CN1013109B - The preparation method of the single substituted p-phenylenediamine compounds of N- - Google Patents
The preparation method of the single substituted p-phenylenediamine compounds of N-Info
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- CN1013109B CN1013109B CN 86107268 CN86107268A CN1013109B CN 1013109 B CN1013109 B CN 1013109B CN 86107268 CN86107268 CN 86107268 CN 86107268 A CN86107268 A CN 86107268A CN 1013109 B CN1013109 B CN 1013109B
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Abstract
Disclosed is the method for making of the single substituted p-phenylenediamine of a kind of N-, this method comprises: following formula: compound is reacted with primary alcohol or secondary alcohol under the condition of hydrogen and noble metal catalyst existence having alkali to exist but do not have.In the formula, R is C
1～C
12Alkyl, phenyl, naphthyl, or in 2-, 4-or 2, the 4-position is by C
1～C
8The phenyl that alkyl replaces; R ' is hydrogen or C simultaneously
1～C
6Alkyl.
Description
For a long time, people wish to find the efficient and economic method of the single substituted p-phenylenediamine compounds of a kind of N-of preparation.This compounds is mainly used in makes antioxidant and antiozonant.Above-mentioned antioxidant and antiozonant are mainly used in to be made rubber product and prepares the intermediate that dyestuff is used.
Traditionally, these materials are prepared through hydrogenation in Aquo System by the alkaline metal salt of nitroso-group arylamine class always.Reduction reaction is normally finished in the presence of traditional hydrogenation catalyst with gaseous hydrogen.An example of this method can be referring to United States Patent (USP) 2,974,169.
In the work afterwards, as United States Patent (USP) 4,313,002 is described, be that the reduction of above-mentioned alkaline metal salt is carried out in another kind of solvent system (for example aromatic hydrocarbons and saturated fatty alcohols), and its step of hydrogenation is still used hydrogen and traditional hydrogenation catalyst.
The shortcoming of these methods be to use some price very high noble metal catalyst (for example platinum and palladium) as hydrogenation catalyst.
United States Patent (USP) 4,448,994 point out, can be in the aqueous solution reduce the alkaline metal salt of nitrosamine with reducing sugar.But with this method is normal such problem takes place: this class salt facile hydrolysis in the aqueous solution, so be unsettled when storing.
United States Patent (USP) 4,479 is introduced in 008, can be with the pentanoic nitrosification, reset and form the 4-nitrosodiphenylamine, and use 5% traditional palladium carbon as catalyzer then, feed the hydrogen of 500-800 pound/square inch pressure, carry out hydrogenation at 80 ℃.All is to make reaction medium with Fatty Alcohol(C12-C14 and C12-C18) in above-mentioned institute in steps.Above-mentioned disclosure explanation need be used for reduction step with the noble metal catalyst of prior art, and just as noted earlier, this catalyzer is very expensive.
According to the present invention, found that the single substituted p-phenylenediamine of N-can prepare like this: 4-nitroso-group amine is reacted with alcohol under the alkaline condition that does not have hydrogen and precious metal to exist.This reaction can play at the same time in the solvent of alcohols of reductive agent effect and carry out.In fact, all following conventional procedures can be carried out in the alcoholic solvent that the present invention uses as reductive agent, these steps are usually directed to prepare the single substituted p-phenylenediamine of 4-by the single-substituted amine of N-, promptly carry out the N-nitrosification, generate 4-nitroso-group intermediate through resetting then.This method can obtain the quite high required final product of productive rate, and only produces the azo-group and the azoxy by product of minute quantity.In addition, also separate easily obtains the single substituted p-phenylenediamine of highly purified N-.
The most amazing is that the inventive method can be used to prepare the single substituted p-phenylenediamine of N-.Experiment in the past shows that the reaction that nitrosobenzene and alcohols take place almost produces zinin quantitatively, and does not produce corresponding amino-benzene in the presence of alkali.For example, Hatton people such as (Hutton) is " with the reaction mechanism of alcohols reduction nitrosobenzene " (seeing J.P.Chem.Soc.(B) 1968, the 191～195 pages) just reported this reaction in the literary composition.This article illustrates at the 195th page the 191st page of narration reaction mechanism.What is interesting is, even in the patent that is mentioned before, when an alkali metal salt of nitrosodiphenylamine is reacted in alcohol (seeing United States Patent (USP) 4,313,002), also still think and to use hydrogen and traditional noble metal catalyst could realize reduction.
The inventive method can be explained by following reaction formula:
In the formula, R is C
1～C
12Alkyl, phenyl, naphthyl, or in 2-, 4-or 2, on the 4-position by C
1～C
8The phenyl that alkyl replaces; R ' is hydrogen or C
1～C
6Alkyl; R* is hydrogen, C
1～C
12Alkyl or phenyl.
Should to choose chemical formula be R to used alcohol that " alcohol of OH, R in the formula " are C in the inventive method
1～C
12Alkyl or phenmethyl.
In aforesaid method, R is C
3～C
8Alkyl or phenyl, R ' are hydrogen or C
1～C
4Alkyl is better.
R " C preferably
4～C
6Alkyl.
In the single substituted p-phenylenediamine class of aforementioned N-product, the most important thing is mutual-amido two polyaniline.This material can be used to prepare well-known antioxidant, i.e. N-alkyl-N-diphenyl-para-phenylene diamine class.But the inventive method is used to prepare following compounds and also is easy to: N-sec.-propyl Ursol D, N-1-methylethyl Ursol D, N-cyclohexyl-p-phenylenediamine, N-1,3-dimethylbutyl Ursol D and N-1,4-dimethyl amyl group Ursol D.
According to the present invention, the alcohol that can be used as reductive agent comprises and contains the saturated primary alcohol and the saturated secondary alcohol of 12 carbon atoms at the most.These pure examples have butanols class, amylalcohol class, hexanol class, enanthol class, octanol class, nonyl alcohol class, decyl alcohol class and phenylcarbinol class.Just can become reductive agent owing to have the alcohol of α hydrogen, so can not use tertiary alcohol.
Those of ordinary skill in the art are appreciated that to generating required final product, select corresponding p-nitroso diphenyl amine easily.When selecting the 4-nitrosodiphenylamine as raw material, also can adopt the 4-nitrosodiphenylamine that contains following groups: 2,2 '-di-isopropyl, 2,2 '-diisobutyl, 2,2 '-di-n-butyl, 2,4 '-di-isopropyl, 2-sec.-propyl-4 '-isobutyl-, 4 ' sec.-propyl, 4 '-n-propyl, 4 '-isobutyl-, 4 '-normal-butyl, 4 '-n-pentyl, 4 '-isopentyl, 4 '-n-hexyl, 4 '-(2-ethylhexyl), 2,2 '-di-isopropyl-4 '-normal-butyl or 2,2 '-diisobutyl-4 '-n-hexyl.
The single-substituted amine of 4-nitroso-group-N-can be by after making the N-nitroso-derivative and mineral acid (for example hydrogen halide) contacting, and transformation takes place and generates.The ripe refining technician of this transformation this area is very familiar, at United States Patent (USP) 4,313,002 and United States Patent (USP) 4,479,008 in just have a detailed description.Need not isolate intermediate product after will be appreciated that rearrangement herein.
Though can make other alkaline matter, in general, reaction is finished in the presence of alkali metal hydroxide.
Basic metal preferably adopts sodium and potassium.In order to make reaction carry out suppressing the formation of this class by product of azo-compound and azoxy compound simultaneously fully, should add the alkali of capacity.Usually, this alkali (OH) should be 0.75: 1 at least with the mole ratio of nitroso compound (NO), is preferably 1: 1 to 2: 1, and the best was 1.25: to 1.5: 1.
Alcohol can be 2 to the ratio (ROH/NO) of the mole number of nitroso compound: to 100: 1, be preferably 5: 1 to 50: 1.The best is 7.5: 1 to 20: 1.In addition, need the alcohol reduction nitroso compound of capacity also to be used as reaction solvent simultaneously.Usually, the concentration expressed in percentage by weight of nitroso compound in alcoholic solution is 20%～30%.
In this reaction, use the pure analogy contain three carbon atoms or to contain more carbon atoms to use methyl alcohol or ethanol better.In addition, in reaction, to reduce the amount of water as far as possible to avoid the hydrolysis of an alkali metal salt.Can add solid alkali for this reason, and not adopt the alkali of aqueous solution form.But way is that this alkali is added to weight concentration preferably in 50% the alcohol solution comparatively easily.
In addition, temperature of reaction can be limited in 50 ℃ to 200 ℃ the wide region, but preferably remains between 50 ℃ and 150 ℃.In general, it is the most convenient that reaction is under atmospheric pressure carried out, but when using low-boiling point alcohol, operation better under elevated pressures.
So far, why not the character that still can not understand nitroso compound of the present invention fully definitely is same as the character of the nitrosobenzene class of being discussed in Hatton people's such as (Hutton) the article.In any case as seen, the result is unexpectedly different from following each experiment.Probably in reaction process, alcohol is oxidized to corresponding aldehydes or ketones.But this reaction mechanism there is no much importance for the advantage of invention in understanding.
Describe the present invention in detail for embodiment more below.Below among each embodiment, by raw material nitroso compound, by product azo-compound or azoxy compound in infrared analysis and high pressure liquid chromatography (HPLC) the detection reaction mixture as 4,4 '-existence of two (the single substituted-amino of N-) zinins and nitrogen benzide etc.In all cases, the by product azo-compound and the azoxy compound that record only account for about 1%～2%.
Embodiment 1
The preparation of N-diphenyl-para-phenylene diamine
Be to load onto an agitator, a prolong and a thermometer on 1 liter the three neck round-bottomed flasks at a capacity.In above-mentioned round-bottomed flask, put into 99.0 gram (0.5 mole) N-phenyl-4-nitrosoanilines, 254 gram n-hexyl alcohols and 40 gram (0.5 mole) aqueous NaOHs (weight percent is 50%).Stir gained and show slightly red deep brown solution, be heated to 100 ℃.When temperature rises to 100 ℃, produce exothermic phenomenon, stop heating this moment.Stop to heat in back 15 minutes.Solution temperature will rise to 120 ℃, and after 15 minutes, temperature rolled back 100 ℃.Continue to stir 1 hour.During churning, solution temperature should remain in 100 ℃～150 ℃ scopes.Then, with HPLC analyze reaction mixture sample, the result does not find the nitroso compound raw material.
After being cooled to room temperature, the abundant cleaning reaction mixture of water.Then excessive alcohol is removed with distillation under vacuum.Distillation is to carry out under the temperature between the pressure between 13.3～66.7 pascals and 165～170 ℃.Obtain 77.1 gram faint yellow oily products (productive rate is 83.8%).After the cooling, this product forms crystallization, and measuring its purity with gas chromatography is 98 ℃.
Other experiment is undertaken by above-mentioned steps substantially, only does some change according to table 1, and its result is also as shown in table 1.(seeing Table 1)
Embodiment 2
The preparation of N-sec.-propyl Ursol D
The preparation of N-sec.-propyl Ursol D is mainly undertaken by embodiment 1 described step.66.0 gram (0.25 mole) N-sec.-propyl-4-nitrosoanilines, 20 gram sodium hydroxide (50%) and 264 gram n-hexyl alcohols are mixed mutually, and be heated to 100 ℃ and kept this temperature 1.5 hours.Then, with HPLC analytical reaction mixed solution.The result shows that the nitroso compound raw material disappears.Adopt vacuum distillation method (99 ℃～101 ℃ of temperature, pressure 13.3～26.6 pascals), make 31.3 gram products (productive rate is 48.6% by weight).
Embodiment 3
The preparation of N-cyclohexyl-p-phenylenediamine
51.0 gram (0.25 mole) N-cyclohexyl-4-nitrosoanilines, 20.0 gram (concentration 50%) sodium hydroxide and 135 gram n-hexyl alcohols are packed in 1 0.5 liter the three neck round-bottomed flasks, this flask is equipped with an agitator, a prolong and a thermometer, be heated to 95 ℃ while stirring then, continue to stir until thermopositive reaction takes place.Stop heating, this moment, temperature can continue to rise to 115 ℃, descended then, can drop to 100 ℃ in 10 minutes.By heating, temperature was remained between 90 ℃ and 95 ℃ in the clock time at 30 minutes.After finishing above-mentioned steps, this mixing solutions no longer contains unreacted nitroso compound.The productive rate of products therefrom be 64%(by weight), its fusing point is 59-61 ℃.
Embodiment 4
2,2 '-preparation of di-isopropyl-N-diphenyl-para-phenylene diamine
With 2,2 '-di-isopropyl-N-phenyl-4-nitrosoaniline (40.0 grams, 0.167 mole), sodium hydroxide (50%; 14.0 gram, 0.17 mole) and n-hexyl alcohol (120 gram) be put in the reactor as described in example 3 above, under agitation heat gained mixture to 100 ℃～105 ℃, and continue heating 1 hour.The infrared analysis of reaction mixture and HPLC analysis revealed, reactant do not transform as yet fully.Again this reaction mixture is heated to 125 ℃ and kept 3.5 hours, cooling then, washing several times.Use this hexanol solution of gas chromatographicanalyzer quantitative assay, learn that productive rate is a 73%(weight).
Above-mentioned each specific practice and each embodiment have illustrated scope and spirit of the present invention.Can derive other specific practice and embodiment by these specific practices and embodiment, they are conspicuous In the view of those skilled in the art.These other ways and embodiment remain the content in the scope of the invention.Therefore, the scope of the invention only should be limited by each claim in the appended claims.
Table 1
Test number 12345
Alcohols MEOH MEOH IPOH IPOH IBOH
Temperature of reaction (℃) ca.65* 115-125 ca.82* 115-125 ca.107*
Reaction times (hour) 1.5 5.7 2.0 2.0 3.0
The result
Residual N-phenyl nitrosoaniline (1)
（%） 100 50 100 0 0
N-diphenyl-para-phenylene diamine product (2)
（%） - 50 - 76 89
Table 1(is continuous)
Test number 6789 10
Alcohols MEOH TPOH MPOH CHOH ETGL
Temperature of reaction (℃) 115* ca.102* 100-105 100-105 100-105
Reaction times (hour) 1.5 5.0 1.0 1.5 3.0
The result
Residual N-phenyl nitrosoaniline (1)
（%） 0 100 0 0 16
N-diphenyl-para-phenylene diamine product (2)
（%） 88 - 66 80 79
* expression is controlled under the reflux temperature.
MEOH=methyl alcohol MBOH=3-methyl isophthalic acid-butanols
IPOH=2-propyl alcohol MPOH=4-methylpent-2-alcohol
Three grades of amylalcohol CHOH=of TPOH=hexalin
IBOH=isopropylcarbinol ETGL=ethylene glycol
Claims (3)
1, the preparation method of the single substituted p-phenylenediamine of N-, this method comprises: make following formula: compound with-" OH reaction, this reaction are to have metal hydroxides to exist, carrying out under the condition of 50 °-200 ℃ of temperature to R, and wherein .R " is C
4-6Alkyl,
R is C
3-8Alkyl, phenyl or in 2-, 4-or 2, on the 4-position by C
1～C
8The phenyl that alkyl replaced, R ' are hydrogen or C
1～C
4Alkyl.
2, the method for claim 1, wherein metal hydroxides is sodium hydroxide or potassium hydroxide.
3, the method for claim 1, wherein temperature of reaction is in 100 ℃～150 ℃ scopes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86107268 CN1013109B (en) | 1986-10-23 | 1986-10-23 | The preparation method of the single substituted p-phenylenediamine compounds of N- |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86107268 CN1013109B (en) | 1986-10-23 | 1986-10-23 | The preparation method of the single substituted p-phenylenediamine compounds of N- |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86107268A CN86107268A (en) | 1988-05-04 |
| CN1013109B true CN1013109B (en) | 1991-07-10 |
Family
ID=4803542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86107268 Expired CN1013109B (en) | 1986-10-23 | 1986-10-23 | The preparation method of the single substituted p-phenylenediamine compounds of N- |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013109B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053180C (en) * | 1995-05-08 | 2000-06-07 | 天津市医药科学研究所 | N-(beta-aminoethyl) aniline compounds, prepn. method thereof |
-
1986
- 1986-10-23 CN CN 86107268 patent/CN1013109B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN86107268A (en) | 1988-05-04 |
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