DE2525986A1 - CUMARIN COMPOUNDS - Google Patents

Description

The invention relates to compounds of the formula

(D

wherein

A for oxygen, sulfur or N-Q,

B for -CO-, -SOp- or a direct bond,

D for an ortho-arylene radical,

X for the remaining members of an aromatic carbocyclic Ring system fused partially saturated heterocycle and

Q. and Y for hydrogen, alkyl, cycloalkyl, aralkyl or Aryl stand,

with the proviso that B is a direct bond when A is oxygen or sulfur, and their manufacture and use as dyes.

The new dyes of the formula I can also contain ionic groups, in particular sulfo groups, but are preferred dyes free from water-solubilizing groups.

Suitable o-arylene radicals D and the partially saturated heterocycles fused aromatic-carbocyclic ring systems

Le A 16 482

- 1 -

709818/1027

25259ö6

are in particular those of the benzene and naphthalene series, which carry substituents customary in dye chemistry can, such as alkyl, alkenyl, cycloalkyl, aralkyl, aryl, halogen, alkoxy, aralkoxy, aryloxy, cyano, Carboxy, alkylsulfonyl, aralkylsulfonyl, arylsulfonyl, Aryloxysulfonyl, arylsulfonyloxy, alkylcarbonylamino, Arylcarbonylamino, alkoxycarbonyl, carbamoyl, alkyl mercapto or aryl mercapto groups which are optionally substituted by alkyl and others more.

Suitable alkyl radicals mentioned in any context are, for example, those with 1-5 C atoms, which can preferably be _{substituted once by OH, C 1 -C 4 alkoxy, cyano, C 1} -C 4 alkoxycarbonyl or halogen, and also CF. ^.

Suitable alkenyl radicals are, for example, vinyl, allyl and butenyl.

Suitable cycloalkyl radicals are preferably cyclohexyl radicals which are substituted 1-3 times, for example by methyl or chlorine could be.

Suitable aryl radicals are above all phenyl radicals which _{can be substituted 1-4 times by halogen, C 1} -C 4 -alkyl, C ₁ -C 4 -alkyl or CN.

Suitable aralkyl radicals are, for example, phenyl-C.-Calkyl radicals, which - as described above - can be substituted in the phenyl radical.

Suitable alkoxy radicals have in particular 1-4 carbon atoms "

In addition to fluorine and bromine, halogen is primarily understood to mean chlorine.

Branched or bulky radicals ₍ such as tertiary butyl groups, for example, are in positions where they do not have any

Le A 16 482 - 2 -

709818/1027

cause steric hindrance, preferably in m- or p-position of a benzene nucleus.

Preferred compounds of the formula I correspond to the formula

D ¹ D ²

φ Χ ⁵ X ⁴ ,

B has the meaning given above,

E for 0, S, NH or NC ₁ -C ^ -alkyl,
D ¹ , D ² , D ⁵ for H, chlorine, fluorine, bromine, cyano, CF ₃ , C ₁ -C ^ -alkyl * C ₁ -C ^ -AIkOXy, phenyl - ^ - C ^ -alkyl, phenyl, cyclohexyl , Phenoxy, benzyloxy, C ₁ -C, -alkylsulphonyl, benzyl-phenyl- or toluylsulphonyl, phenoxysulphonyl, di- (C ₁ -C, -alkyl) -amino-carbonyl, di- (C ₁ -C ^ -alkyl) - amino-sulfonyl, C ₁ -C ^ -alkylamino-carbonyl, C ₁ -C ^ -alkylaminosulfonyl, -C ₁ -Cλ-alkylaminosulfonyl, C ₁ -C, -alkoxycarbonyl, carboxy, C ₁ -C ^ - Alkylcarbonylamino, C ₁ -C ^ -alkylsulfonylamino, benzoylamino, phenylsulfonyloxy or SuIfο; or - two adjacent radicals together - for o-phenylene;

Y ¹ for hydrogen or C, -C.-alkyl,

12th
X, X for H, C ^ C ^ -alkyl, C ₁ -C ^ -AIkOXy, benzyloxy, acetylamino, chlorine or together for -0-CHp-O- or o-phenylene,

XX ⁶ for hydrogen or methyl groups or X and ~ X? together for - (

Z for a direct bond, O, S, NH, N-C.-C, -alkyl or

7 I α ι M-

X'-CX ⁰ and

X ^{8 represent} hydrogen or methyl,

provided that B is a direct bond when

E means O or S.

1 ^
D and D- ^ are preferably H, chlorine or C ₁ -C,

Alkyl,

709818/1027

Le A 16 482 - 3 -

.j. 2525936

The above-mentioned alkyl radicals are preferably unsubstituted such as methyl, ethyl, n-propyl, Isopropyl, η-butyl and tertiary butyl; particularly preferred are methyl and ethyl groups.

Particularly suitable alkoxy radicals are methoxy and ethoxy.

The above applies to bulky residues such as tertiary butyl groups Said (only sterically non-hindering positions).

"1 C

The radicals X -X preferably stand for isolated radicals that are not linked to one another. The rest of B is preferred for a direct bond, or also for CO. Z means be

Y j O

preferably X-C-X "or a direct bond.

Particularly preferred meanings for E are 0, S, NH and

2 1 N - ^ - C ^ -alkyl, in particular 0 and S. The radicals X and D

are preferably hydrogen.

Particularly important compounds of the formula II are those in which

D ¹ for hydrogen, C ^ -C ^ -alkyl (especially methyl),

Chlorine, methoxy or ethoxy, 2 ι

D for a meaning of D, phenyl, benzyl, cyclohexyl or cyano, C ^ -C ^ -alkoxycarbonyl (especially C ₁ -C ₂ -alkoxycarbonyl), mono- or di- (C, -Cp) -alkylaminocarbonyl, mono- or di- (C ₁ -C ₂ ) -alkylaminosulfonyl, C ₁ -C ₂ -alkylsulfonyl, benzylsulfonyl, phenylsulfonyl, toluylsulfonyl and phenoxysulfonyl, D ^ for hydrogen,

E for 0, S, NH or NC ₁ -C ₂ -A ^ yI (especially 0 and S), B for CO or a direct bond,

Z for 0, NH, CH ₂ , CH (CH ₃ ), C (CH ₃ ) ₂ or a direct bond (especially for a direct bond as well as CH ₂ or CH (CH ₃ )),

X ¹ , X ^{2 represent} hydrogen, methyl, methoxy or ethoxy and XX represent hydrogen or methyl.

Such dyes are also preferred in which

D ₁ and D ₂ together represent o-phenylene.

709818/1027 Le A 16 482 - 4 -

The new coumarin compounds of the formula I can be prepared by adding amidinium salts of the formula

Φ ^D

{\ _ C-. NH -I ^ JJ. "-I ₀ ^An " - '

(III)

wherein

A, B, D, X and Y are as defined above and An is an anion, for example a halide ion

treated with acid-binding agents in a manner known per se (cf. DOS 2 430 980).

Suitable acid-binding agents are, for example, hydroxides, carbonates, hydrogen carbonates and acetates of ammonia and of the alkali and alkaline earth metals as well as organic bases, in particular tertiary nitrogen bases. Examples include NaOH, NaCO. ,, K ₂ CO ^, CaCO ,,, sodium acetate, ammonia, pyridine and triethylamine. The procedure is, for example, that the amidinium salts (III) are introduced into aqueous solutions of the suspensions of the acid scavengers in the temperature range from 15 ° to 70 ° C., preferably from 20 ° to 40 ° C., and stirred. The reaction can of course also be carried out in organic solvents or in mixtures of organic solvents and water. The organic solvents used here are customary polar or non-polar solvents such as lower alcohols, for example methanol, ethanol, isopropanol or ethylene glycol; Ketones, for example acetone or methyl ethyl ketone; Nitriles such as acetonitrile; Amides like formamide or dimethylformamide, ethers like dioxane or tetrahydrofuran? Chloralkanes such as chloroform or aromatic solvents such as benzene, toluene, chlorobenzene, xylene and dichlorobenzene are suitable.

The amidinium salts of the formula III are obtained, for example by using compounds of the formula

Le A 16 482 - 5 -

709818/1027

25259S6

/ Μ.

X N - C - L (IV)

X and Y have the meaning given above, L stands for a group which can be split off as an anion and An ₁ "stands for an anion,

with aminocoumarin compounds of the formula

N Λ

(V)

² "O

A, B and D have the meaning given above, condensed with elimination of HL.

The reaction temperature can be varied over a wide range. In general carried out in a temperature range of 15-9O ⁰ C, preferably 40-8O ⁰ C. It is advisable to carry out the condensation in the presence of an inert under the Reationsbedingungen solvent such as toluene, chlorobenzene, dichlorobenzene, xylene, chloroform or SuIfolan.

The groups L which can be split off are customary leaving groups, for example halides, alkyl mercapto groups or Cl ₂ PO-O-ReSt, chloride and bromide being particularly preferred.

The aminocoumarins of the formula V are known or per se known manner accessible (see German Auslegeschrift 1 098 125, 2 005 933 and 2 030 507 as well as German Offenlegungsschrift 2,334,168).

Le A 16 482 - 6 -

709818/1027

'ft

Some of the starting compounds of the formula IV are also known or with the aid of processes known per se accessible, preferably from compounds of the formula

X N-C = O (VI)

wherein

X and Y have the meaning given above.

For example, according to the procedure given in Example 6 of German Auslegeschrift 1 175 810, VI with P ₂ ^S 5 can first be converted into the corresponding thio compound and this then with alkyl halides or dialkyl sulfates, in which the alkyl radical is preferably 1- 2 C atoms, converted into compounds of the formula IV in which L is an alkyl mercapto radical as a leaving group.

Compounds of the formula IV are particularly easily accessible from those of the formula VI by reacting VI with an acid halide, as is the case for the Vilsmeier-Haack reaction (Houben-Weyl, Methods of Organic Chemistry, Volume VII / 1, page 29ff) is commonly used, such as thionyl chloride, phosphorus oxychloride, phosphorus oxybromide, oxalyl chloride or phosgene in a known manner.

Excess inorganic acid halide, with the exception of phosgene and oxalyl chloride, generally interferes with the following Reaction of IV and V does not, and it is even possible to prepare IV from VI and thionyl chloride, phosphorus oxychloride or phosphorus oxybromide in the presence of the aminocoumarin V to make. This is how you get into a drop reaction directly to the amidinium salt of the formula III. Finally, this dropping reaction can also be used, for example, in Perform excess thionyl chloride as a solvent.

The compounds of the formula VI, in turn, are also large-Le A 16 482 - 7 -

709818/1027

2525936

partly known. They are obtained by acylating compounds of the formula

X NH (VII)

wherein X has the meaning given above

with a carboxylic acid Y-COOH or its acid chloride or anhydride in the usual way.

Another process for the preparation of the new compounds of the formula I consists in that components of the formula

X N-C. (VIII)

^ --- 'I ^ OV

X and Y have the meaning given above and V is C ₁ -C ^ -AIkJrI or both V together are -CH ₂₂ or -CH ₂ -CH ₂ -CH ₂ -,

with aminocoumarin compounds of the formula V.

This condensation is carried out in a known manner (see FIG. DOS 2,430,979) in the temperature range of 70-220 ⁰ C in the presence of a high boiling inert organic solvent such as chlorobenzene, xylene, dimethylformamide, SuIfolan, N-methylpyrrolidone or anisole, optionally being the alcohol VOH formed in the reaction can be distilled off together with part of the solvent.

The compounds of formula VIII can in a known manner, for example by heating VII with orthoesters of Formula Y-C (OV), with elimination of VOH.

Le A 16 482 - 8 -

709818/1027

■ Α. 25253 2

The new compounds of the formula I are outstandingly suitable for dyeing and printing fiber materials according to the therefor usual staining methods. In particular, they are used to dye synthetic hydrophobic fiber materials such as super polyamides, Cellulose esters and aromatic polyesters either from aqueous and non-aqueous liquors or im Melt spinning process. Non-textile plastics can also be colored with the new dyes.

Very brilliant yellow dyeings with very good fastness properties are obtained.

Le A 16 482 - 9 -

7098 18/1027

example 1

15 g of 3- (5'-methylbenzoxazolyl-2 ') - 7-amino-coumarin and 9 g of N-formyl-2-methyl-indoline are in 100 ml of anhydrous Suspended chlorobenzene, added dropwise with stirring with 23 ml of thionyl chloride and heated to 75 ° C for 5 hours. To After cooling, the crystalline precipitate is filtered off, washed with toluene and petroleum ether and dried. The received Amidinium salt of the formula

1a) " ™ ' ^m ~ "

carry 10% in 300 g. Ammonia solution, stirred 30 Minutes, sucks off the crystalline precipitate, washes it with water and crystallizes it first from ethyl glycol monomethyl ether (1.2 1), then from toluene (300 ml) using Tonsil as a clarifying agent. 12.6 g of compound are obtained the formula

ν ι * i - CH = N

Dyed on polyester (pH6), the result is a brilliant, green-tinged, fluorescent yellow coloration with a more good color Fastness to light and sublimation. In addition, the dye is characterized by very good drawability on polyester fiber material the end.

Similar valuable properties are shown by those listed in the following table, which are produced in an analogous manner Dyes of the formula

Le A 16 .482 - 10 -

709818/1027

4 rw IA (-j

Le A 16 482 - 11 -

709818/1027

₈ wr "5 ν '^ - -w ⁴

1 , NC = N

\ -: ^/ γ

/ Nv

P w ¹⁰

Ö Φ Ο-Ρ ■ Ρ W

P ω,

CdH
Cn o

O • Η Λ O • Η -P CQ gp: 3 η Jh Φ H
Φ
bO

H
CD
U

-P

€ 2525936

boo

• Η

EE ο ο

ΕΕ

EEE

ι E ^
O I. ι Ε ⁰ "
ο O E. E. E. E ^
O E. E. E ^
CM
O
O H
O ro
E.
ο E. E. E.

ro
E.

OE

'ro

ε ' ο

ro
OE

E.
O

"ε ο

E.
O

EE

ro E O E

ro ro E E

ro E ο Ε

ro E

ro ro
EE
OOEE

to

i-r-i

OEE

ö ο E ο E ο

CM

ro S E R ro ro

E E

ro ro ro
EEE

EOOEOOOE

ro ro ro

EOEEEEEEEEEOEOE

EOEEEEEEEE cm

ro

ro cm E O

rl r- \ π ' CM O U

O G

EO "O pq CQ ro
E.
O

ro ro
E fa

OOE ^ ο " -

O N ΐΜ CM

Ö O O

φ CQ CQ

EEEEEEEEEEEE

ro E o

v_ ^

E O

E E

EE

OEEOEEEEOOEEOEE O E

ro E ο Ε

ro ro EE ο ο

ro E E O

EEEE EE

ro
EEEEEEEEOEEEEEE EE

* 8th%

O O O

EEEE

E ⁰¹

EEEEEEEOEEEEEEE EE

i I I I I I I I I I I I I I> ''

OOOOOOOOOOOOOOO OO

cm ro <t · in vo o- co

Le A 16

- 12 709818/1027

tH NO.EBYW ¹ ¥ ² W ³ ¥ ^ ¥ ⁵ ¥ ⁶ w ⁷ W ⁸ ¥ ⁹ ¥ ¹ ° Z hue φ

polyester

!>. ι ι ι ι

c * 19 0 - HH SO _Q -CrH _K H HH HHHHH - greenish tint

^ 2 6 5 _yellow

το 20 O - HH SOg ^ H ₂ C ₆ H ₅ HHH - (CHg) ₄ - HHH - "

21 0 - HH CONH-C ₅ H- HHH _C H CH CH ^HH ""

έ D 3 3 3

22 S - H H H HHHHH H H CHg "

23 S - CH ₃ HH OCgH ₅ H CH ₃ CH ₃ HHHH CH (CH ₃ ) "

24 NCH ₃ - HH Cl H HH CH ₃ HHHH- "

25 NH CO HHHH · Η H CH ₃ CH ₃ CH ₃ OCH ₃ H- »

26 NH SOo HH HH HH HHHHH CH ₉ "*

² ^

* 4

CO OO

• «4

CJI UD

cn

25259 ^ 6

Example 27 . Yes

21g N-formyl -2.2.4- trimethyl-1,2,3,4-tetrahydroquinoline is dissolved in 200 ml of anhydrous chlorobenzene, mixed with 18 g of thionyl chloride and heated for 2 hours at 50 ⁰ C, and escapes. ₉ Then 36 g of 3 (5'-phenylbenzox-

ο azolyl-2 ') - 7-aminocoumarin added and heated to 80 C for 6 hours, whereby HCl escapes. After cooling, the amidinium salt obtained is filtered off with suction and washed with toluene and petroleum ether and dried, in 500 ml of 10%. Ammonia solution entered and stirred for 30 minutes. The crystalline precipitate is filtered off with suction, washed with water and in the process described in Example 1 cleaned properly. 42 g of compound are obtained formula

It shows very good lightfast and sublimation-fast greenish yellow fluorescent colorations on polyester.

Example 28

23.5g of 1-diethoxymethyl-2-methyl-indoline and 32.3g of 3- (5'-chlorobenzoxazolyl-2 ^! ) -7-amino-coumarin are heated to boiling in 130 ml of N-methylpyrrolidone for 8 hours while the ethanol formed is distilled off. Then ml of solvent are distilled 70 from, the mixture is cooled to 60 ° C, it was stirred with 250 ml of ethanol, cooled to 15 ° C, aspirated and the crystalline precipitate off, washed with 50 ml of ethanol and dried at 70 ⁰ C in Vacuum. 39 g of compound of the formula are obtained

Le A 16 482 - 14 -

709818/1027

CIt IJ X /

N-CH-N

The compound dyes polyester fibers (pH6) in a brilliant, greenish yellow shade with very good sublimation and lightfastness. 1-diethoxymethyl-2-methyl-indoline can be obtained by 12 hours of heating of 133g 2-methylindoline and 330 ml Orthoameisensauretriäthylester to 145 C while distilling off ethanol and subsequent fractional distillation under vacuum (bp _{2146 to 148} ° C).

Le A 16-482

709818/1027

Claims (1)

Patent claims: 1) Curaarin compounds of the formula σ ^ ₀ ? ^ y ~ i ... ρ Ρ A for oxygen, sulfur or N-Q, for -CO-, -SOp- or a direct bond, D for an ortho-arylene radical, X for the remaining members of an aromatic carbocyclic Ring system fused partially saturated heterocycle and Q and Y for hydrogen, alkyl, cycloalkyl, aralkyl or Aryl stand, with the proviso that B is a direct bond, if: Λ Means oxygen or sulfur. Coumarin compound according to Claim 1 of the formula _D 1 «2 wherein B for -CO-, -SO ₂ - or a direct bond E for 0, S, NH or NC.-C, -alkyl, D, D, D- for H, chlorine, fluorine, bromine, cyano, CF ₃ , C ₁ -C ^ -alkyl, Le A 16 482 - 16 - 709818/1027 ORIGINAL INSPECTED C ₁ -C ₄ -AIkOXy, phenyl - ^ - C ^ -alkyl, phenyl, cyclohexyl, phenoxy, benzyloxy, C ₁ -C ^ -alkylsulphonyl, benzyl-, phenyl- or toluylsulphonyl, phenoxysulphonyl, di- (C ₁ -C ₄ - alkyl ) -amino-carbonyl, di- (C ₁ -C ^ -alkyl) -amino-sulfonyl, C ₁ -C - alkylamino-carboriyl, Cj-C ^ -Alkylaminosulfonyl, C ₁ -C ^ -alkoxycarbonyl, carboxy, Cj-C ^ -Alkylca-'bonylamino, C ₁ -C ^ -Alkylsulfonylamino, Benzoylamino, Phenylsulfonyloxy or SuIfο; or - two adjacent radicals together - for o-phenylene; Y ¹ for hydrogen or C ₁ -C, -alkyl, 12th
X, X for H, C ₁ -C ₄ -AlRyI, C ₁ -C ₄ -AlkOXy, benzyloxy, acetylamino, chlorine or together for -0-CHp-O- or o- Phenylene,
XX for hydrogen or methyl groups or X and X common for - (CHp) ₄ -,
Z for a direct bond, O, S, NH, NC.-C, -alkyl or X ' -CX ⁰ and
X ', X stand for hydrogen or methyl, provided that B is a direct bond when E means 0 or S. 3) coumarin compounds according to claim 2, wherein D ¹ and D ^{3 represent} H, chlorine or C 1 -C 4 alkyl. 4) coumarin compounds according to claim 2 or 3, which are free from Sulpho groups and / or o-phenylene radicals, the two adjacent 1 3
Residues of groups D -D can form with one another, are. 5) coumarin compounds according to claim 2, wherein 1
D for hydrogen, C ₁ -C _Zi -alkyl, Chlorine, methoxy or ethoxy, D for a meaning of Dl, phenyl, benzyl, cyclohexyl or cyano, C ₁ -C ₄ -alkoxycarbonyl, mono- or di- (C ₁ -C ₂ ) - Le A 16 482 - 17 - 709818/1027 alkylaminocarbonyl, mono- or di- (C ₁ -C ₂ ) -alky] nniinosulfonyl, C ₁ -C ₂ -AlkVlSulfOHyI, benzylsulfonyl, phenylsulfonyl, Toluy, sulfonyl and phenoxysulfonyl, Tr for hydrogen, E for O, S, NH or NC ₁ -C _£ -alkyl, B for CO or a direct bond, Z for O, NH, CH ₂ , CH (CH ^), C (CH ^) ₂ or a direct bond, for hydrogen, methyl, methoxy or ethoxy and X-X represent hydrogen or methyl. 6) coumarin compounds according to claim 1 of the formula - CH = N J 7) coumarin compounds according to claim 1 of the formula CH ₃ - CH = N-- Cl 8) coumarin compounds according to claim 1 of the formula Cl Le A 16 482 - 18 - 7 0 9 3 1 S '1 P 2 7 2525936 9) Process for the preparation of coumarin compounds according to claim 1, characterized in that amidinium salts are used the formula . i'J ^ -C-. NH - ^. ₀ .- -, _Ό Y wherein A, B, D, X and Y have the meaning given in claim 1 and ArP stands for an anion, with acid binding agents treated. 10) Process for the preparation of coumarin compounds according to claim 1, characterized in that compounds of the formula X N- C '.'
^ - ^) ~ ^ 0V Y wherein X and Y have the meaning given in claim 1 and V is C ₁ -C ^ -AIkYl or both Y together are -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -, with aminocoumarins of the formula wherein A, B and D have the meaning given in claim 1. Le A 16 482 - 19 - 709818/1027 11) processes for dyeing, printing or mass dyeing fiber materials or thermoplastics, characterized in that dyes according to Claim 1 are used. Le A 16 482 - 20 - 709818/1027