WO2014133420A2

WO2014133420A2 - Method for producing 4-aminodiphenylamine and alkylated derivatives thereof

Info

Publication number: WO2014133420A2
Application number: PCT/RU2014/000130
Authority: WO
Inventors: Олег Александрович ГОДЗОЕВ
Original assignee: Godzoev Oleg Alexandrovich
Priority date: 2013-02-28
Filing date: 2014-02-27
Publication date: 2014-09-04
Also published as: RU2553984C2; RU2013109007A; WO2014133420A3

Abstract

Proposed are two variants of a method for producing 4-ADPA and alkylated derivatives thereof using a new catalytic system which includes a base, such as hydroxides of alkali or alkaline earth metals, and aliphatic heterochain polyethers such as ethers of polyethylene glycol (PEG), of polypropylene glycol (PPG), of polytrimethylene oxide (PTMO), or of polytetrahydrofuran, or PEG monomethyl ethers, PPG monobutyl ethers, etc., or block copolymers thereof, such as PEG-PPG-PEG, PEG-PPG-PPG, PEG-PPG-PTMO, or a statistical polymer (PEG-PPG), having a mass ratio of hydroxide to polyether of 1:5-20 respectively.

Description

METHOD FOR PRODUCING 4-AMINODIPHENYLAMINE AND ITS ALIENED DERIVATIVES

Technical field

The invention relates to the field of organic chemistry, and more particularly to the field of production of nitrogen-containing compounds, and in particular to a method for producing 4-aminodiphenylamine (4-ADPA) and its alkyl derivatives used as antioxidants.

State of the art

A known method for producing 4-ADPA through the formation of intermediate 4-nitrodiphenylamine, followed by reduction of the nitrofragment by reacting p-chloronitrobenzene with an aniline derivative such as formanilide or an alkali metal salt thereof, in the presence of an acid acceptor or a neutralizing agent such as potassium carbonate, and optionally using catalyst

[one]·

The disadvantage of this method is the circulation in the process of such reaction compounds as p-chloronitrobenzene or formanilide, the use of which leads to corrosion of equipment and complicates the processing of waste.

There is also a method of producing 4-ADPA by the combination of aniline "head to tail" [2]. This method has one the disadvantage is that the yield of 4-ADPA is unacceptable for the production process.

A known method for producing 4-ADPA by decarboxylation of urethane [3] However, this method is commercially impractical in terms of cost and yield.

A known method of producing 4-ADPA by hydrogenation of p-nitrosodiphenylhydroxylamine, which can be obtained by catalytic dimerization of nitrosobenzene when using aliphatic compounds, benzene, naphthalene or ethylenically unsaturated compounds as a reducing agent [4]. It is also known to obtain p-nitrosodiphenylamine from diphenylamine and alkyl nitrate in the presence of an excess of hydrogen chloride [5].

Currently, the three most developed technologies for producing 4-ADPA and its alkyl derivatives are known:

- synthesis technology of 4-ADPA and its alkyl derivatives

The main disadvantages of the process:

multi-stage process (5 stages), high energy intensity of the process, carcinogenic intermediate products, many liquid and solid wastes [6]

- synthesis technology of 4-ADPA and its alkylated derivatives by Bayer AG:

Diafen "FP"

The main disadvantages of the process: - multi-stage process (4 stages), expensive starting compound (para-chloronitrobenzene), separate reduction of the nitro compound and imine [7] - synthesis technology of 4-ADPA and its alkyl derivatives of Flexys:

The known technological method consists in the condensation of nitrobenzene with an excess of aniline (it is a solvent) or its derivatives, at a temperature not higher than

60-80 C in the presence of a catalytic system consisting of a solvent and a base, such as tetramethylammonium hydroxide (or tetramethylammonium chloride or a solution of zwitterionic salt) with the formation of 4-nitro- and 4-nitrosodiphenylamines followed by their catalytic hydrogenation in the presence of a Pd / C catalyst to 4-ADPA. Then from the obtained product it is possible to obtain alkylated derivatives of 4-ADPA by reductive alkylation in the presence of hydrogen and a catalyst — Pd / C [8]:

Diafen "FP"

The disadvantages of the known technology are the use of thermally unstable quaternary ammonium compounds and its salts as components of the complex main catalyst of the condensation step. This imposes very strict requirements for maintaining the temperature regime in the first three stages of the process. Overheating of the reaction mass above

80 C leads to a significant acceleration of the decomposition of the catalyst, the formation of by-products and a decrease in the selectivity of condensation and hydrogenation. Disclosure of invention

The problem posed by the invention was to improve the process for producing 4-ADPA and its alkyl derivatives by developing a simpler and cheaper method through the use of a new catalyst system and a thermally more stable catalyst at the stage of condensation of aniline and nitrobenzene, as well as the possibility of combining the second and third stage in one stage upon receipt of the alkylated derivatives of 4-ADPA.

The problem was solved by developing two options for low-waste technology for producing compounds of the general formula (1):

where R 1 represents H, R 2 represents H, lower alkyl.

When describing the invention, the following terms were used.

The term “4-ADPA” means 4-aminodiphenylamine.

The term “alkylated 4-ADPA derivatives” means derivatives containing an alkyl substituent such as methyl, ethyl, isopropyl, butyl, isobutyl, 1,3-dimethyl butyl, isopentyl, etc. etc. with a primary nitrogen atom of 4-ADPA.

The term "diaphen FP" means M-phenyl- '-isopropyl-para-phenylenediamine.

The term "6PPD" means H- (1,3-dimethylbutyl) -Y'-phenyl-p-phenylenediamine.

The term “intermediates (for) 4-ADPA” means 4-nitrodiphenylamine, 4-nitrosodiphenylamine (also called p-nitrosodiphenylamine), their derivatives and their salts. Thus, a reference to “one or more 4-ADPA intermediates” refers to one or both neutral compounds, i.e. to compounds that are not in the form of a salt and / or salt of one or both of such compounds. Salt is formed in the reaction mixture by reacting 4-nitro and / or 4-nitroso products with a base. Thus, the reaction mixture obtained by the method of the present invention may include one of the compounds or one of salts, or any combination thereof, depending on the selected specific reaction conditions.

The term "polyester" means a single polyester or a mixture thereof, which is aliphatic hetero-chain polymers containing regularly repeating C — O — C groups in the backbone, such as polyethylene glycol (PEG) esters, polypropylene glycol (PPG), polytrimethylene oxide (PTMO), polytetrahydrofuran or PEG monomethyl ethers, PPG monobutyl ethers, etc. etc., or their block copolymers, such as PEG-PPG-PEG, PEG-PPG-PPG, PEG-11111-PTMO, random polymer (PEG-PPG) etc. etc.

The term "metal hydroxides" means a hydroxide or a mixture of hydroxides of alkali or alkaline earth metals, such metals as Na, K, Li, Ca.

The present invention includes the development of schemes for a two-stage non-waste technology for producing 4-ADPA and its alkyl derivatives (using Diaphen-FP and 6PPD as examples) from aniline and nitrobenzene in a medium of metal and polyester hydroxides.

Brief Description of the Drawings

FIG. 1 is a diagram of a two-stage non-waste technology for producing alkylated derivatives of 4-ADPA from aniline, nitrobenzene and acetone using metal hydroxides and polyesters. The base is metal hydroxides, catalyst 1 is polyesters, catalyst 2 is Pd / C.

FIG. 2 is a diagram of a two-stage non-waste technology for producing 4-ADPA from aniline and nitrobenzene using metal hydroxides and polyesters. The base is metal hydroxides, catalyst 1 is polyesters, catalyst 2 is Pd / C.

FIG. 3 - Glass reactor with the equipment used.

FIG. 4 - General view of the laboratory installation with the reactor.

The best example of carrying out the invention

The invention according to scheme 1 is directed to a method for producing a compound of formula (1), an example of which are alkylated derivatives of 4-ADPA.

Scheme!

(R 1, R 2 are lower alkyl according to the general formula 1); by ketone is meant acetone or methyl isobutyl ketone.

The invention according to scheme 1 (option 1) includes the following stages:

a) condensation of excess aniline or substituted derivatives of aniline and nitrobenzene in the reactor, when temperature from 30 to 150 C, in the presence of a catalytic system, which includes a base, as a catalyst, such as hydroxides of alkali or alkaline-earth metals and at the same time cocatalyst and solvent, which are used aliphatic hetero-chain polyesters at a ratio of 5-20 mass to 1 mass of the base to obtain 4-nitrodiphenylamine or its derivatives and its salts, 4-nitrosodiphenylamine and / or its derivatives, and its salts.

b) reductive alkylation in the polyesters of nitrodiphenylamine and nitrosodiphenylamine in the presence of a Pd / C catalyst, hydrogen and the corresponding ketone in order to obtain, for example, Diafen-FP or 6PPD.

According to the described technological scheme in Fig. 1, an alkylated derivative, for example, diaphen FP, is obtained from aniline and nitrobenzene in quantitative yield; as a waste, 1 equivalent is calculated per diaphen FP of the metal salt, which is isolated in dry and pure form, several equivalents of water. The polyester used in the synthesis, which is used aliphatic heterochain polymers containing regularly repeating C — O — C groups in the backbone, such as polyethylene glycol (PEG) esters, polypropylene glycol (PPG), polytrimethylene oxide (PTMO), polytetrahydrofuran or PEG monomethyl ethers, 11111 monobutyl ethers, etc. etc., or their block copolymers, such as PEG-PPG-PEG, PEG-PPG-PPG, PEG-PPG-PTMO, the statistical polymer (PEG-PPG) is completely regenerated. The reductive alkylation catalyst is also completely regenerated, the excess aniline used in reactor 1 and distilled off after the condensation stage, is fully regenerated in full minus one equivalent for the used nitrobenzene and is completely ready for reuse as a raw material for the production of AF diaphen. The acetone used for reductive alkylation is also completely regenerated minus one equivalent. The methanol used to neutralize the base is quantitatively regenerated.

The invention according to scheme 2 is directed to a method for producing a compound of formula 1, an example of which is 4-ADPA (where R and R are H) from 4-nitrodiphenylamine (4-NDFA), and its salts, and 4-nitrosodiphenylamine (4-NODPA) and / or its salts.

Scheme 2.

(R 1 and R 2 are H according to the general formula 1) The invention according to scheme 2 (option 2) includes the following stages:

a) condensation of excess aniline or substituted derivatives of aniline and nitrobenzene in the reactor, at a temperature of from 30 to 150 ° C, in the presence of a catalytic system, which includes a base, such as a catalyst, such as alkali metal or alkaline earth metal hydroxides and simultaneously cocatalyst and solvent , which is used as aliphatic heterochain polyesters with a ratio of 5-20 mass to 1 mass of the base to obtain 4-nitrodiphenylamine or its derivatives and its salts, 4-nitrosodiphenylamine and / or its derivatives, and salts.

b) reduction in the environment of polyesters in the presence of a Pd / C catalyst and hydrogen of 4-nitrosodiphenylamine or its derivatives and its salts, 4-nitrodiphenylamine and / or its derivatives, and its salts, with the formation and release of 4-ADPA.

If necessary, it is possible to obtain from ADFA its alkyl derivatives, for example, Diafen-FP and 6PPD by reductive alkylation on a Pd / C catalyst in a polyester medium.

According to the technological scheme in figure 2 from aniline and nitrobenzene with quantitative yield receive 4-ADPA, in 1 equivalent per 4-ADPA metal salt, which is isolated in dry and pure form, several equivalents of water that can be used to dilute the acid to neutralize the base after the condensation step 1, are formed as waste. The polyester used in the synthesis is aliphatic heterochain polymers containing regularly repeating C — O — C groups in the main chain, such as polyethylene glycol ethers (PEG), glycol polypropylene (PPG), polytrimethylene oxide (PTMO), polytetrahydrofur or PEG monomethyl ethers, PPG monobutyl ethers, etc., or their block copolymers, such as PEG-PPG-PEG, PEG-PPG-PPG, PEG-PPG-PTMO, the statistical polymer (PEG-11111) is completely regenerated . The hydrogenation catalyst is also completely regenerated, the excess aniline used in reactor 1 and distilled off after stage 2 is totally regenerated in full minus one equivalent per used nitrobenzene and is completely ready for reuse as a raw material for 4-ADPA. The methanol used to separate the salt from the polymer is also completely regenerated.

The implementation of the proposed schemes of chemical processes required the development of a new original installation, shown in figures 3 and 4, allowing you to complete the task set for the invention.

In a laboratory setup, you can get not only ADPA, diafen FP or 6PPD, but almost any alkyl derivative of ADPA. We can say that this installation is universal and also represents the subject of the invention.

This example demonstrates, but does not limit the subject matter of the invention.

The synthesis of AF diaphen in a laboratory setup is a two-stage batch process, including the following stages:

1. condensation of nitrobenzene with aniline in polyesters and a base (metal hydroxides).

2. reductive alkylation on a palladium catalyst in polyesters.

Equipment:

1) a 200 ml glass reactor is a device, the diagram of which is shown in Figure 3, with a jacket and a cover with two GL14 threads, two NS 14 sections, a central section NS 29, and a tap in the lower part with a tap and GL14 thread

2) mechanical stirrer

3) magnetic drive 4) clamps for capillaries with silicone gaskets

5) glass stopper with thin section NS 14

6) capillary for supplying nitrobenzene

7) Teflon capillary for feeding

8) glass rod

9) teflon anchor

10) a glass condenser for cooling the vapors of aniline and water,

11) glass receiver

12) Thermocouple Pt 100

13) Glass Nozzle for stripping

14) Thermostat HUBER unistat 340w

15) Vacuum controller VACUUBRAND Vacuum Controller CVC 2 "

16) vacuum control valve VV 6C 24V

17) BROOKS Mass-Flow Controller 5964

18) readout of BROOKS Mass-Flow Redouts 0154 for mass flow controller 17

19) HPLC nitrobenzene flow forming pump

20) SHIMADZU System Controller SCL-10A for HPLC pump 19 21) The draining column (drying of water and C0 ₂₎ is a V -shaped glass tube 40 cm long packed with pellets of sodium hydroxide, to the exit tube podsedinyaetsya hose with a membrane filter to remove particulate matter from the air

22) VACUUBRAND Diaphragm Pump MZ Diaphragm Pump

23) Glass trap for diaphragm pump

24) oil pump

25) The glass trap for the oil pump is cooled by liquid nitrogen

26) The glass container with nitrobenzene is on the balance to determine the exact weight of the added nitrobenzene

The following examples demonstrate but do not limit the subject matter of the invention. In all the examples below, the solvent (polyesters) and cocatalyst were taken from 6 to 10 masses in relation to 1 mass of the base. Physicochemical constants given in examples 1-2 are similar to the constants in all other examples. Example 1 (KOH + PEG). Getting diaphen AF

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a branch for distillation 14, is placed polyethylene glycol with an average molecular weight of 4000 daltons. Then 5.5 g of potassium hydroxide (85%) is fed into the reactor, and the reactor closes when

about

while stirring, 1000 rpm is heated to 120 C and maintained at this temperature for 20 minutes, then the mixture is cooled to about

60 s in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred 90 more minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return

about

aniline. The reactor is cooled to 60 ° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate Ν "1 is formed. Filtrate N ° 1 is used in stage Ν" 2. The residue on the filter forms a precipitate N ° 1.

LCMS: 215 (M + 1) ⁺ , 30.64% (NODFA), 199 (M + 1) ⁺ , 69.20% (NDFA).

Stage N ° 2 - reductive alkylation

The filtrate N ° l from the N ° l stage is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate a2 is formed. The filter residue is reused as a catalyst in stage N ° 2. Unreacted acetone is distilled off from the filtrate 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C. and then by gravity to receiver 33. The mass of AF diaphen is 15.98 grams (97% based on the used nitrobenzene). The residue after distillation is polyethylene glycol 4000, which is reused in stage N ° l.

Ή NMR (400 MHz, CDC1 ₃ ): 1.18 (d, J = 6.3 Hz, 6H), 3.57 (m, W), 3.28 (br, 1H), 5.32 (br, W), 6.53-6.58 (m, 5H ), 6.95-7.19 (m, 4H).

Getting 4-aminodiphenylamine

Stage Ν ° 1 - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with magnetic drive 3, thermocouple 12, lowered by 120 mm polyethylene glycol with an average molecular weight of 4000 daltons is placed through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and an outlet for distillation 14. Then 5.5 g of potassium hydroxide (85%) is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and held at this temperature for 20 minutes, then the mixture is cooled to about

60 s in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification. Hydrogenation step

To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated to 80 - HO C, the nitrogen cylinder is replaced with a hydrogen cylinder and then pressure is set and manually maintained at 30-60 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to rectification, 4-aminodiphenylamine vapors enter a condenser 10, cooled with 85 ^{° C} circulating water ^. C, and then by gravity to receiver 33. The mass of the obtained 4-aminodiphenylamine was 13.00 grams (97% yield based on the nitrobenzene used). The distillation residue is polyethylene glycol and potassium chloride. The residue is dissolved in 50 ml of methanol at 50 ° C and filtered off from potassium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is pure PEG which is reused in stage N ° l (after several cycles (10) of using PEG, a solution of PEG in methanol is left at room temperature to precipitate PEG, PEG is filtered, methanol is distilled off from the filtrate, and the residue is utilized).

Ή NMR (400 MHz, CDC1 ₃ ): d 7.14 (dd, J = 7.2, 7.2 Hz, 2H),

6.90 (d, J = 8.4 Hz, 2H), 6.79 (d, J = 8.4 Hz, 2H), 6.75 (dd, J = 7.2, 7.2 Hz, 1H), 6.56 (d, J = 7.2 Hz, 2H), 5.40 (br, NH); 3.43 (br, NH);

¹³ C NMR (100 MHz, CDC): d 145.7, 141.8, 133.5, 129.0, 122.9, 1 18.6, 115.9, 114.8.

IR (kW, cm ^"1 ): mNH = 3400, 3355.

MS (EI) 184.

Elemental analysis of C12H12N2: Calculated: C, 78.23; H, 6.57; N, 15.21.

Found: C, 78.10; H, 6.70; N, 14.96.

Example 2 (NaOH + PEG). Obtaining diene FP

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and a branch for distillation 14, is placed polyethylene glycol with an average molecular weight of 4000 daltons. Then fed to the reactor 3.34 g of sodium hydroxide, the reactor closes and at

about

60 s in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled to 60 ^° C, the pressure is brought to atmospheric, the reactor opens and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount required to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through filter 27 using nozzle 28 and receiver 29, a filtrate N ° 1 is formed. The filtrate N-> 1 is used in stage Ns 2. The filter residue forms a precipitate N2 1.

Stage M2 - reductive alkylation

The filtrate N ° l from the N ° l stage is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 ° C, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure of 30-35 atmospheres of hydrogen is set and manually maintained, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate G1 is formed. The filter residue is reused as a catalyst in step N22. Unreacted acetone is distilled off from the filtrate N ° 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, which is cooled recycled water with a temperature of 85 ° C, and then by gravity to receiver 33. The mass of the AF diaphen is 15.48 g (94% based on the used nitrobenzene). The residue after distillation is polyethylene glycol 4000, which is reused in stage N2I.

Getting 4-aminodiphenylamine

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a branch for distillation 14, is placed polyethylene glycol with an average molecular weight of 4000 daltons. Then, 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and heated with stirring at 1000 rpm to 120 ^° C and held at this temperature for 20 minutes, then the mixture is cooled to 60 ^° C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated to 80 - 110 ° C, the nitrogen cylinder is replaced with a hydrogen cylinder and then pressure is set and manually maintained at 30-60 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture filtered through filter 27 using nozzle 28 and receiver 29. Filtrate IV forms. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to rectification, 4-aminodiphenylamine vapors enter the condenser 10, cooled by circulating water with a temperature of 85 ° C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.60 grams (94% yield based on the used nitrobenzene). The residue after distillation is polyethylene glycol 4000 and

o sodium chloride. The residue is dissolved in 50 ml of methanol at 50 ° C and filtered off from sodium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is pure PEG 4000, which is reused in stage JN ° 1 (after several cycles (10) of using the PEG PEG solution in methanol is left at room temperature to precipitate PEG, PEG is filtered, methanol is distilled off from the filtrate, the residue is disposed of). Example 3 (polypropylene col + KOH). Getting diaphen AF

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a branch for distillation 14, is placed polypropylene glycol (Mn = 2700. Then 5.5 g (85%) of potassium hydroxide is fed into the reactor, the reactor closes and with stirring 1000 gh about

Heats up to 120 C and maintains at this temperature 20

about

minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled to 60 C, the pressure is brought to atmospheric, the reactor a methanol solution of hydrochloric acid is opened and added (containing 0.0835 mol of hydrogen chloride - the amount required to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through filter 27 using nozzle 28 and receiver 29 , a filtrate N-> 1 is formed. The N2I filtrate is used in step N ° 2. The residue on the filter forms a precipitate of N ° 1.

Stage N ° 2 - reductive alkylation

The filtrate Ν »ΐ from stage Ν2Ι is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated to 80 ° C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through a filter 27 using the nozzle 28 and the receiver 29. A filtrate is formed Ν «2. The filter residue is reused as a catalyst in stage N ° 2. Unreacted acetone is distilled off from the filtrate N ° 2 using a reflux condenser 34, a condenser 10, and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, cooled by circulating water with a temperature of 85 C, and then by gravity into receiver 33. The mass of AF diaphen is 15.97 grams (97% based on the used nitrobenzene). The distillation residue is polypropylene glycol, which is reused in stage N ° l.

Getting 4-aminodiphenylamine

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polypropylene glycol (Mn = 2700). Then 5.5 g of potassium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 with a speed of OD ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated to 80 - HO C, the nitrogen cylinder is replaced with a hydrogen cylinder and then pressure is set and manually maintained at 30-60 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10, and a receiver 33. The residue is subjected to rectification, 4-aminodiphenylamine vapors enter a condenser 10 cooled by circulating water with

about

temperature of 85 C, and then by gravity to the receiver 33. Mass the obtained 4-aminodiphenylamine was 13.00 grams (97% yield based on the nitrobenzene used). The residue after distillation is polypropylene glycol and potassium chloride. The residue is dissolved in 50 ml of methanol at 50 ^° C and filtered off from potassium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is pure PPG which is reused in stage N2I (after several cycles of (10) using PPG, the solution of PPG in methanol is left at at room temperature for the precipitation of BCP, the BCP is filtered, methanol is distilled off from the filtrate, the residue is disposed of).

Example 4 (polypropylene glycol + ΝαΟΗ). Getting diaphen AF

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polypropylene glycol (Mn = 2700). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to

120 C and maintained at this temperature for 20 minutes, then about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then temperature

about

rises to 80 C and the aniline residues are distilled off, condensing in the capacitor 10, and flow by gravity to the receiver 11, forming a return aniline. The reactor is cooled about

to 60 C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a Nel filtrate is formed. The filtrate N ° l is used in stage Ns 2. The residue on the filter forms a precipitate N ° 1.

Stage N ° 2 - reductive alkylation

The filtrate Ν ° 1 from stage N ° l is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 . A filtrate of Νί? 2 is formed. The filter residue is reused as a catalyst in stage Ν »2. Unreacted acetone is distilled off from the filtrate Ν ° 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 15.48 grams (94% based on the used nitrobenzene). Balance after The distillation is polypropylene glycol, which is reused in the N2I step.

Getting 4-aminodiphenylamine

Stage Ν ° 1 — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polypropylene glycol (Mn = 2700). Then, 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 goth is heated to 120 ^° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, which creates a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes, 40 seconds, flow nitrobenzene is discontinued. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated

about

up to 80 - НО С, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure of 30-60 atmospheres of hydrogen is set and manually maintained, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and a receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to distillation, 4-aminodiphenylamine vapors are transferred to a condenser 10, cooled with 85 ^{° C} circulating water ^. C, and then by gravity to receiver 33. The mass of 4-aminodiphenylamine obtained was 12.60 grams (94% yield based on the nitrobenzene used). The remainder after distillation, it is polypropylene glycol and

o sodium chloride. The residue is dissolved in 50 ml of methanol at 50 ° C and filtered from sodium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is pure PPG which is reused in stage N ° l (after several cycles of (10) using PPG, the solution of PPG in methanol is left at room temperature for precipitation of BCP, BCP is filtered, methanol is distilled off from the filtrate, the residue is disposed of).

Example 5 (polypropylene glycol + LiOH). Obtaining diene FP

Stage NQI - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polypropylene glycol (Mn = 2700). Then 2.00 g of lithium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor; it is lowered through the thread at the top capillary 6 by 120mm, the reactor closes. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled about

to 60 C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml is added acetone, stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate N ° l is formed. The N2I filtrate is used in stage Ν "2. The residue on the filter forms a precipitate N" 1.

Stage N ° 2 — reductive alkylation

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 The filtrate is formed 2. The filter residue is reused as a catalyst in stage 1. Unreacted acetone is distilled off from the filtrate N рата 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is distilled and, the pairs of AF diaphene enter the condenser 10, cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 14.49 grams (88% based on the used nitrobenzene). The distillation residue is polypropylene glycol, which is reused in stage N ° l. Getting 4-aminodiphenylamine

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polypropylene glycol (Mn = 2700). Then 2.00 g of lithium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to about

120 C and maintained at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes, then 15 ml is added to it. water and 8.35 g of 36.5% hydrochloric acid solution. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

up to 80 - НО С, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure of 30-60 atmospheres of hydrogen is set and manually maintained, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and a receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10, and a receiver 33. The residue is subjected to rectification, 4-aminodiphenylamine vapors enter a condenser 10 cooled by circulating water with

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 11.80 grams (88% yield based on the used nitrobenzene). The residue after distillation is polypropylene glycol and

o lithium chloride. The residue is dissolved in 50 ml of methanol at 50 ° C and filtered from lithium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is pure PPG which is reused in the Nel stage (after several cycles (10) of using PPG, the solution of PPG in methanol is left at room temperature to precipitate PPG, the PPG is filtered from the filtrate methanol is distilled off, the residue is disposed of).

Example 6 (polypropylene glycol) + Ca (OH) 2). Getting

diafena FP

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a branch for distillation 14, is placed polypropylene anglycol (Mn = 2700). Then 3.09 g of calcium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled about

to 60 C, the pressure is brought to atmospheric, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29, filtrate N ° l is formed. The filtrate N ° l is used in the stage

N2 2. Residue on the filter forms a precipitate N2 1.

Stage M2 — reductive alkylation

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate Ш1 is formed. The filter residue is reused as a catalyst in stage N ° 2. Unreacted acetone is distilled off from the N9.2 filtrate using a reflux condenser 34, a condenser 10, and a receiver 33. The residue is rectified, the vapor of the FP diaphene enters the condenser 10, cooled by circulating water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the FP diaphene is 15.15 grams (92% based on the nitrobenzene used). The distillation residue is polypropylene glycol, which is reused in the Xal step.

Getting 4-aminodiphenylamine

Stage N ° l - condensation of nitrobenzene with aniline Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polypropylene glycol (Mn = 2700). Then 3.09 g of calcium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. Received the mixture is reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

up to 80 - НО С, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure of 30-60 atmospheres of hydrogen is set and manually maintained, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and a receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to distillation, 4-aminodiphenylamine vapors are transferred to a condenser 10, cooled with circulating water at a temperature of 85 C , and then by gravity to receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.33 grams (yield 92% based on the nitrobenzene used). The residue after distillation is polypropylene glycol and

o calcium chloride. The residue is dissolved in 50 ml of methanol at 50 ° C. and filtered from calcium chloride, then methanol is removed. by vacuum distillation, the distillation residue is pure 11111 ^', which is reused in stage N ° l (after several cycles of (10) using PPG, a solution of 1111 in methanol is left at room temperature to precipitate PPG, PPG is filtered, methanol is distilled off from the filtrate, and the residue is utilized )

Example 7 (polytetrahydrofuran + KOH). Getting diaphen AF

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytetrahydrofuran (Mn = 2000). Then 5.5 g (85%) potassium hydroxide is fed into the reactor, the reactor is closed and heated with stirring at 1000 rpm to 120 ° C and held at this temperature for 20 minutes, then the mixture is cooled to 60 ° C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using a pump 19 and the controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled to 60 ^° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid (containing 0.0835 mol of hydrogen chloride is added - the amount required to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, filtrate N ° l is formed. The filtrate N ° l is used in stage N ° 2. The residue on the filter forms a precipitate N ° 1.

Stage M2 — Reductive Alkhing

The N2I filtrate from stage N ° l is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 The filtrate _N 2 is formed. The filter residue is reused as a catalyst in the Ns2 step. Unreacted acetone is distilled off from the filtrate 2 using a reflux condenser 34, a condenser 10, and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 15.97 grams (97% based on the used nitrobenzene). The distillation residue is polytetrahydrofuran, which is reused in stage N ° l.

Getting 4-aminodiphenylamine

Stage N2I - Condensation of Nitrobenzene with Aniline Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytetrahydrofuran (Mn = 2000, Aldrich). Then 5.5 g of potassium hydroxide (85%) is fed into the reactor, the reactor is closed and 1000 rpm with stirring

about

Heats up to 120 C and maintains at this temperature 20

about

minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. Received the mixture is reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 13.00 grams (97% yield based on the nitrobenzene used). The residue after distillation is polytetrahydrofuran and

o potassium chloride. The residue was dissolved in 50 ml of methanol at 50 ° C and filtered off from potassium chloride, then methanol was removed by vacuum. by distillation, the distillation residue is pure polytetrahydrofuran, which is reused in stage N ° l (after several cycles (10) of using polytetrahydrofuran, a solution of polytetrahydrofuran in methanol is left at room temperature for polymer precipitation, the polymer is filtered, methanol is distilled off from the filtrate, and the residue is utilized) .

Example 8 (polytetrahydrofuran + ΝαΟΗ). Getting diaphen AF

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytetrahydrofuran (Mn = 2000). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and flow by gravity to the receiver 1 1, forming a return aniline. The reactor is cooled to 60 ° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, an N2I filtrate is formed. The filtrate N ° l is used in the stage

N ° 2. The filter residue forms a precipitate of N ° 1.

Stage N ° 2 - reductive alkoxia

The N2I filtrate from stage N <? 1 is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 ° C, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate N ° 2 is formed. The filter residue is reused as a catalyst in the N-> 2 stage. From the filtrate, N ° 2 unreacted acetone is distilled off via the reflux condenser 34, the condenser 10 and the receiver 33. The residue is subjected to distillation, vapors AF diafen enter the condenser 10, cooled by circulating water ^'having a temperature of 85 C, and then by gravity to the receiver 33. Mass diafen AF is 15.48 grams (94% based on the nitrobenzene used). The distillation residue is polytetrahydrofuran, which is reused in the N2I step.

Getting 4-aminodiphenylamine

Stage IIa — condensation of nitrobenzene with aniline Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytetrahydrofuran (Mn = 2000). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to about

120 C and maintained at this temperature for 20 minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. Received the mixture is reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.60 grams (94% yield based on the used nitrobenzene). The residue after distillation is polytetrahydrofuran and

o sodium chloride. The residue is dissolved in 50 ml of methanol at 50 C and filtered from sodium chloride, then methanol is removed by vacuum distillation, the distillation residue is pure polytetrahydrofuran, which is reused in stage N ° l (after several cycles (10) of using polytetrahydrofuran, a solution of polytetrahydrofuran in methanol is left at room temperature for polymer precipitation, the polymer is filtered, methanol is distilled off from the filtrate, and the residue is utilized )

Example 9 (polytetrahydrofuran + LiOH). Getting diaphen AF

Stage N2I - Condensation of Nitrobenzene with Aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytetrahydrofuran (Mn = 2000, Aldrich). Then 2.00 g of lithium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring.

about

Heats up to 120 C and maintains at this temperature 20

about

minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through a thread in the lower part of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled about

to 60 C, the pressure is brought to atmospheric, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29, filtrate N? .l is formed. The filtrate N ° l is used in the stage

N2 2. The residue on the filter forms a precipitate N ° 1.

Stage N ° 2 — reductive alkylation

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate N ° 2 is formed. The filter residue is reused as a catalyst in stage N ° 2. Unreacted acetone is distilled off from the filtrate N ° 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 14.49 grams (88% based on the used nitrobenzene). The distillation residue is polytetrahydrofuran, which is reused in stage N ° l.

Getting 4-aminodiphenylamine

Stage Ml - condensation of nitrobenzene with aniline Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and a branch for distillation 14, is placed polytetrahydrofuran (Mn = 2000). Then 2.00 g of lithium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to about

120 C and maintained at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. Received the mixture is reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% RaUS is charged, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated to 80 - HO C, the nitrogen cylinder is replaced with a hydrogen cylinder and then pressure is set and manually maintained at 30-60 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10, and a receiver 33. The residue is subjected to rectification, 4-aminodiphenylamine vapors enter a condenser 10 cooled by circulating water with

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 1 1.79 grams (88% yield based on the used nitrobenzene). The residue after distillation is polytetrahydrofuran and

o lithium chloride. The residue was dissolved in 50 ml of methanol at 50 ° C and filtered from lithium chloride, then methanol was removed by vacuum. by distillation, the distillation residue is pure polytetrahydrofuran, which is reused in the Nsl stage (after several cycles (10) of using polytetrahydrofuran, a solution of polytetrahydrofuran in methanol is left at room temperature for polymer precipitation, the polymer is filtered, methanol is distilled off from the filtrate, and the residue is utilized).

Example 10 (polytetrahydrofuran Ca (OH) 2). Getting diaphen AF

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytetrahydrofuran (Mn = 2000). Then 3.09 g of calcium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains 14 000130

62 closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled to 60 ° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, filtrate N ° l is formed. The Nel filtrate is used in stage Ns 2. The residue on the filter forms a precipitate of N ° 1.

Stage M2 — reductive alkylation

The Nel filtrate from the N2I stage is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 ° C, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate N ° 2 is formed. The filter residue is reused as a catalyst in stage N ° 2. Unreacted acetone is distilled off from the filtrate N-> 2 using a reflux condenser 34, a condenser 10, and a receiver 33. The residue is rectified, the vapor of the FP diaphene enters the condenser 10, cooled by circulating water with a temperature of 85 ^° C, and then by gravity to the receiver 33. The mass of the diaphene AF is 15.15 grams (94% based on the nitrobenzene used). The distillation residue is polytetrahydrofuran, which is reused in stage N ° l.

Getting 4-aminodiphenylamine

Stage N ° l — condensation of nitrobenzene with aniline Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered through 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytetrahydrofuran (Mn = 2000). Then 3.09 g of calcium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to about

120 C and maintained at this temperature for 20 minutes, then

about

Hydrogenation step

about

up to 80 - НО С, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure of 30-60 atmospheres of hydrogen is set and manually maintained, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and a receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to distillation, 4-aminodiphenylamine vapors are transferred to a condenser 10, cooled with circulating water at a temperature of 85 C , and then by gravity to receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.33 grams (yield 92% based on the nitrobenzene used). The residue after distillation is polytetrahydrofuran and

o calcium chloride. The residue is dissolved in 50 ml of methanol at 50 ° C. and filtered from calcium chloride, then methanol is removed. by vacuum distillation, the distillation residue is pure polytetrahydrofuran, which is reused in the N-? l stage (after several cycles (10) of using polytetrahydrofuran, a solution of polytetrahydrofuran in methanol is left at room temperature for the polymer to precipitate, the polymer is filtered, methanol is distilled off from the filtrate, the residue disposed of).

Example 11 (polytrimethylene oxide (PTMO) + KOH). Getting diaphen AF

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytrimethylene oxide (RTMO) (Mn = 2000). Then 5.5 g (85%) of potassium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring

about

Heats up to 120 C and maintains at this temperature 20

about

minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through a thread in the lower part of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then temperature

about

to 60 C, the pressure is brought to atmospheric, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29, the filtrate jN l is formed. The Nsl filtrate is used in step N ° 2. The residue on the filter forms a precipitate of N2 1.

Stage N ° 2 — reductive alkylation

The filtrate N ° l from the N2I stage is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated to 80 ° C, the nitrogen cylinder is replaced with a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through a filter 27 using the nozzle 28 and the receiver 29. A filtrate N22 is formed. The filter residue is reused as a catalyst in stage 2. Unreacted acetone is distilled off from the filtrate N <2 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to rectification, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 ° C, and then by gravity to ^• receiver 33. The mass of the AF diaphen is 15.97 grams (97% based on the used nitrobenzene). The distillation residue is RTMO, which is reused in the N ° l stage.

Getting 4-aminodiphenylamine

Stage N ° l — condensation of nitrobenzene with aniline Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and tap for distillation 14, is placed polytrimethylene oxide (RTMO) (Mn = 2000). Then 5.5 g (85%) of potassium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and maintained at this temperature. 20

about

minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. Received the mixture is reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 13.00 grams (97% yield based on the used nitrobenzene). The distillation residue is RTMO and potassium chloride. The residue is dissolved in 50 ml of methanol at 50 ° C and filtered from potassium chloride, then methanol is removed by vacuum distillation, the distillation residue is pure RTMO, which is reused in the Nil stage (after several cycles (10) of using RTMO, the RTMO solution in methanol is left at room temperature for the polymer to precipitate, the polymer is filtered, methanol is distilled off from the filtrate, and the residue is disposed of).

Example 12 (ΠΤΜΟ + ΝαΟΗ). Getting diaphen AF

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytrimethylene oxide (RTMO) (Mn = 2000). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring.

about

Heats up to 120 C and maintains at this temperature 20

about

minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, pressure controlled by controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the nitrobenzene supply is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25 in the reactor 1, the OD pressure is set, which is controlled by controller 34, the bulk of the aniline is distilled off in 1 hour, then the temperature

about

rises to 80 C and the aniline residues are distilled off, condensing in the capacitor 10, and flow by gravity to the receiver 11, forming a return aniline. The reactor is cooled to 60 ^° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid (containing 0.0835 mol of hydrogen chloride is added - the amount required to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped , the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a Nal filtrate is formed. The filtrate N ° l is used in stage N ° 2. The residue on the filter forms a precipitate N "1. Stage N ° 2 - reductive alkylation

The filtrate N «l from the Nsl stage is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate W1 is formed. The filter residue is reused as a catalyst in step N 2 2. Unreacted acetone is distilled off from the filtrate Ш1 by means of a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is subjected to rectification, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 15.48 grams (94% based on the used nitrobenzene). The distillation residue is RTMO, which is reused in stage 1.

Getting 4-aminodiphenylamine

Stage NQI Condensation of Nitrobenzene with Aniline

In the reactor 1 (volume 250 ml) with a jacket connected to the thermostat 13, equipped with a mechanical stirrer 2, 8, 9 s Polytrimethylene oxide (RTMO) is placed with a magnetic actuator 3, a thermocouple 12, lowered by 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and an outlet for distillation 14 (MMP = 2000). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring.

about

Heats up to 120 C and maintains at this temperature for 20 minutes, then the mixture is cooled to 60 ^° C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification. Hydrogenation step

To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% PaVC is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated

about

up to 80 - НО С, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure of 30-60 atmospheres of hydrogen is set and manually maintained, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and a receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to distillation, 4-aminodiphenylamine vapors are transferred to a condenser 10, cooled with circulating water at a temperature of 85 C , and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.60 grams (94% yield based on the nitrobenzene used). The distillation residue is RTMO and sodium chloride.

about

The residue is dissolved in 50 ml of methanol at 50 ° C and filtered from sodium chloride, then the methanol is removed by vacuum distillation, the residue upon distillation is pure RTMO, which is reused in stage N <> 1 (after several cycles (10) of using RTMO, a solution of RTMO in methanol is left at room temperature to precipitate the polymer, the polymer is filtered, methanol is distilled off from the filtrate, and the residue is disposed of).

Example 13 (PTMO) + PON). Getting diaphen AF

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytrimethylene oxide (RTMO) (Mn = 2000). Then 2.00 g of lithium hydroxide is fed into the reactor, the reactor is closed, and with stirring 1000 rpm

Heats up to 120 C and maintains at this temperature for 20 minutes, then the mixture is cooled to 60 ^° C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled with 50 ml per minute through capillary 7 and nitrobenzene is fed through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25 in the reactor 1, the OD pressure is set, which is controlled by controller 34, the bulk of the aniline is distilled off in 1 hour, then the temperature rises to 80 C and the aniline residues are distilled off, condensing in the capacitor 10, and fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled about

to 60 C, the pressure is brought to atmospheric, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29, a filtrate N l l is formed. The filtrate Ν ° 1 is used in stage Ns 2. The residue on the filter forms a precipitate N ° 1.

Stage N ° 2 reductive alkylation The filtrate N »l from stage N ° l is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 . A filtrate N <> 2 is formed. The filter residue is reused as a catalyst in stage N ° 2. Unreacted acetone is distilled off from the filtrate N 2 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 14.49 grams (88% based on the used nitrobenzene). The distillation residue is RTMO, which is reused in the N ° l stage.

Preparation of 4-aminodiphenjamine

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with magnetic drive 3, thermocouple 12, lowered by 120 mm polytrimethylene oxide (RTMO) is placed through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13 and an outlet for distillation 14 (Mn = 2000). Then 2.00 g of lithium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring

about

Heats up to 120 C and maintains at this temperature for 20 minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated

about

up to 80 - НО С, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure of 30-60 atmospheres of hydrogen is set and manually maintained, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and a receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to distillation, 4-aminodiphenylamine vapors are transferred to a condenser 10, cooled with circulating water at a temperature of 85 C , and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 1 1, 80 grams (88% yield based on the nitrobenzene used). The distillation residue is RTMO and lithium chloride.

about

The residue is dissolved in 50 ml of methanol at 50 ° C and filtered from lithium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is pure RTMO, which is reused in the Nsl stage (after several cycles of (10) use of RTMO solution of RTMO in methanol leave at room temperature for the precipitation of the polymer, the polymer is filtered, methanol is distilled off from the filtrate, the residue is disposed of). Example 14 (PTMO + CaUyut). Getting diaphen AF

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, is placed polytrimethylene oxide (RTMO) (Mn = 2000). Then 3.09 g of calcium hydroxide is fed into the reactor, the reactor is closed and with stirring 1000 rpm

about

Heats up to 120 C and maintains at this temperature 20

about

minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and is supplied nitrobenzene through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25 in the reactor 1, the OD pressure is set, which is controlled by controller 34, the bulk of the aniline is distilled off in 1 hour, then the temperature

about

rises to 80 C and the aniline residues are distilled off, condensing in the capacitor 10, and flow by gravity to the receiver 11, forming a return aniline. The reactor is cooled to 60 ° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate K ° \ is formed. The N2I filtrate is used in stage JN2 2. The residue on the filter forms a precipitate of Ν ° 1.

Stage Ν ° 2 - reductive alkylation

The filtrate N ° l from stage Ν2Ι is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C, autoclave is charged closes. The autoclave is purged with nitrogen from the cylinder three times, about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 . A filtrate is formed Ν "2. The filter residue is reused as a catalyst in the Ne2 stage. Unreacted acetone is distilled off from the filtrate N ° 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 15.15 grams (92% based on the used nitrobenzene). The distillation residue is RTMO, which is reused in the N ° l stage.

Getting 4-aminodiphenylamine

Stage NQI - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, polytrimethylene oxide (RTMO) is placed (Mn = 2000). Then, 3.09 g of calcium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ° C and held at this temperature for 20 minutes, then the mixture is cooled to 60 ° C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heats up about

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.33 grams (yield 92% based on the used nitrobenzene). The distillation residue is RTMO and calcium chloride.

about

The residue is dissolved in 50 ml of methanol at 50 ° C and filtered from calcium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is pure RTMO, which is reused in the Nel stage (after several cycles of (10) use of RTMO, the RTMO solution in methanol is left at room temperature for precipitation of the polymer, the polymer is filtered, methanol is distilled off from the filtrate, the residue is disposed of). Example 15 (PPG-PEG-PPG Pluronic 10R5 + NaOH). Getting diaphen AF)

Stage Ml - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a branch for distillation 14, is placed PPG-PEG-PPG Pluronic ^® 10R5 (block copolymer of ethylene and propylene oxide, Mn = 2000). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed

o and with stirring 1000 rpm is heated to 120 ^° C and is maintained at this temperature for 20 minutes, then the mixture is cooled to 60 ^° C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, which creates a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced with an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the bulk of the aniline is distilled off

about

1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and fed by gravity to the receiver 11, forming a return

about

aniline. The reactor is cooled to 60 ° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate N ° l is formed. The filtrate N ° l is used in stage N2 2. The residue on the filter forms a precipitate N ° 1.

Stage N ° 2 — reductive alkylation

The filtrate Νί 1 from stage N ° l is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 . A filtrate is formed Ν "2. The filter residue is reused as a catalyst in stage N ° 2. Unreacted acetone is distilled off from the Ne2 filtrate using a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 15.48 grams (94% based on the used nitrobenzene). The residue after distillation is a PPG-PEG-PPG Pluronic ^® 10R5, which is reused in step N2I.

Getting 4-aminodiphenylamine

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a branch for distillation 14, is placed block copolymer PPG-PEG-PPG Pluronic 10R5 (block copolymer of ethylene and propyl enoxide, Mn = 2000). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring.

about

Heats up to 120 C and maintains at this temperature for 20 minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.60 grams (94% yield based on the used nitrobenzene). The distillation residue is Pluronic ^® 10R5 PPG-PEG-PPG and sodium chloride. The residue is dissolved in 50 ml of methanol.

about

at 50 C and filtered from the sodium chloride, then methanol was removed by vacuum distillation residue during the distillation is a pure block copolymer, which is reused in step Nel (after several cycles (10) using PPG- PEG-PPG Pluronic ^® 10R5 polymer solution in methanol is left at room temperature for precipitation polymer, the polymer is filtered, methanol is distilled off from the filtrate, the residue is disposed of).

Example 16. Monobutyl ether PPG + NaOH. Getting diaphen AF

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a branch for distillation 14, is placed monobutyl ether PPG (Mn = 2500). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 with a speed of OD ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then temperature

about

to 60 C, the pressure is brought to atmospheric, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29, an N2I filtrate is formed. The N2I filtrate is used in the JSfe 2 step. The residue on the filter forms a N2 1 precipitate.

Stage II - reductive alkylation

The N2I filtrate from the N2I stage is charged into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C, autoclave is charged closes. The autoclave is purged with nitrogen from the cylinder three times, about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate N22 is formed. The filter residue is reused as a catalyst in the N-> 2 stage. Unreacted acetone is distilled off from the filtrate N ° 2 using a reflux condenser 34, a condenser 10, and a receiver 33. The residue is rectified, the vapor of the FP diaphene enters the condenser 10, cooled by circulating water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the FP diaphene is 15.48 grams (94% based on the nitrobenzene used). The residue after distillation is PPG monobutyl ether (Mn = 2500), which is reused in stage N ° l.

Getting 4-aminodiphenylamine

Stage l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a tap for distillation 14, placed monobutyl ether / 777G (Mn = 2500). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to about

120 C and maintained at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.60 grams (94% yield based on the used nitrobenzene). The residue after distillation is PPG monobutyric ether (Mn = 2500) and sodium chloride. The residue is dissolved in 50 ml

about

methanol at 50 ° C and filtered from sodium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is a pure polymer that is reused in the Nal stage (after several cycles (10) of using PPG monobutyl ether (Mn = 2500) a solution of the polymer in methanol leave at room temperature for polymer precipitation, the polymer is filtered, methanol is distilled off from the filtrate, the residue is disposed of).

Example 17. (PEG-PPG-PEG Pluronic ^® L-81 + ΝαΟΗ). Getting diaphen AF

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and a tap for distillation 14, is placed PEG-PPG-PEG Pluronic ^® L-81 (Mn = 2800). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring.

about

Heats up to 120 C and maintains at this temperature 20

about

minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and is supplied nitrobenzene through capillary 6 at a rate of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled to 60 ^° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid (containing 0.0835 mol of hydrogen chloride is added - the amount required to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped , the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate N ° l is formed. The filtrate N_? L is used in stage N ° 2. The residue on the filter forms a precipitate Ν ^» 1.

Stage N ° 2 — reductive alkylation

The filtrate N ° l from stage N ° l is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C, autoclave is charged closes. The autoclave is purged with nitrogen from the cylinder three times, about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 . A filtrate is formed Ν "2. The filter residue is reused as a catalyst in the Ν ° 2 stage. Unreacted acetone is distilled off from the filtrate N ° 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is subjected to rectification, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 15.48 grams (94% based on the used nitrobenzene). The residue after distillation is PEG-PPG-PEG Pluronic ^® L-81 (Mn = 2800), which is reused in stage N ° l.

Getting 4-aminodiphenylamine.

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a tap for distillation 14, placed PEG-PPG-PEG Pluronic L-81 (Mn = 2800). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring.

about

Heats up to 120 C and maintains at this temperature for 20 minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.60 grams (94% yield based on the used nitrobenzene). The residue after distillation is PEG-PPG-PEG Pluronic ^® L-81 (Mn = 2800) and sodium chloride. The residue is dissolved in 50 ml of methanol at 50 ° C and filtered off from sodium chloride, then the methanol is removed by vacuum distillation, the residue upon distillation is a pure polymer that is reused in stage (after several cycles (10) of using PUR-PPG-PEG Pluronic ^® L-81 (Mn = 2800) a solution of the polymer in methanol is left at room temperature for precipitation of the polymer, the polymer is filtered, methanol is distilled off from the filtrate, the residue is disposed of).

Example 18. (PEG + ΝαΟΗ methyl ether). Getting

diafena FP

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a branch for distillation 14, is placed methyl ether PEG (Mn = 2000). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through 102 capillary 6 with a speed of OD ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the bulk of the aniline is distilled off in 1 hour, then the temperature rises up to 80 C and the aniline residues are distilled off, condensing in the capacitor 10, and fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled about

to 60 C, the pressure is brought to atmospheric, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29, a JSfol filtrate is formed. The JNM filtrate is used in step N2 2. The residue on the filter forms a precipitate of N2 1.

Stage N? 2 — Reductive Alkhing

The filtrate 1 from stage N ° .l is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C, autoclave is charged closes. The autoclave is purged with nitrogen from the cylinder three times, about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate N ° 2 is formed. The filter residue is reused as a catalyst in step N 2 2. Unreacted acetone is distilled off from the filtrate N 2 2 using a reflux condenser 34, a condenser 10, and a receiver 33. The residue is rectified, the vapor of the FP diaphene enters the condenser 10, cooled by circulating water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the FP diaphene is 15.48 grams (94% based on the nitrobenzene used). The distillation residue is PEG methyl ester (Mn = 2000), which is reused in stage N ° l.

Getting 4-aminodiphenylamine

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and tap for distillation 14, PEG methyl ether (Mn = 2000) is placed. Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to about

120 C and maintained at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

temperature 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.60 grams (94% yield based on the used nitrobenzene). The residue after distillation is PEG methyl ester (Mn = 2000) and sodium chloride. The residue is dissolved in 50 ml

about

methanol at 50 ° C and filtered from sodium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is a pure polymer, which is reused in stage JM ° 1 (after several cycles (10) of using PEG methyl ether (Mn = 2000) polymer solution in methanol left at room temperature for polymer precipitation, the polymer is filtered, methanol is distilled off from the filtrate, the residue is disposed of).

Example 19. (d Mesh methylether PEG + ΝαΟΗ). Obtaining dshphen AF

Stage Ν ° 1 - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a branch for distillation 14, is placed dimeshovy ether PEG (Mn = 2000). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ° C and held at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled about

to 60 C, the pressure is brought to atmospheric, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29, an N2I filtrate is formed. The N2I filtrate is used in step N ° 2. The residue on the filter forms a precipitate of N2 1.

Stage N ° 2 - reductive alkylation

The N2I filtrate from the NI stage is charged into a 250 ml autoclave 30, then 0.1 g of 10% Pd / C, autoclave is charged closes. The autoclave is purged with nitrogen from the cylinder three times, heated to 80 ° C, the nitrogen cylinder is replaced with a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through a filter 27 using nozzle 28 and receiver 29. Filtrate 2 is formed. The filter residue is reused as a catalyst in stage 2. Unreacted acetone is distilled off from filtrate 2 using reflux condenser 34, condenser 10 receiver 33. The residue is subjected to distillation, vapors AF diafen enter the condenser 10, cooled by circulating water with a temperature of 85 ° C, and then by gravity to the receiver 33. Mass diafen AF is 15.48 grams (94% based on the nitrobenzene used). The residue after distillation is a PEG hydrochloride ester (Mn = 2000), which is reused in stage N ° l.

Getting 4-aminodiphenylamine

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and a tap for distillation 14, PEG dimethyl ether is placed (Mn = 2000). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to about

120 C and maintained at this temperature for 20 minutes, then

about

the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification.

Hydrogenation step

To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. W

BY

The autoclave is purged with nitrogen from the cylinder three times, heated

about

up to 80 - НО С, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure of 30-60 atmospheres of hydrogen is set and manually maintained, after 1 hour, the autoclave 5 is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29. An IV filtrate is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10, and a receiver 33. The residue is subjected to rectification, 4-aminodiphenylamine vapors enter a condenser 10 cooled with circulating water with

about

temperature of 85 C, and then by gravity to the receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.60 grams

15 (94% yield based on the nitrobenzene used). The residue after distillation is PEG + ΝαΟΗ dimethyl ether (Mn = 2000) and sodium chloride. The residue is dissolved in 50 ml of methanol at 50 ° C and filtered from sodium chloride, then methanol is removed by vacuum distillation, the residue by distillation

20 is a pure polymer that is reused in stage N ° l (after several cycles (10) of use of PEG dimethyl ether (Mn = 2000), a solution of the polymer in methanol is left at room temperature for polymer precipitation, the polymer is filtered, methanol is distilled off from the filtrate, the residue is disposed of).

Example 20. {PEG dimethyl ether + monobutyl ether 11111 + NaOH. Obtaining diene FP

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and a branch for distillation 14, a mixture of PEG dimethyl ether (Mn = 2000) + PPG monobutyl ether (Mn = 2500) is placed. Then, 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and, with stirring, 1000 rpm is heated to 120 ^° C and held at this temperature for 20 minutes, then the mixture is cooled to

60 s in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is fed through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled to 60 ^° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped , the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate N ° l is formed. The filtrate N ° l is used in stage Ns 2. The residue on the filter forms a precipitate N-> 1.

Stage N ° 2 - reductive alkylation The filtrate N-> 1 from stage N ° l is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 ° C, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate N ° 2 is formed. The filter residue is reused as a catalyst in stage N <> 2. Unreacted acetone is distilled off from the Ν-> 2 filtrate using a reflux condenser 34, a condenser 10, and a receiver 33. The residue is rectified, the vapor of the FP diaphene enters the condenser 10, cooled by circulating water with a temperature of 85 ^° C, and then by gravity to the receiver 33. The mass of the diaphene AF is 15.48 grams (94% based on the nitrobenzene used). The residue after distillation is PEG dimesh ether (Mn = 2000) + PPG monobutyl ether (Mn = 2500), which is reused in stage Ν21.

Getting 4-aminodiphenylamine

Stage N ° l - condensation of nitrobenzene with aniline

In the reactor 1 (volume 250 ml) with a jacket connected to the thermostat 13, equipped with a mechanical stirrer 2, 8, 9 s magnetic drive 3, thermocouple 12, lowered by 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to thermostat 13, and an outlet for distillation 14, is placed PEG-free ether (Mn = 2000) + monobutyl ether 11111 (Mn = 2500). Then, 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and at

about

60 s in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture was reduced to 4-aminodiphenylamine without further purification. Hydrogenation step

To obtain 4-aminodiphenylamine, the mixture obtained in the first stage is transferred to an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times, heated to 80 - HO C, the nitrogen cylinder is replaced with a hydrogen cylinder and then pressure is set and manually maintained at 30-60 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through the filter 27 using the nozzle 28 and the receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to distillation, 4-aminodiphenylamine vapors are transferred to a condenser 10, cooled with 85 ^{° C} circulating water ^. C, and then by gravity to receiver 33. The mass of 4-aminodiphenylamine obtained was 12.60 grams (94% yield based on the nitrobenzene used). The distillation residue is PEG dgshetyl ether (Mn = 2000) + PPG monobutyl ether (Mn = 2500) and chloride

about sodium. The residue is dissolved in 50 ml of methanol at 50 ° C and filtered from sodium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is pure polymer, which is reused in stage N ° l (after several cycles (10) of use, PEG dimethyl ether (Mn = 2000) + PPG monobutyl ether (Mn = 2500) a solution of the polymer mixture in methanol is left at room temperature for polymer precipitation, the polymer filtered, methanol is distilled off from the filtrate, the residue is disposed of).

Example 21. Dimethyl ether E + NaOH + KOH. Obtaining diene FP

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and a branch for distillation 14, is placed PEG dimethyl ether (Mn = 2000). Then 1.67 g of sodium hydroxide and 2.75 g (85%) of potassium hydroxide are fed into the reactor, the reactor is closed and heated with stirring at 1000 rpm to 120 C and held at this temperature for 20 minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the capacitor 10, and are fed by gravity to the receiver 11, forming a return

about

aniline. The reactor is cooled to 60 ° C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 100 ml of acetone is added, stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate N ° l is formed. Filtrate N2I is used in stage N ° 2. The filter residue forms a precipitate of N ° 1.

Stage N ° 2 — reductive alkylation

The JSibl filtrate from stage N ° l is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 . Filtrate N-> 2 is formed. The filter residue is reused as a catalyst in stage N ° 2. Unreacted acetone is distilled off from the filtrate N ° 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The remainder is rectified, the vapor of the FP diaphene enters the condenser 10, which is cooled

about

recycled water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of the AF diaphen is 15.65 grams (95% based on the used nitrobenzene). The residue after distillation is PEG dimethyl ether (Mn = 2000), which is reused in the Ν ° 1 stage.

Getting 4-aminodiphenylamine

Stage l - condensation of nitrobenzene with aniline Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and a branch for distillation 14, is placed PEG dimethyl ether (Mn = 2000). Then 1.67 g of sodium hydroxide and 2.75 g (85%) of potassium hydroxide are fed into the reactor, the reactor is closed and heated with stirring at 1000 rpm to 120 ^° C and maintained at this temperature for 20 minutes, then the mixture is cooled to 60 ^° C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml in minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes, then 15 ml of water and 8.35 g of a 36.5% hydrochloric acid solution are added to it. The resulting mixture is exposed reduction to 4-aminodiphenylamine without further purification.

Hydrogenation step

about

up to 80 - НО С, the nitrogen cylinder is replaced with a hydrogen cylinder and then the pressure of 30-60 atmospheres of hydrogen is set and manually maintained, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and a receiver 29. The filtrate IV is formed. The filter residue is reused as a catalyst in stage 2. Water and aniline are distilled off from the filtrate IV using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to distillation, 4-aminodiphenylamine vapors are transferred to a condenser 10, cooled with 85 ^{° C} circulating water ^. C, and then by gravity to receiver 33. The mass of the obtained 4-aminodiphenylamine was 12.73 grams (95% yield based on the nitrobenzene used). The distillation residue is PEG dimethyl ether (Mn = 2000) and an equimolar mixture of sodium and potassium chlorides.

about

The residue was dissolved in 50 ml of methanol at 50 ° C and filtered off sodium chloride, then methanol is removed by vacuum distillation, the residue upon distillation is a pure polymer, which is reused in stage N ° 1 (after several cycles (10) PEG dimethyl ether (Mn = 2000), the solution of the polymer in methanol is left at room temperature for precipitation polymer, the polymer is filtered, methanol is distilled off from the filtrate, the residue is disposed of).

Example 22. Dimethyl ether PEG + NaOH. Getting 6PPD.

Stage N ° l - condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and a branch for distillation 14, is placed dimeshovy ether PEG (Mn = 2000). Then, 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and heated with stirring at 1000 rpm to 120 ^° C and held at this temperature for 20 minutes, then the mixture is cooled to 60 ° C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22, which creates the pressure in the reactor is 100 mbar, the pressure is controlled using controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of OD ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene stops. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then temperature

about

to 60 C, the pressure is brought to atmospheric pressure, the reactor opens and a methanolic solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off, and 50 ml of 4-methylpentan-2-one is added (methyl isobutyl ketone), stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate Νί> 1 is formed. Filtrate Nel is used in stage N ° 2. The filter residue forms a precipitate of N2 1.

Stage N ° 2 — reductive alkylation

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate Ns2 is formed. The filter residue is reused as a catalyst in the N-> 2 stage. Unreacted 4-methylpentan-2-one (methyl isobutyl ketone) is distilled off from the filtrate N ° 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to rectification, pairs 6 of PPD H- (1,3-dimethylbutyl) - Ν'-phenyl- para-phenylenediamine) enter the capacitor 10,

about

cooled by circulating water with a temperature of 85 ° C, and then by gravity to receiver 33. Weight 6 PPD is 18.35 grams (94% based on the used nitrobenzene). The residue after distillation is PEG dimesh ether (Mn = 2000), which is reused in stage NI. Ή NMR (400 MHz, CDC1 ₃ ): 0.91 (d, J = 6.6 Hz, ZN), 0.94 (d, J = 6.5 Hz, ZN), 1.15 (d, J = 6.2 Hz, ZN), 1.26 (dt, J = 13.6 Hz, J = 6.6 Hz, 3H), 1.76 (m, 1H), 3.25 (br, 1H), 3.48 (m, W), 5.36 (br, 1H), 6.53-6.58 (m, 4H), 6.96-7.01 (m, 5H).

Example 23. The statistical polymer (Π3Γ-ΠΠΓ) + ΝαΟΗ.

Getting 6PPD.

Stage N ° l — condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and a branch for distillation 14, a statistical polymer (PEG-PPG) is placed (Mn = 2500). Then 3.34 g of sodium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring.

about

Heats up to 120 C and maintains at this temperature 20

about

minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes and 40 seconds, the flow of nitrobenzene is stopped. The reaction mixture is stirred for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled about

to 60 C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 50 ml of 4-methylpentan-2-one is added (methyl isobutyl ketone), stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate N_ »l is formed. The JSf l filtrate is used in stage N ?. 2. The residue on the filter forms a precipitate N ° 1. Stage N ° 2 - reductive alkylation

The N2I filtrate from the N2I stage is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / C is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

it is heated to 80 C, the nitrogen cylinder is replaced by a hydrogen cylinder and then pressure is set and manually maintained at 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is established, the reaction mixture is filtered through filter 27 using nozzle 28 and receiver 29 A filtrate N22 is formed. The filter residue is reused as a catalyst in step N22. Unreacted 4-methylpentan-2-one (methyl isobutyl ketone) is distilled off from N? 2 filtrate using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to rectification, pairs 6 of PPD (K- (1,3-dimethylbutyl) - Ν'-phenyl -para-phenylenediamine) enter the capacitor 10,

about

cooled by circulating water with a temperature of 85 C, and then by gravity to receiver 33. The mass of 6PPD is 18.35 grams (94% based on the used nitrobenzene). The distillation residue is a statistical polymer (PEG-PPG) (Mn = 2500), which is reused in stage N2I. Example 24. Statistical polymer (PEG-PPG) + KOH.

Getting 6PPD.

Stage N ° l condensation of nitrobenzene with aniline

Into reactor 1 (volume 250 ml) with a jacket connected to a thermostat 13, equipped with a mechanical stirrer 2, 8, 9 with a magnetic drive 3, a thermocouple 12 lowered 120 mm through a thread in the upper part of the reactor, clamped with a clamp 4 connected to the thermostat 13, and a branch for distillation 14, a statistical polymer (PEG-PPG) is placed (Mn = 2500). Then, 5.50 g (85%) of potassium hydroxide is fed into the reactor, the reactor is closed and 1000 rpm with stirring

about

Heats up to 120 C and maintains at this temperature for 20 minutes, then the mixture is cooled to 60 C in 20 minutes. 60 ml of aniline is added to the reactor, capillary 6 by 120 mm is lowered through the thread in the upper part, and the reactor is closed. A capillary 7 is inserted into the tap through the thread at the bottom of the reactor, the tap remains closed. The vacuum pump 22 is turned on, creating a pressure in the reactor of 100 mbar, the pressure is controlled using the controller 15 and valve 16, then the valve opens and air begins to be bubbled at a speed of 50 ml per minute through capillary 7 and nitrobenzene is supplied through capillary 6 at a speed of 0.1 ml per minute using pump 19 and controller 20. After 74 minutes 40 seconds, the flow of nitrobenzene is stopped. Reaction mixture mix for another 90 minutes. Then, using a three-way valve in the vacuum line, the diaphragm pump is replaced by an oil pump 24. Using an oil pump 24 and a trap 25, a pressure of 0.1 mbar is set in reactor 1, which is controlled by controller 34, the main part of aniline is distilled off in 1 hour, then the temperature rises to 80 ° C and the aniline residues are distilled off, condensing in the condenser 10, and are fed by gravity to the receiver 11, forming a return aniline. The reactor is cooled about

to 60 C, the pressure is brought to atmospheric pressure, the reactor is opened and a methanol solution of hydrochloric acid is added (containing 0.0835 mol of hydrogen chloride - the amount necessary to neutralize the base placed in the reactor), then methanol is distilled off and 50 ml of 4-methylpentan-2-one is added (methyl isobutyl ketone), stirring is stopped, the mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29, a filtrate is formed. The filtrate N2I is used in stage N_> 2. The residue on the filter forms a precipitate N ° 1.

Stage M2 - reductive alkylation

The N2I filtrate from stage N ° l is loaded into an autoclave 30 with a capacity of 250 ml, then 0.1 g of 10% Pd / G is loaded, the autoclave is closed. The autoclave is purged with nitrogen from the cylinder three times,

about

heats up to 80 C, the cylinder with nitrogen is replaced with a cylinder with hydrogen and then set and manually maintain a pressure of 30-35 atmospheres of hydrogen, after 1 hour, the autoclave is cooled, atmospheric pressure is set, the reaction mixture is filtered through a filter 27 using a nozzle 28 and a receiver 29. A filtrate N ° 2 is formed. The filter residue is reused as a catalyst in stage 2. Unreacted 4-methylpentan-2-one (methyl isobutyl ketone) is distilled off from the filtrate N ° 2 using a reflux condenser 34, a condenser 10 and a receiver 33. The residue is subjected to rectification, pair 6 PPD (N- (l, 3-dimethylbutyl) - Ν'-phenyl-para-phenylenediamine) enters the condenser 10, cooled by circulating water with a temperature of 85 C, and then by gravity to the receiver 33. The mass of 6PPD is 18.94 grams (97% based on used nitrobenzene). The distillation residue is a statistical polymer (PEG-PPG) (Mn = 2500), which is reused in stage N ° l.

Industrial applicability

The invention is applicable in the field of organic chemistry, namely, in the field of production of nitrogen-containing compounds and allows to obtain 4-aminodiphenylamine (4-ADPA) and its alkyl derivatives used as antioxidants in a simpler and cheaper way.

Claims

CLAIM

1. The method of obtaining 4-amino diphenylamine and its alkyl derivatives of the General formula (1):

(one)

where R 1 represents H and R 2 represents H or lower alkyl,

by condensation of an excess of aniline or its derivatives with nitrobenzene in the presence of a catalytic system that includes a base and a solvent, which are both a catalyst and cocatalyst, respectively, when heated, followed by reduction of the resulting product in the presence of a Pd / C catalyst and hydrogen, characterized in that the condensation of aniline with nitrobenzene is carried out at

about

at a temperature of 30-150 C, aliphatic heterochain polyesters are used as cocatalyst and solvent, alkali or alkaline earth metal hydroxides are used as a base and catalyst, with a mass ratio of hydroxide to polyester of 1: 5-20, respectively, and a mixture of 4- nitrosodiphenylamine or its substituted derivatives and its salt, and 4-nitrodiphenylamine and / or, or its substituted derivatives, and its salt, which is subjected to reductive alkylation in the presence of the corresponding ketone in the medium of aliphatic hetero-chain polyesters with the formation of alkylated derivatives of 4-ADPA.

2. The method according to p. 1, characterized in that the polyesters use esters of polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene oxide (PTMO), polytetrahydrofuran or PEG monomethyl esters, monobutyl ethers PPG etc. etc., or their block copolymers, such as PEG-PPG-PEG, PEG-PPG-PPG, PEG-PPG-PTMO, random polymer (PEG-PPG).

3. The method according to p. 1, characterized in that the condensation

about

carried out at a temperature of 60-80 C.

4. A method for producing alkylated derivatives of 4-amino diphenylamine of the general formula (1):

one

where R represents H, R represents H, by condensation of an excess of aniline or its derivatives with nitrobenzene in the presence of a catalytic system that includes a base and a solvent, which are both a catalyst and cocatalyst, respectively, when heated, followed by reduction of the resulting product in the presence of a Pd / C catalyst and hydrogen, characterized in that the condensation of aniline with nitrobenzene is carried out at

about

at a temperature of 30-150 C, aliphatic heterochain polyesters are used as cocatalyst and solvent, alkali or alkaline earth metal hydroxides are used as a base and catalyst, with a mass ratio of hydroxide to polyester of 1: 5-20, respectively, and a mixture of 4- nitrosodiphenylamine or its substituted derivatives and its salt, and 4-nitrodiphenylamine and / or, or its substituted derivatives, and its salt, which is subjected to hydrogenation in an environment of aliphatic heterocyclic polyesters from 4-ADPA.

5. The method according to p. 4, characterized in that, if necessary, 4-ADPA is subjected to reductive alkylation in the presence of a ketone to obtain alkylated derivatives.

6. The method according to p. 4, characterized in that the polyesters use esters of polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene oxide (PTMO), polytetrahydrofuran or monomethyl ethers of PEG, monobutyl ethers of PPG etc. etc., or their block copolymers, such as PEG-PPG-PEG, PEG-PPG-PPG, PEG-11111 ^' - PTMO, random polymer (PEG-PPG).

7. The method according to p. 4, characterized in that the condensation

about

carried out at a temperature of 60-80 C.