JPS59112947A - Manufacture of 4-nitrodiphenylamine - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention + A process for producing 4-nitrodiphenylamine over a period of several months between 4-nidrobarocamp/zene and a secondary aromatic amine in the presence of potassium and copper compounds. It is related to.

However, the reaction between halogen nitrobenzene and aromatic amine was unsuccessful with the known method of Nagasuke ItI. Thus, carrying out the reaction in the presence of an alkali carbonate and a copper compound as catalysts can be carried out as is known from German Patent No. 185.663.

It is known from history that the medicament reaction can be greatly accelerated if recycled potassium is added and the water of reaction is removed by co-distillation. No. 2,927,943 Example 1 Pure 4-nitrodiphenylamine is obtained under these conditions in a yield of 73% of theory over 21 hours. Furthermore, during the reaction of halogenated nitrobenzene with aromatic amines, the formation of nitrobenzene by remote dehalogenation (U.S.%
U.S. Pat. No. 3,313.854, column 3, lines 64 and 65) Contamination of the large h1 by the formation of tar and by-products poses the disadvantage of lengthening the reaction time. No. 936.

To overcome these drawbacks, a symmetrical bath U is added as a cocatalyst to the reaction mixture.

However, all the polar solvents currently used in reeds also have drawbacks. Thus, the dimethylpolamide used in U.S. Pat. do not. U.S. Patent No. 3. Hexamethyl phosphoric acid triamide used by No. 055,940 and U.S. Pat. No. 3,3ta, gs4
The formanilide used by -1 has acceleration properties only to an unsatisfactory extent in catalytic amounts in the presence of t'lil compounds. Dimethyl sulfoxide, acetanilide and salicylanilide used in 1 according to German Patent Application No. 1,518.307 and No. 1.117.594 also show only a weak effect. He'-methylpyrrolidone according to No. 633°811;
or ε- according to Japanese Patent No. 1 Ke 561022,751
Applied to caprolactam.

1. of polyneedle described in U.S. Pat. No. 4,155,936. +N addition also has its drawbacks. Depending on the treatment method, the filling remains in the target product or in the waste water.

Another possibility to reduce total tar production is rice [↓1%
Pestle No. 3.121.736 is a Schiff base of aminocarboxylic acid, alkyldiaminopolycarboxylic acid and its salts, disaltylardiaminoalkane, θ~hydroxybenzalaminophenol, polyphosphate, carboxymethylmercaptosuccine or salicylaldehyde. The addition of is recommended.

When using these 'substances, a problem arises in the process [8].

Now, in the presence of potassium carbonate and copper compounds, in the presence of potassium carbonate and copper compounds, the carbon atoms in the carbon atoms are the same or different in the carbon atoms. represents an alkyl group having 1 to 9 alkyl groups, and X represents chlorine or odor, in the halogenide Lobenzent formula (1) corresponding to
R3 and l-4 (-1 R1 and R2 in formula (II)
In formula 2, by reaction with a primary aromatic amine corresponding to, which has the same meaning as i.
A process has now been found for the preparation of 4-nitrosophenylamine corresponding to R', R2, R'' and R' as defined above, in which a rubidium or cesium compound or a mixture of the two is used. In addition, there is a feature of this method.

1 to 3 carbon atoms as the alkyl group corresponding to C6 in formula (1)
Each of these preferably includes an alkyl group.

A method for producing 4-nitrochlorobenzene and hyaniline or lano-4-nitrodiphenylamine is preferably used.

The following are excluded as examples of copper catalysts that can be used in the process of the invention: iodide '1 (uj (1), copper chloride (')
, copper chloride (n), lead bromide (+), copper bromide (II), cyanide steel (1), copper oxide (1), copper oxide (II), copper carbonate (II), basic copper carbonate (It), copper(II) sulfate, nitric acid@A(If), copper(II) formate, copper(If) acetate and organic and inorganic coordination compounds of -valent or divalent copper.

Oxygenated copper compounds, such as oxidized steel (RI), copper carbonate (■)
, basic carbonic acid @'-1: copper oxide (1) is preferred,
At that time, p per mole of halogen nitrobencef
o, o.

The copper catalyst is added in negative amounts of 1 to 0.1, preferably 0.01 to 0.05 mol. The copper catalyst itself or -
They can be used by mixing together.

Examples of haloquine nitrobenzenes include: 4-nitrochlorobenzene, 4-nitrobromobenzene, 4-nitro-2-methyl-chlorobenzene, and 4-nitrochlorobenzene.
-Nitro-3-methyl-chlorobenzene - Examples of 6-class aromatic amines include:
Aniline, o-toluidine, m-toluidine, p-1 luidine, 4-ethylaniline, 4-butylanili〉',
4-isopropylaniline, 3.5-trimethylaniline and 2,4-trimethylaniline.

Of course, aromatic amines can also be used in mixtures, especially in the form of mixtures of specific substances. In general, about 1 to 6 moles per mole of halocarbon nitrobenzene, preferably L < i
．． 5 to 3 mol and especially 17 to 2.5 mol of aromatic amine are used.

Examples of rubidium or cesium compounds include: chloride, bromide, iodide, monochloride, oxide, hydroxide, carbonate, bicarbonate, formate, acetate, propion. acid salts, cyanides and phosphorus salts, and mixtures thereof, but especially weak acid salts or inorganic acids such as carbonates, acetates, formates and cyanides. Cesium compounds are preferred. The salt used can be formed in the reaction vessel from the hydroxide and the corresponding acid, or from a suitable acid derivative.

1 mole of nitrobenzene =, = Ho, 05
Add the rubidium and cesium compounds at a mole t corresponding to ~57, preferably 01-12 cesium carbonate.

Excess back-Q potassium can be used in our or our M's 1.51 years ago.

The water produced during the reaction is distilled using an entraining agent to obtain 9 anti-Lr1
, it is disadvantageous to remove it from the mixed 8vA. Examples include the following as entraining agents: xylene, toluene, benzene, chlorobenzene, chlorotoluene, aniline and/or toluidine, preferably xylene or toluene.

If necessary, the entire process of the invention can be carried out in the presence of a diluent, such as an inert organic hydrocarbon, such as xylene. Furthermore, the aromatic primary amine itself can be used as a solvent.

The reaction temperature of this method can be set within a wide range.

This temperature is generally 140-225°C, preferably 18°C.
The temperature is 0 to 210°C.

This method can be carried out continuously or non-continuously by the method of certification.

It is likewise possible to work up the reaction mixture in different ways. Salts in the reaction mixture can be physically separated by centrifugation or filtration at elevated temperatures. After washing with hot xylene and after drying, a light gray powdery solid′+
AC5 remains. Unreacted halogen nitrobenzene and primary aromatic amines can be removed from the waste using steam, with most of the nitrodiphenylamines occurring as particulate matter. Other possibilities include partially distilling the loss under vacuum and then obtaining the product in the residue, or by crystallization to substantially separate the 4-nitrodiphenylamine, and then I. , and/or a precipitant, such as xylene, may be mixed with the sludge. In this case, 4-
Produces nitrodiphenylamine in an extremely pure state,
It can then be further processed directly under these conditions.

Copper catalyst can be used repeatedly. In order to achieve sufficient activity, less wind catalyst than is normally used is added, if necessary, in fresh form. To remove by-products, a portion of the resulting mother liquor is divided into portions for each chord. Preferably at elevated temperature (85-95°C) to remove salts.
It is also possible to stir the reaction mixture with the water necessary to ferment the salt. a) Treating the organic layer to ashes by similar separation, for example by steam distillation or by removing components that are more easily volatile than 4-nitrodiphenylamine.

By this method, it is possible to produce 4-nitrodiphenylamine in a yield of 85 or more and with high purity in 119 mol in a short p1 reaction. In this process, by-products are produced only in small quantities.

The 4-nitrodiphenylamine produced by the process of the present invention can be easily reduced to aminodiphenylamine by known methods, and these can be reduced even in one place (V)
It is a valuable intermediate product in the manufacture of stabilizers for dyes or rubbers.
No. 16 Diagram).

Example 1 1 mole of 4-chloronitrobenzene, 1°9 mole of aniline, 1.25 mole of dried potassium carbonate, copper(II) oxide
l / 42 mol, dry cesium carbonate 17950
mol and xylene 1/l 7 l were poured into a three-liter flask with a volume of g 2 L equipped with a separation column with a stirrer and a water separator at a stirring speed of 40 Or, p, z. .

The reaction mixture was heated to 195° C. with stirring.

The contents of the flask were held at this temperature until 10-10.51 nl of water had separated, and the 4-chloronitrobenzene content of the sample was determined by liquid chromatography. If this content was less than the initial value of 1.5 h, the reaction was stopped by cooling. Otherwise, the reaction continued until this value was reached. The duration of complete external reaction was rarely 5-6 hours.

50 rrJ of water were added at 100° C. and volatile components were removed using steam. The aqueous phase of the flask contents was separated and the organic phase solidified upon cooling. A gray-green granular material 21ey was obtained which, according to analysis by liquid chromatography, had a 4-4-year yield based on 4-chloronitrobenzene, corresponding to a yield of 87-chi.
Contains nitrodiphenylamine.

Example 2 The same procedure as Example 1 was repeated using 1/930 mol of cesium cyanide instead of cesium carbonate.

88,7 based on the 4-chloronitrobenzene used
4-nitrodiphenylamine was obtained with an IX ratio of -%.

Example 3 1.9° 5 mol of aniline, charcoal (4?:l'J) 1.3 mol of lithium, 1/45 mol of copper oxide (n), 1/850 mol of cesium acetate, 1/20 mol of water and 1 mol of water /12
Daish as before, except for j, which uses mole? ! The method of l l was performed.

Approximately 11 Td! of water was removed. The yield of 4-nitrodiphenylamine is 8
9. It happened in the second section.

Claims (1)

[Claims] 1. Rubidium or cesium compound or a mixture of the two; i, r 4-nitrohalogen benzene in the presence of potassium carbonate and a copper compound, characterized in that it is added to the reaction mixture; A method for preparing 4-nitrodiphenylamine by reaction with a primary aromatic amine. Z 4-Nitrodiphenylamine corresponds to the formula in which R1, R2, R3 and R4 are the same or different and are an alkyl group containing 1 to 9 carbon atoms or 1 to 9 carbon atoms. The method described in No. 1 (1) above, which is characterized by the following: 3. Anilinto reaction of 4-ditrotalolobenzene,
Process according to claim 1, characterized in that 4-nitrodiphenylamine is produced. 4. The method described in item 1 of the sub-requirement for material measurement, in which the presence of a weak organic or inorganic salt as a rubidium or cesium compound is the ti-1f characteristic. 5. Using a cesium compound is 11+ sign,
The method described in Section 1 or Section 4 of the equation. 6 In each case, the halogen nitrobenzene used 1
Using rubidium or a cesium compound in a molar amount corresponding to 0.05 to 52 cesium carbonate on a molar basis,
And 0.001~o, I mole amount? Claim 1118 characterized in that it is used! The method described in Section 1. 7 For each (7), add 1 mole of the halocone nitrobenzene to be used, and add 1 mole of rubissium or cesium to 0.1 to 1 ? of cesium. f: used, and then using a copper catalyst in front of 0.01-0.05 mol is 4.'Q characteristic, special eA
'iii> Scope of Requirement The method described in item 1. 8. The method according to item 1 of the publication, in which the reaction is carried out at 140 to 225°C. 9. The method according to claim 1, wherein the reaction is carried out at 18() to 210'C. 10. Use an entrainer (e71.tra) to remove water generated during the reaction.
2. A method according to claim 1, characterized in that the removal is carried out by distillation using .iner).