DE2410634A1 - 3-BENZOFURYLCUMARINE - Google Patents

Description

A hydrogen, methyl, methoxy, ethoxy, benzyloxy, ß-hydroxyethoxy, Chlorine, bromine, dimethylamino or diethylamino,

A hydrogen, methyl, chlorine or bromine,

R ^{1 is} hydrogen, methyl, methoxy, ethoxy, benzyloxy, ß-hydroxyethoxy, chlorine, bromine, dialkylamino with a total of 1 to 8
C atoms, pyrrolidino, piperidino, morpholino, piperazino, N-methylpiperazino, chloromethyl, bromomethyl or a radical of the formula II

, 1 Ί

-CH ^ N,

(B- ⁵ )

(e)

II

R ^ hydrogen, methyl, methoxy, ethoxy, benzyloxy, chlorine or Bromine,

B and B independently of one another are hydrogen or optionally substituted alkyl, cycloalkyl, phenylalkyl or

1 ?
Phenyl, where B and B together with the nitrogen too

can be connected to a heterocyclic 5- or 6-ring, B- ⁵ hydrogen, alkyl with 1 to 4 carbon atoms, benzyl, hydroxyalkyl, ß-cyanoethyl, carbalkoxymethyl, ß-carbalkoxyethyl,

73/74

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ß-Hydroxy-y-chloro-, -r-methoxy- or -f-phenoxypropyl or Benzyl

η zero or 1 and
Χ ^θ mean an anion.

Examples of possible dialkylamine residues for R are: Dimethyl amino, diethylamino, di-n-propylamino, - di-ipropylamino, D-n-butylamino, D-I-butylamino, methylethylamino, Methyl-n-propylamino, methyl-i-propylamino, methyl-n-butylamino, Methyl-n-hexylamino, ethyl-n-propylamino and n-propyln-butylamino.

1 2

Particularly suitable for B and B are: alkyl having 1 to 10 carbon atoms, which is replaced by hydroxy, alkoxy having 1 to 3 carbon atoms, an amino group or phenyl optionally substituted by methyl or ethyl may be substituted - im individual, for example, methyl, ethyl, n-propyl, i-propyl, η-butyl, i-butyi, ß-ethylhexyl, ß-hydroxyethyl, ß-methoxyethyl, ß-ethoxyethyl, p-hydroxypropyl, ^ - methoxypropyl, p-ethoxypropyl, r-hexoxypropyl, y-dimethyl, r-diethyl or r-Dibutylaminopropyl, benzyl and ß-phenylethyl, optionally cycloalkyl having 5 to 6 ring members substituted by alkyl having 1 to 4 carbon atoms, such as cyclopentyl, cyclohexyl and 2-methylcyclohexyl, and optionally by chlorine, bromine, Alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms substituted phenyl, such as p-chloro- and p-bromophenyl, o-, m- and p-tolyl, p-ethylphenyl and p-methoxy- and p-ethoxyphenyl.

1 p
In the event that B and B are closed together with the nitrogen to form a ring, the pyrrolidine, piperidine, morpholine, piperazine and N-methylpiperazine groupings are preferred.

For Br , alkyl, hydroxyalkyl, carbalkoxymethyl and ß-carbalkoxyethyl are preferably those radicals which have 1 to 4 carbon atoms per alkyl group, specifically for example methyl, ethyl, n- and iso-propyl, η-butyl, ß- Hydroxyethyl, ß-Hydroxypropyl, Carbomethoxymethyl, Carboäthoxyrnethyl,

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Carbobutoxyme thyl, ß-Carbomecnoxyäthyl, ß-Carboäthoxyäthyl and ß-carbobutoxyethyl.

Anions Χ ^θ are, for example, chloride, bromide, nitrate, rhodanide, sulfate, methosulfate, ethosulfate, pormate, acetate, p-toluenesulfonate, tetrachlorozincate or tetrafluoroborate.

Of particular industrial importance are compounds ^of: Formula Ia

Yes

in the ■ "

Rr 7-dialkylamino with 1 to 4 carbon atoms per alkyl, preferably 7-dimethyl- or 7-diethylamino or a radical of the formula II

1, 2

(χ ^θ )

4th
R denotes methoxy or ethoxy or, in particular, hydrogen

1 ο -χ α
and B, B, W, ri and X have the meanings given.

1 2
Preferred radicals B and B are, for example: Alkyl.mit 1

1 to 4 carbon atoms, ß-hydroxyethyl, benzyl, phenyl or B and B together with the nitrogen pyrrolidino, piperidino, morpholino or N-methylpiperazino.

Preferred radicals W are: methyl, ethyl, benzyl, ß-hydroxyethyl or ß-cyanoethyl.

Individual preferred radicals of the formula II are, for example) ₂ , —CH ₂ N (C ₂ H ₅ ) ₂ , —CH

-CH ₂ N (C

-CH ₂ N (C ₂ H ₄ OH) ₂ , -CH,

-CH ₂ C ₆ H ₅

-CHpN ^ ^? , ^C 6 ^H 5

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J)

CH ₂ -IQ, -CH ₂ NJ, -CH ₂ N _x J), £ CHpN (CH,) J CH ^ SOj, ⁸ , -E-CH ₉ -N (CH CH ₀ N (CH,) ο ^

CH ₂ CH ₂ OH

CH ^ COO

CH ₂ ,
CH

H ^ C- (O) -SO ⁸ , -fCH _p N (C _p H _R ) Jc _o H _R S0 ₄ ⁸ ,

CH ₃ SO ₄ ,

--CH ₂ N (C ₄ H _g ) ₂
CH,

--CH ₂ -N (C ₂ H ₄ OH) ₂ CH

1/2

CH ₀ -N (CH,), • ^C 6 ^H 5

CH ₃ SO ₄ ⁰ ,

φ ^CH 3
CH ₂ -N-CH ₂ -C ₆ H ₅

C ₂ H ₅

CH C00 °,

BF

C ₂ H ₄ OH _

• CH _O -N ~ b 2 W CH

2 ^Θ Γ / - ^ ^€ 1/2 ZnCl ₄ , --CH, -N_JiT.

CH ₃ SO ₄ ⁰ or

CH,

CH ₃ SO ₄

The compounds of the formula I in which R is a 7-dialkylamino group are brilliant fluorescent yellow dyes. They are suitable for dyeing synthetic fibers, especially polyamides and polyesters, as well as for production brilliant textile prints based on pigmented plastics and for the production of daylight luminous pigments. The others in the present invention are

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The compounds written are farolless to light yellow and show an intense blue fluorescence in solution or in a finely divided state. They are suitable for the optical brightening of textile fiber material made of polyamides, cellulose esters, acrylonitrile polymers and polyesters as well as paper and as
Additives in detergents.

To prepare the compounds of the formula I, one can use salicylaldehydes of formula III

CHO

III

with benzofuranacetic acid derivatives of the formula IV

,1

IV
YH ₂ C

in which Y is a carboxyl group or a modified carboxyl function, such as, for example, a cyano, carboxamide and
in particular represents a carboxylic ester group, in an
implement themselves in a known manner and optionally quaternize the compounds obtained.

Details of the preparation of the dyes and optical brighteners of the formula I can be found in the following working examples, in which parts and percentages, if
not otherwise noted, refer to the weight.

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example 1

15.5 parts of 5-piperidinomethylsalicylaldehyde and 14.5 parts of benzofuran-2-acetic acid ethyl ester are refluxed for 5 hours in 80 parts of isopropanol with the addition of 5 parts of piperidine. It is then cooled to 5 ° C., and the precipitated product is filtered off with suction, washed with alcohol and dried. 18.4 parts (72 % of theory) of the compound of the formula are obtained

Ό0

The melting point is 211 to 213 ° C,

5-Piperidinomethylsalicylaldehyde can be prepared from 5-chloromethylsalicylaldehyde, for example according to M. Descamps, J. van der Eist and F. Buion (Chem. Therap. 1966 , 87), benzofuran-2-acetic acid ethyl ester, for example according to E. Bisagni and R. Royer ( Bull. Soc. Chim. Fr. 1962 , 86) from 2-acetylbenzofuran.

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Example 2

To a mixture of 9 parts of the gumarin extract from Example 1 and 200 parts of 1.2 ~ dichloroethane are added at tree temperature to 12.6 parts of dimethyl sulfate, heated to 50 G for 3 hours and then cooked 5 hours under reflux, The Reaktxonsgemxsch is cooled to 10 G, the product is filtered off with suction, washed with 1,2-dichloroethane and dried. 9.6 parts ($ 81 of theory) of the compound of the formula are obtained

GH ₃ SO ₄

The melting point is 245 - 245 ° C

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Example 5

15 »5 parts of 5-I'iethyl3.minomethyl-salicylaidehyd and 15.3 parts of benzofuran-2-acetic acid ethyl esters are mixed with 50 parts of isopropanal and 2 parts of pyrrolidine. Lie mixture is heated for 1 hour at 50 G and then boiled for 1 hour under reflux, Vann is cooled to 5 C and the precipitate is filtered off with suction, washed with methanol and dried. Kan receives 19 parts (73 % of theory) of the compound

formula

The melting point is 1I ^ - I15 ° C.

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Example 4

6.3 parts of I) III ethyl sulfate are added dropwise to a solution of 8.7 parts of the coumarin extract from Example 3 in 65 parts of 1,2-chloroethane. The mixture is stirred for 4 hours at room temperature and then refluxed for a further 1 hour. It is then cooled to 10 G, the precipitate is filtered off with suction, washed with 1,2-1ichloroethane and dried. 10.8 parts (91 ^a of theory) of the compound of the formula are obtained

The melting point is 211-214 ° C.

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Example 5

7.6 parts of 4-methoxysalieylaldehyde and 10.2 parts of benzofuran-2-acetic acid ethyl ester were refluxed for 1 hour in 40 parts of isopropanol with the addition of 2 parts of pyrrolidine. It is then cooled to 5 G, the precipitate is filtered off with suction and recrystallized from ethylene glycol monomethyl ether. 8.9 parts (61 ^ύ / ο of theory) of the compound of the formula are obtained

The melting point is 205 - 207 ° C

Example 6

6.1 parts of salicylaldehyde and 10.2 parts of benzofuran-2-acetic acid ethyl ester are refluxed for 3 hours in 40 parts of ethanol with the addition of 2 parts of pyrrolidine. It is then cooled to 5 G, and the precipitated product is filtered off with suction and washed with methanol. This gives 9.5 parts (73 ^c ß> of theory) of the compound of formula

The melting point is 177 - 178 ° C.

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A mixture of 7> 5 parts of 3,5-di.niethylsalicylaldehyde, 10.2 parts of benzofuran-2-acetic acid ethyl ester, 55 parts of isobutanol and 2 parts of piperidine is refluxed for 3 hours. It is then cooled to 5 G, the precipitate is filtered off with suction, washed with ethanol and dried. One erhält.11,1 parts (77 f ° eggs theory) of the compound of formula

The melting point is 182-183 ° C.

Example 8

9.6 parts of 3,5-dichlorosalicylaldehyde and 10.2 parts of benzofuran-2-acetic acid ethyl ester are refluxed for 3 hours in 110 parts of isopropanol with the addition of 2 parts of pyrrolidine. Bann cooled to 5 C -AB-, the precipitate is suctioned off, washed with ethanol and dried Man obtained 13.1 parts (79 i ° of theory) of the compound of formula

The melting point is 211-213 ° C.

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4.3 parts of salicylaldehyde and 7 parts of 5,7-dimethylbenzofuran-2-acetic acid ethyl ester are refluxed for 2 hours in 24 parts of isopropanol with the addition of 1 part of piperidine. It is then cooled to 5 ° C., the product is filtered off with suction, washed with ethanol and dried. 6.6 parts (76 % of theory) of the compound of the formula are obtained

O,

The melting point is 237 to 239 C.

Example 10

9.7 parts of 4-diethylaminosalicylaldehyde and 10.2 parts of benzofuran-2-acetic acid ethyl ester are refluxed for 4 hours in 25 parts of ethanol with the addition of 1 part of pyrrolidine. It is then cooled to 5 ° C., the precipitate which has separated out is filtered off with suction and washed with ether. 8.9 parts (53 % of theory) of the yellow dye of the formula are obtained

H ₅ C ₂

Ό0

The melting point is 188 to 190 ⁰ C,

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16.5 parts of ^ -dimethylaminosalicylaldehyde and 20.4 parts of benzofuran-2-acetic acid & ethyl ester are in 50 parts of isopropanol with the addition of 3 parts of pyrrolidine refluxed for J hours. Then a.uf 5 C cooled, the precipitate filtered off with suction and washed with ether. Man receives 18.8 parts ($ 62 of theory) of the yellow dye of the formula

0 0

The melting point is 278 - 280 ° C.

Example 12

6.8 parts of 4-dimethylaminosalicylaldehyde and 7 »0 parts benzofuran-2-acetic acid ethyl ester are in 25 parts isobutanol under Addition of 1 part of piperidine heated to 80 ° C. for 5 hours. Afterward it is cooled to 5 ° C., the precipitate is filtered off with suction and washed with ethanol and dried. You get 4> 3 parts ($ 43 of theory) of the yellow Dye of the formula

The melting point is 230 - 232 ° C.

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4.1 parts of 5j7-dichlorobenzofuran-2-acetic acid ethyl ester and 3.3 parts of 4-diethylaminosalicylaldehyde are refluxed for 3 hours in 20 parts of isopropanol with the addition of 10 drops of pyrrolidine. Add 30 parts of ether and cool
to -10 ° C, sucks off the precipitate and washes with ether. 2.7 parts * (45 % of theory) of the yellow dye of the formula are obtained

.Cl

The melting point is 210 to 212 C,

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The compounds listed in Table 1 are obtained after a similar procedure the general Foimel

Table 1

E.g. «Ι R ₂ H A ₂ Fluorescence in
Methanol 14th H ₂ GN ^ ⁵ H H blue-violet CH ₅ H 15th H C- / ' ³ ~ ^7
C 3 ^H 7 E. H H blue-violet 16 ^ C _? H ₄ OH
H ₂ CN ^{ά 4} H H H blue-violet 17th H H H blue-violet 18th H Cl "IT blue-violet 19th H ₂ ON (C ₂ H ₅ ), ' H CH ₅ Cl blue-violet 20th H ₂ OQ H H CH ₅ blue-violet 21 £ K ₉ CN (CH-) ρ J (^ tI »SO,
2 5 H' H blue

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^Α 2 H H H H H H E. H H H E. H Cl Cl CH, CH,

E.g.

Fluorescence in methanol

[H ₂ CN (C ₃ H ₇ ) JCH ₅ SO ₄

CH ₃

[h "c-n

'C ₄ H ₉

CH ₂ C ₆ H

H ₂ C

-ti

C ₂ H ₄ OH

1/2 ZnCl.

CH ₃ COC

H ₂ CN (C ₂ H ₄ OH) ₂ CH ₅

CH ₅ SO ₄

• CH,

^C 6 ^H 5

CH,

CH ₃ SO ₄ ^

-SO H

blue

"blue blue blue

blue blue

blue

blue

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3sp. © © H ^A 1 A ₂ Fluorescence in
Methanol 50 CE ₅ - H GH ₂ . GH ₅ blue 31 CH ₅ H H H blue 32 Cl Eq Cl Cl greenish blue 33 Eq Cl Cl Cl greenish blue 34 CH ₅ GH ₅ CS, CH ₅ greenish blue 35 Cl Cl greenish blue

In a similar manner of work, the ones listed in Table 2 are also obtained Compounds of the general formula

Table 2

example ^R 1 λ; ^A 2 36 N (C ₂ H ₅ J ₂ 5-CHj H 37 N (C ₂ H ₅ J ₂ -5'CH ₅ CH ₅ "■ -.- ■ 38 N (C ₀ H ₁ -J- 6-N (GH ₅ J ₂ H 39 N (CHJ ^ 5-Cl Cl 40 N (CH ₅ ); 5-CH ₅ H 41 N (CHj) ₂ 6-N (CH ₅ J ₂ H

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Claims (8)

Claims in the A hydrogen, methyl, methoxy, ethoxy, benzyloxy, ß-hydroxyethoxy, chlorine, bromine, dimethylamine or diet hy 1 ami no,
ρ A hydrogen, methyl, chlorine or bromine, Hydrogen, methyl, methoxy, ethoxy, benzyloxy, ß-hydroxyethoxy, chlorine, bromine, dialkylamino with a total of 2 to 8 carbon atoms, pyrrolidino, piperidino, morpholines, Piperazino, N-methylpiperazino, chloromethyl, bromomethyl or 1 ί (Φ) R is hydrogen, methyl, methoxy, ethoxy, benzyloxy, chlorine or bromine, 12th B and B independently of one another are hydrogen or optionally substituted alkyl, cycloalkyl, phenylalkyl or phenyl, where B and B together with the nitrogen form a heterocyclic 5- or 6-membered ring can be connected B ^ hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl, ß-cyanoethyl, carbalkoxymethyl, ß-carbalkoxyethyl, ß-Hydroxy-ρchlor-, -f-methoxy- or -f-phenoxypropyl or benzyl, η zero or one and. . X mean an anion. -18- 509838/0994 24'IUbJ * ο.ζ. 30 433 2. 3-benzofurylcoumarin compounds according to claim 1, characterized 1 2
characterized in that B and B independently represent hydrogen, alkyl having 1 to 10 carbon atoms, which can be substituted by hydroxy, alkoxy having 1 to 3 carbon atoms, an amino group optionally substituted by methyl or ethyl or phenyl, optionally by Alkyl with 1 to 4 carbon atoms substituted cycloalkyl with 5 or 6 ring members or optionally with chlorine, bromine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms substituted phenyl and W for alkyl, hydroxyalkyl, carbalkoxymethyl and ß-carbalkoxyethyl with 1 to 4 carbon atoms per alkyl group, ß-cyanoethyl, ß-hydroxy-jf-chloro-, -f-methoxy- or -r-phenoxypropyl or benzyl. 3. 3-benzofurylcoumarin compounds according to claim 1, characterized 12 1 characterized in that A and A are hydrogen, R is 7-dialkylamino with 1 to 4 carbon atoms per alkyl group or the remainder of the formula .B 1 -ι (φ) (χ ^θ ) 'Λ and R is hydrogen, methoxy or ethoxy and 1 2 "5 β
B, B, Έτ, η and X have the meanings given. 4. 3-Benzofurylcoumarinverbindungen according to claim 3> thereby 2 1 characterized in that R is hydrogen and R is the remainder of the formula ¹ - ¹ CH ₂ , 1 2 stand, where B and B are alkyl with 1 to 4 carbon atoms, 1 2 ß-hydroxyethyl, benzyl or phenyl or B and B together with nitrogen a pyrrolidine, piperidine, -19- 509838/0994 O.Z. 30 "433 Form morpholine or N-Methylpiperazinresi, B "'stands for methyl, ethyl, ß-hydroxyethyl, ß-cyanoethyl or benzyl and η and Χ ^{θ have} the meaning given. 5. ^ -Benzofurylcoumarinverbindungen according to claim 1 to 4, characterized in that the anion · Χ ^θ chloride, bromide, rhodanide, sulfate, methosulfate, ethosulfate, pormate, acetate, p-toluenesulfonate, tetrachlorozincate or tetrafluoroborate. 6. Process for the preparation of 3-benzofurylcoumarin compounds according to Claim 1, characterized in that one salicylaldehydes of the formula ,1 .CHO and benzofuranacetic acid derivatives of the formula A ¹ Y-CH ₂ ^ 2 in which Y is a carboxyl group or a modified carboxyl function means reacting with one another in a manner known per se and the compounds obtained, if appropriate quaternized. 7. Use of 3-benzofurylcoumarin compounds according to Claim 1 for the optical brightening of textile fiber material made of polyamides, cellulose esters, polyesters and Acrylonitrile polymers as well as paper and as an additive to detergents. 8. Use of ^ -Benzofurylcoumarinverbindungen of formula according to claim 1, in which R is a 7-dialkylamino group -20- 509838/0994 - O.Z-. 30 433 SM stands for dyeing fibers made of synthetic polyamides and polyesters, for textile printing and for the production of daylight luminous pigments. BASF Aktiengesellschaft 50 9838/0994