DE1545880A1 - Process for the preparation of derivatives of 4- [benzoxazolyl- (2 ')] -naphthoic acid- (1) - Google Patents

Description

Process for the preparation of derivatives of 4 - / _ Jenzoxazolyl- (2 ^f J_7-naphthocic acid - (. 1)

Bs was found dal 'nan derivatives of \ -J_ Jenzoxazolyl- (2') _ 7-naphthocsäure- (1) lormel the allgCMeinen

in which Y is a carboxyl, an esterified carboxyl, a carboxylic acid amide, a carboxylic acid hydrazide, a Carboxylic acid nitrile group and the radicals IL and I ^ hydrogen, a low molecular weight containing up to 4 carbon atoms Alkyl group or together in an adjacent position a fused hydroaromatic Rinp mean

BATH ORIGINAL

909860/1686

- 2 - Fw 4 «JO2

can if one o-aninophenolc the general Forriel

II

OU

with acid chlorides of 4-carbalkoxy-naphthoic acid (1 year or the 4-cyano-naphthoic acid-UJ of the formula

III

X = IMOU, CN

where U is a low molecular weight up to 4 carbon atoms containing alkyl group means, converts, the obtained N-acyl compounds of the general formula

IV

expediently in an inert gas atmosphere, preferably nitrogen, in high-boiling solvents, advantageously at temperatures above 200 ° C, preferably 215 to 220 ° C, optionally in the presence of catalysts,

909850/168 « _{BA0 0RIGINAL}

Iw 4 90

iiitz unil those formed with the elimination of water 4- / ~ oenzoxazolyl- (2 'J _7-nap lit hoc s: iu rc- (1) -ester or -nitrile of I'orncl

i ', c! "Ebeneni'al Is after saponification to the free acid (V, X = C) O.ij and" iborfüiirunji in the carboxylic acid chloride, in 4- / iJenzoxazolyl-iZ'J_7-naphthoes; iure- (1) - ester, and -anidc -iiydrazide transferred !! position in another method for Mr. animal 4- / iJenzoxazolyl- (2 'J_7-naphthoic acid 1 1J (V, X = Ct) O; iJ bestcnt in the condensation of 1 mole of Dichloride of N'aplithalin-dicarbonsMure-l 1, 4) (VIJ nit 1 mole of the above; amino-piicnols (II) in the presence of acid-binding agents, e.g. tertiary anines such as methylaniline, to the .J-acyl compounds en (VIIJ

VI

909850/1686

- 4 - IV

VII

which after saponification of the acid chloride residue are heated by firing in an inert gas atmosphere, advantageously nitrogen, in high-boiling solvents, e.g. 1,2,4-trichlorobenzene at internal temperatures of over 200 ° C, preferably 215 to 22) ° C, iiCfiebenenfal Is in the presence of zinc chloride, into the corresponding 4- / iienzoxazolyl- (2 ') _ 7-naphthoic acid UJ CV, X = Ci) OiIJ can be transformed. From these the corresponding derivatives can be obtained in a manner known per se.

As o-aminophenols (11}, for example, can be used will:

o-aminophenol, 3-amino-4-hydroxytoluene, 4-amino-3-hydroxytoluene, 3-amino-2-hydroxy-toluene, 5-atnino-4-hydroxy-1,2-xylene, 4-Amino-5-hydroxy-1,3-xylene, 5-Aniino-4-hydroxy-1,3-xylene, 3-amino-4-hydroxy-1-tert-butyl-benzene, 5-amino-hydroxy-h yd bark, 5, b, 7,8-tetrahydro-i -araino-r 2-naphthol, 5, 0, 7, B-Tetrahydro-S-amino ^ -naphthol.

909850/1686

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As 4-carbalkoxy-naphthoic acids- (l) (III, X * CUOU) ■ are mentioned:

4-Carboethoxy-naphthoic acid (1 ) , 4-Carboethoxy-naphthoic acid (i), 4-Carbopropoxy-naphthoic acid (1), 4-Carb-isopropoxy-naphthoic; iure- (1), 4-Carbo-butoxy naphthoic acid- (1), 4-carb-iso-butoxy-naphthoic acid- (1).

This ilalbester can by saponification of the appropriate Naphthalene-1,4-dicarboxylic acid dicster with a half Equivalent of an alkali or Urdalkali-hydroxyds in simple Way to be made.

Alcoholic or phenolic compounds which can be used for the esterification of the 4- _J / ~ uenzoxazolyl- (2 ^l ) _7-naplithoic acid- (1) (V, X = COOiI) include:

Mono- and polyvalent aliphatic, cycloaliphatic, araliphatic alcohols, phenols, naphthols, etc. such as methanol, ethanol, n-1'ropanol, isopropanol, n-uutanol, tert.-butanol, ictanol, cyclohexanol, 2-, 3-, 4-methylcyclohexanol, 2-chloroethanol- (1), l-chloropropanol- (2), glycol, propanediol- (1,2), n-ßutanediol- (1,3) and - (1,4), 2-methyl-n-butane -diol- (1,3), n-ilexanediol- (2,5), glycerin, pentaerythritol, uiethylene glycol, triethylene glycol, glycol monomethyl ether, glycol monoethyl ether, glycolraono-n-butyl ether, 3-methoxy-n-butanol- (1),

Glycid, phenol, o-, a- and p-cresols, xylenols, benzyl alcohol,

9 0 9 8 5 0/1 68β BAD ORIGINAL

b - Fw 4 9ü2

2-l> henylethanol- (1), 4-isopropylbenzyl alcohol, 2-dimethylaminoethanol- (1J, 2-Ui; ithylamino-; ithanol- (1), 2-Ui-n-butylamino-ethanol- (IJ ₁ 1 -Üiraethylamino-propanol- (2J.

The amines which are used to prepare the 4-i-benzoxazolyl- (2 *} 7 " naphthoic acid (i) amides can also belong to the most varied of series, for example the aliphatic, cycloaliphatic, araliphatic, aromatic, aromatic and heterocyclic series Amino compounds which contain further substituents such as hydroxy or acid groups are also suitable.

Ammonia, Metliyl-, ethyl, n-propyl, _t n-ßutyl-, ISU dutyl-, dimethyl-, Üi.ithyl- and di-n-butylamine, cyclohexylamine, and ethanol-Diiithanolamin, ß-methoxy-ethylamine, Amino-acetic acid, methylaminoessinic acid, 2-amino-ethane-sulphonic acid, 2-methylaminoethane-sulphonic acid, ß-dimethylamino-ethy larain, aniline, aniline-3- and -4-sulphonic acid, N-methylaniline, ilenzyl- and ß-I ' henylethylamine, N-methyl-N-benzylamine, piperidine, morpholine and piperazine.

üie 4- / "" uenzoxazolyl- (2 ^l ) _7-naphtho- (1) nitriles can also be obtained from the carbonamides of the general formula

BATH 909850/1681

- 7 - I w 4 90 2

VIII

by contributing ?; of water-releasing agents, such as l'hos]) chloro oxychloride or phosphorus pentoxide, i ', e »also al Is in the presence of organic solvents.

To prepare the Säurchydrazide one zwcckuäi'i fencing \\ of the Methylestern or Cnloriden of 4- j_ .ienzoxazolyl- (2 ') _7-naphtiiocs; iuren- (1 J (V, X = CO jiij ¹ and brings it with Hydrazine or with hydrazine derivatives substituted by organic radicals !! for the reaction.

The acid chlorides of the 4-carbalkoxynaphthoic acids (1J (III, X = COOU) can be obtained in a manner known per se, ζ. J> . By reacting the 4-carbalkoxynaphthoic acids (1) with thionyl chloride.

The reaction of the o -. \ Minophenols (.II) with the acid chlorides of 4-carbalkoxy-naphthoic acids-C1) and 4-cyano-naphthoic acid- (1) is advantageously carried out in an organic solvent, e.g. Toluene or chlorobenzene, in the presence of a tertiary üase to bind the hydrochloric acid which is split off, ζ.ύ. Dimethylaniline, at an elevated temperature, preferably about 50 to 100 ° C,

BATH ORIGINAL

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taken. When the reaction mixture cools, it crystallizes the acylamino compound (IV), is filtered off and freed from adhering solvent by steam distillation.

The N-acyl compounds (IV) are converted into the benzoxazoles (V) in high-boiling solvents. As such, 1,2,4-Trichlorbenzoi or is particularly suitable but mixtures of trichlorobenzene. The internal temperature of the reaction mixture should be above 200 ° C., preferably at 215 to 220 ° C. Compounds such as zinc chloride or p-toluenesulfonic acid can be used as catalysts.

The compounds of the formula (I) obtained according to the invention can also be converted into one another by the following reactions The nitriles (Y «CN) can be converted into carboxylic acid esters (Y * COOK, K * low molecular weight alkyl radical) by heating in alcohols, e.g. from the methyl ester (Y - COOCl ^) by transesterification with another alcohol containing up to 4 carbon atoms, which may be substituted can be obtained in the presence of the alcoholate of this alcohol.

The derivatives of 4- / ~ benzoxazolyl- (2 ') __ 7-naphthoic acid- (1) ders obtained by the process of the present invention

909850/1688 ^eAD

- y - Iw 4Uo2

general formula (I) are colorless or almost colorless Products that are used as UV absorbers, especially for production materials, e.g. Papers, extraordinary put are suitable.

example 1

23 parts by weight of naphthalene-1, ^ - dicarboxylic acid monoraethyl ester (Melting point: 150.5 to 151.0 ° C) are in 87 parts by weight of toluene with Ib, 4 parts by weight of thionyl chloride 8ΰ ° C implemented. After the excess thionyl chloride has been removed, the still warm solution of the acid chloride is left to a mixture, preheated to 75 ° C, of 14.1 parts by weight of 5-amino-4-hydroxy-1,2-xylene, 12.7 parts by weight of dimethylaniline and 70 parts by weight of toluene and stirred another 3 hours at 75 ° C. The precipitated acylamino compound is filtered off with suction and mixed with cyclohexane and methanol washed or freed from adhering solvent by steam distillation. To close the ring, the dried acylamino compound is heated (32.7 parts by weight from the melting point 253 to 257 ° C) with 72 parts by weight of 1,2,4-trichlorobenzene and 0.1 part by weight of zinc chloride in a nitrogen atmosphere about 2 hours to 215 to 220 ° C (internal temperature). While cooling, 48 parts by weight of methanol are added. The crystallized benzoxazole derivative (X) is filtered off with suction and washed twice with 25 parts by weight of cyclohexane each time and

BATH ORIGINAL

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- 10 - Iw 4 90 2

dries. 29.5 parts by weight of crude product are obtained. After recrystallization from toluene with the addition of activated charcoal, the pure 4 -, ^ S ¹ , ϋ'-dimethylbenzoxazolyl- (2 ') _ 7-1-naphthoic acid methyl ester (XJ with a melting point of 17 to 108 ° C. The naphthalene-1 used above , 4-dicarboxylic acid monomethyl ester can be prepared in the following ways:

4 8.8 (lightweight naphthalene-1, "4 -di carboxylic acid -dime thy les te r from the solidification point ö 4.9 ° C are in 200 parts by volume Methanol dissolved warm. At 40 ° C. the mixture is allowed to stir well a solution of 8 parts by weight of sodium hydroxide in 25 parts by weight of water is added dropwise and the mixture is stirred for a further half an hour under reflux after. Two thirds of the methanol are then distilled off. The residue is mixed with ½ parts by weight of water and concentrated with a mixture of 35 parts by weight. Acidified hydrochloric acid and 100 parts by weight of water. The deposited precipitate is filtered off with suction, free from Washed hydrochloric acid and stirred with a solution of 30 parts by weight of sodium hydrogen carbonate in 100 parts by weight of water, the saponification products dissolving, while unreacted methyl ester remains undissolved and is filtered off will. The carboxylic acid is made by acidifying with a mixture

ο of 35 parts by weight of conc. Hydrochloric acid and 50 parts by weight

Reprecipitated water, suctioned off and washed in with water

^ and dried. 40 parts by weight of crude half-ester are obtained, σ »can be obtained by recrystallization from 1000 parts by weight of toluene

ο cleans. The naphthalene crystallizing from the filtrate 1,4-dicarboxylic acid aonomethyl ester is sufficient after drying pure ad melts clear at 150.5 to 151 ° C. Yield:

BATH ORIGINAL

Fw 49b2

29 parts by weight of Jalbester; Equivalent weight titrated 229 (ber. 230).

Uie listed in Table 1 methyl esters IX and XI can be used in analogous way using the o-aminophenol and 5-Amino-4-hydroxy-hydrindens are shown.

T Λ B ü LL h 1

h'ormcl no.

ution Konstit Melting point

Ibü - 1ö1 ^u C

167-168 °. C.

COOQI.

138 - T39 ° C

909850/1686

BATH ORIGINAL

- 12 - Fw 4902

Example 2

The listed in Table 2 carboxylic acid XlI can on can be produced in the following way:

111 parts by weight of the compound IX are suspended in 1430 parts by weight of ethanol (91> Hg). At 80 ° C allowed a Lösun stirring ;; of 25 parts by weight of potassium hydroxide in 35 parts by weight of water are added dropwise and the mixture is heated under reflux cooling for a further 2 hours. After that will be

050 parts by weight of ethanol distilled off. Uer residue will with üü parts by weight of conc. Hydrochloric acid added, the Carboxylic acid precipitates. After dilution with 1000 parts of water, the mixture is stirred for 1 hour, filtered off with suction and washed with water. 10 parts by weight of 4-i-benzoxazolyl- (2 ') -naphthoic acid- (i) are obtained from melting point 274 to 275.5 ° C. The carboxylic acid XIII can, starting from the compound X, in analogous Way to be obtained.

Example 3

Another way to prepare the carboxylic acid XII consists in the following reaction sequence:

253 parts by weight of the dichloride of naphthalene-dicarboxylic acid- (1,4) (VI) with a melting point of 92 to 94 ° C are in 550 Ge

909850/1686

BATH ORIGINAL

- 13 - number 4952

parts by weight of acetone dissolved by heating to 40 ° C. to this solution is left with an approx. 40 C warm solution 109 parts by weight of o-aminophenol in 300 parts by weight Dimethylaniline and 1100 parts by weight of acetone in 45 minutes run up. The mixture is then heated for 2 hours at boiling temperature, diluted with 2000 parts by volume of 2N sulfuric acid and subjected the whole to a steam distillation. The precipitated, cooled product is filtered off with suction and washed neutral with water. After drying 307 parts by weight of the crude ilalbamide of naphtha are obtained lin-dicarbons; iure- (1,4),

307 parts by weight of the dried ilalbamide are with 2 parts by weight of zinc chloride mixed in 1335 parts by weight of 1,2,4-trichlorobenzene in a nitrogen atmosphere for 3 hours heated to 215 to 220 ° C. with stirring. After cooling, the reaction product which has crystallized out is suctioned off, Stirred with 1000 parts by volume of petroleum ether, suctioned off again, washed with petroleum ether and dried. You get 2u4 parts by weight of the crude 4- ^ ~~ öenzoxazolvl- (2 ') _7-naphthoic acid (i) (XII). For cleaning, this acid is added to a mixture of 1000 parts by volume of 2N sodium hydroxide solution and 2000 parts by volume of water, stirred for 2 hours at 80 to 90 ° C, sucks off undissolved constituents while hot

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14 - l-w 4Üü2

saturate the filtrate at M) tiis ¹ J) ⁰ C with table salt. The precipitated sodium solute is sucked off after the cold to 20 ° C and washed with 3t)) parts by volume of saturated sodium chloride solution.

The faint sodium salt is dissolved in 3000 parts by volume of water at H) to ¹ ° C, clarified with the addition of 7.5 parts by weight of charcoal, and the hot filtrate is concentrated to a concentration. Hydrochloric acid acidic to Congo paper. The acid which has precipitated is filtered off with suction in the cold, washed neutral with water and dried. 140 weights of the pure 4- ] _ licnzoxazolyl- (2'J_7-naphthoic acid (1) with a melting point of 274 to 275 ° C. are obtained.

tie i played 1 4

From 41.2 parts of the carboxylic acid XIII, 21.3 (weight parts Thionyl chloride and 45) Volunentei len toluene is the carboxylic acid chloride XV (melting point 15 to 1½ ° C) in the usual '..' ice produced,. '»after removal of the excess thionyl chloride one passes ammonia into the toluene solution in the overshoe a, whereby the carbonamide XVI precipitates out as a colorless precipitate. The precipitated product is filtered off with suction by steam distillation freed from adhering toluene, sucked off again and then stirred with a dilute sodium carbonate solution, to pull out any remaining carboxylic acid. After thorough nibbling and drying, you get 3D parts of the Compound XVI from melting point 280 to 2R2 ° C.

909850/1686

BATH ORIGINAL

- 15 - Fw 490 2

The acid chloride XIV can, starting from the carboxylic acid XII, can be obtained in an analogous manner.

Example 5

32 parts by weight of the carbonamide XVI are refluxed with 17 parts by weight of phosphorus oxychloride for 75 minutes (internal temperature 105 ° C.). The cooled reaction mixture is poured onto approximately 1000 parts by weight of liis. The precipitated product is filtered off with suction and washed with water. After drying, 30 parts by weight of crude product with a melting point of 205 to 200 ° C. The 4- £ ~ S \ ü'-dimethylbenzoxazolyl- (2 ') -7-naphtho- (1) nitrile XVII can be purified by recrystallization from butanol and then melts at 209 to 210 ° C.

Example 0

33.1 parts by weight of the methyl ester X (Table 1) are heated with 300 parts by weight of β-dimethylamino-ethanol under a slight vacuum of about 200 torr with stirring and slow distillation for up to 7 hours at a bath temperature of about 110 °. As a catalyst for the transesterification, 0.4 parts by weight of sodium β-dimethylamino-ethylate in the form of a (about 5 to 10 ecm) solution are added in four portions. Finally, all of the remaining ß-Uiroethylaraino-ethanol is distilled off and the residue is crystallized from ethanol with the addition of

_BAD OWGiNAi 909850/1686

- 1ü - Fw 4902

Activated charcoal. 33.8 parts by weight of crude product are thus obtained. Further recrystallization gives pure β-methylamino-ethyl ester XVIII from melting point 108 to 110 ° C.

Example 7

23.3 parts by weight of compound XVIII are dissolved in 300 parts by volume of ethyl acetate in the liquid. Then, at 30 ° C , 8 parts by weight of dimethyl sulfate are added while stirring, resulting in an almost colorless crystal pulp. Bring it to the boil briefly , cool down and take a sauna. The filter residue is covered four times with 25 parts by volume of LIssigsliureüthylester. 28.5 parts by weight of almost colorless, quartile salt XIX are obtained.

example B

Hydrogen chloride gas is passed into a suspension of 30 parts by weight of compound XVII in 70 parts by weight of methanol while cooling with III s hydrogen chloride gas until saturation. After 15 hours standing, the mixture with 2 parts by weight of water is added and boiled for one hour under Uurchleiten of hydrogen chloride, lieim cooling to S divorced ⁰ C, 22 parts by weight of crude product of Compound X from which one after recrystallization from toluene with addition of animal charcoal Melting point from 107 to 13 ° C shows.

909850/1686 bad original

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Example 'J

. 31.7 parts by weight of the compound XIII are known per se Converted into the acid chloride (XV) with 14 parts by weight of thionyl chloride in 175 parts by weight of toluene. After removing the excess thionyl chloride, nan the still warm solution is added dropwise with stirring to a mixture of 40 parts by weight of SO tiger hydrazine hydrate and 300 parts by weight of isopropanol and the whole is stirred in for 2 hours Reflux. The precipitate is sucked off after the cold and treated with steam. After drying at 105 ° C If you get 30.4 parts by weight of raw product, that is mainly Compound XXVI, next to it some bisacylated hydrazine (XXIXJ contains.

To separate off XXIX, the crude product is extracted at 100 ° C. with 200 parts by weight of dioxane, allowed to crystallize and the extraction is repeated. May be after the crystallization and precipitation of the residues from the dioxane by the addition of water gives 24 _t b parts by weight of the crude compound XXVI which by transesterification crystallization from chlorobenzene with the addition of purified activated carbon. Melting point 239 to 241 C (with decomposition).

The residue which is insoluble in dioxane can be recrystallized from dimethylformamide. Pale yellow crystals are obtained

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- 18 - Fw 4i) ti2

from the decomposition point 301 to 34 ° (XXIX).

Example 10

14.3 parts by weight of the compound XXVI are brought to 80 ° C. with 4 parts by weight of pyridine and 200 parts by weight of chlorobenzene heated. A solution of 1.8 parts by weight of p-i'lcthoxy-benzoyl chloride is added dropwise under the oil, and two more are stirred Hours at 80 ° C. The precipitate sucked off at 5 ° C is treated with steam, sucked off again and dried. net. IU parts by weight of the pale yellow compound are obtained XXVII from melting point 2ü3 to 2o4 ° C.

Example 11

38 Gewientsteile of compound XIII are converted in manner known per se with Iu S ₁ weight parts of thionyl chloride in 218 parts by weight of toluene in the Säurcchlorid (XV). After the excess thionyl chloride has been removed, the still warm solution is added dropwise to a 70 ° warm mixture of 333 parts by weight of chlorobenzene, 10 parts by weight of pyridine and 20.5 parts by weight of p-chlorobenzhydrazide and the mixture is stirred for three hours. The precipitated product is suctioned off in the cold, treated with steam, suctioned off again and dried at 105.degree. 54.7 parts by weight of the colorless compound XXVIII with a melting point of 295 to 296.5 ° C. (with decomposition) are obtained.

909850 / 16S6

T Λ B E L L Ii

Iw 4 ¹ Ju 2

l ^: ormel Mr.

Constitution melting point

COJiI 274-275.5 ° C

-COOiI

280-28 2 C

ISU- IOC)? C.

- ιοί c

ti C 3

'/ Vc

280-282 ° C

909850/1686

forncl ir.

Konsti does i on Melting point

VII

jf <> U - 210 ° C

Λ \ i I I

.i (

3 '

.i l.

Cl.

- ti J C

CU

ι; ι

¹ S 'Ci, 173 - 2 <) 3 L.

, -Ci

909850/1686

Iw

Fornel no

Constitutional Melting point

XXI

XXII

., ₃ ι:

_SU .

XXIII

.1 C 3

-CJ-.- Cl > -C.! J

ι - t "

W / ^CA , ⁵ ^ ' ¹

XXIV

Ii, LJ

YY - .. 1

XXV

ORIGINAL BATHROOM 909850/169

τ Zl

Iw ii> 2.

ί υ 11 ic 1 »r.

KonsLi LuLion

jLιUi.c U; UiIK L

XXVI

XXVII

I Λ.

.j "

■ :. - N

• 5j - .41 ° t. », Antcr Jersetzungj

Ji. i - 104 ¹ I "

λXV Hi

Λ X

ι _ * ■ -

(anter ^ e rsetzunpj

XXIX

301-3-4 ° C

(with decomposition

909850/1686

_BATH

Claims (4)

I 'Λ T I! N T Λ V S I »K Il C Il Ij method to the extreme hunt; of larolless or almost colorless derivatives of 4- / _ rienooxazulyl-12 ^ _7-naphthoic acid (1J der al 1 r. weeping lurnel in Y a carboxyl, an esterified Cnrüoxyl-, a carbonarid-, a larbonsäurcliydruzid-, a C.arbonsäureni tri lgroupjje and the ueste U, and U ₁ lasscrstof f, a low molecular weight, Ms to 4 carbon atoms containing alkyl group or qeneii \ sam in neighboring Stelluni; a condensed hydroarunjtisehen cinema, signify, characterized, run, o -. \ ninopiienole of the general tornel ^ V <v. /Nile, II OH with the acid chlorides of 4-carbalkoxy-naphthoic acids- (1J the general formula 909850/1686 Fw 49ö2 iIOOC Vx III (X * COOK), where R denotes a low molecular weight alkyl group containing up to 4 carbon atoms or reacts the N-acyl compounds obtained with the acid chloride of 4-cyano-naphthoic acid- (1) (III, X-CN) VS-X IV Expediently heated in an inert gas atmosphere, in high-boiling solvents, optionally in the presence of catalysts, and the 4- / ~ denzoxazolyl- (2 ') -7-naphthoic acid (1) esters formed with elimination of water Vx (X = COOR) or the 4- £ benzoxazolyl- (2 ') _ 7-naphtho- (1) -nitriles (X * CN), if desired after saponification to the free acids and conversion into the carboxylic acid chlorides with alcoholic or phenolic compounds , with amines, hydrazine or with substituted by organic radicals 9 0 9 8 5 0/1686 _B AD 154588D - 25 - Fw 4962 Reacts hydrazine compounds. 2) Method according to claim 1, characterized in that » that one mole of the o-aminophenols of the general formula II with 1 hol of the dichloride of naphthalene-dicarboxylic acid-0.4) ^VI converts the N-acyl compounds obtained ^^ XVCOCI VII OH R ₂ ^ after saponification of the acid chloride residue, expediently in an inert gas atmosphere in high-boiling solvents, given if in the presence of catalysts, and the 4- / "Benzoxazolyl- (2 ') _ 7-naphthoic acids- (i) formed with elimination of water BATH ORIGINAL e f, ' Fw 4962 (X - COOiI), optionally after conversion into the carboxylic acid chlorides with alcoholic or phenolic compounds, with amines, hydrazine or with organic compounds Reacts radicals substituted llydrazine compounds. 3) Method according to claim 1, characterized in that that compounds of the general formula (I) in which Y has the meaning of a -CONI ^ group, by action of dehydrating agents such as phosphorus oxychloride or Phosphorus pentox / d, optionally in the presence of organic solvents, is converted into the corresponding nitriles. 4) Process according to claim 1, characterized in that compounds of the general formula (I) in which Y has the meaning of a CN group, by heating with low molecular weight, containing up to 4 carbon atoms Converts alcohols, advantageously in the presence of hydrogen chloride, into the corresponding carboxylic acid esters. BATH ORIGINAL S09B & Q / 1S8S - 27 - Fw 49fa2 S) Process according to claim 1, characterized in that compounds of the general formula (I) »in the Y has the meaning of a COOCHj group, with a higher, optionally substituted alcohol having up to 4 carbon atoms in the presence of the alcoholate this alcohol is transesterified. b) Compounds of the general formula (I) in which Y is a carboxyl, an esterified carboxyl, a carboxylic acid anide, a carboxylic acid canhydrazide, a carboxylic acid nitrile group and the radicals R and Wj are hydrogen, a low molecular weight alkyl group containing up to 4 carbon atoms or together in an adjacent position denote a fused hydroaromatic ring. BATH ORIGINAL 909850/1686