TW379210B - Method of preparing 4-aminodiphenylamine - Google Patents

Abstract

A method of preparing 4-ADPA is disclosed wherein aniline or substituted aniline derivatives and nitrobenzene are reacted under suitable conditions to produce 4-nitrodiphenylamine or substituted derivatives thereof and/or 4-nitrodiphenylamine or substituted derivatives thereof and/or their salts, either or both of which are subsequently reduced to produce 4-ADPA or substituted derivatives thereof can be reductively alkylated to produce p-phenylenediamine products or substituted derivatives thereof which are useful as antiiozonants. A second embodiment of the invention is the tetrasubstituted ammonium salts or alkyl substituted diamonium salts of 4-nitrodiphenylamine, 4-nitrosodiphenylamine and the substituted derivatives thereof where each substituent of the tetrasubstituted ammonium ion is independently selected from the group consisting of alkyl, aryl and arylalkyl groups and each alkyl substituent or the alkyl substituted diammonium salt is independently selected.

Description

Patent Application No. 8 11 Ο 2 6 9 0 Δ 7 Chinese Manual Correction Page (June 1988) B7 V. Description of the invention (S) 1 δ carbon atom. Examples of substituted aniline derivatives include, but are not limited to, 2-methoxyaniline, 4-monomethoxybenzylamine, 4-chlorobenzylamine, para-methylbenzidine, 4-mononitroaniline, 3-bromoaniline , 3-Bromo-4 monoaminotoluene, p-monoaminobenzylcarboxylic acid, 2,4-diaminobenzyl toluene, 2,5-dichlorobenzylamine, 1,4-phenylenediamine, 4,4 '— Dibenzylaminomethane, 1, 3, 5-triaminobenzyl and mixtures thereof. Aniline or a substituted aniline derivative can be added directly or under the reaction system conditions, and formed on the spot by adding a compound that can form a benzylamine or related benzylamine derivative. Azobenzene is produced by using different amounts in the reaction according to the reaction conditions. The method of controlling azobenzene production is the ratio of benzylamine to nitrobenzene. Therefore, as the ratio increases *, the amount of azo bulk decreases. As illustrated in the following M and the following examples, other variables, such as the amount of base and oxygen, can also affect the amount of azobenzene produced. Therefore, when using the technology of the present invention, those skilled in the art can perform the reaction of the present invention to control the amount of azobenzene produced. '' Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Appropriate solvents include, but are not limited to, solvents such as dimethylsulfinium, N-methylpyrrolidone , Dimethylformamide, benzylamine, pyridine, nitrobenzene, non-polar hydrocarbon solvents such as methylbenzyl, hexane, ethylene glycol dimethyl ether, diisopropylethylamine, etc., and mixtures thereof . Preferably, an excess of aniline or a substituted aniline derivative is used in the above reaction and an excess of the molecular weight of nitrobenzene. The benzene or substituted aniline derivative is used as a solvent. As described in more detail below * A solvent mixture may be used in which one or more suitable solvents are mixed with other solvents, such as controlling the amount of aprotic solvents such as methanol. Appropriate bases include, but are not limited to, organic and inorganic bases, such as base-9-this paper size applies Chinese National Standard (CNS) A4 specifications (210'〆297 mm) Λ 6 Β 6 V. Description of the invention ( 1) Background of the present invention 1 Description of the present invention The present invention relates to a method for preparing 4-aminodiphenylamine (4-ADPA), and more specifically * is based on a method for preparing 4-ADPA in the presence of a base In the case of reacting benzylamine with nitrobenzene and controlling the total amount of proton materials, such as water, a large amount of 4-nitrophenylamine salt and / or 4-nitrosodiphenylamine salt is produced. Of a mixture. The present invention also relates to the process M for the preparation of 4-ADP A intermediates and the fluorinated p-phenylenediamine product with respect to the available antioxidant. 2-Phase Technology It is known that 4-ADPA can be prepared by nucleophilic aromatic substitution of the fluorene structure, in which a benzylamine derivative is used instead of a halide. This method is the preparation of 4-ADPA intermediate, that is, the reduction of the nitro moiety after 4-nitrodiphenylamine (4-ADPA). Reacting chloronitrobenzene with an aniline derivative, such as methylanilide or its fluorene, in the presence of an acid acceptor or neutralizing agent, such as potassium carbonate, and optionally using a catalyst Salt while making 4-NDPA. See, for example, US 4,187,423; US 4,683,332; ϋ.S. 4,155,936; US 4,670,595; U. S. 4,122,118; ϋ.S. 4,614,817; ϋ.S. 4,209,463; .Fill in 4'page) Equipment-Line-Ministry of Economic Affairs -3- Central Standards > «0 Bei Gong Xiao« · Cooperative printed copy. Out of 6 and 71, 0, eclipse 14 and rot 4, there are 5 U.S .; anti 9 pairs of 24 things 7'18 18 quotients 4. of 5. Generation U. Take quilts 6 to 14 at 6 19 and 4 missing, S. Law U Fangsheng set up amine system. Benzene. It is necessary to use another material to start. In addition, this benzene is required. The base is nitrocellulose and amine, and benzene is used for the proper phase. Do not ask for amines in each case. This production can be discarded because of the strong water in A K. Α side using the Chinese family "China (CNS)> F4 specification (210 father 297 male dragon) 81. 4. 10,000 ¾ (H) V. Description of the invention (2) Λ 6η 6

The Ministry of Economic Affairs of the People's Republic of China and the Ministry of Economic Affairs of the People's Republic of China also knows that the M-Industry Cooperative Co., Ltd. M-M is also known to be made from head-to-tail coupling 4-ADPD. See, for example, G.B.1,440,767 and U.S.4,760,186. The shortcomings of this method are unacceptable in commercial processes. Decarboxylation of carbamates is also known to give 4-NDPA. See U.S. 3,847,990. However, this method is not commercially practical in terms of price and output. •. It is known to use aliphatic compounds, naphthalene, or unsaturated ethylenic compounds as kanogens, made by para-nitroso-diphenylhydroxylamine, which can be catalyzed by nitrosbenzene dimerization, Hydrogenated to make 4-ADPA. Refer to, for example, U.S. 4,178,315 and 4,40 4,401. It is also known to prepare para-nitrosodiphenylamine from dibenzylamine and alkyl nitrates in the presence of excess hydrogen chloride. See, for example, U.S. 4,518,803 and 4,479,008. It is also known to make 4-mononitrosodiphenylamine by reacting acetanilide with nitrobenzene in D MS 0 in the presence of sodium hydroxide and potassium carbonate in 801C for 5 hours. See Ayyangar et al., Tetrahedron Letters, V ο 1.31 * HO. 22 · pp. 3217—3220 (1990). See also, W o h1 * Chemische Berichte, 36, p. 41 3 5 (19 0 3) W and Chemische Berichte, 3 4 > p. 2442 (1 9 0 1) ° However, because of nitroso diphenyl The low yield of amines makes them impractical in commercial cuisine. In addition, such method boxes use aniline derivatives * meaning • acetanilide, thus increasing the price of starting materials. The process of the present invention does not include a halide source, thereby reducing the expensive step K of removing halide from the wastewater. In addition, the process of the present invention is more hydrocarbon-based in terms of manufacturing price and raw material price, because the present invention directly uses aniline and nitro (please read K1 first, and then write 4 pages). Packing-Private paper size遑 Use the China Ming Jia Bi (CNX) specifications (210X297g ¢) V. Description of the invention (3) Λ 6 It 6 Printed by the Ministry of Industry and Economics and K Industrial Consumer Cooperatives without using aniline and nitrobenzene Of its derivatives. SUMMARY OF THE INVENTION The present invention is directed to methods for preparing 4-ADP A intermediates or substituted derivatives thereof, such as 4-nitrodiphenyl limbs (4-NDPA) and their salts, and / or 4-nitroso Diphenylamine (p-NDPA or 4-NDPA) and / or its derivatives, in which aniline or substituted stupid limbs are brought into reactive contact in a suitable solvent system, then in the presence of sickle and proton-controlling materials such as water, React under heavy conditions. The resulting reaction mixture contains a large amount of 4-ADPA intermediate or its substituted derivative, including 4-mononitrodibenzylamine and / or 4-nitrosodiphenylamine salt. According to the technology of the present invention, this process can be used to obtain high yields of 4-nitroso products (para-nitrosodiphenylamine and its salts) with a small amount of 4-mononitro products. The 4-nitroso reaction product mixture can then be directly hydrogenated, or the 4-nitroso product can be isolated and successively hydrogenated to produce high yields of 4-ADPA. Similarly, high yields of 4-Cryl products (4-mononitrodiphenylamine and its salts) can be obtained with trace amounts of 4-nitroso products. At the same time, 4-nitro products can be isolated, or 4-nitro This product is hydrogenated to give a high yield of 4-ADPA. In addition, both the 4-mononitro and 4-nitroso products can be produced * cannot be separated. But the reaction mixture can be directly hydrogenated to obtain 4_ADPA. The 4-ADPA produced is used to prepare the alkylation product of para-phenyldiamine, which can be used as an antioxidant and an antioxidant. Alternatively, the 4-ADP A intermediate can be alkylated using a ketone and a solvent in the same reaction vessel. J In the practical examples of the present invention, the proton material that exists during the reaction between styrylamine or substituted aniline derivatives and nitrobenzene is controlled by the use of a susceptor during the reaction (please read the two notes before you write it first) (On this page) Order _ Private paper scales for use in the domestic market (CNS) IM specifications (210X29 / public goods) 81. 4. 10,000 sheets (H) V. Description of the invention (4) Λ 6 Π 6 Ministry of Economy 屮Central Standards, and the total amount printed by the beta industry consumer cooperatives. In another specific embodiment, the proton material is continuously removed by steam distillation to control the amount of proton material present during the reaction of benzene or substituted aniline derivatives with nitrobenzene. The present invention further relates to 4-mononitrodiphenylamine , 4-mononitrosodiphenylamine and its substituted derivatives of tetra-substituted ammonium salts or alkyl-substituted diammonium salts. Each of the substituents of tetra-substituted ammonium phosphonium is independently selected from the group consisting of alkyl, aromatic Each of the alkyl substituents of the diammonium salt substituted with a aryl group and an arylalkyl group is independently selected. Detailed description of the present invention The method for making 4-ADPA intermediates according to the present invention includes the steps of: a) Reactively contacting aniline or substituted aniline derivative with nitrobenzene in a suitable solvent; b) at a suitable temperature and with a proper check Control proton materials, such as water, in a restricted area, such as a reactor, by reacting aniline or substituted benzene. Amine derivatives with nitrobenzyl to produce 4-diphenyldiphenylamine or its substituted derivatives with A salt and / or 4-mononitrosodiphenylamine or a substituted derivative thereof and a salt thereof. In order to produce 4-ADP A or a substituted derivative thereof, the method includes the following steps: c) kanhara 4-mononitrosodiphenylamine or a substituted derivative thereof with a salt thereof and / or 4-nitrodibenzylamine or Its substituted derivative and its salt produce 4 — ADPA 〇 In order to produce alkylated para-monobenzyl diamine or its substituted derivative, this method includes the step ": (Please read the precautions below and fill in the ^ page) Packing-Private Paper "Ruler Λ Side Uses Chinese Family Furniture (CNS) Ή Specifications (210x297 male dragon) 81. 4. 10,000 sheets' (H) V. Description of Invention (5) Λ 6 Π 6 Central Standard of the Ministry of Economic Affairs And Shelley Consumer Cooperative printed d) phosphogenated alkylation step c) of 4-ADPA or its substituted derivative. As used herein, 4—ADP A Intermediate # means 4—nitrodiphenyl Amine, 4-mononitrosodiphenylamine (also referred to as para-nitrosodiphenylamine), its substituted derivative and its salt. Therefore, "one or more 4-ADPA intermediates" refers to one or two neutral compounds, that is, not in the form of a salt, and / or one or two of these compounds. The salt is generated from the reaction trace compound of the 4-mononitro group and / or the 4-mononitroso product. Therefore • The reaction mixture produced by the method of the present invention may include a compound or salt or its sister compound. The molar ratio of benzylamine or substituted aniline derivative to nitrobenzene can be changed from the amount of nitrobenzyl to excess benzylamine or substituted aniline derivative. It is preferred to use an excess of aniline or a substituted aniline derivative for the reaction. The ratio of 4-nitro to 4-nitroso produced by the reaction of the present invention can be controlled by changing the ratio of aniline to nitrobenzene. For example, * the higher the ratio of benzylamine to nitrobenzene, the higher the ratio of 4-nitroso to 4-mononitro. Conversely, the higher the ratio of nitrobenzyl to aniline, the higher the ratio of 4-nitro to 4-nitroso. The term " substituted benzylamine derivative " is used herein to mean that aniline includes one or more electrons or ion-exchanging substituents on the aromatic sheet. Applicable substituents include, but are not limited to, * halides, -N02, -HH2, alkyl fluorene, alkyl sulfonium groups, -S03, -COOH and aryl groups containing at least --NH2 group Alkyl or alkylaryl. Halides are selected from chlorides, bromides and fluorides. Preferred alkyl and alkoxy groups contain from 1 to about 6 carbon atoms. The preferred aryl aryl * alkyl and alkyl aryl g groups include about 6 to about. Please read the following precautions before filling in this page. Each paper rule on the page is made of China National Standard (CNS) T4 (210x25). 7 males; a :) 81. · 4. 10,000 sheets (Η) — 8 Patent application No. 8 11 Ο 2 6 9 0 Δ 7 Chinese manual revision page (8 June 2008) B7 V. Description of the invention (S ) 1 δ carbon atom. Examples of substituted aniline derivatives include, but are not limited to, 2-methoxyaniline, 4-monomethoxybenzylamine, 4-chlorobenzylamine, para-methylbenzidine, 4-mononitroaniline, 3-bromoaniline , 3-Bromo-4 monoaminotoluene, p-monoaminobenzylcarboxylic acid, 2,4-diaminobenzyl toluene, 2,5-dichlorobenzylamine, 1,4-phenylenediamine, 4,4 '— Dibenzylaminomethane, 1, 3, 5-triaminobenzyl and mixtures thereof. Aniline or a substituted aniline derivative can be added directly or under the reaction system conditions, and formed on the spot by adding a compound that can form a benzylamine or related benzylamine derivative. Azobenzene is produced by using different amounts in the reaction according to the reaction conditions. The method of controlling azobenzene production is the ratio of benzylamine to nitrobenzene. Therefore, as the ratio increases *, the amount of azo bulk decreases. As illustrated in the following M and the following examples, other variables, such as the amount of base and oxygen, can also affect the amount of azobenzene produced. Therefore, when using the technology of the present invention, those skilled in the art can perform the reaction of the present invention to control the amount of azobenzene produced. '' Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Appropriate solvents include, but are not limited to, solvents such as dimethylsulfinium, N-methylpyrrolidone , Dimethylformamide, benzylamine, pyridine, nitrobenzene, non-polar hydrocarbon solvents such as methylbenzyl, hexane, ethylene glycol dimethyl ether, diisopropylethylamine, etc., and mixtures thereof . Preferably, an excess of aniline or a substituted aniline derivative is used in the above reaction and an excess of the molecular weight of nitrobenzene. The benzene or substituted aniline derivative is used as a solvent. As described in more detail below * A solvent mixture may be used in which one or more suitable solvents are mixed with other solvents, such as controlling the amount of aprotic solvents such as methanol. Appropriate bases include, but are not limited to, organic and inorganic bases, such as base-9-this paper size applies Chinese National Standard (CNS) A4 specifications (210'〆297 mm) ί A 6 Π 6 Ministry of Economic Affairs棂 Zhun Er β Industrial Consumption & Co., Ltd. Printing 5. Description of the invention (7) Gold releases such as Najinjian, alkali metal hydrides, hydroxides and alkoxides * For example sodium hydride • lithium hydroxide, sodium hydroxide • Hydroxide, potassium hydroxide, t-potassium butoxide, and the like, and mixtures thereof. Other acceptable materials include, but are not limited to, phase transfer catalysts such as tetra-substituted ammonium hydroxide mixed with a suitable alkali source. Each substituent is independently selected from alkyl, aryl or arylalkyl groups. Among them, the alkyl group, the aryl group and the arylalkyl group are preferably those having 18 atomic broken atoms, including tetraalkylammonium hydroxide * such as tetramethylammonium hydroxide, aryltrialkylammonium hydroxide, such as phenyltrimethyl hydroxide Press * Arylalkyltrialkylammonium hydroxide, such as benzyltrimethylammonium hydroxide, alkyl hydroxide to replace diammonium, such as bis-dibutylethylhexamethyldiammonium hydroxide, and other phase transfer catalysts and Appropriate test compounds such as appropriate mixtures with aryl ammonium salts, crown ethers and the like, and amine sickles, such as lithium bis (trimethylsilyl) amide, and the like, including mixtures thereof . A preferred material (base) for use as a base is tetraalkylammonium hydroxide such as tetramethylammonium hydroxide * preferably * by adding amidine to a benzylamine or substituting an aniline derivative to form a mixture * and then reacting with nitrobenzyl mixing. Alternatively, the remainder can be added after mixing aniline or substituted aniline derivatives with nitrobenzene. The material can be added on the surface M or below K. The amount used in this process has a wide range of changes. For example, depending on the required degree of azobenzene minimization (· tn i n i π i z a t i ο η), the amount of bases can be restricted for the reaction or the nitrobenzyl or benzylamine or substituted aniline derivative fi can be restricted for the reaction. The reaction was carried out at a temperature which was changed at Dafanyuan. For example, the temperature may be in the range of about 101 ° C to about 150 ° C: within the range of the garden. For example, about 0 ° to about 100 ° C, preferably about 10 ° to about 901 °. The optimum temperature for carrying out the reaction of the present invention is about S01C to about 80 ° F. * For example, at 75 ° C. If there is (please read the precautions on the back first and then use this page) Private paper ruler A is in use a by the home standard (cns) Specifications (2 丨 ox29 · / public; a :)-economy Ministry of Standards, Standard A, Consumer Goods Cooperation, Du Printing Λ 6 _____ Β 6 _ V. Description of the Invention (8) Using benzylamine as a solvent under oxygen reaction conditions, when the reaction temperature increases, the amount of depleted nitrogen benzene will be generated Will increase. However, if the reaction is performed in aniline under anaerobic conditions, the higher temperature does not necessarily increase the amount of hydrazine. If the generation of tritium nitrogen is not a problem, higher temperatures are more suitable. However, if it is necessary to minimize the amount of azobenzene, a lower temperature or anaerobic reaction will be more suitable. In addition, in order to minimize the amount of nitrogen benzene when the reaction is performed at a higher temperature, a solvent other than aniline can be used and the tb ratio of aniline or a substituted aniline derivative, p-nitrobenzyl, can be controlled. It is important to control the amount of protons in the reaction. Generally, when the reaction is carried out in aniline, the water content of the reaction exceeding about 4% H2O (based on the volume of the MU reaction mixture) will inhibit the reaction of benzylamine with nitrobenzene and make it inconspicuous. Reducing the amount of water to 4% K makes the reaction possible under acceptable conditions. When tetramethylammonium hydroxide is used as the boll and aniline is used as the solvent, the amount of water is reduced, for example, it is reduced to 0.5% based on the volume of the K reaction mixture. With the selective loss of 4-nitrodibenzylamine and 4-one The total amount of nitrosodiphenylamine and / or its hydrazones is increased so that more 2-nitrodiphenylamine is produced but still in a minimum. Therefore, the present reaction can be performed under anhydrous conditions. When using aniline as a solvent, the proton material > the controlled amount is an amount that can suppress the reaction between aniline and nitrobenzene, such as about 4% of the reaction product of K, which is about 20%. The upper limit of the proton material in the reaction varies with the solvent. For example * When DMS0 is used as the solvent, and tetramethylammonium oxide is used as the plutonium, the upper limit of the tritium material in the reaction is about 8% based on the product of the reaction mixture. Η20 ° When using the benzene limb as the solvent At the time, the upper limit is the minimum product of the reaction mixture, which is 4961U0 ^ In addition, the acceptable amount of proton material (please read the precautions before filling in the private page). As home 榣 Half (CNS) T4 specification (2Ι ×× 297 male; ϋτ): 81. 4. 10,000 sheets (Η) 11 V. Description of the invention (9) A 6 η 6 Printed by the Central Ministry of Economic Affairs 屮 榀 工 工 工 合作 协Depending on the base type, the amount of sickle and alkali cations are changed * and used in different solvent systems. However, the technology of the present invention is within the scope of this technology, and is used to determine the specific upper limit of the proton material of a specific solvent * base type and amount, Siyang ion and the like. The minimum amount of proton material necessary to maintain the selectivity of the desired product is also based on the solvent • sickle type and amount * salty cations and analogs * which can also be determined by those skilled in the art. Because the amount of proton material is important in the reaction, when using aniline as the solvent, reduce the amount of #proton material as much as possible and then add it back to the required amount. Add 0.5% by volume to the reaction. Protonic materials that can be used in addition reactions known to those skilled in the art include, but are not limited to, water, methanol, and the like. Methods for measuring the amount of proton material and minimizing the amount of proton material are well known in the art. For example, the Karl-Fischer device can be used to determine the water content of the reagent, and dried by distillation and / or reduced pressure, dried under P20s and other reagents, for example, aniline and its analogs * Including its mixture, azeotropic distillation can reduce the amount of water. In a specific embodiment for controlling the amount of proton material during the reaction of phenylamine or substituted aniline derivative with nitrobenzene, a drying agent is added during the reaction of aniline or substituted aniline derivative with nitrobenzene. For example, when the proton material is water • Use elixirs to remove aniline or to replace aniline derivatives with nitrobenzene. The water content during the reaction with nitrobenzene makes the nitrobenzene have a higher conversion rate. 4 Mononitrodiphenylamine or its substituted derivative has higher yield. During the reaction of aniline or substituted aniline derivatives with nitrobenzene, in addition to the use of appropriate sickle, the elixir is a compound used herein. Examples of suitable drying agents include, but are not limited to, anhydrous sodium sulfate, molecular sieves (molecular, please read the precautionary notes on the first copy, copy, and copy), packing, private paper, 5 side-use, a, home samples ( CHS) TM specifications (210x297 male *) 81. 4. 10.00.00 sheets (Η) V. Description of the invention (10) Λ 6 i? 6 Ministry of Economic Affairs 屮 榀) For example, 4A, 5A, and 13X forms of Union Carbide Corporation, calcium chloride, tetramethylammonium hydroxide dihydrate, anhydrous bases such as KOH and HaOH, M, and activated aluminum. In another specific example of controlling the amount of proton material during the reaction of benzylamine or substituted aniline derivative with nitrobenzene • The proton material is continuously removed from the reaction mixture by distillation. When the proton material is water, the preferred method is to azeotropically distill the water continuously with a water / aniline azeotrope. Distillation of proton materials into ores is currently the preferred method for controlling the amount of proton materials during the reaction of aniline or substituted benzylamine derivatives with nitrobenzene. In the reaction between aniline or substituted benzylamine derivatives and nitrobenzyl, a relatively small amount of base Linbin was used to remove proton materials to obtain a very high nitrobenzene conversion rate and high yield of 4 mononitrodiphenylamine and 4 — Nitrosodiphenylamine and / or its salts or its substituted derivatives. The reaction can be carried out under aerobic or anaerobic conditions. Under aerobic conditions, the reaction must be performed as described above in a reaction zone exposed to aerobic conditions, usually in the air. Under aerobic conditions, the pressure at which the reaction proceeds can be changed and the optimal pressure K and the optimal mixing of pressure and temperature / pressure conditions can easily be determined by those skilled in the art. For example, the reaction can be carried out at room temperature, in a pressure range of about 14 to about 150 psig, such as about 14 to about 150 psig. Under anaerobic conditions, a neutral gas is present, 'e.g., krypton or argon, and the reaction is performed in an atmospheric krypton or a subtractive or booster cavity. The best conditions for the reaction parameters, such as temperature, alkali • solvent M and the like, can be easily determined by those skilled in the art.偁 When aniline is used as a solvent under anaerobic conditions, the reaction can be observed to have less 偁 nitrobenzene production.》 When DMS0 and other similar solvents are used as solvents, i (Please read the precautions below) #Fill in the VF) equipment-line-private paper scale free use China Ming Jia (CNS) specifications (210x297 public; ¢) Η 6 5. Description of the invention (11)

The Ministry of Economic Affairs of the People's Republic of China's Central Government has observed less azobenzene production at 1V · 'cooperative Du Yin M. 4-Nitrodibenzylamine or a substituted derivative thereof and / or 4-nitrosodiphenylamine or a substituted derivative thereof and / or a salt thereof can be reduced to 4-ADP A or a substituted derivative thereof. Neutral compounds can be produced from salts using water and / or acids. Refer to Example 1D. In addition, the salts can also be used as shown in Example 1A. This primordial action can be performed by many conventional methods, such as mixing a hydride source * such as sodium borohydride mixed with palladium- or platinum-carbon catalysts. Preferably, the hydrogenation is carried out by catalyzing the hydrogenation in the presence of platinum-or palladium-carbon, nickel and the like in the presence of hydrogen. This hydrogenation method is detailed in > Catalytic Hydrogenation in Organic Synthesis ", P.N. Rylander * Academic Press * H.Y. P.299 (1979), which is incorporated herein by reference M. This hydrogenation can be performed in different solvents, but not limited to toluene, xylene, aniline · 4-ADPA, water and mixtures thereof. Preferably, the hydrogenation is performed using a platinum carbon or palladium carbon catalyst in a suitable solvent, for example, toluene, 4-ADPA, xylene or aniline, a mixture thereof, or containing water as a solvent, 100 ps ig H2 to about A hydrogen pressure of 340 psig H2, a mixture at a temperature of about 80 ° C. Anti-oxidants can be made by the thermally known method to perform the primogenic alkylation of 4-ADPA. See U.S., 4,900,868. Preferably, 4-ADP A is reacted with didanone or aldehyde in the presence of hydrogen and meal carbon as a vehicle. The ketones include methyl isobutyl ketone (MIBK), acetone, methyl isoamyl methyl ester and 2-octanone. Using ketones as solvents in the same reaction vessel can perform 4-ADPA intermediate "Kanyuan action and alkylation of Kan raw materials. With reference to U, S.4, "3.191 and J. Chem. Soc '. 1 of Banerjee et al., Please read the precautions below and fill in this page. The private paper size is used in conjunction with China's furniture (CNS) T4 specification (210x297 (Public *) 81. 4. 10,000 sheets (H) A 6 It 6 Printed by the Ministry of Economic Affairs of the People ’s Republic of China, “Industrial Cooperation & Printing” 5. Description of Inventions (12)

Chem. Comm. 18, 1275-76 (1988). The predicted equivalents of the reactants and reagents listed above are relative to one or more of the different reagents and reagents with the same general quality, such as H02, which are simple variables. In addition, if the substituent is designed to be hydrogen, the exact chemical nature of the substituent when it is not hydrogen at this position is not critical so that it does not affect overall activity and / or synthetic processes. The above-mentioned chemical reactions are generally disclosed in terms of their wide application to the method of the present invention. Sometimes, the reaction conditions in the disclosed range may not be applicable to each reactant and reagent. For example, some suitable bases may not be soluble in every solvent. Those skilled in the art know the reagents and reagents needed at this moment. In each case, it is well known that the artisan can successfully carry out this reaction by using the futong method, for example, by making appropriate adjustments to temperature, pressure, etc., by changing to another traditional reagent such as other solvents or Bases can be applied to the method of the present invention by routinely modifying reaction conditions and the like, or by reactions disclosed herein or non-traditional. In all preparation methods, all starting materials are known or can be prepared from known starting ' materials. Without further thoughts, it is enthusiastic for those skilled in the art to use the present invention to the fullest extent possible as described above. Therefore, the following specific embodiments can only be used as an illustration, and do not limit the remaining rights in any aspect of the disclosure. All reagents were used except for drying with solvents and drying as described below. Unless otherwise indicated, all products were determined by HP LC according to the following method. Materials and methods: Aniline or substituted benzylamine derivatives and nitrobenzyl are test grades, and the Chinese standard (CHS) fM specification (2 丨 0x ^ 7 mm) is used without entering a private paper ft ruler. 4. 10,000 sheets (H) (please read the precautions on the back before filling in the private page) Pack · 15 A 6 η 6 V. Description of the invention (13), used in one step purification. Solvents were purchased from Aldrich Chemical and were anhydrous grade. Tetramethyl hydroxide was purchased as M pentahydrate-0 before drying in a P205 dryer under vacuum for several days. The solid formed by titration proves that the dry material is dihydrate. HPLC analysis: Reverse phase HPLC analysis of the reaction mixture. Use a 5 M Beckman / Altex Ultrasphere—OPS (4.6X 150mm). Column when using a three-gradient assisted system. Rushing time (m i η) Flow rate (m 丨, / Mh)% ΑΠΝ ΜρΠΗ 〇 1.5 9010 〇 (Please read the precautions for the back first! Φ 璘 Write: ： · 4 ^ lv Binding-Order

Printed by the Central Ministry of Economic Affairs of the People's Republic of China, M οι 2 2 5 5 ο 1 〇 | 1 1 1 3 4 4

3 0 0 0 0 0 0 6 6 3 1 1 9 Q 0 0 0 5 5 0 0 3 2 2 4 4 1 1 8 0 0 5 5 2 2 4 4 ο ο | amine benzyl P nitrate and amine Aminobenzyl lower two base strips of nitric acid have I • position 'Temperature pair chamber and ND sharp in PAA | Example 4 Real product 1 > Application example A Antiyin. Net paper ruler A side use China Bl Standard Complete (CNS) TM specifications (210 fathers, 297 males) 16 81. 4. 10,000 sheets \ Η) Line-Central Standards Department of the Ministry of Economic Affairs! S: Industrial Consumption 1Ϊ · Cooperative Du Printing Λ 6 ___ Π6 _-_ V. Description of the Invention (14) NDPA) Product. The reaction mixture was directly hydrogenated to obtain 4-ADPA. Prepare a 500 mL three-necked round bottom flask with a magnetic stirrer. The reaction vessel was charged with 1.96 lOl of aniline and hexylbenzene (4.3 mL, 42 nmole). Tetramethylammonium oxide dihydrate (17.7 g, 140 maioles) was added as a solid reaction mixture. After 2 hours, almost all of the nitrobenzene was consumed in this reaction, but the reaction had to be stirred for 18 hours. At this point, more than 99% of nitrobenzyl has been consumed. HPLC analysis of the reaction mixture indicated the yield of the following products based on nitrobenzene: 4-HDPA (6.4mmole > 137g * 15¾), P-NDPA (30'6inmole, 6.1g, 73%), 2-NDPA (0.3mmole * .0.064g, 0.7%), azobenzene (3.6nimole, 3,6mmole, 0.65g, 8.5%), biphenyl piperazine (0.8 mmole, 0.014g, 1.9%), diphenyl piperazine-1 N-oxide (0.3mmole, 0.05s, 0.7%) 〇 ___ Water (16ml) was added to the mixture and the whole reaction was transferred to a 300cc autoclave for hydrogenation. 1% platinum / carbon catalyst (0.5g dry weight) was added to the autoclave. The reaction mixture was heated to 80¾ under 150psig H2. Absorption of hydrogen was completed within 30 minutes. HPLC analysis indicated that 35.9 mmole 4-ADPA was produced, which was the best 97% yield compared to M4-NDPA and P-NDPA based on their ear counts. B) This example is the reaction between aniline and nitrobenzene in dimethylarsine under anaerobic conditions at room temperature. Under argon, 4 mL of DMS0 * aniline (200 wL, 1.9 mmole) and gaseous tetramethylammonium dihydrate (330 mg · 2.5mnole) were added to a 2 5 nL round bottom entropy flask. The reaction was performed at room temperature for 4 hour. Nitrobenzene-converted paper uses 8 Chinese Standards (CNS) TM specifications (210 > < 297 male dragons) 81. 4. 10,000 sheets (H) -17-(Please read the precautions on the back first Fill in 4 pages) Binding · Binding-Thread ·

Iftr, Ministry of Economic Affairs, Central Standards, Cooperating with Zhibei Workers, Du Duan Printing Λ 6 Ιϊ 6 V. Description of Invention) The rate of change is 68%. HPLC indicates the following yields. M nitrobenzene is based. 4 Yixin 卩 & (30.5%) ,? 1 "10? &Amp; (33.6%), azabenzene (2.6%), azobenzene oxide (trace). C) This example is the net reaction of benzylamine and nitrobenzene at room temperature. Add benzylamine (1.8 mL) and nitrobenzene. (0.02 mL, 0.19 mmole) to a 25nL round bottom flask in a glove box filled with argon. To this solution was added tetramethylammonium hydroxide dihydrate (330 mg · 2.5Bΐηο1β). After a few hours all nitrobenzyl will be consumed. HPLC analysis indicated the following yields of nitrobenzene as the basis: 4 — NDPA 10%, P — NDPA 76%, azobenzene 7%, and diphenylpyrazine 5%. D) This example is the reaction of aniline and nitrobenzene in DMS0 under aerobic conditions at room temperature. This example also illustrates the use of water and acids to generate 4-NDPA and P-NDPA from their salts. The reaction mixture contained 4 mL of DMSO benzylamine (200 wL, 2.1 Emole) and nitrobenzene (200, 1.9 mmole). Add a portion of tetramethylammonium hydroxide dihydrate. After the reaction was stirred for 18 hours, nitrobenzene had been consumed by 80%. The reaction was poured into 200 mL of water and 4-NDPA precipitated immediately. The solution was cooled with ice for several hours, and then dried at 100 t: dry refining. The filtrate was treated with glacial acetic acid until the pH was neutral and P-NDP A precipitated. Pass the precipitate through and dry at 100 ° C. Separation is based on the loss of nitrobenzene: 4-HDPA (66%) · P-HDPA (29%). E) This example is the reaction between aniline and nitrobenzene in DMS0 under aerobic conditions. Add benzylamine (0.05 eeole, 4.6 g) * fluorenylbenzene (0.05 mole, 6.1 g) and 75iL DMS0 250mL mL bottom 焼 bottle. Private paper scales used by Chinese homeowners «Bi (CNS) T4 specifications (210X297);« :) 81. 4. 10,000¾ (Η) (please note the following first #please fill in the form page) Pack-18 May Description of the invention (L6) Λ 6 η 6 Standard of the Ministry of Economic Affairs and the central government and £ 3: Printed by the Industrial Cooperative Cooperative, a part of tetramethylammonium hydroxide dihydrate (0.2mole, 25.44g) is added to the solution. The reaction mixture was heated to 80 F in an oil bath: and the temperature was maintained for 5 hours. The reaction was analyzed by HPLC. The yield of K-nitrobenzyl is used as the benchmark; 4-NDPA (35%), P-HDPA (51%), and azobenzene (3.1%). 'F) This example is the reaction of aniline $ nitrobenzene in DMF under aerobic conditions. Aniline (200 * 2.1mmole) and nitrobenzyl (200, 1.9mnole) were dissolved in 5mL DMF. Tetramethylammonium hydroxide dihydrate (1.0g, 7.8Bmole) was added to the reaction. After 2 hours of reaction, 39% of nitrobenzene was lost. Yield K was based on nitrobenzene loss: 4-NDPA 99% · P — KDPA trace. Example 2 This example illustrates that the reaction of the present invention can be carried out within a temperature range. K The following method prepared four identical reactions and performed in air at 0, 23, 50, and 80 C. 49 mL of benzylamine and nitrobenzene (1.0, 9.5 mmole) were added to a 50 mL round bottom flask. Tetramethylammonium hydroxide was dihydrated (4.40g, 34.6mm) was added and the reaction was performed for 5 hours. The product yield was determined by HPLC and M was consumed as the basis for nitrobenzene moles. Selectivity was the number of ears of the product and the loss of nitrobenzene. The ratio of moles. The yield is the conversion rate multiplied by the selectivity. Gambling 1 {Please read the back notice first and then write this page) Binding-Stitching-Line 'Temperature t: Nitrobenzene Product%% 鱅Tracing seat ___; _ 馕 桦 · & Suspected private paper scale in use a a 家 榀 Bi (CNS) Ή Specifications (210X297 Gonglong 81. 4 / 10,000 sheets. (H) -19 V. Description of the invention (17) Λ 6 Π 6 Economic Central Standards and Consumer Price Cooperation Du printed 0 52% P-HDA 34 18 4 — NDPA 18 9.3 2 — NDPA 2. 2 1.0 Diphenazine piperazine 0.6 .3 0.3 ΊZ% P-HDPA • 71 51 4 — NDPA 12 8.5 \ _ Triazine 17 12 Dibenzidine piperazine Trace dibenzidine piperazine-N-oxidation , Trace amount 50 98¾ P — NDPA 88 86 4 — NDPA 7.8 7.6 2 — NDPA 1.7 1.6 azobenzene * 22 21 80 100¾ P — NDPA 89 89 4-NDPA 7 7 2-HDPA 2 2 俚 M Rong 5 5 R5 * Large Some of the azabenzyl hydrocarbons are produced by oxidative coupling of benzene limbs. Refer to DT Sawyer paper ° Chinese paper standard (CHS) 210 Specifications (210X297g ¢) 81. 4.] 0 000 sheets (H) (Please read the precautions on the back first to complete this page) 5) Λ 6 η 6 V. Explanation of the invention (,) X 3 Example 3 This example illustrates the importance of controlling the amount of proton material in the reaction. Four identical reactions were performed, except that the amount of water added to the mixture changed, which included 0, 10, 50, and 100. Therefore, the amount of aniline (2 mL) and water added to the mixture includes 1, 10, 50 and 100. Add aniline (2mL) and nitrobenzene (2inL) to a 25nL round bottom flask and add different amounts of water. Add 1 part of tetramethylammonium hydroxide dihydrate. The reaction was performed in a room temperature blank and a sample was prepared after 16 hours. A definitive group reaction was performed using methanol instead of water. (Please read the first note and fill in the loose pages first.) The staff of the Ministry of Economic Affairs, the Central Bank, and the prospective employees should cooperate with you to print Du Shourong? · Volume (u L)% mm ο 1 e ratio production (mmo 1 e) water volume added * 4-NDPA + P-NDPA 4-NDPA + P-NDPA / 2-NDPA + diphenyl piperazine 0 2.2 6.2 0.83 10 2.45 8.5 0.68 50 3.45 11.5 0.18 100 4.7 5.0 0.05 Volume (/ i L)% plus λ field "β mmt I · 10 0.25 8.8 0.67 50 1. 25 16 0.57. 100 0. A7 line-for private paper ruler Chinese Β house «Bi (CNS) TM specifications (2) 0 x 297 mm) 81. 4. 10,000«. (Η) -21 V. Description of the invention (19) Λ 6 Π 6 * The volume ratio of water to methanol. The amount of water present in the reaction when no water was added in this example came from tetramethylammonium hydroxide dihydrate. Example 4. This example illustrates the use of different solvents in the operation of the method of the present invention to produce 4-«0? 纟 and / or? One rib? / ^ 产品。 Product. The reactions listed in Table 3 were performed as indicated in Example 1, except that the solvent of Example 1 was changed to that indicated in the table. Box 3 (please read the precautions and fill in the wv first) Packing-Solvents Ν -methylpyrrolidone DMSO / THF »〇 $ _ Reaction conditions 1D 1B 1 η Line · Central Ministry of Economic Affairs! § Printed by Zhuhai Cooperative Consumer Cooperatives. Example 5 This example illustrates that different bases can be used to produce 4-NDPA and / or P-HDPA products when operating the method of the present invention. The reactions listed in Table 4 were performed as instructed in Example 1, except that the base in Example 1 was changed to those indicated in the table. Xian Rong 4 · Na Jin State

Anti-cooking stove XD 8 sheets of paper on the paper side «Complete (CHS) & H size (2 丨 0x297g; ¢) 81. 4, 10,000 sheets' (H) 22 V. Description of the invention (2 ()) Λ 6 Π 6

HaH 1D HaOH 1D KOH 1D t — potassium butoxide 1D bis (di'methylsilyl) lithium ammonium 1B, 1D NaOH / Kp c0s 1 IV, 1 F 32. Example 6 This example illustrates the unexpected increase in selectivity and nitrobenzene conversion rate when using the method of the present invention when compared with the method disclosed by Ay Angar, et al. The reaction of acetoanilide, nitrobenzyl, and NaO ^ K2C03 in DMSO was carried out according to the process described by Ayyangar * et al. Tetrahedron Letters, Vol. 31, NO. 22 pp3217-3220 (1990). Analysis of this reaction product by HP LC indicated a 37% conversion of nitrobenzene and the following yields based on M-nitrobenzene were obtained. 4-NDPA (6%), P-NDPA (4.5%), azobenzene (0.7%). When the reaction is carried out according to the technique of the present invention *, the conversion rate of nitrobenzene and the selectivity to the desired product are comparatively increased. For example, when carrying out the reaction described in Example 1D *, mix the stupid limb (0.05mole), nitrobenzyl (0.05mole) and tetramethylammonium hydroxide dihydrate (0.2mole) in 75 mL DMS0. . The reaction was stirred at room temperature for 5 hours, and then analyzed by HPLC color analysis to obtain the following results. The conversion of nitrobenzene was (85%). Although the production based on nitrobenzyl: 4-hDpa (18%), p-NDPA (51%), azabenzyl (3%). The reaction of acetamidine and nitrobenzene was also performed at room temperature. Putting sugar sugar on a piece of paper ”Ruler A for free B Family« if (CNS) T4 size (210x297 male; ¢) 81 · 4. 10,000,000 sheets' (H) (Please read the back first Precautions (1) Fill in this page) Equipment · V. Description of the invention (21) Λ 6 Π 6 (0.05mole), hexaphenyl (0.05nole), NaOH (0.2mole) and K2CO3 are dissolved in 75mL DMSO. The reaction was stirred at room temperature (23¾) for 5 hours. Analysis of the reaction confirmed that nitrobenzene was not converted and no product was measured. Example 7 This example illustrates how the ratio of P-NDPA / 4-HDPA can be controlled by the ratio of aniline / nitrobenzene. When the reaction volume of hydrazone and the amount of tetramethylammonium hydroxide dihydrate remain the same, in a typical reaction of P aniline / nitrobenzene with a volume ratio of 1, benzylamine and nitrobenzyl K in a typical reaction, aniline (2 mL) and Nitrobenzene (2 mL) was placed in a 25 mL round bottom flask. Tetramethylammonium hydroxide dihydrate (33 mg '2.5 mmole) was added and the reaction was performed at room temperature in air for 14 hours. The reaction products were then analyzed by HPLC. Form 5 (please read the precautions before filling out this page). Packing-Line-Volume Ratio Cagemine / A certain ratio p-NDPA / 4-HDP.A— 33

Printed by the Ministry of Economic Affairs, the Central Bureau of Quasi-Bureau Consumer Electronics Cooperative, M 1 10 50 Example 8 4 6 Private paper ruler and edge-use medium B Furniture (CNS) T4 Specification (210 > < 297 Gonglong) 81 _ 4 10,000 sheets (H) V. Description of the invention (22) This example illustrates the effect of the amount of proton material in the presence or addition of the reaction on the conversion rate and the yield of 4-NDP A and P — NDP A. When the total reaction volume is kept constant, the amount of water added to aniline, nitrobenzyl and tetramethylammonium hydroxide dihydrate added to DMSO is changed from 0 to 500 wL (0 * 50 * 150 · 300, 500 WL). Typical reactions include aniline, (200 WL, 2.1mmoU), nitrobenzene (200 «L, 1.9mniole), tetramethylammonium hydroxide dihydrate (330mg, 2.5mmole) and water (50« L) at 3.55ibL anhydrous DMS0. The reaction was allowed to proceed for 24 hours at room temperature under an aerobic state, after which a sample was prepared for HPLC analysis. Add water skullcap (η 1.Ί% conversion rate on water lacquer) to nitrite cage yield (mmole) 4-NnPA + P-NDPA 0 2.3 89 150 50 3.5 73 99 150 6 63 62 300 9.75 12 0.23 500 14.7 0.05 First read the back of the note and fill in the Ministry of Economic Affairs 屮 榀 榀 榀 /! 0 Bei Gong Xiao You cooperation Du printed example 9 This example shows that when the proton material added to the reaction is kept constant, the increase of alkali is the most correct 4— HDPA and P-NDPA produced the most significant effects. Three identical reactions were performed except that the amount of tetramethylammonium nitrate oxide was changed separately. In the standard paper use, the standard was completed (CNS) < f 4 specifications (2 丨 0X297 male dragon) 81, 4. 10,000 sheets' (H) V. Description of the invention ¢ 23) type reaction * Aniline (2mL), nitrobenzene (2mL), water (100 uL) It was mixed with tetramethylammonium hydroxide dihydrate (330 ns, 2.5 enole), and reacted in air at room temperature for 24 hours. In the case of a large amount of precipitation in the solution, 10 mL of benzylamine was added to dissolve the reaction product before preparing the sample. All reaction products were analyzed by HPLC. Nongrong 7 (Please read the precautions below and fill in this page) Central Standards of the Ministry of Economic Affairs, ^ β Industry Consumer Cooperative Cooperative Printed Water Added Grams mMo 1 es Production (mmo 1 e) 鹊Base 4 -NDPA + P-ΜΠΡA 100 4 .7 0.330 2.5 0.05 100 4 .7 0.660 5.0 0.15 1 00 4 .7 1-RB 12.5 1-24- Example 10 This example illustrates aniline, nitrobenzene in the 50V anaerobic state Reacts with tetramethylammonium hydroxide hydrate. With a mechanical mixer 9 adding funnel * thermometer 9 and a 500mL four-necked round-bottomed bottle with a nitrogen inlet containing 90mL aniline. Purge the aniline with nitrogen and add a portion of tetramethylammonium hydroxide dihydrate (54g 1 0. 42mo 1 e) 0 Stir the reaction mixture under nitrogen and heat to 50 氮气 〇 When the temperature of the reaction vessel is 逹 50t: When * will Nitrobenzene (10 mL · 95 mmo 1 e) was added dropwise to a vigorously stirred mixture of benzylamine and m. The nitrobenzene was added in 30 minutes. The reaction was stirred for 90 minutes and then analyzed by HPLC. Nitrobenzene conversion rate = SB Family Standard Complete (CNX) TM specifications (210X297 public: ¢) in private paper standards 81. 4. 10,000 sheets (H) 26 V. Description of invention ¢ 4) 100%. The yield of M-nitrobenzyl was used as the benchmark: P-NDPA (88.5%), 4-NDPA (4.3%), dibenpyrazine (3.6%), and azabenzyl (3.6%). Example 11 This example illustrates that tetramethylammonium ion salt of 4-NDP A and P-HDPA can be produced using the method of the present invention. Aniline (3. ObL > and tetramethylammonium hydroxide dihydrate (330mg, 2.5mmole) was sown in a controlled atmosphere dry box under argon. The aniline was directly transferred to 1 mL in the presence of a mixture of benzylamine and alkali. In nitrobenzene. When the aniline-base solution was added, the reaction turned red immediately and a precipitate formed. The mixture was stirred for 5 minutes and the reaction product was passed. The red precipitate was washed with some dry ether and dried. H-NMR spectroscopic analysis of the solid: (DMSO) 53.1 (s) * 6.1 (d, l), 6.5 (t * 1) * 6.6 (d, l), 6.76 (d, l), 6.8 (t, l),

7.04 (t, 1), 7.5 (d, 1). Adding acetic acid d4 to the NMR test tube immediately produced a red to yellow color change and the samples were analyzed by 1H-NMR spectroscopy. The obtained spectrum is consistent with true 4-NDP A. A portion of the red solid was dissolved in moist acetonitrile and analyzed by HPLC to indicate that 4-NDP A was the main component. Ministry of Economy + Central #Associate Bureau Staff Consumer Cooperatives Seal 31 (Please read the precautions before filling out the seven pages) Example 12 This example illustrates the change from 4 — ADPAW1 to N — (1, 3 — dimethylbutyl ) One N * -phenyl pair, one phenylenediamine, and one antioxidant used to protect the rubber knee products. 52g produced by the reaction of aniline with nitrobenzene (relying on the process of Example 10) 4 private paper scales using the Chinese standard (CNS) «Η size (210x297g; ¢) 81. 4. 10,000 sheets (H) Λ 6 ___ Β 6 V. Description of the invention (25)-ADPA, 100g of methyl isobutylformamidine (MIBK) and 0.3g of 3% platinum carbon catalyst were put into a 1-liter Parr autoclave. After purging with hydrogen, the reaction mixture was heated to 170-175 t! And 800 psig of hydrogen was used. The mixture was reacted for 95 minutes and made into a sample. GC analysis indicated that 0.4% of unreacted 4-ADPA was present. The reaction mixture was cooled and the catalyst was removed over time to remove water and excess MIBK. The 7U product was cooled to crystallize into a purple solid. Analysis by standard methods in the GC indicated 95.9% purity. The same reaction using methyl isoamyl ketone with acetone has the same results. The following examples use modified HPLC analysis methods. The coupling reaction products were analyzed by standard methods other than HPLC. All reactions were monitored using a Waters 600 Column HPLC equipped with a Vydac 201HS54 (4.6 X 250mm) column and a 254nm UV detector. {Please read the precautions and fill in this page first) Ministry of Economic Affairs, Central Government Standards >! * Ίβ 工 消 ίν · Cooperative India-grade stamping time (ra i η)% Solvent A% Solvent B (40 % (Water) Methanol in ACN) 0 75 25 35 20 80 40 0 100 45 0 100 46 75 25 5R 7B --- 25_ For paper ruler Aϋ, Zhongming Home Brown (CNS) A4 size (210x297 8;) 81. 4. 10,000 ft '(Η) 28 Λ 6η 6 Central Standards of the Ministry of Economic Affairs, Cooperating with the Dumpling Co., Ltd. Printing 5. Description of the invention) N-methylbenzylamine (5.7mg), Nitrobenzene (13.0 mg), diphenylhydrazine (4.5 mg), 4-nitroso diphenylamine (68.1 mg), 4-monofluorenyl diphenylamine (7.2 mg), hydrazine (4.7mg) and 25% tetramethylammonium hydroxide aqueous solution (130) were dissolved in 50mL of acetonitrile to make an external standard. The same standard solution is produced under conditions where aniline derivatives are used. Example 13 This example illustrates the vacuum distillation of aniline / water azeotrope from aniline, nitrobenzene or tetramethylammonium hydroxide (TMA (H)). Water is continuously removed during the reaction. A 22-liter round-bottom flask equipped with an agitator planter, Dean-Stark condenser * thermoelectric heater, nitrobenzene, and a fulfond baffle was charged with 15.11bs of 25% TMA (H) in water. (6.7L, 18.8Moles TMA (H)). The water was removed to a concentration of 35% by vacuum evaporation (55torr). During this step, the reaction temperature was steadily raised to between 50-55¾. Aniline (22.21bs, 9.88L, 108Mole) was charged into the reactor and continuous vacuum distillation was performed at 55 torr. Water and aniline M azeotrope formally removed until the ratio of water to TMA (Η) was 4: 1. The reaction temperature increased to 7510 during this process. When an appropriate molar ratio of water to alkali was obtained * Nitrobenzene (4.831bs, 1.79L * 17.82Mole) was added continuously for more than 3 hours. During the addition, the water and aniline were continuously removed from the reaction in a 55torr box by steam distillation. A good water / benzylamine removal rate is the amount of condensate removed equal to the weight of nitrobenzene added throughout the addition period. The analysis of the conversion rate of the blue-controlled nitrobenzene by HP LC can determine the end of the reaction (please read the precautions on the back first # Fill this page). Packing. This paper is used in the standard of CNS IM standard. (2 丨 0 > < 297 Gonglong) 81. 4., ό, ΟΟΟ ^ '(Η) 29 Π 6 V. Description of the invention (27). Typical yields were determined by HPLC analysis at 100% conversion of nitrobenzene: 4 mononitrodiphenylamine 92.1%, 4-nitrodiphenylamine 3.4% * azobenzene 3.4% * and diphenylhydrazone Piperazine 0.9%. Example 14 This example illustrates the use of different solvents in the reaction between aniline, nitrobenzyl and «(to produce 4-ADP A intermediate. 0.65s (5.3mmole) nitrobenzene was added to 0.5g ( 5.3 mmole) aniline and 0.95 g (6.5 mrole) of tetramethylammonium hydroxide dihydrate in a solution of 8 ml of solvent. After stirring the solution for 12 hours at 70 t: nitrogen, the reaction products were analyzed by HPLC and the results are summarized in Form 8. Men's Chess 8 (please read the back of the note first # Fill this page) Ministry of Economic Affairs, Central Government Standards and C3: Industry Consumers Cooperative Co., Ltd. Printed Nitrobenzene Diben, Yield Agents Lianlongma Thi 4- ΗηΠΑ 4-NDPA Benzene 99.5 0.64 76.4 20.9 1.5 Hexane 94.8 1.1 36.0 34.1 23.5 Ethionase 100 1 .24 51.4 27 19.8 Dimethyl ether diisopropyl 50 0.9 45 4.3 0 Ethylamine Example 15 Description of this example In the reaction between aniline · nitrobenzene and table, different paper sizes can be used. ZhongmingΗ Home Samples (CNS) TM specifications (210x297g *) 81. 4. 10,000 sheets (Η) 5. Description of the invention ( 28) Λ 6η 6 transfer catalyst K produces 4 A. DPA intermediate In a typical reaction, a three-necked round bottom flask equipped with a Dean-Stark condenser was charged with 5 s (0.091 mo U base) water-soluble tetrabutylammonium hydroxide and 55 g (0.59 mole) of aniline. At 70 t: 20 mmHg The water was removed by azeotropic distillation using 35b1 benzylamine. At 701: 5 minutes of super pass, 11.2g (0.091 mole) of nitrophenyl 6 was introduced from the dropping funnel to the reaction at 20 BnHg •. · / 7〇υ stirring for 4 hours. The results of analyzing the reaction products by 1 ^ 1 ^ are listed in Table 9. In the case of using bis-dibutylethylhexamethyldiamine ammonium hydroxide as sickle, the reaction conditions are somewhat Slightly different. Mix 50 mL of water-soluble quaternary ammonium hydroxide solution (0.0575 mm OH hydroxide) with 200 mL of aniline. At 67 t: remove water by vacuum distillation until 28iaL of water is removed. At 501 : Nitrobenzene (23.2mmole · 2.85g) was added dropwise to the reaction under nitrogen. Sample K was prepared for analysis after stirring the reaction for 2 hours. (Please read the back without any precautions before filling (Wood Page) Packing-After the production of nitrobenzene diphenyl by the Ministry of Economic Standards and Industrial Cooperatives Co., Ltd._ 镛 提 岭 么 哆 A-NnnP A 4-NDFA Tetramethylammonium hydroxide tetramethylammonium hydroxide 77.5% 0 52.1 9.7 3.4 Tetrapropylammonium hydroxide 100¾ 0.25 63.8 18.3 17.5 Pentamyl oxide 83.6% 0.85 33.0 9.6 43.2 Benzoyl oxynitride 10096 0.1 74.7 12.4 11.7 Trimethylammonium 18-crown one 99.496 0,33 77.8 11.5 6.54 Private paper 51-foot A side for middle 囷. Min Jia standard finished (CNS) 1? * »Specifications (210X29 · / 犮) _ 31 A. 81. 4. 10,000 sheets '(H) η 6 V. Description of the invention (29) 6 + 2_ Gas oxygen 彳 b double one 85.3% __- 1 ~ Ding? ^, A certain six-field diammonium 76 贲 Example 1 δ This example shows that the externally added dry refining agent can be used to absorb water in the reaction instead of the azeotropic distillation method described in Example 13. A 500 mL three-necked round bottom flask equipped with a mechanical stirrer and a Dean-Stark condenser was charged with 59.01 g (0.162 Mole base) of a 25% water-soluble tetramethylammonium hydroxide solution. Water was removed by vacuum distillation at 20 torr · (17 pL). Styrylamine (88.05g) was added, and 18.1 moisture was removed under an annual vacuum to form a 3: 1 water-to-alkali molar ratio. Stop steaming and add the appropriate dry brightener. Nitrobenzene (19.18 g * 0.155 mole) was added over 1 hour under nitrogen. The temperature was maintained at 70t during the addition. Reverse E was continued for 1 hour after the nitrobenzene addition was completed. The experimental results are summarized in Table 10. First read the back of the note # copybook / page-mounted printed by the Central Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperative Co., Ltd. Added nitrobenzene dibenzyl output% dried dried and attached with mm m piped_Nnnpa 4.-ΝΠΡ A think None — 52.3¾ 0.34 46.7 2.0 1.0 Anhydrous sulfur 14.75 61.996 0.50 58.6 2.2 0.8 Sodium 4 A points 28.1 78.296 1. 0 68.0 5.. 1 4.8 For private paper rulers, use the “Ming (CHS) TM Specification (210X297)” ¢) 81, 4. 10,000 sheets' (H) V. Description of the invention (3Q) Example 17 This example shows how to use the volume of tetraalkylammonium ions as a phase transfer solvent to reduce the production in the reaction. The amount of diphenhydrazine. The experimental method used was the same as described in Example 15. The results are summarized in Table 11. Table 11. Nitrobenzene dibenzyl chloride production 96 ft__a, rate of 4-4-NΠPPA 4-NDPA buried (please read the precautions before writing this page) Ministry of Economic Affairs, Central Standards and Industry A Consumer Cooperatives Printed Ethyl hydroxide 100% 2. 24 43 34 12. 1 Methyl ammonium hydroxide tetra 100% 0. 25 63.8 18.3 17.5 Propyl ammonium benzyl hydroxide 100 ¾ 0., 1 74.7 12.4 11.7 dimethyl m] Tetra 77.5 ¾ 0 52.1 9.7 3.4 Butyl hydroxide phenyl 48% 22 15 12 23 -Z: A compared with Example 18 This example is sharp. In this reaction, different substituted aniline derivatives can be used. Lending paper scales in the middle of a S home sample complete (CNS) T4 specifications (210X297 public: 〇81 · 4 · 10,000 sheets (Η) 33 V. Description of the invention 〇31) Λ 6 Π 6 Ministry of Economic Affairs The results of the analysis of the reaction products by HPLC were summarized in Table 12. A) 3-Bromoaniline: A solution of 10 ml (0.09 mole) of 3-bromobenzylamine and 1.5 g (O. Olmole) tetramethylene hydroxide dihydrate was stirred under a nitrogen pressure of 70 Torr. 0.9 ml (8.7 8 mmole) of nitrobenzene was added dropwise via a syringe, and the solution was stirred for 12 hours under a nitrogen pressure of 70 Torr. B) 4-Nitrobenzylamine: Stir 4 mononitroaniline (1.38g, O. Olmole) under 70t! Nitrogen pressure in 3ml with 1.81g (0.012mole) tetramethylhydroxide dihydrate Dimethanine solution. 1 ml of nitrobenzene was added dropwise via a syringe and the solution was stirred for 12 hours under 70 t: nitrogen pressure. C) Para-toluidine: A solution of para-toluidine (3 s * 28 mmole) and 0.9 s (6 mmole) tetramethylammonium hydroxide dihydrate was stirred under a nitrogen pressure of 70C. 0.5 ml of nitrobenzene was added dropwise via an injector, and the solution was stirred for 12 hours under a nitrogen pressure of 70.10. D) 4-Analine aniline Sodium 4-Analine aniline (4.8 g, 0.03 niole) and 0.9 g (6 mmole) were used to oxidize tetramethylammonium dihydrate in 2 ml of dimethylimine solution under a nitrogen pressure of 70 Torr. 0.718 (5.60 | 11> 016) nitrobenzene was added dropwise via a syringe and the solution was stirred for 12 hours under a 70¾ nitrogen scrape. E) 4-Methoxyaniline under nitrogen K70TC mixed with 4-methoxybenzylamine (3g, 0.03mmole) and 0.95g (6mnole > osmium tetramethylammonium dihydrate in 2ml di (Please read the back first And the matters needing attention # Fill in this page) Private paper ruler A free use BH furniture (CNS) «M Regulations (2〗 〇297297; tt) v 81. 4. 10,000 sheets (H) -34-. ·, The Ministry of Economic Affairs of the Central Government and the A Industrial Consumers Cooperatives, Sister Yin, V. Description of the Invention (32) A Yashuo solution. Add nitrobenzene (0.6g, 5mm〇U) dropwise via a syringe and at 70t: nitrogen The solution was stirred for 12 hours. F) 2-methoxybenzylamine was stirred at 70 TC under nitrogen pressure of 4.9 g, 0.03 mole of 2-methoxyaniline and 1 :: U (7.58 mmole) tetramethylammonium hydroxide dihydrate. 0.75s (6.09nnole) nitrobenzene was added dropwise via a syringe and the solution was stirred for 12 hours under 70 * 0 nitrogen pressure. Table 12 Conversion of aniline nitrobenzene yields 4-NODPA halved amount% 4 — HDPA derivate 2 —methoxybenzamine 100 55 44 4 monomethoxyaniline 100 74 20 4 —chloroaniline 98 61 8 Para-toluidine 100 19 9 4 Mononitroaniline 99 0 73 3 —Nano 1 00 R1 9 Example 1 9 This example shows how different diamine nucleophiles can be coupled to the para position of nitrobenzyl (para position) ° Nitrobenzene (2nl, 0.02ib0U) was injected into a hydrocarbon under 70% nitrogen by a syringe. The paper was 51 feet long and was used in the middle of the house. The standard was completed (CNS) «210 定 Η (210x297 公 龙) 81. 4. 10,000 '(H) (please read the precautions before filling this page) 5. Description of the invention (33) The Ministry of Economic Affairs and the Central Ministry of Economic Affairs & Co., Ltd. & Co., Ltd. print and add to 1.08g (O.Olmole) 1 * 4-phenylenediamine, 3.6 g (0.02 mole) of tetramethylammonium hydroxide pentahydrate in 2 ml of a solution of dimethylasicon. The solution was stirred under these conditions for 4 hours. The whole fraction (al Uuot) was analyzed for LC, MS, LC-MS. As a result, Ν, Ν '_ (4-nitrosophenyl) -1,4-monobenzyldiamine · N— (4-nitrophenyl) -fluorene'-(4-nitrosophenyl) -1 , 4-phenylenediamine and N, N '_ (4-nitrobenzyl) -1,4-phenylenediamine. Under the same reaction conditions, other diamine-based nucleophiles such as 4,4'-methyldianiline and 2,4-diaminotoluene can also obtain the same results. Example 20 This example illustrates the hydrogenation of 4-NODPA / tetramethylammonium (TMA) salt and 4-HDPA / TMA salt to 4-ADPA using different solvents. The hydrogenation was carried out in a 300c c stainless steel autoclave equipped with a stirrer and temperature control. A) Put 4-NODAP / TMA salt (12.4g, 0.0464mmole) into an autoclave with 150mL toluene. Add 1% platinum / carbon catalyst (300mg: dry weight) to the autoclave. The reactor was vented with nitrogen and placed under 200 psig of hydrogen. The hydrogen pressure remained constant during the hydrogenation. Stir at 1500rpra and heat up to 80 °. It is assumed that the reaction is completed when the hydrogen absorption is completed. Remove material and filter to remove catalyst. Samples were made with the calendar. * Reverse phase HPLC analysis indicated 100% radical conversion, 97% 4- ADPA production. Β) The mixture of 4-NODPA 18. (71g, 262mmole) and 4-NDPA / TMA body (7s · 24mmole) is packed into a pressure of 150g of aniline (please read the precautions on the back #Fill this r) Zhang Shouxiao's Chinese Standards (CNS) Specifications (210x297 public goods) 81. 4. 10,000 sheets (Η) V. Description of the invention < 3 4) Λ 6 Π 6 Ministry of Economic Affairs Consumer Cooperatives 52. Heater. Add 1% platinum / carbon catalyst (300 mg dry weight). The reactor was vented with nitrogen and placed under 200 psig of hydrogen. The hydrogen remained unchanged during the reaction. M 1500 rpm sowing reaction, let the temperature reach 80 it. The reaction is assumed to be complete when hydrogen uptake is complete. The material is removed and the catalyst is removed. The organic layer was made into a sample, and HP LC analysis of the opposite phase indicated 100% matrix conversion and 98% 4-ADPA yield. · 'C) A mixture of 4-H0DPA / TMA salt (36.5g, 135mmole) and 4-NDPA / TMA salt (3.4s, 12ranole) was put into a 51-g 4- △ 0-4 heat sink. The reactor was vented with nitrogen and placed at 200? "8 Torr 1 ?, and the hydrogen remained unchanged during the reaction. The reaction was stirred at 1500r pm, and the temperature reached 80t !. It is assumed that the reaction is complete when the hydrogen absorption ends. The catalyst was removed by filtration. A sample of the organic layer was made and analyzed by reversed-phase HPLC analysis to indicate 100% matrix conversion * 4-DPA was the only major yield. Example 21 This example illustrates the use of a supported nickel catalyst in aniline 4—NODP A was hydrogenated to 4-ADPA. 50s 4—MODPA, 200g of aniline and 2.085 nickel on a silicon aluminum alloy carrier were placed in a 1 liter ffi heater. After the oxygen was eliminated • the mixture was heated to 80X; 20〇BL / Bin hydrogen feed rate. Limit the feed rate M so that the maximum force is 280 psig. After 120 minutes, the flow rate of hydrogen indicates that the reaction is complete. Take a sample for analysis and indicate that 0.1¾ of unreacted 4-N0DPA remains. The product is .4-ADPA ° Depends on the use of general or special solvents • Examine their analogs and / or operating conditions, such as other temperatures and forces, instead of the invention used in the previous examples (please read the precautions behind the back #Fill this I) -Wood and Paper a Η Family standard completed (CNS) IM specifications (210X297 male *) 81. 4. 10,000 sheets' (H) A 6 B 6 V. Invention description 65) and the previous example can be successfully repeated. From the foregoing, we know this well Those skilled in the art can easily determine the essential characteristics of the present invention, and without departing from the spirit and scope of the invention * can make different changes to the uninvented and improve it to suit different uses and conditions. (Please read the historical meaning on the back of Qi first Please fill in this page for further details.) Binding. Order: Line-Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, this paper is printed in Chinese Standard B (National Standard (CNS) A4) (210x297 mm)

Claims (1)

Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs No. 81102690 Patent Application A8 B8 Chinese Patent Application Scope Amendment (June 88) VI. Application Scope _ [~ | -------—. | Λ—4 .; Supplement this year and month " 01 1.—A method for making one or more kinds of 4-monoaminodiphenylamine interstitials, including: (a) combining benzylamine or substituted aniline derivatives with Nitrobenzene is selected from benzylamine, nitrobenzene, dimethylformamide, dimethylformamide, N-methylpyrrole, pyridine, methylbenzyl, hexane, ethylene glycol dimethyl ether, diisopropyl Reactive contact is carried out with the solvent of the ethylethylamine and mixtures thereof, in which the substituent of the substituted aniline derivative is selected from the group consisting of a free halide, a N 0 2, a N Η 2, a (C!-C β) alkyl group, ( c:-C β) an alkoxy group, a S 0 3, a COOH and an aryl group, an aryl (Ci-Ce) alkyl group or a (Ca-Ce) alkaryl group containing at least one NH 2 group, wherein The halide is selected from the group consisting of chloride, bromide and gaseous compounds; and < b) at a temperature of 0 ° C to 150 ° C, and the alkali metal and alkali metal are hydrogenated. , Alkali metal hydroxides, alkali metal alkoxides, tetra-substituted ammonium hydroxide and alkyl-substituted diammonium hydroxide, amines, crown ethers combining alkali sources, and groups of bases in a controlled amount, The reaction of phenylamine or substituted aniline derivative with nitrobenzene in a limited area in the presence of protic materials produces one or more 4-monoaminodibenzylamine (4-ADPA) intermediates, in which the control of protonic materials The amount is less than the amount that inhibits the reaction of stilbene or substituted aniline derivatives with nitrobenzene. 2. The method according to item 1 of the Shen He patent scope, wherein the solvent is selected from benzylamine, dimethyl arylene, dimethylformamide and toluene. 3. The method according to item 1 of the scope of patent application, wherein the protic material is selected from methanol, water and mixtures thereof. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (谙 Please read the notes on the back before filling in this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs No. 81102690 Patent Application A8 B8 Chinese Patent Application Scope Amendment (June 88) VI. Application Scope _ [~ | -------—. | Λ—4 .; Supplement this year and month " 01 1.—A method for making one or more kinds of 4-monoaminodiphenylamine interstitials, including: (a) combining benzylamine or substituted aniline derivatives with Nitrobenzene is selected from benzylamine, nitrobenzene, dimethylformamide, dimethylformamide, N-methylpyrrole, pyridine, methylbenzyl, hexane, ethylene glycol dimethyl ether, diisopropyl Reactive contact is carried out with the solvent of the ethylethylamine and mixtures thereof, in which the substituent of the substituted aniline derivative is selected from the group consisting of a free halide, a N 0 2, a N Η 2, a (C!-C β) alkyl group, ( c:-C β) an alkoxy group, a S 0 3, a COOH and an aryl group, an aryl (Ci-Ce) alkyl group or a (Ca-Ce) alkaryl group containing at least one NH 2 group, wherein The halide is selected from the group consisting of chloride, bromide and gaseous compounds; and < b) at a temperature of 0 ° C to 150 ° C, and the alkali metal and alkali metal are hydrogenated. , Alkali metal hydroxides, alkali metal alkoxides, tetra-substituted ammonium hydroxide and alkyl-substituted diammonium hydroxide, amines, crown ethers combining alkali sources, and groups of bases in a controlled amount, and a controlled amount of The reaction of phenylamine or substituted aniline derivative with nitrobenzene in a limited area in the presence of protic materials produces one or more 4-monoaminodibenzylamine (4-ADPA) intermediates, in which the control of protonic materials The amount is less than the amount that inhibits the reaction of stilbene or substituted aniline derivatives with nitrobenzene. 2. The method according to item 1 of the Shen He patent scope, wherein the solvent is selected from benzylamine, dimethyl arylene, dimethylformamide and toluene. 3. The method according to item 1 of the scope of patent application, wherein the protic material is selected from methanol, water and mixtures thereof. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (谙 Please read the notes on the back before filling in this page) 6. Scope of patent application 4. The method according to item 1 of the scope of patent application, wherein the solvent system includes water having a maximum volume of about 4 v / v% based on the total volume of the reaction mixture of aniline and K. 5. The method according to item 1 of the scope of patent application, wherein the solvent system includes water having a maximum volume of about 8 v / v% of the total volume of the reaction mixture of dimethylarsine and M. 6. The method according to item 1 of the scope of patent application, wherein the solvent system includes a total volume of aniline and M reaction mixture based on methanol of up to about 3 v / v%. 7. The method according to item 1 of the scope of patent application, where * The base is mixed with aniline or a substituted substituted stilbene amine derivative to form a mixture, and the mixture is then reactively contacted with nitrobenzene. δ. A method according to item 1 of the scope of patent application, wherein aniline or a substituted aniline derivative is mixed with nitrobenzene to form a mixture, and a base is added to the mixture. 9. The method according to item 1 of the application, wherein the solvent is aniline and the base is tetraalkylammonium hydroxide or alkyl hydroxide. 10. The method according to item 1 of the scope of patent application, wherein aniline or a substituted aniline derivative reacts with nitrobenzene under aerobic conditions. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Reaction under anaerobic conditions. 1 2 · The method according to item 1 of the scope of patent application, wherein in step (b >) there is a desiccant with M to control the amount of protonic material present during the reaction of aniline or substituted phenylamine derivative with nitrobenzene. 1 3. According to the application The method of item 12 of the patent scope, wherein the desiccant is selected from the group consisting of anhydrous sodium sulfate, molecular sieve, calcium chloride, and tetramethylammonium hydroxide dihydrate. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumers 'Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A8 B8 __§ ___— Applicable patent scope' A group of anhydrous potassium hydroxide, anhydrous sodium hydroxide and activated aluminum. The method, wherein the amount of protonic 15 lining in step (b) is controlled by continuous distillation of the protonic material. '$ According to the method in the scope of patent application No. 丨 4, wherein the protonic material is water' 1 It was removed by continuous azeotropic distillation using a water / benzylamine azeotrope. The method according to item 1 of the U.S. patent application wherein the substituted aniline derivative was selected from the group consisting of 2-methoxyaniline, 4- Methoxyaniline, 4-Chloroaniline, p-methylbenzylamine, 4-nitrobenzylamine, 3-bromoaniline, 3-benzyl-4-methylaminobenzyl, para-aminobenzoic acid, 2, Groups of 4-diaminomethylbenzyl, 2, 5-dichloroaniline, 1,4-monophenyldiamine, 4,4, ~ methyldibenzylamine and 1, 3, 5-triaminobenzene. 17 ___ • ~ 'A method for making 4-monoaminodiphenylamine (4-ADPA) or a substituted derivative thereof, including: (&) Choosing benzylamine or substituted benzylamine derivatives with nitrobenzene Amine, 5-Zenylbenzene, Dimethoate, Dimethylmetamine, N-Methylcopper, Pyridine, Methylbenzyl, Hexane, Glycol Dimethyl Ether, Diisopropylethylamine, and The solvent of the mixture is used for reactive contact, and the substituent of the ψ substituted aniline derivative is' selective halide, ~ Ν 0 2, -N Η 2, (C:-U) alkyl, (C!-C s) a group consisting of alkoxy, ~ SO3, -COOH and an aryl, aryl (h-Ce) alkyl or (c ^ -Ce) alkaryl group containing at least one NH2 group, wherein the halide system Select groups of free chloride, bromide and fluoride (b) At a temperature of 0 ° C to 150 ° C, and select free alkali metal, metal hydride, alkali metal hydroxide, alkali metal alkoxide, and oxygen (please read the note on the back first) Please fill in this page again for matters} ----- Order ------ Mff ----- 1 This paper size applies to China National Standard (CNS) A4 (2ι〇 × 297 thin) Employees of Central Bureau of Standards, Ministry of Economic Affairs Printed by Consumer Cooperatives A8 B8 C8 D8 6. Application for patents covering tetra-substituted ammonium and hydroxide. Alkyl-substituted diammonium, amine, crown ether combined with alkali source *, and bases of groups of mixtures, and controlled amounts In the presence of a protonic material, a benzylamine or a substituted benzylamine derivative is reacted with a nitrobenzene in a limited area to produce one or more 4-DPA intermediates, wherein the controlled amount of the protonic material is less than the inhibitory benzamine Or the amount of the substituted aniline derivative reacted with nitrobenzyl, wherein the one or more 4-ADPA intermediate systems are selected from 4-nitrodibenzylamine, 4-nitrosodiphenylamine, and substituted derivatives thereof And its salts; K and (〇 to produce 4-ADPA or substituted derivatives thereof under the conditions of 4-ADP A intermediate body. 1 δ. The method according to item 17 of the scope of patent application, wherein the solvent is selected from aniline, dimethylarsine, 'dimethylformamidine, methylbenzyl and mixtures thereof. 19. The method according to item 17 of the scope of the patent application, wherein the protonic material is selected from methanol, water and a mixture thereof. 20. The method according to item 17 of the scope of the patent application, wherein the solvent system comprises water having a total volume of aniline and the reaction mixture of up to about 4 ν / ν% based on the total volume. 2 1. The method according to item 17 of the scope of the patent application, wherein the solvent system comprises a mixture of dimethylarsine and M, and the total volume of the substance is based on water with a maximum of about 8 ν / ν%. 22. The method according to item 17 of the scope of patent application, wherein the solvent system includes methanol with a maximum volume of about 3 ν / ν% based on the total volume of the reaction mixture of aniline and K 0 2 3. The method according to item 17 of the scope of patent application Dissolve, in which the base is mixed with aniline or a substituted benzylamine derivative to form a mixture, and the mixture is then reactively contacted with nitrobenzene. This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) (please read the precautions on the back before filling out this page) Order A8 B8 C8 D8 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 7 ^ 210 6. Application scope of patent 24. The method according to item 17 of the scope of patent application, wherein aniline or substituted benzylamine derivative is mixed with 5-stilbenyl to form a mixture, and a base is added to the mixture. 0 2 5 The method of item 17 in the patent scope of SQ, wherein the solvent is aniline, and tetraalkylammonium hydroxide or alkyl hydroxide is substituted for di | ammonium hydroxide. 26. The method according to item 17 of Shenyin's patent, in which benzylamine or substituted penamine derivative reacts with nitrobenzyl under aerobic conditions. 27. The method according to item 17 of the application, wherein the aniline or substituted benzylamine derivative reacts with nitrobenzene under anaerobic conditions. 28. The method according to item 17 of the scope of patent application, wherein the 4-ADPA intermediate system uses hydrogen at a hydrogen partial pressure of 100 psig to 340 psig and optionally free platinum on carbon, palladium and nickel on carbon. The group of catalysts are reduced in the presence of the catalyst. 29. The method according to item 17 of the scope of patent application, wherein a desiccant is used in the step sand to control the amount of protonic material present during the reaction of the benzylamine or substituted benzylamine derivative with the nitrobenzyl. 30. The method according to item 29 of the scope of the patent application, wherein the desiccant is selected from the group consisting of anhydrous sodium sulfate, molecular sieve, calcium oxide, tetramethylammonium hydroxide dihydrate, anhydrous potassium hydroxide, anhydrous sodium hydroxide and activation. Groups of aluminum. 3 1. The method according to item 7 of the scope of patent application, wherein step (b > the amount of proton material is controlled by continuous distillation of the proton material. 3 2 · The method according to item 3i of the scope of patent application, wherein The protonic material is water 'and the water system is removed by continuous azeotropic distillation with water / benzylamine azeotrope. 3 3. The method according to item 7 of the patent application scope, wherein the substituted benzylamine derivative is selected from the group consisting of 2 — Methoxybenzylamine, .4-monomethoxyaniline, 4-chloroaniline, p-toluidine, 4-nitroaniline, 3-bromoaniline, 3--5-CNS) A4 ^ (210X297, ^) -(Please read the notes on the back before filling this page) A8 B8 C8 D8 < > 79210 6. Scope of patent application Bromine-4 monoaminotoluene, para-monoaminobenzoic acid, 2, 4-diaminotoluene, 2,5-dichloroaniline, 1,4 —Phenylenediamine, 4,4′-methyldibenzylamine and 1,3,5-triaminobenzyl group. 34. —A method for producing a p-benzylideneamine or a substituted derivative thereof, including: (a) selecting aniline or substituted benzylamine derivatives and nitrobenzyl from benzylamine, nitrobenzyl, Reactive contact with solvents of dimethylarsine, dimethylformamide, N-methylpyrrolidone, pyridine, methylbenzyl, hexane, ethylene glycol dimethyl ether, diisopropylethylamine and mixtures thereof Where the substituent of the substituted aniline derivative is selected from free halides, -N0 2, -NH2, (Ci-Cs) alkyl, d-Ce) alkoxy, -SO3, -COOH and contains at least one A group consisting of aryl, aryl (Ci-Ce) alkyl or (Ci-Ce) alkaryl groups of a HH2 group, in which the halide is selected from the group consisting of free chloride, bromide and fluoride; (b) in 〇 to 1 50 ° C, and in the choice of alkali metal, alkali metal hydride, alkali metal hydroxide, hafnium metal alkoxide, `` tetra-substituted ammonium hydroxide and alkyl-substituted diammonium, amine In combination with the crown ether of the source, and the base of the mixture, and the controlled amount of R-substances, the benzylamine or substituted benzylamine derivative and nitrate are present. Benzene reacts in a limited area to produce one or more 4-ADP A intermediates, where the controlled amount of protic material is less than the amount that inhibits the reaction of aniline or g-substituted aniline derivatives with nitrobenzene; ⑵ Reduction 4 — ADPA Intermediate M produces 4-ADPA or a substituted derivative thereof; M and < d) 4-ADPA or a substituted derivative thereof in the reductive alkylation step (c). This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page) '11 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A8 II D8 Patent Application Scope 3 5 The method according to item 34 of the scope of patent application, wherein the solvent is selected from aniline, dimethylarsine, dimethylformamide, methylbenzyl and a mixture thereof. 36. The method according to item 34 of the scope of patent application, wherein the protic material is selected from methanol, water and a mixture thereof. 37. The method according to item 34 of the patent application, wherein the solvent system includes water having an aniline and M reaction mixture volume of up to about 4v / v% based on volume. 38. The method according to item 34 of the patent application, wherein the solvent system includes water having a maximum volume of about 8v / v% based on the volume of the reaction mixture of dimethyl δ® and M. 39. The method according to item 34 of the patent application, wherein the solvent system comprises methanol of up to about 3 v / v% based on the volume of the reaction mixture of aniline and M. 40. The method according to item 34 of the application, wherein the base is mixed with a benzylamine or a substituted aniline derivative to form a mixture, and then the mixture is reacted with the nitrobenzyl and reacts in a reactive manner. 41 'The method according to item 34 of the scope of patent application, wherein aniline or a substituted benzylamine derivative is mixed with nitrobenzene to form a mixture, and a base is added to the mixture. 42. The method according to item 34 of the patent application, wherein the solvent is benzylamine and the test is tetraalkylammonium hydroxide or alkyl substituted diammonium hydroxide. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) 43. According to the method of applying for the scope of patent No. 34, benzylamine or substituted _ κ derivatives and nitrobenzyl Reaction under oxygen conditions. 44. The method according to item 34 of the scope of patent application, wherein the aniline or substituted aniline derivative reacts with nitrobenzene under anaerobic conditions. 45. The method according to item 34 of the scope of patent application, wherein Methyl isobutyl ketone, methyl isoamyl ketone and 2-octyl groups are alkylating 4-AD ρ A or its substituted derivative. —7 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) A8 II D8 6. Application scope 46. The method according to item 34 of the scope of application for patent, in which step (b) has a desiccant To control the amount of protonic materials present during the reaction of aniline or substituted benzylamine derivatives with nitrobenzyl. 47. The method according to item 46 of the application, wherein the desiccant is selected from the group consisting of anhydrous sodium sulfate, molecular sieve, calcium chloride, tetramethylammonium hydroxide dihydrate, anhydrous potassium hydroxide, anhydrous sodium hydroxide, and activated aluminum. 48. The method according to item 34 of the scope of patent application, wherein the amount of the protic material in step (b) is controlled by continuously distilling the protic material. 49. The method according to item 48 of the patent application, wherein the protic material is water and the water system is removed by continuous azeotropic distillation with water / aniline azeotrope K. 50. The method according to item 34 of the scope of patent application, wherein the substituted benzylamine derivative is selected from the group consisting of 2-methoxybenzylamine, 4-monomethoxyaniline, 4-chlorobenzylamine, and para-methylbenzylamine. , 4-mononitroaniline, 3-bromobenzylamine, 3-bromo-monobenzylamine, para-aminobenzylcarboxylic acid, 2,4-diaminobenzylamine, 2,5-dichlorobenzylamine 1,2,4-phenylenediamine, 4,4'-methyldiphenylamine and 1,3,5-triamine group. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (read the precautions on the back and then fill out this page) 51. —A kind of 4 mononitrodiphenylamine tetra-substituted ammonium salt > Tetramethylammonium salt of dibenzylamine, tetrapropylammonium salt of 4-mononitrodibenzylamine, tetrabutylammonium salt of 4-mononitrodiphenylamine, benzyltrimethyl Groups of ammonium salts, benzyltrimethylammonium salts of 4-mononitrodibenzylamine, and their substituted derivatives. 52. A tetra-substituted ammonium salt of 4-mononitrosodiphenylamine, which is selected from the group consisting of a tetramethylammonium salt of 4-nitroso-dibenzylamine, and a tetrapropyl group of 4-nitroso-dibenzylamine Ammonium salt, 4-mononitrodiphenylamine tetrabutylammonium salt, 4-mononitrodiphenylamine benzyltrimethylammonium salt, 4-mononitrodibenzylamine Chinese National Standard (CNS) A4 specification (210X297 mm) C8 D8 6. Patent application group of trimethylammonium salt and its substituted derivatives. 53. —An alkyl substituted diammonium salt of 4-nitrodibenzylamine or 4-nitrosodibenzylamine, which is selected from bis-dibutylethyl which includes 4-nitrodiphenylamine Hexamethylene diammonium salt and bis-dibutylethylhexamethylene diammonium salt of 4-mononitrosodiphenylamine. (Please read the notes on the back of the page first and then fill out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -9-This paper size applies to China National Standard (CNS) A4 (210X297 mm)