CN101735074A - Method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine from carbonyl aniline - Google Patents
Method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine from carbonyl aniline Download PDFInfo
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- CN101735074A CN101735074A CN200810195142A CN200810195142A CN101735074A CN 101735074 A CN101735074 A CN 101735074A CN 200810195142 A CN200810195142 A CN 200810195142A CN 200810195142 A CN200810195142 A CN 200810195142A CN 101735074 A CN101735074 A CN 101735074A
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- aniline
- nitrosodiphenylamine
- carbonyl aniline
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- bromide
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Abstract
The invention belongs to the technical field of organic synthesis and relates to a method for preparing 4-nitrodiphenylamine and 4-nitrosodiphenylamine from carbonyl aniline. In the existence of appropriate alkali, a phase transfer catalyst and a solvent, the carbonyl aniline and nitrobenzene undergo a condensation reaction, so the 4-nitrodiphenylamine and 4-nitrosodiphenylamine can be prepared with high selectivity. Compared with a conventional method, the method has the characteristics of simple preparation process, high yield rate, benefit for environmental protection and the like.
Description
Technical field: the present invention relates to a kind of organic synthetic method, be specifically related to be prepared by carbonyl aniline the method for 4 nitrodiphenyl amine and 4-nitrosodiphenylamine, 4 nitrodiphenyl amine and 4-nitrosodiphenylamine are used for hydrogenation preparing rubber antioxidant intermediate 4-aminodiphenylamine usually.
Background technology: the method for present industrial production 4-aminodiphenylamine has: pentanoic method, aniline process, formylaniline method, oil of mirbane method.First three is planted technology and all has shortcomings such as technical process is long, a large amount of reluctant waste water of generation; and the oil of mirbane method that developed recently gets up is to be that raw material carries out condensation reaction and prepares 4 nitrodiphenyl amine, 4-nitrosodiphenylamine with aniline and oil of mirbane; hydrogenation preparing 4-aminodiphenylamine then; this process recovery ratio height; the three wastes are few; both be beneficial to environment protection, reduced cost again.But this technical difficulty is higher, and production control is relatively more difficult, and is impure many in the product.Chinese patent CN1266052A has announced a kind of method by carbonyl aniline and oil of mirbane prepared in reaction 4 nitrodiphenyl amine, CN1249017C has announced a kind of method by carbonyl aniline and oil of mirbane prepared in reaction 4 nitrodiphenyl amine and 4-nitrosodiphenylamine subsequently, these two kinds of methods have following characteristics: the one, and raw material is easy to get, and carbonyl aniline can be by urea and aniline reaction preparation; The 2nd, reaction process does not need to use tetramethyl ammonium hydroxide, and the alkali that uses is the sodium hydroxide of cheapness; The 3rd, good product quality has greatly reduced the side reaction that takes place owing to the sterically hindered effect of amide structure on the oil of mirbane ortho position; Four are to use oil of mirbane to substitute nitro-chlorobenzene, can not produce chlorine-contained wastewater; The 5th, reaction yield is not subjected to the influence of water, therefore need not use siccative separately, or distillation plant is installed.But it uses the polar organic solvent dimethyl sulfoxide (DMSO) as solvent, needs to separate before hydrogenation to avoid hydrogenation catalyst to poison.
Summary of the invention: the present invention mainly improves the carbonyl aniline law technology, improves and mainly is to add phase-transfer catalyst, thereby avoid using dimethyl sulfoxide (DMSO) as solvent.
The present invention by carbonyl aniline and oil of mirbane in the presence of mineral alkali, phase-transfer catalyst and organic solvent, at 60-150 ℃, condensation reaction 3-24h, product 4 nitrodiphenyl amine, 4-nitrosodiphenylamine.
The alkali that can Gong select for use is generally mineral alkali, as basic metal, alkalimetal hydride, alkali metal hydroxide, and for reactive, the mineral alkali in preferably organizing below one or more such as NaOH, KOH, LiOH, Ca (OH)
2, NaH, CaH
2, preferred again NaOH, KOH, LiOH, preferred again KOH.The mass ratio of alkali and carbonyl aniline is 0.2: 1～3: 1, and preferred mass ratio is 0.5: 1～1.5: 1.
The phase-transfer catalyst that can Gong select for use is the one or more combination thing in quaternary amine, quaternary amine alkali, quaternary alkylphosphonium salt, polyoxyethylene glycol, polyoxyethylene glycol dialkyl ether, pyridine, the cyclic crown ether class etc.Preferred quaternary amine and poly(oxyethylene glycol) 400-20000, the preferred benzyltriethylammoinium chloride of quaternary amine, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyl tributyl ammonium chloride, tetramethyl ammonium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, the octadecyl trimethylammonium bromide, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tributyl brometo de amonio, 4 bromide.Preferred again Tetrabutyl amonium bromide, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride.
The mass ratio of phase-transfer catalyst and carbonyl aniline is 0.005: 1～0.5: 1, preferred 0.01: 1～0.2: 1.
The solvent that can Gong select for use has aniline, oil of mirbane, dimethyl formamide, N-N-methyl-2-2-pyrrolidone N-, the trimethyl carbinol, propyl carbinol, ethanol, methyl alcohol, acetonitrile, toluene, benzene, acetone etc.But the present invention is not limited to above-mentioned organic solvent, for reactive, preferentially uses oil of mirbane and aniline, adopts oil of mirbane to avoid the influence of solvent in reaction, and adopts aniline to make solvent, a certain amount of carbonyl aniline of can regenerating, the yield of raising product.
The volume ratio of solvent and carbonyl aniline is 1: 1～100: 1 a scope, preferred 1: 1～30: 1.
Temperature of reaction is preferably 60-150 ℃, and preferred 80-130 ℃, if temperature of reaction is low, speed of reaction is just slow, and temperature surpasses 150 ℃, product 4 nitrodiphenyl amine, 4-nitrosodiphenylamine poor selectivity.Reaction times is preferably 3～24h, preferred 5～12h.
Reaction atmosphere does not have strict restriction, can react in nitrogen, air or oxygen.
Explanation the present invention that can be detailed in following examples, but the present invention is not limited to these.
Embodiment: the present invention is described in detail by following example:
Example 1. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 3.0g, Tetrabutyl amonium bromide 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 0.96% carbonyl aniline in the solution, 2.33% 4 nitrodiphenyl amine, 2.50% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 78.2%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 52.4%, 4-nitrosodiphenylamine yield 60.8%.
Example 2. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, LiOH 3.0g, cetyl trimethylammonium bromide 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 100 ℃ of stirring reaction 7h, contain 2.33% carbonyl aniline in the solution, 1.46% 4 nitrodiphenyl amine, 1.72% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 47.6%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 32.5%, 4-nitrosodiphenylamine yield 41.4%.
Example 3. is with the carbonyl aniline of 3.0g, oil of mirbane 5mL, KOH 3.0g, cetyl trimethylammonium bromide 0.4g, aniline 55mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 1.18% carbonyl aniline in the solution, 2.38% 4 nitrodiphenyl amine, 2.44% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 73.5%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 52.9%, 4-nitrosodiphenylamine yield 58.6%.
Example 4. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 3.0g, cetyl trimethylammonium bromide 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 120 ℃ of stirring reaction 7h, contain 0.55% carbonyl aniline in the solution, 1.74% 4 nitrodiphenyl amine, 1.94% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 87.6%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 38.8%, 4-nitrosodiphenylamine yield 46.7%.
Example 5. is with the carbonyl aniline of 3.0g, oil of mirbane 4mL, NaOH 3.0g, cetyl trimethylammonium bromide 0.2g, aniline 56mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 130 ℃ of stirring reaction 7h, contain 0.11% carbonyl aniline in the solution, 1.12% 4 nitrodiphenyl amine, 0.97% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 97.5%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 24.8%, 4-nitrosodiphenylamine yield 23.2%.
Example 6. is the carbonyl aniline of 3.0g, oil of mirbane 6mL, Ca (OH)
22.0g, cetyl trimethylammonium bromide 0.3g, aniline 54mL, adding 100mL is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 6h, contain 1.45% carbonyl aniline in the solution, 0.26% 4 nitrodiphenyl amine, 0.14% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 67.9%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 5.7%, 4-nitrosodiphenylamine yield 3.3%.
Example 7. is the carbonyl aniline of 3.0g, oil of mirbane 6mL, CaH
22.5g, cetyl trimethylammonium bromide 0.3g, aniline 54mL, adding 100mL is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 5h, contain 1.38% carbonyl aniline in the solution, 0.45% 4 nitrodiphenyl amine, 0.26% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 69.2%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 10.0%, 4-nitrosodiphenylamine yield 6.2%.
Example 8. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, NaH 3.0g, cetyl trimethylammonium bromide 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 5h, contain 1.18% carbonyl aniline in the solution, 0.69% 4 nitrodiphenyl amine, 0.41% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 73.5%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 15.4%, 4-nitrosodiphenylamine yield 9.9%.
Example 9. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 2.0g, cetyl trimethylammonium bromide 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 1.86% carbonyl aniline in the solution, 0.22% 4 nitrodiphenyl amine, 0.45% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 58.8%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 4.8%, 4-nitrosodiphenylamine yield 10.7%.
Example 10. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 2.5g, cetyl trimethylammonium bromide 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 1.41% carbonyl aniline in the solution, 1.78% 4 nitrodiphenyl amine, 2.02% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 68.5%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 39.4%, 4-nitrosodiphenylamine yield 48.3%.
Example 11. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 3.0g, tetrabutylammonium chloride 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 2.01% carbonyl aniline in the solution, 1.38% 4 nitrodiphenyl amine, 1.73% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 54.8%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 30.8%, 4-nitrosodiphenylamine yield 41.7%.
Example 12. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 3.0g, Macrogol 2000 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 2.18% carbonyl aniline in the solution, 1.09% 4 nitrodiphenyl amine, 1.30% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 51.0%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 24.3%, 4-nitrosodiphenylamine yield 31.3%.
Example 13. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 3.0g, polyethylene glycol 6000 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 2.35% carbonyl aniline in the solution, 1.35% 4 nitrodiphenyl amine, 1.47% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 47.1%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 30.1%, 4-nitrosodiphenylamine yield 35.4%.
Example 14. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 3.0g, palmityl trimethyl ammonium chloride 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 1.48% carbonyl aniline in the solution, 2.08% 4 nitrodiphenyl amine, 2.25% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 66.7%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 46.4%, 4-nitrosodiphenylamine yield 54.2%.
Example 15. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 3.0g, octadecyl trimethyl ammonium chloride 0.3g, aniline 54mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 1.99% carbonyl aniline in the solution, 1.82% 4 nitrodiphenyl amine, 2.65% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 55.2%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 40.6%, 4-nitrosodiphenylamine yield 63.8%.
Example 15. is with the carbonyl aniline of 3.0g, oil of mirbane 6mL, KOH 3.0g, Tetrabutyl amonium bromide 0.3g, aniline 30mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 2.13% carbonyl aniline in the solution, 3.79% 4 nitrodiphenyl amine, 2.72% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 69.1%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 54.4%, 4-nitrosodiphenylamine yield 42.2%.
Example 16. is with the carbonyl aniline of 6.0g, oil of mirbane 12mL, KOH 6.0g, Tetrabutyl amonium bromide 0.6g, aniline 40mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 3.00% carbonyl aniline in the solution, 4.30% 4 nitrodiphenyl amine, 3.31% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 66.5%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 47.6%, 4-nitrosodiphenylamine yield 39.6%.
Example 17. is with the carbonyl aniline of 6.0g, oil of mirbane 36mL, KOH 6.0g, Tetrabutyl amonium bromide 0.6g, aniline 18mL adds 100mL and is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 110 ℃ of stirring reaction 7h, contain 3.16% carbonyl aniline in the solution, 4.90% 4 nitrodiphenyl amine, 3.72% 4-nitrosodiphenylamine.Wherein the carbonyl aniline transformation efficiency is 61.1%, and product yield is in carbonyl aniline 4 nitrodiphenyl amine yield 59.7%, 4-nitrosodiphenylamine yield 49.0%.
The present invention also can not adopt the aniline solvent, makes solvent with excessive oil of mirbane and participates in reaction, and details are example as follows.
Example 18. is with the carbonyl aniline of 1.5g, oil of mirbane 30mL, KOH 1.3g, octadecyl trimethyl ammonium chloride 0.15g, adding 100mL is equipped with in the four-hole boiling flask of reflux condensate device and agitator, at 105 ℃ of stirring reaction 7h, contain 0.04% carbonyl aniline in the solution, 3.01% 4 nitrodiphenyl amine, 0.71% 4-nitrosodiphenylamine.The transformation efficiency 99% of carbonyl aniline wherein, product yield be in carbonyl aniline 4 nitrodiphenyl amine yield 77.4%, 4-nitrosodiphenylamine yield 19.7%.
Claims (10)
1. method for preparing 4 nitrodiphenyl amine and 4-nitrosodiphenylamine by carbonyl aniline, it is characterized in that carbonyl aniline is in the presence of mineral alkali, phase-transfer catalyst and organic solvent, with oil of mirbane at 60-150 ℃, condensation reaction 3-24h, product 4 nitrodiphenyl amine, 4-nitrosodiphenylamine.
2. method according to claim 1 is characterized in that mineral alkali is selected from basic metal, alkalimetal hydride, alkali metal hydroxide.
3. method according to claim 2 is characterized in that mineral alkali chooses one or more in following group, NaOH, KOH, LiOH, Ca (OH)
2, NaH, CaH
2
4. according to claim 1 or 3 described methods, it is characterized in that the quality of alkali and the mass ratio of carbonyl aniline are 0.2: 1～3: 1.
5. method according to claim 1 is characterized in that phase-transfer catalyst is that one or more choose the catalyzer in following group, quaternary amine, quaternary amine alkali, quaternary alkylphosphonium salt, polyoxyethylene glycol, polyoxyethylene glycol dialkyl ether, pyridine, cyclic crown ether.
6. method according to claim 5 is characterized in that quaternary amine is selected from benzyltriethylammoinium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyl tributyl ammonium chloride, tetramethyl ammonium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, the octadecyl trimethylammonium bromide, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tributyl brometo de amonio, 4 bromide.
7. method according to claim 1 or 5 is characterized in that the quality of phase-transfer catalyst and the mass ratio of carbonyl aniline are 0.005: 1～0.5: 1.
8. method according to claim 1 is characterized in that organic solvent selects aniline, oil of mirbane, dimethyl formamide, N-N-methyl-2-2-pyrrolidone N-, the trimethyl carbinol, propyl carbinol, ethanol, methyl alcohol, acetonitrile, toluene, benzene, acetone for use.
9. according to claim 1 or 8 described methods, the volume ratio that it is characterized in that organic solvent and carbonyl aniline is 1: 1～100: 1.
10. method according to claim 1 is characterized in that setting-up point between 80 ℃～130 ℃, and the reaction times is between 5～12h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232275A (en) * | 2018-10-26 | 2019-01-18 | 科迈化工股份有限公司 | A kind of preparation method of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285344A (en) * | 1999-08-19 | 2001-02-28 | 金湖石油化学株式会社 | Process for preparation of 4-nitrodiphenylamine and 4-nitrosodiphenylamine from carbanilide |
| CN101277923A (en) * | 2005-05-16 | 2008-10-01 | 株式会社锦湖石油化学 | Method for preparing 4-aminodiphenylamine |
-
2008
- 2008-11-06 CN CN200810195142A patent/CN101735074A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285344A (en) * | 1999-08-19 | 2001-02-28 | 金湖石油化学株式会社 | Process for preparation of 4-nitrodiphenylamine and 4-nitrosodiphenylamine from carbanilide |
| CN101277923A (en) * | 2005-05-16 | 2008-10-01 | 株式会社锦湖石油化学 | Method for preparing 4-aminodiphenylamine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232275A (en) * | 2018-10-26 | 2019-01-18 | 科迈化工股份有限公司 | A kind of preparation method of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine |
| CN109232275B (en) * | 2018-10-26 | 2021-06-11 | 科迈化工股份有限公司 | Preparation method of 4-nitrodiphenylamine and 4-nitrosodiphenylamine |
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Application publication date: 20100616 |