DE580519C - Process for the preparation of 2-oxy-3-arylaminonaphthalenes - Google Patents

Description

GERMAN EMPIRE

ISSUED ON
JULY 12, 1933

REICH PATENT OFFICE

PATENT LETTERING

M 580519 CLASS 12 q GROUP

I. G. Farbenindustrie Akt.-Ges. in Frankfurt a. M. *) Process for the preparation of 2-oxy-3-arylaminonaphthalenes

Patented in the German Empire on February 26, 1932

It has been found that those not previously described in the literature can be used 2-Oxy-3-arylaminonaphthaIine of the following general formula:

OH

wherein R is substituted an arbitrarily or unsubstituted carbocyclic or heterocyclic group, and R 'is hydrogen, alkyl, aralkyl or aryl, by heating 2, 3-dioxynaphthalene can with primary or secondary amines of the carbocyclic or heterocyclic series, to temperatures above 170 ⁰ obtained. The prerequisite for this is that the amine in the o-position to the amino group has no further amino group and no hydroxyl group, otherwise azines or oxazines are formed during the condensation with 2, 3-dioxynaphthalene (see Beilstein, Handbuch der Organic Chemistry, 4th ed., Volume VI, p. 983, and Supplementary Volume VI, p. 480). The procedure here is expediently such that the water formed according to the reaction scheme, the slightly violent splashing of the reaction mass and the reaction temperature are reduced, distilled off during the reaction.

OH

OH

OH

HHN —R I
R '

+ H ₂ O
R.

The preparation of 2-oxy-7-phenylaminonaphthalene from 2,7-dioxynaphthalene and aniline is known (cf. Ber. D. Deutsche Chemischen Gesellschaft 23 [1890], p. 529; 26 [1893], p. 3087; 25 [ 1892], Ref., P. 302; Patent 60103). It was not expected that the 2,3-dioxynaphthalene as o-dioxy compound as easily as it would respond 2, 7-dioxynaphthalene with Aniliri and smooth. Because, of course, here the opportunity to o condensations, o-ring closures and Similar complications existed. How the homologues and substitution products of aniline would behave with both 2,7-dioxynaphthalene and 2,3-dioxynaphthalene was completely unknown up to now. It measured to be described as surprising and unexpected,

*) The patent seeker stated as the inventor:

Dr. Herbert Kracker in Frankfurt a. M.-Höchst.

that the 2,3-dioxynaphthalene, for example, uses aniline, its homologue, when heated and substitution products, the 2-oxy-3-arylaminonaphthalenes, smoothly and without the formation of appreciable amounts of by-products results.

The one described in the reports of the German Chemical Society 39 [1906], p. 1041 Method for the preparation of i-Qxy-2-phenylatninonaphthalin from i-naphthol and nitrosobenzene is used for the preparation of the isomeric 2-oxy-3-phenylaminonaphthalene out of the question. Because apart from the fact that the yield in this process is very low, it would be based on 2-naphthol applied, the 2-oxy-i-phenylaminonaphthalene and not the desired 2-oxy-3-phenylaminonaphthalene.

The bodies obtainable by the process described form valuable intermediate products, for example for the production of azo dyes.

The following examples illustrate the representation of a number of the claimed as 2-Oxy-3-arylaminonaρhthaline, without the Possibility to limit further isomers by suitable substitution in the aryl radical and get homologues.

Examples

i. 80 parts by weight of 2,3-dioxynaphthalene and 150 parts by weight of aniline are 8 to 10 hours in a birectifier provided The flask was heated to 170 to 180 ° while the water formed was distilled off. After cooling, the excess aniline is blown off with steam or dissolved by pouring into dilute hydrochloric acid and the residue to remove any 2,3-dioxynaphthalene still present extracted with sodium carbonate solution. The now residue is diluted in Sodium hydroxide solution dissolved and acidified after filtering. You can also do this that one dissolves the residue after removal of the aniline in sodium hydroxide solution, nitrated and 2-oxy-3-phenylaminonaphthalene is precipitated by carbonic acid; any still existing 2,3-Dioxynaphthalene remains in solution.

The body is thus obtained as a pale gray powder with a melting point of 121 to 123 °; After dissolving from benzene, it forms white leaves, mp 129 to 130 ⁰ .

If, instead of aniline, o-toluidine, we obtain the 2-oxy-3- (2'-methyl-phenylamino) -naphthalene, melting at 152-153 ^0th

Analogously one gets with

p-toluidine, 2-oxy-3- (4'-methylphenylamino) naphthalene,

F. 144 to 145 ⁰

o-anisidine 2-oxy-3- (2'-methoxyphenylamino) -naphthalene, F. 105

p-Anisidine 2-Oxy-3- (4'-methoxyphenylamino) -naphthalene, F. 95

o-chloroaniline 2-0xy-3- (2'-chlorophenylamino) -naphthalene, F. 139

p-chloroaniline ... the 2-oxy-3- (4'-chlorophenylamino) -naphthalene, F. 179 p-phenetidine ... the 2-oxy-3- (4'-ethoxyphenylamino) -naphthalene, F. 124

- io6 °

- 96 °

- 140 °

- i8o °

- 125 ⁰

With aminodimethylbenzenes, aminotrimethylbenzenes, aminodimethoxybenzenes etc. are the corresponding in the reaction with 2,3-dioxynaphthalene in the same way 3-Arylamino derivatives obtained.

2. 80 parts by weight of 2,3-dioxynaphthalene and 200 parts by weight of 2-naphthylamine are heated according to the procedure of Example 1 while distilling off the resulting water to 12 hours at 180 to 200 ^0th After cooling, the melt cake is finely powdered and ^{heated with 60 parts by weight of 40 °} Be sodium hydroxide solution and water while stirring. After cooling, the unchanged 2-naphthylamine is sucked off and carbonic acid is introduced into the solution. You can also acidify with any acid and extract the precipitated product with sodium carbonate. The 2-oxy-3- (2'-naphthylammo) naphthalene is thus obtained as a white powder, mp 152 to 153 °, white needles from benzene, mp 159 to 160 °.

Analogously, one obtains with i-naphthylamine the 2-oxy-3 "(ι'-naphthylamino) -naphthalene, F. 119 to I2O °.

When using aminonaphthol ethers, chloronaphthylamines, aminodiphenyls,

Aminodiphenylamines, aminocarbazoles, etc. are obtained in the same way the corresponding j 3j-Arylamine derivate 'des, 2-Oxynaph.thalins.

3. 80 parts by weight of 2,3-dioxynaphthalene are reacted as in Example 1 with 150 parts of monomethylaniline. According to the described in Example 1 Method separated, one obtains the resulting 2-0xy-3-phenylmethylaminonaphthalin as a brownish powder melting at 112-113 ^0th

If other monoalkylarylamines are used instead of monomethylaniline (e.g. chloroethylaniline, methylnaphthylamine, etc.), monoaralkylarylamines (e.g. benzylm-toluidine, Benzylaniline, etc.) or diarylamines (e.g. diphenylamine, phenylnaphthylamine etc.), the corresponding ones are also obtained in the reaction with 2,3-dioxynaphthalene Derivatives.

In a similar way, 2,3-D1-oxynaphthalene is obtained from 2 and the amines of heterocyclic ring systems are the corresponding 2-oxy-3-arylaminonaphthalenes. The following table describes some of the new bodies available in this way:

For representation
base used

Product received

Name and formula picture appearance

Melting point

Solubility in dilute sodium hydroxide solution

2-aminopyridine

2-oxy-3- (2'-pyridylamino ") naphthalene

OH dark
Crystals

62-64 ⁰

easily soluble

_x J-NH ₂

6-aminoquinoline

H "N-,

2-oxy-3- (6'-quinolylamino) naphthalene

brownish

Crystal

chen

108-i

easily soluble

6-aminoindazole

^H * ^N

2-oxy-3- (6'-indazolylamino) naphthalene

,OH

weak
brownish
Crystals

158-159 ⁰

easily soluble

2-aminocarbazole

2-Oxy-3- (2'-carbazolylamino) naphthaJin

gray,

loose

Crystal

chen

243-244

NH,

Claims (2)

Claims: i. Procedure for the representation of 2-oxy-3-arylaminonaphthalenes of the following general formula: wherein R is an arbitrarily substituted or unsubstituted carbocyclic or heterocyclic radical and R 'is hydrogen, very difficult to dissolve Means alkyl, aralkyl or aryl, characterized in that 2,3-D1-oxynaphthalene with primary or secondary amines of the carbocyclic or • heterocyclic series, which are in the o-position to the amino group no further amino group and no hydroxyl group wear, heated to temperatures above 170 °. 2. Embodiment according to claim 1, characterized in that the water formed during the reaction is distilled off.