CN1266052A - Process for preparing tetranitro-diphenylamine from N-carbonylaniline - Google Patents
Process for preparing tetranitro-diphenylamine from N-carbonylaniline Download PDFInfo
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- CN1266052A CN1266052A CN99122890A CN99122890A CN1266052A CN 1266052 A CN1266052 A CN 1266052A CN 99122890 A CN99122890 A CN 99122890A CN 99122890 A CN99122890 A CN 99122890A CN 1266052 A CN1266052 A CN 1266052A
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- reaction
- mirbane
- oil
- alkali
- hydroxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
Abstract
Disclosed herein is a process for preparing 4-nitrodiphenylamine using a nucleophilic aromatic substitution for hydrogen, comprising reacting carbanilide and nitrobenzene in a polar organic solvent in the presence of a base and a drying agent at a temperature of from 20 DEG C to 150 DEG C. This process is advantageous in that relatively cheap alkaline salts are used, and 4-nitrodiphenylamine can be produced at high selectivity and conversion without generating the environmentally hazardous corrosive reaction byproduct.
Description
The present invention relates to a kind ofly, under the existence as sodium hydroxide and polar organic solvent,, prepare the method for 4 nitrodiphenyl amine (below be called " 4-NDPA ") with highly selective and transformation efficiency by the reaction of carbanilide and oil of mirbane at alkali.Can be used as the raw material for preparing 4-aminodiphenylamine (below be called " 4-ADPA ", it is a kind of intermediate of antioxidant) by conventional hydrogenation according to the 4 nitrodiphenyl amine of the present invention preparation.
The method that is used to prepare present commercially available 4-ADPA mainly is divided into two kinds of methods: the first, and the Monsanto method is a kind of with the nitrated parachloronitrobenzene that obtains of chlorobenzene, then with the method for formanilide reaction.Products therefrom is hydrogenated to 4-ADPA then by conventional methods.But the problem of this method is, in reaction process, for example produces corrosive wastewater and a certain amount of organic and inorganic waste liquids, the processing that they need expend very much by chlorine.The second, can mention the Ouchi method.In this Ouchi method, pentanoic and Sodium Nitrite reaction form N nitrosodiphenyl amine, carry out Fischer-Hepp then and reset.After this, in and products therefrom, be hydrogenated to 4-ADPA then in a usual manner.But the problem of back one method is, owing to nitrosification produces a certain amount of harmful waste liquid.
Except above method, known by aniline coupling end to end (referring to, United States Patent (USP) 4760186) or the hydrogenation of nitroso-group phenylbenzene oxyamine prepared 4-ADPA.But the problem of these methods is that they are uneconomical and the 4-ADPA productive rate is low.
In recent years, proposed to use the method for the nucleophilic aromatic substitution reaction of hydrogen, to substitute the prior art method that can produce debatable objectionable impurities.One of these methods are at alkali, and under the existence as Tetramethylammonium hydroxide (below be called " TMA (OH) "), the reaction by aniline and oil of mirbane prepares 4-NDPA and 4-nitroso-group diphenylamine.According to these alternative methods, can obviously reduce the refuse amount that is produced, and the generation of environmentally hazardous substance is minimized, referring to, american Journal of the Chemical Society, 1992,114 (23), 9237-8; United States Patent (USP) 5117063, United States Patent (USP) 5253737, United States Patent (USP) 5331099, United States Patent (USP) 5453541, United States Patent (USP) 5552531 and United States Patent (USP) 5633407.But the shortcoming of these methods is, used expensive TMA (OH), and used TMA (OH) is difficult to reclaim.In addition, another problem of these methods is, when aniline reacts at the ortho position of oil of mirbane, produces 2-nitrodiphenylamine as by product (below be called " 2-NDPA ") and azophenlyene, thereby reduced degree of purity of production.
In addition, other currently known methods that uses NASH to react comprises a kind of at alkali, under the existence as TMA (OH), prepares the method for 4-ADPA by the reaction of aniline and nitrogen benzide.Referring to, organic chemistry magazine (J.Org.Chem.), 1994,59 (19), 5627-5632; United States Patent (USP) 5382691, United States Patent (USP) 5618979, European patent 726889, WO 95/12569 and Japanese Patent 9504546.
The present invention has adopted the NASH reaction.Also have, the present invention adopts the N-anilide to substitute aniline as raw material.Therefore, the present invention is the method that a kind of reaction by oil of mirbane and N-anilide prepares 4-NDPA.The invention has the advantages that it adopts cheap alkali base and does not produce by product, but the reaction of the ortho position when using aniline then there is problem.
The present invention relates to a kind of method that is used to prepare 4-NDPA, wherein in the presence of alkali, use the carbonyl aniline in the N-anilide to obtain 4-NDPA as raw material and oil of mirbane reaction.4-NDPA is mainly as the raw material for preparing 4-ADPA by hydrogenation, and 4-ADPA is a kind of intermediate of antioxidant.The invention has the advantages that its adopts the carbanilide be easy to get from urea and aniline as raw material, and adopt the alkali of sodium hydroxide and so on, optionally obtain 4-NDPA simultaneously with high yield.
With the prior art of oil of mirbane reaction problem is arranged when separating 4-NDPA about aniline, because the reaction on the oil of mirbane ortho position produces 2-NDPA and azophenlyene by product.Yet,, will greatly reduce the by product that reaction obtains on the oil of mirbane ortho position owing to the sterically hindered effect of amide structure as long as use carbanilide as raw material according to the present invention.
In addition, according to the present invention, reaction atmosphere for example is transformed into oxygen, or control alkali and temperature of reaction can eliminate the problem of prior art method, that is, the generation of nitrogen benzide and zinin can improve the selectivity to 4-NDPA like this.
The invention has the advantages that, can as basic metal or alkaline-earth metal, obtain 4-NDPA by using a kind of alkali with high yield.In addition, in the present invention, owing to do not produce corrosive wastewater, as comprise the waste water of chlorine, therefore can eliminate the factor of etching reactor.In addition, because therefore the not obvious influence that is subjected to water of reaction yield need not to use separately siccative, or distillation plant is installed.This has reduced production cost.
The present invention relates to the method for a kind of synthetic 4-NDPA, wherein will be dissolved in as the carbanilide of raw material in the polar organic solvent, alkali is added in the gained solution, then this mixture and oil of mirbane reaction are formed 4-NDPA.Being used for solvent of the present invention will wait according to the compatibility of the solubleness of carbanilide, itself and alkali and select.The example of this solvent includes, but not limited to polar organic solvent, as methyl-sulphoxide (below be called " DMSO "), dimethyl formamide (below be called " DMF "), N-N-methyl-2-2-pyrrolidone N-, oil of mirbane, aniline and analogue.In these solvents, DMSO, DMF and N-N-methyl-2-2-pyrrolidone N-show excellent reactivity.Productive rate is the highest when especially, using DMSO.
The volume ratio of solvent and oil of mirbane is about 100: about 1: 1 of 1-, preferred about 30: about 1: 1 of 1-.The example of used alkali includes, but not limited to organic or inorganic alkali, as sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH)
2), potassium tert.-butoxide (t-BuOK), Tetramethylammonium hydroxide, sodium hydride (NaH), hydrolith (CaH
2) and analogue.Except above-mentioned alkali, also can use the alkali of basic metal or alkaline-earth metal and so on.In these alkali, sodium hydroxide, potassium hydroxide and sodium hydride show hyperergy and productive rate.The mol ratio of alkali and carbanilide is about 1: about 10: 1 of 10-, preferred about 2: about 6: 1 of 1-.
The mol ratio of oil of mirbane and carbanilide is about 0.5: about 20: 1 of 1-, and the consumption of oil of mirbane is high more, and then the reaction yield of speed of reaction in fast more and identical time is high more.If but the amount of oil of mirbane surpasses aequum, will produce the zinin by product and reduce selectivity 4-NDPA.Temperature of reaction is about 150 ℃ of about 20-, about 80 ℃ of preferably about 50-.If temperature of reaction is lower than about 20 ℃, speed of reaction is slack-off.If temperature of reaction is higher than about 150 ℃, can increase the generation by product.
In order to remove the water that when reaction begins or carries out, is produced in the reaction soln, carry out the vacuum distilling operation, or use siccative.Material as siccative for example comprises Anhydrous potassium carbonate, anhydrous sodium sulphate, anhydrous magnesium sulfate, sodium hydroxide, potassium hydroxide, sodium hydride, molecular sieve and analogue.But because therefore the inventive method and the not obvious influence that is subjected to the water yield in the reaction process do not have tangible productive rate difference at the use siccative with between distilling.Reaction can be carried out under nitrogen or oxygen atmosphere or in the air.Under nitrogen atmosphere, can produce by product, as nitrogen benzide, zinin and analogue, and under oxygen atmosphere, then suppress production of by-products, thereby improved selectivity 4-NDPA.
Embodiment
Following examples only are used to illustrate the present invention, in any case be not used in the scope of the present invention that limits.
In following examples, reactant and product adopt nucleus magnetic resonance (NMR) spectrum and gas chromatograph-mass spectrometer to come Analysis and Identification.In addition, use gas-chromatography to come analytical reaction thing and product to determine its number of quantitative analysis according to following condition:
50 millimeters * 0.2 millimeter * 0.331 μ m of capillary column: ULTRA 2 (crosslinked 5%Ph Me siloxanes)
Carrier gas: nitrogen
Pressure head: 18psig
Stove: 100 ℃ (2 minutes) to 280 ℃, β=10 ℃/minute
Detector and temperature: FID (280 ℃)
Splitting ratio: 50: 1
Make-up gas flow velocity: 38 millimeters
For the quantitative analysis of every kind of product, use pyrene as internal standard substance.By the gas-chromatography factor with internal standard substance be used for area than, can calculate product and mol ratio as the carbanilide of reactant.
Embodiment 1
In being furnished with 100 milliliters of three-necked flasks of condenser and agitator, 1.77 gram (8.34 mmole) carbanilides, 10 milliliters of (78.0 mmole) oil of mirbane, 0.8 gram (33.3 mmole) sodium hydride and 20 milliliters of DMSO pack into, under oxygen atmosphere, stirred the gained mixture 4 hours down then in 60 ℃.When the reaction beginning, add 100 milligrams of pyrenes as internal standard substance.After with ethyl acetate extraction gained reaction soln, analyze products therefrom by gas-chromatography, the productive rate that shows 4-NDPA is 99% mole (8.29 mmoles, 1.78 grams).
Embodiment 2
This embodiment illustrates the influence of the kind of change alkali to the 4-NDPA productive rate.
In being furnished with 100 milliliters of three-necked flasks of condenser and agitator, 1.5 gram (7.07 mmole) carbanilides, 5 milliliters of (48.7 mmole) oil of mirbane, 28.3 mmole sodium hydroxide pack into as alkali and 30 milliliters of DMSO, under oxygen atmosphere, the gained mixture was reacted 3 hours down at 80 ℃ then.When the reaction beginning, add 100 milligrams of pyrenes as internal standard substance.After with ethyl acetate extraction gained reaction soln, analyze products therefrom to determine 4-NDPA by gas-chromatography.Repeat above test for several times, wherein according to the kind of following table 1 listed change alkali.Analytical results provides in table 1.
The productive rate of the kind 4-NDPA of table 1 alkali (% mole) sodium hydroxide 91 sodium hydrides 88 potassium hydroxide 79 potassium tert.-butoxides 40 calcium hydroxides＜1 hydrolith 0
Embodiment 3
This embodiment illustrates the influence of the amount of change alkali to the product productive rate.
In being furnished with 100 milliliters of three-necked flasks of condenser and agitator, 1.5 gram (7.0 mmole) carbanilides and 5 milliliters of (48.7 mmole) oil of mirbane are dissolved among 30 milliliters of DMSO.Then, in sodium hydroxide (as alkali) the adding solution with following the amount of Table 1, under oxygen atmosphere, the gained mixture was stirred 3 hours down at 80 ℃ then.When the reaction beginning, add 100 milligrams of pyrenes as internal standard substance.After with ethyl acetate extraction gained reaction soln, analyze products therefrom to determine 4-NDPA by gas-chromatography.Repeat above test 3 times, each amount according to following table 2 listed change alkali.Analytical results provides in table 2.
The productive rate of the amount * 4-NDPA of table 2 alkali (% mole) 1 372 774 96
* the amount of alkali is represented with the equivalence ratio of sodium hydroxide and carbanilide.
Embodiment 4
This embodiment illustrates the influence of siccative to the product productive rate.
Be furnished with the comprising in 2.0 gram 100 milliliters of three-necked flasks of salt of wormwood of condenser and agitator as siccative, with 1.5 gram (7.07 mmole) carbanilides, 5 milliliters of (48.7 mmole) oil of mirbane and 1.1 gram dissolution of sodium hydroxide in 30 milliliters of DMSO.Under oxygen atmosphere, the gained mixture was reacted 3 hours down at 80 ℃ then.When the reaction beginning, add 100 milligrams of pyrenes as internal standard substance.After with ethyl acetate extraction gained reaction soln, analyze products therefrom to determine 4-NDPA by gas-chromatography.Equally, repeat above test 2 times, sieve 4A as siccative or there is not siccative with 2.0 mol.Analytical results provides in table 3.
Table 3 siccative 4-NDPA (% mole) does not have 91 salt of wormwood, 96 molecular sieve 4A 93
Embodiment 5
This embodiment illustrates and changes the influence of temperature of reaction to the product productive rate.
Be furnished with the comprising in 2.0 gram 100 milliliters of three-necked flasks of lime carbonate of condenser and agitator as siccative, with 1.5 gram (7.07 mmole) carbanilides, 5 milliliters of (48.7 mmole) oil of mirbane and 1.1 gram dissolution of sodium hydroxide in 30 milliliters of DMSO.Under oxygen atmosphere, the gained mixture was reacted 3 hours down at 80 ℃ then.When the reaction beginning, add 100 milligrams of pyrenes as internal standard substance.After with ethyl acetate extraction gained reaction soln, analyze products therefrom to determine 4-NDPA by gas-chromatography.Repeat above test, wherein according to following table 4 listed change temperature of reaction.Analytical results provides in table 4.
80 ℃ 9650 ℃ 62 room temperatures 5 of table 4 temperature of reaction 4-NDPA (% mole)
Embodiment 6
This embodiment illustrates the influence of the kind of change reaction solvent to the 4-NDPA productive rate.
In being furnished with 100 milliliters of three-necked flasks of condenser and agitator, with 1.5 gram (7.07 mmole) carbanilides, 5 milliliters of (48.7 mmole) oil of mirbane and 1.1 gram dissolution of sodium hydroxide in 30 milliliters of DMSO.Under oxygen atmosphere, the gained mixture was reacted 3 hours down at 80 ℃ then.When the reaction beginning, add 100 milligrams of pyrenes as internal standard substance.After with ethyl acetate extraction gained reaction soln, analyze products therefrom to determine 4-NDPA by gas-chromatography.Repeat above test for several times, wherein according to following table 5 listed change solvent types.Analytical results provides in table 5.
The kind 4-NDPA of table 5 reaction solvent (% mole) DMSO 91N-N-methyl-2-2-pyrrolidone N-42DMF 30 oil of mirbane＜1
Embodiment 7
This embodiment illustrates and changes the influence of reaction atmosphere to the amount and the kind of gained by product.
In being furnished with 100 milliliters of three-necked flasks of condenser and agitator, 1.77 gram (8.34 mmole) carbanilides, 4 milliliters of (39.0 mmole) oil of mirbane, 0.8 gram sodium hydroxide and 20 milliliters of DMSO pack into, under oxygen atmosphere, the gained mixture was reacted 2 hours down at 60 ℃ then.When the reaction beginning, add 100 milligrams of pyrenes as internal standard substance.After with ethyl acetate extraction gained reaction soln, analyze products therefrom to determine 4-NDPA and by product by gas-chromatography.Use nitrogen atmosphere replace oxygen atmosphere to come the above test of repetition.Analytical results provides in following table 6.
Table 6 atmosphere 4-NDPA (% mole) zinin (% mole) nitrogen benzide (% mole) oxygen 90＜1 does not record nitrogen 71 28 1
Embodiment 8
This embodiment illustrates the influence of the amount of change oil of mirbane to the 4-NDPA productive rate.
In being furnished with 100 milliliters of three-necked flasks of condenser and agitator, 1.77 gram (8.34 mmole) carbanilides, oil of mirbane and 0.8 gram (33.3 mmole) sodium hydride are dissolved among 20 milliliters of DMSO, under oxygen atmosphere, the gained mixture was reacted 2 hours down at 60 ℃ then.When the reaction beginning, add 100 milligrams of pyrenes as internal standard substance.After with ethyl acetate extraction gained reaction soln, analyze products therefrom to determine 4-NDPA by gas-chromatography.Repeat above test for several times, wherein according to the amount of following table 7 listed change oil of mirbane.Analytical results provides in following table 7.
Table 7 oil of mirbane/carbanilide (moles/mole) 4-NDPA (% mole) 1.2 472.3 794.7 909.4 99
Comparative Examples
This Comparative Examples explanation, when using aniline to substitute carbanilide as raw material, the productive rate of 4-NDPA descends.
Be furnished with the comprising in 2 gram 100 milliliters of three-necked flasks of salt of wormwood of condenser and agitator as siccative, with 1.3 gram (14.0 mmole) aniline, 5 milliliters of (48.7 mmole) oil of mirbane and 1.1 gram (27.5 mmole) dissolution of sodium hydroxide in 30 milliliters of DMSO, under oxygen atmosphere, the gained mixture was reacted 3 hours down at 60 ℃ then.When the reaction beginning, add 100 milligrams of pyrenes as internal standard substance.After with ethyl acetate extraction gained reaction soln, analyze products therefrom by gas-chromatography, show that the productive rate of 4-NDPA and nitrogen benzide is respectively 2.7% (0.038 mmole, 81 milligrams) and 8.6% (1.20 mmoles, 219 milligrams).
Advantage according to method of the present invention is, has used cheap basic salt, and the selectivity of 4 nitrodiphenyl amine and transformation efficiency height, does not produce environmentally harmful corrodibility byproduct of reaction simultaneously.
Although the preferred embodiments of the invention have been described, those skilled in the art should be appreciated that, under the situation that does not deviate from the disclosed scope of the invention of claims and purport, can carry out various improvement, interpolation and replacement.
Claims (11)
1. the nucleophilic aromatic by hydrogen replaces the method for preparing 4 nitrodiphenyl amine, comprises, in the presence of alkali, carbanilide and oil of mirbane is reacted in polar organic solvent.
2. according to the process of claim 1 wherein that described alkali is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium tert.-butoxide, Tetramethylammonium hydroxide, sodium hydride and hydrolith.
3. according to the process of claim 1 wherein that described polar organic solvent is selected from methyl-sulphoxide, dimethyl formamide, N-N-methyl-2-2-pyrrolidone N-, oil of mirbane, aniline.
4. according to the process of claim 1 wherein that temperature of reaction is about 150 ℃ of about 20-.
5. according to the process of claim 1 wherein that reaction atmosphere is oxygen, nitrogen or air.
6. the nucleophilic aromatic by hydrogen replaces the method for preparing 4 nitrodiphenyl amine, comprises, in the presence of alkali and siccative, carbanilide and oil of mirbane is reacted in polar organic solvent.
7. according to the method for claim 6, wherein said alkali is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium tert.-butoxide, Tetramethylammonium hydroxide, sodium hydride and hydrolith.
8. according to the method for claim 6, wherein said siccative is selected from Anhydrous potassium carbonate, anhydrous sodium sulphate, anhydrous magnesium sulfate, sodium hydroxide, potassium hydroxide, sodium hydride and molecular sieve.
9. according to the method for claim 6, wherein said polar organic solvent is selected from methyl-sulphoxide, dimethyl formamide, N-N-methyl-2-2-pyrrolidone N-, oil of mirbane, aniline.
10. according to the method for claim 6, wherein temperature of reaction is about 150 ℃ of about 20-.
11. according to the method for claim 6, wherein reaction atmosphere is oxygen, nitrogen or air.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990007198A KR100283374B1 (en) | 1999-03-04 | 1999-03-04 | The method for preparing 4-nitrodiphenylamine from carbanilide |
| KR7198/1999 | 1999-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1266052A true CN1266052A (en) | 2000-09-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99122890A Pending CN1266052A (en) | 1999-03-04 | 1999-12-09 | Process for preparing tetranitro-diphenylamine from N-carbonylaniline |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2000256282A (en) |
| KR (1) | KR100283374B1 (en) |
| CN (1) | CN1266052A (en) |
| AU (1) | AU1513700A (en) |
| WO (1) | WO2000051966A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100302862B1 (en) * | 1999-07-08 | 2001-09-13 | 박찬구 | Method of preparing 4-nitrodiphenylamine and 4-nitroaniline from phenylurea |
| KR100621310B1 (en) | 2005-05-16 | 2006-09-06 | 금호석유화학 주식회사 | Method for preparing 4-aminodiphenylamine |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2851514A1 (en) * | 1978-11-29 | 1980-06-12 | Bayer Ag | METHOD FOR PRODUCING NITRODIPHENYLAMINE DERIVATIVES |
-
1999
- 1999-03-04 KR KR1019990007198A patent/KR100283374B1/en not_active IP Right Cessation
- 1999-11-12 JP JP11322643A patent/JP2000256282A/en active Pending
- 1999-12-04 AU AU15137/00A patent/AU1513700A/en not_active Abandoned
- 1999-12-04 WO PCT/KR1999/000738 patent/WO2000051966A1/en active Application Filing
- 1999-12-09 CN CN99122890A patent/CN1266052A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000256282A (en) | 2000-09-19 |
| AU1513700A (en) | 2000-09-21 |
| KR100283374B1 (en) | 2001-02-15 |
| KR20000059541A (en) | 2000-10-05 |
| WO2000051966A1 (en) | 2000-09-08 |
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