DE2304201A1 - DISPERSE Azo Dyes - Google Patents

Description

PATENTANWÄLTE DR-ING. H. FINCKE DIPU.-ING. H. BOHR DIPL.-ING. S. STAEGER

Telephone: - · 2ί 60 40 Tiltgromme: Claims Munich Postal checking account: Munich 270-U

Bank details Bayer. Veremsfaonk Munich, account 420404

β Munich ι. January 29, 1973

23104 - Dr.K / hr Case Dd. 246962

IMPERIAL CHEMICAL IKDUSiDRIES LBIITED ₁ London, Great Britain

"Disperse azo dyes ¹ *

Priority : January 28, 1972, Great Britain No. 4046/72

The invention relates to heterocyclic compounds of the! Hiophene series. " as a dye intermediates or as biocides are of value.

According to the invention, compounds of the formula

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suggested, wherein X is optionally substituted Alkyl or phenylsulfonyl, cyano, carbonamido or a Carboxylic acid or carboxylic acid ester group; Y represents hydrogen, lower alkyl or optionally substituted phenyl stands; and Z is nitro, cyano or carbonamido.

Throughout this specification the terms "lower alkyl" and "lower alkoxy" refer to the designation of Alkyl or alkoxy radicals with 1 to 4 carbon atoms.

The carbonanido groups represented by X and Z own the ponael

- CCIf

wherein 2 is hydrogen, lower alkyl or phenyl and

ΐ for hydrogen or. Lower alkyl, such as carbonamido, H-Kethylcarbonamido-, Ϊϊ, ΐί-Diethylearbonamido- or N-phenylcarbonamido groups.

Examples of lower alkyl radicals. represented by Y are methyl, ethyl, n-propyl, and n-butyl.

Examples of substituted phenyl radicals represented by Y are, are üiitrophenyl, chlorophenyl, lolyl and Mtrophenyl.

The optionally substituted alkylsulfonyl groups, the represented by X are preferably optionally substituted lower alkylsulfonyl groups, such as, for example, ethylsulfonyl and ethylsulfonyl, hydroxy-lower alkylsulfonyl, such as e.g. ß-hydroxyethylsulfonyl, and lower alkoxy-lower alkyl

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sulfonyl, such as β-ivethoxyethylsulfonyl. examples for substituted phenylsulfonyl groups represented by X. ■ are tolylsulfonyl, chlorophenylsulfonyl and Uitrophenylsulfonyl ·

Seispiele for Carbonsäureestergruppen that -Be represented by X are the Cyclohexylearbonylgruppe but iedrigalkyl- particular I \ ^T and substituted 2Iiedrigalkylester _s such as Kethoxycarbonyl, ethoxycarbonyl and n-Butoxyearbonyl, Chloroniedrigaikoxy-earbonyl, vie for example, ß-Chloroäthoxycarbonyl, hydroxy-lower alkoxy earbonyl, such as β-hydroxyethoxycarbonyl, phenyl-lower alkoxy-carbonyl, such as benzyloxycarbonyl and β-phenylethoxy-carbonyl, and lower alkoxy-lower alkoxycarbonyl, such as β ~ (methoxy- or ethoxy-) - ethoxycarbonyl.

Those compounds according to the invention in which Z stands for a nitro group can be obtained by citrating the corresponding H-acylamino compounds of the above formula, in which Z stands for hydrogen, and subsequent hydrolysis of the H-acylamino compound. The nitration may in a sulfuric acid medium are preferably carried out at temperatures ranging from -5 to 10 carbon, or in a mixture of Sssigsäure and acetic anhydride at 35 to 4O ⁰ C. The subsequent hydrolysis is then carried out by heating in a dilute aqueous solution of an acid such as sulfuric acid. When compounds are used in the nitration where Y is phenyl or substituted phenyl, the nitration often results in the introduction of a second sitro group into the phenyl radical, especially when the nitration is carried out in sulfuric acid.

If, however, X stands for a carboxylic acid group, then the

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The nitration can be carried out under such conditions that only one liitro group is introduced into the Ihiophene ring, since otherwise there is a tendency that the carboxylic acid group through a second liitro group is replaced.

The compounds in which X and / or Z represent a carbonanido group can be obtained by car. the corresponding ii-acylamino compounds of the formula, in which X and / or Z is a carboxylic acid group, by treatment with thionyl chloride in an inert solvent, e.g. Toluene, converted into the corresponding acid chloride; the resulting acid chloride with the corresponding Asiin der

Formula 1 \ E converts and then hydrolyzes the ΐϊ-Acvl aminegruppe.

When the carboxylic acid ester group represented by X is is something other than a lower alkoxycarbonyl group, then such compounds can be obtained in an expedient manner are replaced by a second exchange, whereby one of the named compounds, in which X stands for a lower alkoxycarbonyl group, or the corresponding acyl derivative with the corresponding Alcohol, such as 3-kethoxyethanol, cyclohexanol or iS-phenylethanol, in the presence of a catalyst, such as ietra-n-butyl titanate, is reacted, whereupon, if from an H-acyl derivative is assumed, then the Acyl group is removed by hydrolysis.

The compounds in which Z represents a cyano group may be prepared from the corresponding IT Acylverbindunren wherein Z represents a hydrogen atom, are prepared by reaction with phosphoryl chloride and li-Kethylfonaanilid, the vcLei

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corresponding IT-acyl compound is obtained, wherein Z is for Zomyl s-eht, which when converted into the oxime and subsequent Treatment with acetic anhydride to form the cyano compound ergicx, which is then deacylated in the usual way.

The compounds in which X is something else; as one Carbonamide or carboxylic acid group, Y for xledrigalkyl and Z stands for a carbonamide group can be obtained are made by reacting a cyano compound der'Pormel XOOCCr * Clv, where X is other than carconanido or Carboxylic acid, with an amide of the formula

X lower alkyl COCH ₀ CCM

, 2

1 2

wherein 2 and ϊ have the meanings given above, and nit sulfur in ethanol medium, which is a base, such as z.3. Diet hyiamine contains.

The compounds in which X and / or Z stands for a group of the J-formula -COIiH ₂ can be obtained by mild hydrolysis of the corresponding compounds in which X and / or Z stands for a cyano group, for example by the fact that can subjects the cyano compounds to the action of a 95% sulfuric acid at δC.

The above-mentioned li-acyl compounds can be obtained by treating the appropriately substituted 2-aminothiophene with an acylating agent such as an acid anhydride or an acid chloride, for example acetic anhydride or acetyl chloride, in which case the II-acetyl derivative is obtained, or with a mixture of formic acid and

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Acetic anhydride, the X-pormyl derivative then being obtained ■ will. The correspondingly substituted 2-Aininoxhiophene, the as starting materials for the production of the invention Compounds used are themselves known compounds and are prepared by the usual methods of preparation obtained from Ihiophene derivatives.

Specific examples of compounds of the invention are 2-anino-3 ~ (ciethylsulfonyl- ₄ or phenylsulfonyl) -5-nitrothiophen, 2-amino-5-nitroxhiophene-3-carboxylic acid and the 3rd of these with methanol, ethanol, n-3utanol , Cyclohexanol, benzyl alcohol, ß-phenylethanol and ß-kethoxyethanol, 2-Aininc-3-cyano-4-Eexhyl-S-carbonamidothiophene and 2-amino-3-cyano- 4-methyl-5-carlDonaBiidothiQphen and 2-amino 3-carbethoxy-4- (nitrophenyl) -5-nitrothiophene.

3 a preferred class of compounds according to the invention are the compounds of the formula

where X and Y have the meanings given above and Y is preferably hydrogen or lower alkyl and X is preferably stands for a carboxylic acid ester group

The compounds according to the invention are suitable as diazo components in the manufacture of azo dyes, namely especially of disperse azo dyes, or as biocides for influencing the growth of microorganisms, such as ζ · 2. Bacteria, slime, and mold, for the ultimate purpose

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the compounds are preferably in the form of aqueous Dispersions used, which optionally contain organic liquids and / or contain dispersants.

The 3rfindung is explained in more detail by the following examples, wherein the parts ur & percentages are expressed by weight are.

example 1

213 parts of 2-Aeetylaiaino-3-äthoxyearbonylthiophene are dissolved in 2C00 parts of sulfuric acid at 0 to 10 ⁰ C, and then a mixture of 67 parts of nitric acid (SG 1.50) and 200 parts of sulfuric acid is slowly added, the temperature by external cooling is kept between 0 and 5 C. The Geraisch is then poured onto ice and water, and the precipitated 2-acetylamino-3-ethoxycarbonyl-5-nitrothiephen (Pp 144 ⁰ C) is filtered off. The pesticide is stirred for 24 hours in a mixture of 200 parts of ethanol and 90 parts of sulfuric acid at 80 ° C., the solution is cooled, and the precipitated 2-amino-3-athoxycarbonyl-5-nitrohtiophene is filtered off, washed with ethanol and then with water and dried. The product melts at 240 to 242 ^Ofx

Vs

The 2-acetylamino-3-ethoxycarbonylthiophene was obtained by itself by heating 2-amino-3-ethoxycarbonylthiophene with acetic anhydride.

Instead of the 2-acetylamino-3-ethoxycarbonylthiophene used in the above example becomes an equivalent amount of 2-pormylamino-3-ethoxycarbonylthiophene (that by treating 2-amino-3-ethoxycarbonylthiophene with a mixture of formic acid and acetic anhydride) is used, wherein 2-amino-3-ethoxycarbonyl-5-iiixrothiophene is obtained.

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2-Aiaino-3-metho: ^ carbonyl-5-nitrothiophene (bp 227 ° C), 2-Amino-3-ethoxycarbonyl-4-nieth.yl-5-2iitrothiophene (bp 204 C) and 2-amino-3-isobutoxycarlDonyl-5-nitrothiophene (bp 138 ° C) are obtained in a similar manner by nitration of 2-acetylamino-3-methoxycarbonyl-3-onylthiophene, 2-acetylamino-3-ethoxycarbonyl-4-methylthiophene "or 2-acetylamino-3-isobutoxycarbonylthiophene.

Example 2

A mixture of 1.5 parts of nitric acid (SG 1.50), 2 parts of acetic acid and 2 parts of acetic anhydride is added to a suspension of 5 parts of 2-fformylarcino-3-cyanothiophene (prepared by treating 2-amino-3 -cyanothiophene with a mixture of formic acid and acetic anhydride) in 20 parts of acetic acid, the temperature of the mixture being kept between 35 and 40 ^° C. The mixture is poured into ice and water. Sodium acetate is then added to remove mineral acidity and the mixture is stirred until no acetic anhydride remains. The resulting 2-formylamino-3 - cyano-5-nitrothiophene (Pp 216-218 ⁰ C) is deacylated by heating in 8 £ sulfuric acid solution in ethanol at 80 C.

Example 3

Instead of the 2-acetylamino-3 ~ ethoxycarbonylthiophene from Example 1 is an equivalent amount of 2-pormylaminothiophene-3-carboxylic acid used, being 2-amino-5-nitrothiophene-3-carboxylic acid with a Pp above 310C is obtained.

Example 4

28.9 parts of 2-acetylamino ~, 3-ethoxycarbonyl-4-phenylthiophene gradually to a mixture of 130 parts of sulfuric acid and 13 »5 parts of nitric acid (SG 1.50) at -5 ⁰ C

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added · The mixture is stirred for 1 hour at -5 to OG • and then poured into 1700 parts of ice and water. The precipitated Peststoff vird filtered off and heated for 1 hour in an 8 #igen solution of sulfuric acid in ethanol at 80 ⁰ C. The solution is cooled and the pesticide is then filtered off, washed and dried. The pesticide consists of a mixture of 2-amino-3-ethoxycarbonyl-4- (o-nitrophenyl) -5-nitrothiophene and 2-amino-3-ethoxycarbonyl-4- (pnitrophenyl) -5-nitrothiophene.

If a titration in acetic anhydride medium is used instead is carried out from sulfuric acid, then the product obtained is 2-amino-3-ethoxycarbonyl-4-phenyl-5-nitrothiophene.

Example 5

10 parts of 2-acetylaiaino-3-ethoxycarbonyl-5-nitrothiophene (manufactured as in Example 1) in 50 parts of ß-kethoxyethanol, which contains 1 leil of tetra-n-butyl titanate, dissolved, and the mixture is heated to boiling for 10 hours. The mixture is cooled, 50 parts of water are added and the precipitated 2-ethylamino-3- (ß-methoxyethoxycarbonyl} -5-nitroxhiophene (Pp 112 to 113 ° C) is filtered off and dried. Hydrolysis of this compound in a hot 4.5-liter sulfuric acid solution in ethanol gives 2-amino-3- (β-methoxyethoxycarbonyl) -5-nitrothiophene.

Example 6

Sin mixture of 10 parts of 2-amino-3-ethoxycarbonyl-5-nitrothiophene, 100 parts of n-butanol and 1 part of tetra-n-butyl titanate are stirred for 18 hours at the boiling point. The mixture will cooled, and the precipitated 2-amino-3-n-butyloxycarbonyl-5-nitrothiophene (Pp 136 to 139 ° C) is filtered off, washed with ethanol and dried. The corresponding n-heptyl

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- ίο -

ester, which is prepared in a similar way from n-heptanol, melts "at 86 to S9 ° C.

Example 7

A mixture of 18.7 parts of acetoacetanilide, 90 ropes of ethanol, 3.2 parts of sulfur, 13.5 parts of ethyl cyanoate and. 7 parts Diethylamine is stirred for 6 hours .beim boiling point. The mixture is cooled, and the precipitated 2-AiTino-3-carbäthoxy- ^ methyl-J-Ii-phenylcarbamoyl-thiophene (Jp 174 to 176 ° G) is filtered off, washed with ethanol and dried

Example 8

Instead of the 2-acetylamino-3-ethoxycarbonylthiophene used in Example 1 becomes an equivalent amount of 2-formylamino-3-carbonamidothiophene used, and the isitration at -10

w:
thiophene (Pp 266 to 268 ⁰ C) obtained.

up to -5 C. It becomes 2-aiziino-: 5-carbonamido-5-nitro-

. Example 9

Sin mixture of 21.6 parts of 2-? Ormylamino-5-nitrothiophene-3-carboxylic acid, 11.9 parts of thionyl chloride and 500 parts of toluene are stirred for 2 hours at the boiling point. The mixture is filtered, the piltrate is cooled to 5 C, and then 14.6 parts of diethylamine are added. The mixture is 1 Stirred for an hour, and the precipitated 2-? Ormylamino-3-is, IJ-diethylcarbonamido-5-nitrothiophene is filtered off. This is the result of treatment in a 5% hot sulfuric acid solution in ethanol 2-amino-3-K ', K-diethylcarbonamido-5-nitrothiophene.

Example 10

A mixture of 22.7 parts of 2-acetylamino-3-ethoxycarbonyl-4-methylthiophene, 261 parts of K-methylformanilide and 28.4 parts

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230A201

rhosphoryl chloride is stirred at 90 to 95 ° C. for 90 minutes. 300 parts of 4N aqueous liatric acetate solution are added, and the mixture is stirred at 90 ° C for 10 minutes. The oily one The pesticide is separated from the liquid and crystallized from ethanol, with 2 ~ acetylamino-3-ethoxycarbonyl-4-ethyi-5-formylthiophene (Pp 174 to 176 ° C) is obtained.

Sin G-eiüisch from 12.7 parts of this thiophene compound, 6.95 '! rush hydroxylamine hydr ο chloride, 10.1 parts sodium bicarbonate, 300 parts of ethanol and 50 parts of water are stirred for 90 minutes at the boiling point and filtered, and the pilate is cooled, and the oxime (Pp 214 G) which precipitates becomes isolated. A mixture of 8.5 parts of the oxide and 30 parts of acetic anhydride is stirred for 30 minutes at the boiling point and then added to 200 parts of water, and the 2-acetylainino-3-ethoxycarbonyl-4-ethyl-5-cyanothiophene is then isolated. Subsequent hydrolysis in an aqueous alkaline medium gives 2-alaino-3-ethoxycarbonyl-4-ethyl-5-cyanothiophene.

Example 11

An equivalent amount of 2-acetylamino-3-pnenylsulfonylthiophene (which was obtained by condensation of Ph.enylsulfonylaeetorJ.tril with 2,5-dihydroxy-1,4 -dithiane in the piperidine-containing ethanol and subsequent acetylation) used, whereby 2-amino-3-phenylsulfonyl-5-nitrothiophene (Pp 155 to 157 ⁰ C) is obtained.

Example 12

Its solution of 1 part of 2-amino-3-ethoxycarbonyl-4-methyl-5-cyanothiophene in 10 parts of sulfuric acid is kept at 0 C for 24 hours. The solution is poured into water, and that

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precipitated 2-amino-3-ethoxycarbonyl-4Hnethyl-5-carboi> · amicLothiophene is filtered off and dried.

Claims;

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Claims (3)

Compounds of the formula wherein X is optionally substituted alkyl or phenylsulfonyl, Cyano or carbonamido or a carboxylic acid or carboxylic acid ester group; Y stands for hydrogen, lower alkyl or optionally substituted phenyl; and Z is kitro, cyano or carbonamido. 2. Compounds according to claim 1, characterized in that that Z stands for the liitro group. 3. Compounds according to claim 1 or 2, characterized in that X stands for a carboxylic acid ester group, Y stands for hydrogen or lower alkyl and Z stands for nitrox « WlTENTANWXtTI WWN <5 .. H. Fiä-CKF. D'fH.-lNG. H. BOW 'ΟΙΊ, -Ι .'- Λ. S. STmEöE » 309831/1216