collect filtrate, at 75-80 DEG C, carry out decompression precipitation, drying, weighs and calculates its productive rate.
Specific embodiments
The building-up process of a kind of 3-fluoro-N-dimethyl O-Phenylene Diamine that the present invention relates to comprises the following steps:
Under the protection of nitrogen and under nickel katalysis, add sodium sulfide solution and 197g o-Nitraniline that 78.5g massfraction is 21% in reactor, sealing is warming up to 105-110 DEG C, and pressure is upgraded to 1.5-2MPa, stirs reduction 4h, is cooled to less than 40 DEG C filtrations; By filter cake heating and melting, underpressure distillation, collects 150-200 DEG C of cut and is O-Phenylene Diamine.On four-hole bottle is, difference device agitator, prolong, dropping funnel and thermometer, add 202g O-Phenylene Diamine, 30mL ethanol, add 3.6g sodium bicarbonate after stirring and dissolving in batches, make pH remain on about 8 in reaction process; Stir lower control temperature at 6-8 DEG C, slowly add 302g methyl-sulfate, maintain the temperature at 20-22 DEG C after adding and continue reacting by heating 2h, extract with benzene after reacting completely; Be the sodium bicarbonate aqueous solution of 5% and the water washing extraction liquid of 200mL with 150mL massfraction, Anhydrous potassium carbonate is dry, removes extraction agent under reduced pressure, obtains white crystal with sherwood oil recrystallization.In the 500mL three-necked bottle that thermometer, electric mixer and dropping funnel are housed, add 78.5gN-dimethyl O-Phenylene Diamine, 20mL fluorine solution, 0.6g massfraction be 0.35 Pt/C make its abundant stirring and dissolving; Control temperature of reaction below 10 DEG C, slowly add 20mL ethanol and pass into nitrogen, at maintaining the temperature at 20-25 DEG C, continue reflection 1-2h; After reaction terminates, 150g water and 150mL ethyl acetate is added in reaction flask, stir 20-25min, rear phase-splitting, upper organic phase 150g and 150g15% salt acid elution, the organic phase 40g anhydrous sodium sulphate obtained and 15g activated carbon treatment, filter, collect filtrate, at 75-80 DEG C, carry out decompression precipitation, drying, weighs and calculates its productive rate.
Example 1
Under the protection of nitrogen and under nickel katalysis, add sodium sulfide solution and 197g o-Nitraniline that 78.5g massfraction is 21% in reactor, sealing is warming up to 105 DEG C, and pressure is upgraded to 1.5MPa, stirs reduction 4h, is cooled to less than 40 DEG C filtrations; By filter cake heating and melting, underpressure distillation, collects 150 DEG C of cuts and is O-Phenylene Diamine.On four-hole bottle is, difference device agitator, prolong, dropping funnel and thermometer, add 202g O-Phenylene Diamine, 30mL ethanol, add 3.6g sodium bicarbonate after stirring and dissolving in batches, make pH remain on about 8 in reaction process; Stir lower control temperature at 6 DEG C, slowly add 302g methyl-sulfate, maintain the temperature at 20 DEG C after adding and continue reacting by heating 2h, extract with benzene after reacting completely; Be the sodium bicarbonate aqueous solution of 5% and the water washing extraction liquid of 200mL with 150mL massfraction, Anhydrous potassium carbonate is dry, removes extraction agent under reduced pressure, obtains white crystal with sherwood oil recrystallization.In the 500mL three-necked bottle that thermometer, electric mixer and dropping funnel are housed, add 78.5gN-dimethyl O-Phenylene Diamine, 20mL fluorine solution, 0.6g massfraction be 0.35 Pt/C make its abundant stirring and dissolving; Control temperature of reaction below 10 DEG C, slowly add 20mL ethanol and pass into nitrogen, at maintaining the temperature at 20 DEG C, continue reflection 1h; After reaction terminates, 150g water and 150mL ethyl acetate is added in reaction flask, stir 20min, rear phase-splitting, upper organic phase 150g and 150g15% salt acid elution, the organic phase 40g anhydrous sodium sulphate obtained and 15g activated carbon treatment, filter, collect filtrate, at 75 DEG C, carry out decompression precipitation, drying, weighing and calculating its productive rate is 87.6%.
Example 2
Under the protection of nitrogen and under nickel katalysis, add sodium sulfide solution and 197g o-Nitraniline that 78.5g massfraction is 21% in reactor, sealing is warming up to 108 DEG C, and pressure is upgraded to 1.8MPa, stirs reduction 4h, is cooled to less than 40 DEG C filtrations; By filter cake heating and melting, underpressure distillation, collects 180 DEG C of cuts and is O-Phenylene Diamine.On four-hole bottle is, difference device agitator, prolong, dropping funnel and thermometer, add 202g O-Phenylene Diamine, 30mL ethanol, add 3.6g sodium bicarbonate after stirring and dissolving in batches, make pH remain on about 8 in reaction process; Stir lower control temperature at 7 DEG C, slowly add 302g methyl-sulfate, maintain the temperature at 21 DEG C after adding and continue reacting by heating 2h, extract with benzene after reacting completely; Be the sodium bicarbonate aqueous solution of 5% and the water washing extraction liquid of 200mL with 150mL massfraction, Anhydrous potassium carbonate is dry, removes extraction agent under reduced pressure, obtains white crystal with sherwood oil recrystallization.In the 500mL three-necked bottle that thermometer, electric mixer and dropping funnel are housed, add 78.5gN-dimethyl O-Phenylene Diamine, 20mL fluorine solution, 0.6g massfraction be 0.35 Pt/C make its abundant stirring and dissolving; Control temperature of reaction below 10 DEG C, slowly add 20mL ethanol and pass into nitrogen, at maintaining the temperature at 20-25 DEG C, continue reflection 1.5h; After reaction terminates, 150g water and 150mL ethyl acetate is added in reaction flask, stir 23min, rear phase-splitting, upper organic phase 150g and 150g15% salt acid elution, the organic phase 40g anhydrous sodium sulphate obtained and 15g activated carbon treatment, filter, collect filtrate, at 78 DEG C, carry out decompression precipitation, drying, weighing and calculating its productive rate is more than 87%.
Example 3
Under the protection of nitrogen and under nickel katalysis, add sodium sulfide solution and 197g o-Nitraniline that 78.5g massfraction is 21% in reactor, sealing is warming up to 110 DEG C, and pressure is upgraded to 2MPa, stirs reduction 4h, is cooled to less than 40 DEG C filtrations; By filter cake heating and melting, underpressure distillation, collects 200 DEG C of cuts and is O-Phenylene Diamine.On four-hole bottle is, difference device agitator, prolong, dropping funnel and thermometer, add 202g O-Phenylene Diamine, 30mL ethanol, add 3.6g sodium bicarbonate after stirring and dissolving in batches, make pH remain on about 8 in reaction process; Stir lower control temperature at 8 DEG C, slowly add 302g methyl-sulfate, maintain the temperature at 22 DEG C after adding and continue reacting by heating 2h, extract with benzene after reacting completely; Be the sodium bicarbonate aqueous solution of 5% and the water washing extraction liquid of 200mL with 150mL massfraction, Anhydrous potassium carbonate is dry, removes extraction agent under reduced pressure, obtains white crystal with sherwood oil recrystallization.In the 500mL three-necked bottle that thermometer, electric mixer and dropping funnel are housed, add 78.5gN-dimethyl O-Phenylene Diamine, 20mL fluorine solution, 0.6g massfraction be 0.35 Pt/C make its abundant stirring and dissolving; Control temperature of reaction below 10 DEG C, slowly add 20mL ethanol and pass into nitrogen, at maintaining the temperature at 25 DEG C, continue reflection 1-2h; After reaction terminates, 150g water and 150mL ethyl acetate is added in reaction flask, stir 25min, rear phase-splitting, upper organic phase 150g and 150g15% salt acid elution, the organic phase 40g anhydrous sodium sulphate obtained and 15g activated carbon treatment, filter, collect filtrate, at 80 DEG C, carry out decompression precipitation, drying, weighing and calculating its productive rate is more than 87%.
Claims (3)
1. a synthetic method for 3-fluoro-N-dimethyl O-Phenylene Diamine, is characterized in that the synthesis of O-Phenylene Diamine:
(1) under the protection of nitrogen and under nickel katalysis, in reactor, add sodium sulfide solution and 197g o-Nitraniline that 78.5g massfraction is 21%, sealing is warming up to 105-110 DEG C, and pressure is upgraded to 1.5-2MPa, stir reduction 4h, be cooled to less than 40 DEG C filtrations;
(2) by filter cake heating and melting, underpressure distillation, collects 150-200 DEG C of cut and is O-Phenylene Diamine.
2. the synthetic method of a kind of 3-fluoro-N-dimethyl O-Phenylene Diamine according to claim 1, is characterized in that N-dimethyl O-Phenylene Diamine:
(1) difference device agitator, prolong, dropping funnel and thermometer on four-hole bottle is, add 202g O-Phenylene Diamine, 30mL ethanol, add 3.6g sodium bicarbonate after stirring and dissolving in batches, make pH remain on about 8 in reaction process;
(2) stir lower control temperature at 6-8 DEG C, slowly add 302g methyl-sulfate, maintain the temperature at 20-22 DEG C after adding and continue reacting by heating 2h, extract with benzene after reacting completely;
(3) be the sodium bicarbonate aqueous solution of 5% and the water washing extraction liquid of 200mL with 150mL massfraction, Anhydrous potassium carbonate is dry, removes extraction agent under reduced pressure, obtains white crystal with sherwood oil recrystallization.
3. the synthetic method of a kind of 3-fluoro-N-dimethyl O-Phenylene Diamine according to claim 1, is characterized in that:
(1) in the 500mL three-necked bottle that thermometer, electric mixer and dropping funnel are housed, add 78.5gN-dimethyl O-Phenylene Diamine, 20mL fluorine solution, 0.6g massfraction be 0.35 Pt/C make its abundant stirring and dissolving;
(2) control temperature of reaction below 10 DEG C, slowly add 20mL ethanol and pass into nitrogen, at maintaining the temperature at 20-25 DEG C, continue reflection 1-2h;
(3) after reaction terminates, 150g water and 150mL ethyl acetate is added in reaction flask, stir 20-25min, rear phase-splitting, upper organic phase 150g and 150g15% salt acid elution, the organic phase 40g anhydrous sodium sulphate obtained and 15g activated carbon treatment, filter, collect filtrate, at 75-80 DEG C, carry out decompression precipitation, drying, weighs and calculates its productive rate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410633366.2A CN104447356B (en) | 2014-11-11 | 2014-11-11 | A kind of synthetic method of the fluoro-N-dimethyl o-phenylenediamine of 3- |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410633366.2A CN104447356B (en) | 2014-11-11 | 2014-11-11 | A kind of synthetic method of the fluoro-N-dimethyl o-phenylenediamine of 3- |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104447356A true CN104447356A (en) | 2015-03-25 |
| CN104447356B CN104447356B (en) | 2016-07-06 |
Family
ID=52894193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410633366.2A Active CN104447356B (en) | 2014-11-11 | 2014-11-11 | A kind of synthetic method of the fluoro-N-dimethyl o-phenylenediamine of 3- |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104447356B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169853A (en) * | 1978-02-06 | 1979-10-02 | Texaco Development Corporation | Homogeneous ruthenium catalysts useful in the reduction of ortho-substituted nitroaromatics to amines |
| US4423247A (en) * | 1976-04-24 | 1983-12-27 | Basf Aktiengesellschaft | Manufacture of aralkylarylamines and alkylarylamines |
| CN102276482A (en) * | 2011-04-11 | 2011-12-14 | 常州大学 | Preparation method of 2-methoxyl-5-bromaniline |
| CN102633654A (en) * | 2011-03-17 | 2012-08-15 | 江苏康恒化工有限公司 | O-phenylenediamine preparation process by means of hydrogenization with nano nickel serving as catalyst |
| CN102936223A (en) * | 2012-11-02 | 2013-02-20 | 江苏中丹药物研究有限公司 | Synthesis method and purification method of 5-iodo-2-methylbenzimidazole |
-
2014
- 2014-11-11 CN CN201410633366.2A patent/CN104447356B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4423247A (en) * | 1976-04-24 | 1983-12-27 | Basf Aktiengesellschaft | Manufacture of aralkylarylamines and alkylarylamines |
| US4169853A (en) * | 1978-02-06 | 1979-10-02 | Texaco Development Corporation | Homogeneous ruthenium catalysts useful in the reduction of ortho-substituted nitroaromatics to amines |
| CN102633654A (en) * | 2011-03-17 | 2012-08-15 | 江苏康恒化工有限公司 | O-phenylenediamine preparation process by means of hydrogenization with nano nickel serving as catalyst |
| CN102276482A (en) * | 2011-04-11 | 2011-12-14 | 常州大学 | Preparation method of 2-methoxyl-5-bromaniline |
| CN102936223A (en) * | 2012-11-02 | 2013-02-20 | 江苏中丹药物研究有限公司 | Synthesis method and purification method of 5-iodo-2-methylbenzimidazole |
Non-Patent Citations (1)
| Title |
|---|
| 曹艳萍: "N,N′-二甲基邻苯二胺的合成研究", 《延安大学学报(自然科学版)》, no. 02, 30 June 2003 (2003-06-30) * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104447356B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101891606B (en) | New method for synthesizing rhodium caprylate (II) | |
| CN103880762B (en) | A kind of preparation method of 1,2,3-triazole compound | |
| CN103965125A (en) | Synthetic method of 3,3'-binitro-5,5'-di-1,2,4-triazole | |
| CN102816077A (en) | Application of urotropine as catalyst in aminomethylbenzoic acid synthesis | |
| CN103113240B (en) | Process for directly synthesizing p-aminophenol through hydrogenation of nitrobenzene | |
| CN105330560A (en) | Enzalutamide intermediate preparation method | |
| CN104447356A (en) | Synthesis method of 3-fluoro-N-dimethyl o-phenylenediamine | |
| CN104151236A (en) | Method for efficiently synthesizing quinoline | |
| CN103709045A (en) | Preparation method of 4-chlorine-3-trifluoromethyl aniline hydrochloride | |
| CN107501338B (en) | Preparation method of 2, 6-diaminopyridine condensed 4-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| CN104370830A (en) | Synthetic method of 5-trifluoromethyl uracil | |
| CN103319417B (en) | Method for preparing triclabendazole sulfoxide | |
| CN106892828A (en) | A kind of paranitroanisole Hydrogenation for paraphenetidine method | |
| CN106831549B (en) | A kind of method of asymmetric synthesis of Claritin carbinoxamine | |
| CN102532010B (en) | Preparation method of 2-chloro-3-aminopyridine | |
| CN103664766A (en) | Preparation method of 2-aminopyridine-4-methyl alcohol | |
| CN102558068A (en) | Water-phase synthetic benzimidazole compound and crystallization method thereof | |
| CN105924401A (en) | Maleic hydrazide synthetic process | |
| CN105562070A (en) | Modified MoS2-Me/HZSM-5 catalyst preparation method | |
| CN105481740A (en) | Method for preparing isothiocyano methyl formate | |
| CN104402830A (en) | Synthesis method of 2-chloropyrimidine | |
| CN105218436B (en) | A method of preparing 4- Chloro-2-Pyridyle methyl formate | |
| CN113968803B (en) | Method for synthesizing 2, 6-difluoro-3-propyl sulfonamide benzoic acid | |
| CN105481792A (en) | Synthetic method with respect to pramipexole impurity C | |
| CN107698503A (en) | A kind of preparation method of 8 fluorine quinoline and the preparation method of the fluorine quinoline of 3 iodine 8 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201230 Address after: Room 2211, Jinning Road, Linghua District, Shandong Province Patentee after: Jining xinruida Information Technology Co., Ltd Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
|
| TR01 | Transfer of patent right |