CN1370768A

CN1370768A - Synthesis of N,N'-di-sec-alkyl p-phenylenediamine

Info

Publication number: CN1370768A
Application number: CN 01138850
Authority: CN
Inventors: 张跃臻; 魏奇
Original assignee: LIAONING TIANHE FINE CHEMICAL CO Ltd
Current assignee: LIAONING TIANHE FINE CHEMICAL CO Ltd
Priority date: 2001-12-16
Filing date: 2001-12-16
Publication date: 2002-09-25
Anticipated expiration: 2021-12-16
Also published as: CN1177802C

Abstract

The present invention relates to a process of the synthesis of N, N'-di-sec-alkyl p-phenylenediamine as one kind of organic chemical product. Material p-nitroaniline or p-phenylenediamine and alphatic ketone in a molar ratio of 1 to 3-5condense with C3-C12 alphatic alkyl ketone; and in the presence of copper oxide, chromium oxide or barium oxide dispersed on silica gel as catalyst, the condensate is reduced by hydrogen into N, N'-di-sec-alkyl p-phenylenediamine. The reaction conditions are temperature of 130-180 deg.c and pressure of 3.5-8.0 Mpa. The present invention has the features of high yield and high purity and the product is used as the antioxidant additive for organic petrochemical product with some derivatives being intermediate for dye and medicine.

Description

N, the synthetic method of N '-di-sec-alkyl Ursol D

Technical field the invention belongs to the preparation of organic chemical industry's product, particularly N, the synthetic method of N '-di-sec-alkyl Ursol D.

Background technology sees the preparation N of report, the synthetic method of N '-di-sec-alkyl Ursol D: with p-Nitroaniline or Ursol D and aliphatic ketone is starting raw material, the two carries out condensation reaction, in the presence of hydrogenation catalyst, with hydrogen condensation product is reduced into N, N '-di-sec-alkyl Ursol D.The hydrogenation catalyst that uses in the document roughly can be divided into two classes, (one) metal and carrier model thereof, for example skeleton nickel, platinum-carbon, palladium-carbon; (2) cobaltous sulfide, nickelous sulfide sulfides.Adopt aforesaid N, during the synthetic method of N '-di-sec-alkyl Ursol D, use the metal mold hydrogenation catalyst not have outstanding advantage, when metal catalyst is used for the hydrogenation of insatiable hunger combination compound usually, hydrogenation to multiple key of polarity and nonpolar rehabilitation lacks selectivity, is accompanied by the phenyl ring of can not ignore and is hydrogenated, and reaction such as carbonnitrogen bond hydrocracking takes place, cause yield to descend, product is difficult purifies.Metal catalyst is compared easy poisoning and deactivation, and metal catalyst with practical value costs an arm and a leg, for example platinum, palladium.As hydrogenation catalyst, the metallic sulfide shortcoming is active low, uses under high temperature, high pressure usually, and synthetic cost is higher.

Summary of the invention the objective of the invention is to overcome above technical deficiency, and a kind of yield height is provided, the N that purity is good, the synthetic method of N '-di-sec-alkyl Ursol D.

N, the synthetic method of N '-di-sec-alkyl Ursol D, carry out condensation reaction with p-Nitroaniline or Ursol D and aliphatic ketone, under hydrogen atmosphere, make hydrogenation catalyst with the cupric oxide-chromic oxide-barium oxide mixed oxide that is scattered on the silica gel, under suitable temperature, pressure, the condenses reduction is prepared N, N '-di-sec-alkyl Ursol D.

For achieving the above object, in preparation method of the present invention, p-Nitroaniline or Ursol D and described alkenolic mol ratio are with 1: 3-5 is advisable.Being applicable to that " alkyl ketone " of the present invention refers to contains having or unbranched aliphatic ketone of 3-12 carbon atom, for example: acetone, butanone, 2 or 3 pentanones etc.The aliphatic ketone water content is low more good more, preferably carries out processed for the ketone that contains more water, for example can adopt the desiccant dehydration method, methods such as azeotropic distillation evaporation.When employing liquid phase reaction mode at intermittence, suitable temperature of reaction is: 130-180 ℃, reaction pressure is: 3.5-8MPa.Being suitable for catalyzer of the present invention in the reaction process is to be scattered in the powder shape thing that is made of cupric oxide-chromic oxide-barium oxide on the silica gel.Weight compositing range: cupric oxide 31-24%, chromic oxide 23-20%, barium oxide 0-6%, the silica gel of 46-50%.Effective usage quantity of catalyzer is: every mole of p-Nitroaniline or Ursol D restrain catalyzer with 20-40, can adopt constant voltage or transformation mode hydrogen make-up in reactor.The reaction process of condensating reductive alkylation can be followed the tracks of with vapor-phase chromatography easily, and N in reaction solution, the production rate of N '-di-sec-alkyl Ursol D are reaction end when reaching maximum or mixed economy best results value.Catalyzer in the reaction solution separates with filter method.Adopt the method for nitrogen protection air distillation that crude product is separated with the ketone of excessive use, the low boilers such as water of generation; can adopt methods such as underpressure distillation that crude product is carried out purifying at last; the high yield of result, high purity make N, N '-di-sec-alkyl Ursol D.

The present invention has the N of preparation, N '-di-sec-alkyl Ursol D yield height, the characteristics that purity is good.

Be suitable for its foreign matter content of p-Nitroaniline of the present invention or Ursol D and should be lower than 1.5%.When using sodium sulfide method synthetic Ursol D, preferably water, alcohol carries out recrystallize or other method is carried out pre-treatment.

Embodiment is following to illustrate effect of the present invention with by way of example.

Embodiment 1 synthetic N, N '-di-sec-alkyl Ursol D

With 54 gram (0.5mol) Ursol D, 10 restrain aforesaid catalyzer (cupric oxide 24%, chromic oxide 20% successively, barium oxide 6%, 50% silica gel), 288 gram (4mol) butanone join in 1 liter the pressure reactor that magnetic stirring apparatus is housed, use nitrogen successively, the air in the hydrogen exchange reactor.Filling the hydrogen gauge pressure to reactor is 5.0MPa, and the control mixing speed is 300-400 rev/min, with 1.5 ℃/minute reaction solution is warming up to 165 ℃, and in 165 ± 5 ℃, the pressure surge scope keeps reaction between 3.5-8.0MPa.With gas chromatography reaction process is followed the tracks of, monitored.N in reaction solution, N '-di-sec-butyl-p-phenyl enediamine's production rate reaches more than 98%, stopped reaction.Be cooled to room temperature, shift out reactant, the reaction solution that leaches catalyzer in nitrogen protection down distillation concentrate, liquidus temperature to 160 ℃, the result obtains the overhead product about 190 grams, analysis revealed is made up of about 80% butanone and 16% isopropylcarbinol.The underpressure distillation concentrated solution is collected 158-166 ℃/15mmHg and is close to colourless distillate 101.5 grams, 92.3% of theoretical yield.Use SE-30,5m * 0.25mm chromatographic column, GC4001 type gas chromatograph adopts area normalization method to analyze to exist in the distillate main content greater than 98% material, through the mass spectrometry analysis, proves that this main content is N, N '-di-sec-alkyl Ursol D.

Embodiment 2 replaces with 69 gram (0.5mol) p-Nitroaniline at the Ursol D that embodiment 1 uses, butanone 288 gram (4mol) adds same catalyzer in 14 grams and the example 1, in 140 ℃ react 3 hours after, temperature is elevated to 165 ℃, below carries out similarly handling in the example 1.Result: N, N '-di-sec-butyl-p-phenyl enediamine's yield 91%, purity 98%.

The oxidation-resistance experiment

Adopt breakdown time assay method (SH/0314-22) to measure by the synthetic N of above method, N '-di-sec-alkyl Ursol D joins in the gasoline, to the oxidation-resistance influence of gasoline.Experimental procedure is as follows: collect 90 ^#Gasoline with 110 ℃ of overhead products as sample, 50 gram samples are charged in the oxidation test bullet body, fill oxygen, the body that seals is placed 100 ℃ thermostatical oil to 620KPa, the record elastic force pressure is from the time that the highest 175KPa of reducing to uses, and this time is the oxidation induction period of sample.The results are shown in Table 1.

Table 1, the oxidation inhibitor addition and inductive phase relation

Add N in the sample, N '-di-secondary

Butyl Ursol D amount (ppm) 08 10 15 20

The oxidation induction period of sample (minute) 180 360 400 490 510

Embodiment 3 is with 54 gram (0.5mol) Ursol D, 116 gram (4mol) acetone, used catalyzer joins in the reactor in the 10 gram examples 1, temperature of reaction 140-147 ℃, carry out under the 3.5-7.5MPa, hydrogen pressure, N in reactant, N '-di-secondary propyl paraphenylenediamine's production rate reaches 98% o'clock termination reaction, cools off, shifts out reactant, the elimination catalyzer, concentrate, underpressure distillation is collected 140-150 ℃/5-6mmHg overhead product, about 50 ℃ of its fusing point, obtain 88 gram products at last, through the mass spectrometry analytical proof is N, N '-di-sec-alkyl Ursol D, yield 91%.

Synthetic N, N '-di-sec-alkyl Ursol D makes the antioxidant addn of organopolysiloxane oil Chemicals, and some Ursol D alkyl derivative is the intermediate of synthetic dyestuff, medicine.

Claims

1, a kind of N, the synthetic method of N '-di-sec-alkyl Ursol D, it is characterized in that with p-Nitroaniline or Ursol D and aliphatic ketone be raw material, mol ratio 1: 3-5, use the oxide compound that is scattered on the silica gel to be hydrogenation catalyst, temperature 130-180 ℃, the synthetic preparation of hydrogen pressure 3.5-8.0MPa.

2, N according to claim 1, the synthetic method of N '-di-sec-alkyl Ursol D is characterized in that aliphatic ketone is to contain having or unbranched alkyl ketone of 3-12 carbon atom.

3, N according to claim 1, the synthetic method of N '-di-sec-alkyl Ursol D, it is characterized in that being scattered in oxide compound hydrogenation catalyst on the silica gel, the silica gel of weight meter 46-50%, the cupric oxide of 31-24%, 23-20% chromic oxide, the barytic meal of 6-0%.

4, N according to claim 1, the synthetic method of N '-di-sec-alkyl Ursol D is characterized in that every mole of p-Nitroaniline or Ursol D, uses the 20-40g hydrogenation catalyst.

5, N according to claim 2, the synthetic method of N '-di-sec-alkyl Ursol D is characterized in that the alkyl ketone of preferentially selecting for use is acetone, butanone, 2 or 3 pentanones.