DE2649167A1 - NEW NAPHTHOLACTAM-4-CARBONIC ACIDS AND THE PROCESS FOR THEIR PRODUCTION - Google Patents

Description

CIBA-GEIGYAG. CH-4002 Basel

DR. BERG DIP L.-FNQ. STAPF DIPL.-ING. SCn ^ r.eE DH. OR. SAiJOWAIR

PA " ZH ΤΛ t-: u ^r ? -: iT £
8 MÖNCHEN 80 · Ivi AU ERKI RC H ERSTR. 45

Case 1-10 157/1 + 2
Germany

LEGAL FILES 27,469 October 28, 1976

New naphtholactam-4-carboxylic acids and processes for their

Manufacturing

The invention relates to new functional ones

Derivatives of naphtholactam-4-carboxylic acids of the formula

= 0

Y X

where X is -CN or the group -CO-R, where R is a radical of the formulas -OR or -N; ^ "l, where R, R- and R" are aliphatic radicals, araliphatic, cycloaliphatic or aromatic radicals and R, and R _? can also mean hydrogen, and Y stands for hydrogen or halogen and a process for the preparation of the carboxylic acids and their derivatives.

The novel compounds characterized in that o-Xylylendicyanid with glyoxal in the presence of a base and a solvent at temperatures below 50 ⁰ C to 1,4-dicyanonaphthalene is reacted, and then either a) the 1,4-dicyanonaphthalene in a basic or preferably acidic medium saponified to 1,4-dicarboxylic acid, which converts 1,4-naphthalene-dicarboxylic acid either into a functional derivative and then with a 10 to 50% strength

ORIGINAL INSPECTED

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Converting excess nitric acid to the 8-nitro-1,4-naphthalenedicarboxylic acid derivative and reducing this to the 8-amino derivative, or by nitrating the 1,4-dicarboxylic acid directly and then reducing it to 8-aminonaphthalene7 1,4-dicarboxylic acid, and then the 8-amino derivatives either by spontaneous ring closure or by heating into the 1,8-naphtholactam-4-carboxylic acid or its functional derivatives, or b) the 1,4-dicyannaphthalene with a 10 to 507 ₀ excess of nitric acid in The 8-position is nitrated and then the nitro group is reduced to the 8-amino group, the kaphtholactam ring closure is brought about by spontaneous formation or heating and the 4-position cyano group, if it has not already been saponified during the reduction of the 8-nitro group, optionally via the 4-carbonamido stage -l, 8-naphtholactams "saponified in a basic or acidic medium.

The stages a) and b) are also available as self-employed to consider inventive alternatives independently.

The implementation of o-xylylene cyanide with glyoxal takes place according to the following formulas

CH CN
fY ₊ HC = O

HC = O

CN »

for example at temperatures from -20.degree. C. to -40.degree. C., preferably between 0.degree. and 30.degree.

The bases for the conversion of glyoxal and o-xylylene cyanide are inorganic and organic Compounds into consideration, e.g. those of lithium, sodium, potassium, rubidium, cesium or ammonium from

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Type, for example, the hydroxides, alcoholates or tert. Amines, such as lithium, sodium or potassium hydroxides, Sodium or chewing methylate, sodium or potassium ethylate, Triethylamine or pyridine.

Aprotic and protic solvents, preferably water-miscible organic solvents, are used as solvents Solvents such as methanol, ethanol, isopropanol, butanols, dioxane and dimethylformamide can be considered.

The reaction is preferably carried out in an anhydrous organic solvent, such solvents being preferred are in which the base used is partially or completely soluble.

The glyoxal used as the starting material can either be in the form of its commercially available aqueous ones Solution, e.g. 30 or 40% aqueous solutions or in the form of one that releases glyoxal under the reaction conditions Compound, such as trimeric and polymeric glyoxal, glyoxal bisulfite, G ^ oxal sulfate and glyoxal acetals, be used.

The reaction product of o-xylylene cyanide and Glyoxal, i.e. the 1,4-dicyannaphthalene produced can can be saponified with basic or acidic substances at temperatures above 50 ° C. without isolation.

Inorganic and organic compounds come into consideration as bases, e.g. those of lithium, Sodium, potassium, rubidium, cesium or ammonium of the type, for example, of the hydroxides, alcoholates or tert. Amines, such as lithium, sodium or potassium hydroxides, sodium or potassium methylate, sodium or potassium ethylate, Triethylamine or pyridine.

The solvents used are water and organic, higher-boiling, preferably water-miscible, higher-boiling solutions: medium, e.g. those boiling between 50 and 210 ° C,

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into consideration, such as monohydric or polyhydric alcohols, such as propyl alcohols, butyl alcohols, ethylene glycol, 1,2-propanediol and glycerin.

Mineral acids are used for the acidic saponification, e.g. hydrochloric acid, sulfuric acid and phosphoric acid and aliphatic carboxylic acids such as acetic acid and Propionic acid. The saponification is carried out in the presence of water, preferably at reflux temperature carried out.

As a diluent or solvent for poorly soluble Cyanide, glacial acetic acid can be used.

The o-xylylene cyanides used as starting materials can be carried out very easily and in very good yields from the corresponding o-xylylene dihalides Reaction with alkali metal cyanides. For example, o-xylylene dicyanide is produced by reacting o-xylylene dibromide produced with potassium cyanide in a 70% yield of pure recrystallized product (J.0. Haiford and B. Weissmann, J. Org. Chem. JL7, 1649, 1952; E.F.J. Atkinson and J.P. Thorpe, J. Chem. Soc. _91, 1699, 1907). The o-xylylene dihalides can in turn after known processes either by direct halogenation of o-xylene or by halomethylation of toluene or benzyl chloride and distillative separation of o- and p-xyl3 ^ 1endichloriden (I.G. Farbenindustrie AG, PB 580 No. 5 ;. PB 14998 Nos. 94, 99 and 100).

The nitration of 1,4-dicyano-naphthalene or the Naphthalene-1,4-dicarboxylic acid or its functional Derivatives are usually made with nitric acid in a suitable solvent, such as or especially acetic acid Sulfuric acid. A not too large excess of the theoretically required amount of Nitric acid, i.e. between 5 and 50%, preferably between 10 to 15 and 20 to 30% excess. The saltpeter

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acid is advantageous in the form of the technically customary Mixed acid (H ^ SO, iHNO- 1: 1) added. The work-up takes place in the usual way, e.g. by pouring on ice.

The subsequent reduction of the nitro group des 8-nitro-l, 4-dicyano-naphthalene or e-nitronaphthalene-l ^ -dicarboxylic acid or their Fractional derivatives take place e.g. with zinc or preferably iron powder in the presence of strong inorganic or organic acids such as hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid. the the latter is preferably used because it can also serve as a solvent.

The reduction can also be catalytic, in the presence of metal catalysts, such as Raney metals, in particular Raney nickel to those described for Raney catalysts Conditions.

You can also carry out the reduction with sulfides, for example by heating the acid in aqueous-alkaline solution with sodium sulfide.

As functional derivatives, all derivatives of the carboxyl group are to be cited, which are usually used for improvement the solubility and / or to protect the carboxy group serve, such as carboxamides and especially ester groups. The cyano groups of 1,4-Dic3 ^ an-naphthalene are saponified Before the nitration, the detour via the functional derivatives of the 1,4-dicarboxylic acid obtained can be considered. If the S-nitronaphthalene-l ^ -dicarboxylic acid is heated in an alcohol in the presence of dry hydrogen chloride, the corresponding 4-monoesters are obtained, their catalytic reduction with Raney nickel leads directly to the 1,8-naphtholactam-4-carboxylic acid alkyl ester. Depending on Starch of the esterifying agent can also be used to get the doubly esterified products, e.g. through the

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esterification with dialkyl sulfates in active solvents, such as dimethylformamide, and alkali.

The 1-position carboxyl group is less easily esterified.

Suitable alcohols and phenols that can be used for esterification are:

Methanol, · "■

Ethanol, n-propanol, i-propanol, Butanol, sec-butanol, isobutanol, 2-ethylhexanol, 2,2-dimethylpentanol, 2,2,4-trimethylpentano1, Dodecyl alcohol, Octadecy! Alcohol, Benzyl alcohol, cyclohexanol, allyl alcohol, methyl alcohol, cinnamon alcohol, Lauryl alcohol, oleyl alcohol, diethylene glycol monomethyl ether or monoacetate, Triethylene glycol monobutyl ether, o-, m-, p-cresol, o-, m-, ρ-chlorophenol,

p-bromophenol, "

o-, m-, p-nitrophenol, 2,4-dinitrophenol, · o-, m-, p-methoxybenzene, o-, m-, p-Hydroxj ^ acetophenon,

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o-cyelohexylphenol, furfuryl alcohol,

8-hydroxyquinoline, "

1- or 2-naphthol and 4-hydroxymethylpyridine.

Primary and secondary amines suitable for amide formation are: methylamine,
D ime thy1amin,
2-Cyanäthy1amin, Aethj'lamin,

Diethylamine,

Bis (2-cyanoethyl) amine, ethanolamine,

Dimethanolamine, Propylamine,

Ethyleneimine,

Butylamine,

K, N-dimethylpropylenediamine (1,3), dibutylamine,

Cyclohexylamine, N-Methj ^ l- ⁴ aniline,

Benzylamine, -

4- (methyl-, chloro- or nitro-) benzylamine, bis- (2-methoxya'thyl) -amine, Diisopropylamine, dimethylamine, N-methylpiperazine, Diethylamine,

N-Hydroxya'thylpiperazin, Aniline,

3-chloro-4-methylaniline, pyrrolidine,

Diphenylamine,

Piperidine,

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N-Methy1-eyelohexylamine,

N-ethyl-cyclohexylamine,

Dicyclohexylamine,

2-aminopyridine,

Morpholine,

8-aminoquinoline and

2-aminothiazole.

o-, m-, p-chloroaniline, ο-, m-, p-toluidine, ο-, m-, p-nitroaniline, o-, m-, p-phenetidine, 1-, 2-aminonaphthalene, p-aminobenzoic acid methyl ester, 2-aminobenzothiazole, 2-aminothiazole, α- and ß-tetrahydrofurfurylamine, α- and ß-tetrahydrofurfuryl-N-methylamine, N- (a-tetrahydroxypyranylmethyl) -N-methylamine, a-tetrahydropyranyl-N-methylamine, 3-aminosulfolane, l-carbo'ethoxy-2-aminothiophene, 1-amino-2-carbo'ethoxy-5-methyl-thiophene and 3-aminopyridine.

The naphthalene derivatives of the present invention are valuable intermediate products for the production of dyes, e.g. dyes of the dispersion series. In particular, the functional derivatives of 1,8-naphthalene-4-carboxylic acid described above are available as immediate starting products for syntheses in the range of disperse dyes.

In the examples below, the parts mean, unless otherwise stated, parts by weight, the Percentages by weight and temperatures are given in degrees Celsius. Between parts by weight and parts by volume there is the same relationship as between grams and cubic centimeters.

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example 1

15.6 parts by weight of o-xylylene cyanide and 8.5 parts by weight of glyoxal hydrate (trimer) (3 C ₂ H ₂ O ₂ .2 H ₂ O) with a content of 80% glyoxal to be released are stirred in 200 parts by volume of methanol. The reaction mixture

11.2 parts by weight of powdered potassium hydroxide are added in portions at 15 with stirring and nitrogen.

After the addition of potassium hydroxide, the reaction mixture is stirred for 15 hours at room temperature and continue under nitrogen. The slightly brown-colored reaction mixture is then removed under vacuum Freed methanol and diluted with 500 parts by volume of water. The precipitated, crude 1,4-dicyannaphthalene is filtered off with suction and washed neutral with water. 11 parts by weight of 1,4-dicyannaphthalene are obtained (61.8% of Theory) as slightly brown-colored needles with a melting point of 175 to 15 ° C.

After recrystallizing once from alcohol with the aid of 5 parts by weight of activated carbon, one obtains 5.5 parts by weight of the compound

(101)

as beautiful needles with a melting point of 204 to 205 ° C.

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264S1S1

EejLspiel 2

78 parts by weight of o-xylylene dicyamide and 42 parts by weight of glyoxal hydrate (trimer) (3 £ 9 ^ 2®? - 2 H ^ O) with a content of glyoxal iron 8'OX to be released are stirred in 400 parts by volume of methanol.

mrd hex 0 to 5 ° with stirring and nitrogen 56 parts by weight of powdered potassium hydroxide in portions offset.

After the addition of potassium hydroxide, the mixture is stirred for a further 12 hours at 0 to 5 ° under nitrogen, the slightly brown-colored reaction mixture is then neutralized with dilute hydrochloric acid . This gives 88 parts by weight of 09% of theory) of _l:, 4 © icyannaphthalins of formula

CN - '(102)

as a slightly brown colored crystalline powder with a melting point of 158 to 168.

The crude product is taken up in 700 parts by volume of 1 ₅ 2 ~ oxoethane, 50 parts by weight of sodium chloride are added and the mixture is refluxed. 44.5 parts by weight of phosphorus oxychloride in 50 parts by volume of 1,2-dichloroethane are slowly added dropwise. The reaction mixture is then refluxed for 5 hours, freed from insoluble parts by filtration and concentrated to dryness in vacuo. 67 parts by weight of 1,4-bieyannaphthalene (75% of theory) are obtained as

-7.fl3--8.l-3 / l1tO-.

slightly brown colored crystalline powder with a melting point of 198 to 204 °.

Example 3

A stirred flask containing 480 g of 937 ° sulfuric acid is added to a Temperature from 20 to 25 46.4 g of technical naphthalene-1,4-dicarboxylic acid (Content 93%). The thick suspension obtained is cooled to 0 and left at 0 to 2 external cooling, a mixture consisting of 22 g 63% nitric acid and 22 g within 30 minutes Add 937 ° sulfuric acid dropwise. You can still do that Stir for 5 hours at 0 to 5 ° and then pour the mixture onto 1 kg of fine ice. Filter the precipitated product on a suction filter and washed neutral with water, whereupon the product obtained the formula

COOH

COOH

dries in vacuo at 70. Yield 45g.

For purification, 45 g of crude product are heated with Bring 225 ml of glacial acetic acid to the boil briefly, then let it cool down and filter the precipitated product at room temperature away. The nitro compound is thus obtained as a light gray one Powder which completely dissolves in water when soda is added. Melting point 252 °.

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- YL - Λ

Example 4

52 parts of S-nitro-naphthalene-l ^ -dicarboxylic acid are dissolved in 700 parts of absolute ethyl alcohol and with constant introduction of hydrochloric acid gas on for 12 hours Boiled under reflux. The solution obtained is evaporated in vacuo. The 8-nitronaphthalene-1-carboxylic acid-4-carboxylic acid ethyl ester obtained in this way the formula

COOH

COOC ₀ H ₁ -

melts at 178 to 180 °.

If the monoester is hydrogenated, the ethyl 1,8-naphtholactam-4-carboxylate described in the example becomes obtained, which proves that the esterification of the carbon, acid group is done in the 4-position.

Example 5

130 parts of e-nitro-naphthalene-l ^ -dicarboxylic acid are dissolved in 500 parts of dimethylformamide, 40 parts of sodium hydroxide are added and the mixture is stirred for 30 minutes 170 parts by volume of diethyl sulfate were added all at once. the The temperature rises to 90. The mixture is stirred for two hours without taking the temperature into account and then filtered the solution removes little impurities and carries in 2500 parts by volume of a 10% sodium chloride solution and 50 parts by volume of a 30% sodium hydroxide solution. After brief stirring, the 8-nitro-naphthalene-1,4-dicarboxylic acid diethyl ester from melting point 107 to 109 °

709819/1 1 10

-τα-

vacuumed, washed and dried.

Example 6

32 parts of 8-nitro-naphthalene-1,4-dicarboxylic acid diethyl ester are stirred in 200 parts of glacial acetic acid and after adding 20 parts of iron powder for 6 hours boiled on reflux. For work-up, it is filtered hot and the filtrate with the same volume of water diluted and the so deposited 1,8-naphtholactam-4-carboxylic acid ethy The ester is filtered off, washed neutral and dried. The product obtained in good yield the formula

CO

COOC ₀ H ₁ -

melts at 216 to 218 °. The analysis gave the following values

CHN

calculated: 69.7 4.6 5.8

found: 69.3 4.5 5.6

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Example 7

29 parts of S-nitro-naphthalene-l ^ -dicarboxylic acid dimethyl ester (Can be prepared analogously to Example 5 with dimethyl sulfate) in 500 parts of ethyl acetate dissolved and hydrogenated with Raney nickel. The falls ljS-naphtholactam- ^ carboxylic acid methyl ester almost completely off. After the hydrogenation has ended, it is filtered and the residue is extracted with methylene glycol. By Evaporation of the extraction solution becomes the ester of the formula

HN CO

COOCH

obtained from melting point 264 to 266 °. The analysis resulted in the following values:.

C H N calculated: 68.72 3.99 6.17 found: 68.5 4.0 5.9 - · Example 8

24 parts of 1,8-naphtholactam-4-carboxylic acid ethyl ester are in 180 parts of water and 20 parts a 30% sodium hydroxide solution is refluxed for one hour, with complete dissolution occurring. These is filtered while hot with charcoal and the filtrate is acidified. The precipitated 8-amino-1-naphtholactam-4-carboxylic acid is filtered off after cooling, washed with water and dried.

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Example 9

26 parts of 8-nitro-naphthalene-1,4-dicarboxylic acid are dissolved in 200 parts of water and 20 parts by volume of a 307o strength sodium hydroxide solution and after addition boiled under reflux for 2 hours from 12 parts of sodium sulfide. The solution is filtered hot with charcoal and the filtrate with 50 parts by volume of conc. Acidified hydrochloric acid. The 1,8-naphtholactam-4-carboxylic acid falls in the process in good yield. It is filtered off, washed and dried.

Example 10

44 parts of naphthalene-1,4-dicarboxylic acid are in Portions added to 900 parts of concentrated sulfuric acid and stirred into a homogeneous suspension. then a few crystals of iodine and 36 parts of bromine are added and the whole is stirred overnight at room temperature. To the Work-up is poured onto ice, filtered off and washed neutral with water. The 8-bromo-naphthalene-1,4-dicarboxylic acid thus obtained can be purified by recrystallization from glacial acetic acid.

Example 11

60 parts of 8-bromo-naphthalene-1,4-dicarboxylic acid are introduced into -560 parts of concentrated sulfuric acid and a mixture of 14 parts of a 98% strength nitric acid and 20 parts within one hour with stirring at 20-25 ° concentrated sulfuric acid added dropwise. Temporarily if solution occurs, then the S-nitro-S-bromo-naphthalene-1,4-dicarboxylic acid falls partially off. It is filtered off by pouring the reaction mass into ice, washing until neutral

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and dry deposited. The product obtained was in Form of the 5-nitro-S-bromonaphthalene-1,4-dicarboxylic acid dimethyl ester analyzed.

Example 12

37 parts of S-nitro-S-bromonaphthalene-l ^ -dicarboxylic acid dimethyl ester are stirred in 250 parts by volume of glacial acetic acid and after adding 20 parts of iron powder for four hours on Held at reflux. After cooling to room temperature, the residue is filtered off and poured into 200 parts by volume of water and 80 parts by volume of a 30% sodium hydroxide solution boiled under reflux for two hours. It is filtered hot and falls the 4-bromo-naphtholactam-5-carboxylic acid by acidification. Its methyl ester has a melting point of 263-265 °.

Example 13

A mixture consisting of 21.3 g of naphtholactam-5-carboxylic acid is stirred 23.6 g of thionyl chloride, 100 ml of chlorobenzene and 1 ml of pyridine for 5 hours at one temperature from 83-85 °, then allowed to cool, stirred for a further 30 minutes at a temperature of 20-25 ° and isolated then the precipitated acid chloride of the formula

HN

coei

by filtration. It is washed with chlorobenzene and vacuumed well.

The acid chloride thus obtained is added to 50 ml of isobutanol and heated the mixture for 5 hours to re-

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- ■ jL »T ~ -

river temperature. The ester formed is then isolated by filtration and washing several times with isobutanol, then with methanol. Obtained after drying in vacuo at 70 ° one is the isobutyl ester of the formula

COOCH ₀ - CH

in the form of fine golden yellow crystals.

If, with otherwise the same procedure, equivalent amounts of the following are used instead of isobutanol Alcohols listed in the table under I, the corresponding esters of naphtholactam-5-carboxylic acid listed under II are obtained.

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Tabel

Alcohols

II Naphtholactam-5-carboxylic acid ester

HN

H ₃ C-CH ₂ -CH ₂ -OH

H ₃ C

H ₃ C

HN

CH-OH

COOCH-CH-CH 0

HN

H ₃ C-CH ₂ -CH ₂ -CH ₂ -Ol

COO CH 0

CH ₃

HN

H ₀ C-CH ₀ -CH-OH

COOCH ₉ -CH-Ch-CH

HN

H ₉ C ₄ -CH-CH ₂ -OH

COOCH-CH ₂ -CH ₃ .OCH,

HN

HV OH

COO-CH ₂ -CH-C ₄ H ₉

COO ~ <H

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If

Tabel

Alcohols II.
Naphtholactam-5-carboxylic acid ester

H ₃ COC ₂ H ₄ -OH

H ₅ C ₂ -OC ₂ H ₄ -OH ₀ J-

CH ₂ -OH

COOC ₂ H ₄ -OCH ₃

COOC H, -0-C ₉ H,

HN

COOCH

HN

COOC ₂ H ₄

HN

COOC ₂ H ₄

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Example 14

A mixture consisting of 23.1 g of naphtholactam-5-carboxylic acid chloride is stirred, 35 g p-toluidine and 100 ml chlorobenzene for 6 hours at a temperature of 98 - 100 °, then filtered off the precipitate formed at 40 ° and washed it with chlorobenzene, then with methanol, then with dilute hot hydrochloric acid, then with hot water until the filtrate reacts neutrally and then again with methanol. After drying the product of the formula is obtained in a vacuum at 70 °

HN

COHN η: V- CH

in the form of fine crystals of yellow-brown color.

If, with otherwise the same procedure, equivalent amounts of the amounts in the following table are used instead of p-toluidine Amines listed under I, the corresponding amides of column II are obtained. When using volatile amines and ammonia is used in an autoclave.

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St.

Tabel

Amines

Naphtholactam-5-carboxylic acid amides

NH,

H ₂ N-CH ₃

CH

HN

HN

C ₂ H ₅

C ₂ H ₅

H ₀ N-CH

CH,

.0

CONH,

0 ^A

HN

HN

COHN-CH, 0

CH

HN

C ₂ H ₅

CON

HN-

O ^C 2 ^H 5

HN

COHN-CH ₂ -CH-CH ₃

COHN-CH

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Tabel

Amines

II Naphtholactam-5-carboxylic acid: amides

H ₂ N-CH-C ₂ H ₅

HN

HN-

C ₂ H ₄ -OH

C ₂ H ₄ -OH

CH.

H ₀ N-CH ₀ -CH ₀ -CH ₀ -N

Z 2 I Li

CH.

η y ~ NH-C ₂ H ₅

HN

COHN-CH-C ₀ H ₁ 0 CH ₃

^C 4 ^H 9

CON

HN

⁰ C ₄ H ₉

C ₀ H-OH • ζ 4

CON '

0 ^ C ₂ H ₄ -OH

HN

COHN-CH ₀ -CH ₀ -CH ₀ -N

CH,

CH,

HN COHN
O

CON

^C 2 ^H 5

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264916?

Tabel

Amines II Naphtholactam-5-carboxylic acid amides

HN

{ V CH ₂ -NH-CH ₃

CH,

HN CON '
O

HN COHN-CH, 0

I N-

CH ₂ -CH ₂ -NH

ην — r COHN- (O

(NH \ f

con y

HN

0 NH

/ - ^ CON

HN

0-

NH,

COHN

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• .M table

No. I.
Amines Il
Naphtholactam-5-carboxamides 19th CH ₃
Q-NH ₂ . 0
HN <f COHN -T ~ \
^ o -
HN \ 20th Q-NH-C ₂ H ₅ Cl 21 0-NH ₂ LiJ ^C1 COHN - \\ ^V "^ · ci

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Example 15

A mixture consisting of 21.2 g of naphtholactam-5-carboxamide, 100 ml of dimethylformamide and 25 g is heated
Thionyl chloride to 80 ° with stirring and then keeps it at the same temperature for 4 hours. One pours. the
Mix on 500 g of ice, isolate the precipitated product by filtration and wash it thoroughly with water. After drying and subsequent recrystallization from ethylene glycol monoethyl ether, the product of the formula is obtained

in the form of fine yellow-brown crystals.

709819/1110.

Claims (1)

Claims 1. Functional derivatives of naphtholactam-4-carboxylic acids the formula wherein X is -CN or the group -CO-R, wherein. R is a radical of the formulas "OR or -NCT-nl, where R, R ₁ and R ₂ are araliphatic, cycloaliphatic or aromatic radicals of aliphatic radicals ^, and R and Ro can also be hydrogen, and Y is hydrogen or Halogen stands. 2. 5-Bromo-1,8-naphtholactam-4-carboxylic acid. S / 1,8-naphtholactam-4-carboxylic acid ester of the formula HN-CO Y CO-OR where R is an organic radical, in particular an aliphatic, is araliphatic, cycloaliphatic, aromatic or heterocyclic radical, and Y is chlorine, bromine or preferably H, 4. 1,8-Naphtholactam-4-carboxamides of the formula 7 098 19/1110 264916? HN - CO Y CO-N wherein R ₁ and R ~ hydrogen atoms or organic radicals, such as aliphatic. are cycloaliphatic, araliphatic, aromatic or heterocyclic radicals, and Y is chlorine, bromine or, preferably, hydrogen. 5. 1,8-naphtholactane-4-nitriles of the formula NH-CO Y CN where Y is chlorine, bromine or preferably hydrogen, 6. 8-nitro-naphthalene-1,4-dicarboxylic acid. 7. 8-nitro-naphthalene-1,4-dicarboxylic acid ester of the formula CO-R ¹ CO-R " where R ¹ and R "are the same as R-, 8. 1,4-Dicyan ~ 8-nitro-naphthalene. 709819/1110 - ae-- 9, process for the preparation of functional derivatives of naphtholactam-4-carboxylic acids of the formula, 0 where X is -CN or the group -CO-R, where R is a radical of the formulas -OR or -N ^- C ^ _R l, where R, R ^ and R are aliphatic radicals, araliphatic, cycloaliphatic or aromatic radicals and R, and R ₂ is also hydrogen can, and Y is hydrogen or halogen, characterized in that o-Xylylendicyanid with glyoxal in the presence of a base and a solvent at temperatures below 50 ⁰ C to 1,4-dicyanonaphthalene is reacted and then either a) the 1,4-dicyano-naphthalene in basic or preferably acidic medium saponified to 1,4-dicarboxylic acid, 1,4-kaphthalene-dicarboxylic acid either into a functional Converts derivative and then with a 10 to 507oigen excess of nitric acid to the 8-nitro-1,4-naphthalenedicarboxylic acid derivative converts and reduces this to the 8-amino derivative, or by converting the 1,4-dicarboxylic acid nitrated directly and then to 8-amino-naphthalene-1,4-dicarboxylic acid reduced, and then the 8-amino derivatives either by spontaneous ring closure or by heating into the 1,8-kaphtholactam-4-carboxylic acid or its functional derivatives, or b) the 1,4-dicyannaphthalene with a 10 to 50% strength Excess nitric acid is nitrated in the 8-position and then the nitro group is reduced to the 8-amino group, the Kaphtholactararringschluss by spontaneous formation or 703819/1110 Warming induces and the 4-position cyano group when it has not already been saponified during the reduction of the 8-nitro group, possibly via the stage of 4-carbonamido-1,8-naphtholactams saponified in a basic or acidic medium. 10, method according to claim 9, characterized in, that 1,4-dicyano-naphthalene is converted into 1,4-dicarboxylic acid in a basic or preferably acidic medium saponified, the 1,4-naphthalene-dicarboxylic acid either in converts a functional derivative and then.with a 10 to 50,000 excess of nitric acid to form 8-nitrol, 4-naphthalene-dicarboxylic acid derivative converts and reduces this to the 8-amino derivative, or by converting the 1,4-dicarboxylic acid nitrated directly and then to S-amino-naphthalene-l ^ -dicarboxylic acid reduced, and then the 8-amino derivatives either by spontaneous ring closure or by heating into the 1,8-naphtholactam-4-carboxylic acid or its functional derivatives. 11. The method according to claim 9, characterized in that 1,4-dicyannaphthalene with a 10 to 50,000 excess of nitric acid in the 8-position nitrated and then the nitro group is reduced to the 8-amino group, through the naphtholactam ring closure 709819/1110 Creates spontaneous formation or heating and the 4-position cyano group, if not already in the Reduction of the 8-nitro group was saponified, optionally via the stage of 4-carbonamido-1,8-naphtholactam saponified in a basic or acidic medium. 709819/1110