DE2336551A1 - METHOD FOR PRODUCING DIPHENYLAMIDES - Google Patents

Description

Partial application from patent application no. P 23 21 116.7 of April 26, 1973 (Case 150-3385)

r ■ ^r 'e

D '. ^v . I '■ -.': Rzik

Cr. ¹ - ¹ -'- I.'- - ^ g

D-. f- ■ ". ·. i- 'i- -'si

SANDOZ A.G. BASEL C

Case 15O-3385 / I

Process for the preparation of diphenylamines

The present invention relates to diphenylamines of the formula

R ₁ R.

(D,

wherein R is a tertiary alkyl radical with 4-9 carbon atoms, R _{2 is} an alkyl radical with 1-18 carbon atoms, a cycloalkyl or aralkyl radical with up to 12 carbon atoms

R _{3 is} hydrogen, an alkyl, cycloalkyl or cycloalkylalkyl radical with up to 9 carbon atoms, halogen, CN, CF ₃ , ^R iv, COOMe, COOZ or

CONHZ, ^ll0 V> -

^R 2

309851/1131

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Me is hydrogen, Ni, Zn, Mn or Cu, Z is an alkyl radical with 1-9 carbon atoms and η is 1 or 2.

The compounds of the formula are preferred

(NH)

²ⁿ (la),

where R 'is a tertiary alkyl radical with 4-6 carbon atoms, R' is an alkyl radical with 4-9 carbon atoms, R 'is hydrogen, halogen, an alkyl radical with

1-9 carbon atoms r H0_7q \ _ / or -COOH, and η 1 or 2. R '

The compounds of the formula are also preferred

(Ib),

where R "and R" denote a tertiary butyl radical and the NH "group is ortho or para to the Diphenyl bond is located.

Unless otherwise specified, the alkyl radicals are primary, secondary or tertiary radicals, or any branched residues of naturally occurring aliphatic hydrocarbons. Examples of primary Residues are methyl, ethyl, propyl, butyl, pentyl,

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Hexyl and the unbranched alkyl radicals with 7-18 carbon atoms, Examples of secondary alkyl radicals are isopropyl and 2-butyl.

Examples of tertiary alkyl radicals are tertiary butyl and 2-methyl-2-butyl.

Examples of cycloalkyl radicals are cycloalkylpentyl, cyclohexyl, cycloheptyl, and cyclododecyl. Examples of cycloalkylalkyl radicals are cyclohexylmethyl, 2-cyclohexylethyl.

Examples of aralkyl radicals are benzyl and 2-phenylethyl. The halogens here are fluorine, chlorine or bromine, preferably chlorine.

Z is preferably methyl or ethyl. Me is preferably hydrogen or Ni. The amino groups in formula (II) are preferably in the ortho and para positions, based on the direct bond which connects the two benzene rings in formula (II). Also are those compounds of the formula (II) are preferred in which only one amino group occurs.

As compounds of the formula (I), where

A =

are to be mentioned

'2

^A - Q) NH. A.

3 0 9 8 5 1/119 1

Case 150-3385 / 1

NH ₀ , A

COOH, A

Cl,

tert.C ₄ H _g

tert. C ₄ H ₉

Cl, HO

SeC-C ₄ H ₉ NH SeCC ₄ H ₉

The invention also relates to a process for the preparation of compounds of the formula (I) which thereby is characterized / that one compounds of the formula

(ID,

where R ,, R-, R and η have the above meaning, reduced to the amine.

The compounds of the formulas (Ia) and (Ib) are prepared in an analogous manner by the compounds of formula

R, ¹ Ri

(NO

(Ha),

309851/1191

Case 150-5385 / I

or the compounds of the formula

(Hb)

reduced to the amine.

The compounds of the formula (I) can be used for the preparation of stabilizers for organic Materials. Such stabilizers are, for example, those of the formula

where R.

(Y)

(III)

and R-, the above

Have meaning

Hydrogen or the CO radical, which is connected to Y to form a 5- or 6-membered ring, a saturated or unsaturated, p-valent aliphatic, cycloaliphatic or araliphatic hydrocarbon radical with up to 22 carbon atoms and / or an optionally substituted aromatic radical with up to 22 carbon atoms, the radicals mentioned directly or via the intermediate member -COO- or

309851/1191

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-CONH- are tied to the remainder in square brackets, and once or twice through Sulfur or oxygen atoms or be interrupted by -COO- or -CONH- and / or Halogen, OH, CN or COOH as substituents can carry

η 1 or 2

m 1 or 2

ρ means 1, 2, 3 or k ,

and if n = 1 and p = 2 Y can also stand for the direct bond.

The compound of the formula (III) is prepared in such a way that a compound of the formula (I) with a Compound of formula

Y (COOH) (IV)

wherein Y is bonded to the carboxyl group directly, via -00C- or -NH-CO-, or to a functional group Derivative thereof, and if Me is a divalent cation, the compound obtained, if appropriate converts into the corresponding salt.

This process is an acylation. This analogy reaction can be carried out by generally known methods will. If the carboxylic acid of the formula (IV) is sufficiently volatile, e.g. stearic acid, adipic acid or terephthalic acid, the two starting materials can be heated together, with elimination of water the desired end product is created. One can in

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the melt at temperatures of about 120-220, below normal or reduced pressure, work or even under Use of inert solvents, such as xylene, this during the reaction is slowly distilled off and serves as an entrainer to remove the water that is split off. To the Catalysts such as boric acid can be used to accelerate the reaction. The implementation of the amine with the carboxylic acid can also be carried out under milder conditions if the in reagents customary in peptide chemistry, such as Biscyclohexyl carbodiimide is used. As functional derivatives of the carboxylic acids of the formula (TV) their anhydrides come into question, such as succinic anhydride, phthalic anhydride, homophthalic anhydride, the anhydride of diglycolic acid and that of thiodiglycolic acid. The acylation can also be carried out very well with the chlorides of the acids of the formula (IV), preferably below Use of acid-binding agents. If one starts from compounds of the formula (IV) in which ρ is greater than 1, only one of the carboxyl groups in the polycarboxylic acid can be used for the acylation reaction use so that the remaining carboxyl groups remain free and the compound of formula (III) in Radical Y appear as a substituent; but you can also the reaction conditions and the ratio of Choose both starting materials so that all the carboxyl groups of the starting materials of the formula (IV) cause the acylation reaction join in so that the rest of Y's

309851/1191

Compound of formula (III) does not contain a carboxyl group as a substituent. To get to compounds of the formula (III) to reach, in which X is the CO radical, the one with Y to form a 5- or 6-membered ring is connected, one has to use the corresponding polycarboxylic acids or their suitable functional derivatives go out. All polycarboxylic acids which form 5 or 6-membered cyclic imides are suitable for this purpose can, such as maleic anhydride, succinic acid, glutaric anhydride, phthalic anhydride, Homophthalic acid, tricarbalic acid, benzene-1,2,> or -1,2,4-tricarboxylic acid and pyromellitic acid.

In these cases, Y is linked directly to the remainder in the square brackets of the formula (III). The connections, in which Y is linked to the remainder in square brackets via the intermediate link -COO- also obtained by a compound of formula I with oxalic acid or a functional derivative the same brings to reaction and the product obtained with an organic amine of the formula

₂ ) P (V)

where Y and ρ have the meaning given above.

For example, a compound of the formula (I) is reacted with an ester of oxalic acid, an amino group being obtained the compound of the formula (I) is allowed to react with one mole of oxalate. Such conversions are ongoing smooth when heating the mixed reaction partners

309851/1191

Case 150-3385 / I

with elimination of one mole of alcohol from one mole of used oxalic ester. Low molecular weight oxal esters, such as diethyl oxalate and dimethyl oxalate are particularly suitable for this implementation. From such amide esters of oxalic acid one can through Reaction with organic amines substituted diamides of oxalic acid, i.e. compounds of the formula (III), in which Y is linked to the remainder in square brackets via the intermediate link -CO-NH-:

N-CO-COO-alkyl H

N-CO-CO-NH-Y H

The latter oxalic acid diamides can also be prepared according to the invention by adding an ester amide to the Oxalic acid of the formula

Alkyl-OOC-CO-N-Y

with a compound of the formula (I). This analogy reaction takes place easily if the two reactants vey ^ j-ä ^ t jujtö, heated together until the

- 10 - Case 150-3385 / 1

Alcohol elimination has ended. Per amino group in the Compound of formula (I) is used with one mole of one Compound of formula (V). As can be seen from the introduction to this section, Y in the compounds of formula (III) and (IV) also stand for the direct bond, provided that η 1 and ρ mean 2. The compounds so defined are symmetrical oxamides of the formula:

Such compounds are easily obtained from one mole of a functional derivative of oxalic acid, such as a low molecular weight ester or of oxalyl chloride, by reaction with two moles of an amine of the formula (I) in which η stands for the number 1. This analogy procedure is very smooth and is well known. The radical R ^ in the formula (III) can mean the carboxyl group, in addition the radical Y can also be substituted by carboxyl groups. These carboxyl groups can be present in free form or in the form of salts of nickel, zinc, manganese or copper. Such salts can easily be prepared by customary methods. The preferred production process consists in «that you have a soluble salt of the carboxylic acids in question, in particular an alkali salt, dissolved in water or in organic solvents, with a soluble salt of

Nickel * converts zinc, manganese or copper. By double

309851/1191

- 11 - Case 159-3385 / 1

Implementation creates the desired heavy metal salt of the formula from the soluble reactants (III). The latter are usually sparingly soluble and can be easily filtered and washed in pure Shape to be isolated.

The following example shows the preparation of the Connections described. The parts mean parts by weight, degrees Celsius.

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example 1

250 parts of 3,5-di-tert-butyl-4-hydroxy-4'-nitrobiphenyl are dissolved in 2000 parts of alcohol, add 70 parts of Raney nickel and leave with H “at normal pressure React for 3 hours at 40-5O ° C. After the reaction has ended the catalyst is filtered off, the yellow solution is evaporated in vacuo and the remaining solution is crystallized yellow oil from petroleum ether. In this way, pale yellow crystals with a melting point of 112-113 ° C. of the formula are obtained

<Q) <P) 2

The same product is obtained if the Bechamp reduction (Fe / HCl + H ₂ O) is carried out.

In an analogous manner, i.e. by reducing the corresponding nitro compounds, those listed in Table 1 were obtained Products manufactured.

309851/1191

Case 150-3385 / 1

Table 1

^R l ^R l ^R 2 ^R 3 M.p. NH ₂ H H 131-133 ° H NH ₂ H 112-113 ° NH ₂ NH ₂ H 177-178 ° - NH ₂ COOH H 285-287 ° NH- Cl H 145-146 ° H NH ₂ - @ - 0H 125-127 °

means -C (CH)

• J J

309851/1191

Claims (11)

Claims 1. Diphenylamines of the formula Case 150-3385 / 1 (D / wherein R is a tertiary alkyl radical with 4-9 carbon atoms, R- is an alkyl radical with 1-18 carbon atoms, a cycloalkyl or aralkyl radical with up to 12 carbon atoms R is hydrogen, an alkyl, cycloalkyl or cycloalkylalkyl radical with up to 9 carbon atoms, halogen, CN, CF ₃ , ^R l \ _, > COOMe, COOZ or coNHz, ys ^R 2 Me is hydrogen, Ni, Zn, Mn or Cu, Z is an alkyl radical with 1-9 carbon atoms and η is 1 or 2. 2. Compounds of the formula (NH ₂ ) (Ia), where R £ is a tertiary alkyl radical with 4-6 carbon atoms, R 'is an alkyl radical with 4-9 carbon atoms, an alkyl radical with R 'hydrogen, halogen J R ' 1-9 carbon atoms, η and η is 1 or 2. R ^{1 or} - 309851/1191 15 - Case 150-3385 / 1 3. Compounds of the formula RJ ¹ X NH ₂ (Ib), pH ^R 2 where R ' ¹ and R "denote a tertiary butyl radical and the NH ₂ group is in the ortho or para position to the phenyl bond. 4. Process for the preparation of compounds of the formula (I) according to claim 1, characterized in that compounds of the formula (II), wherein R ^, R ₂ , R and η have the meaning according to claim 1, reduced to the amine. 5. Process for the preparation of compounds of the formula (Ia) according to claim 2, characterized in that one compounds of the formula r; (Ha>, ^(Ν0 2 ^} η 309851/1191 Case 150-3385 / 1 where R ', R', R 'and η have the meaning according to the patent claim 2, reduced to the amine. 6. A process for the preparation of compounds of the formula (Ib) according to claim 3, characterized in that one compounds of the formula (Hb) wherein R "and R" have the meaning according to claim 3, reduced to the amine. 7. The compound of formula -NH, 8. The compound of formula 309851/1191 Case 15O - 3 385/1 9. The compound of formula HO Cl NH, 10. The compound of formula (CH ₃ ) NH, 11. The compound of formula C ₄ H ₉ (SeC) NH, The patent attorney s 3700 / SI / MEW 309851/1191