CA1061784A - Disperse dyestuffs - Google Patents
Disperse dyestuffsInfo
- Publication number
- CA1061784A CA1061784A CA313,664A CA313664A CA1061784A CA 1061784 A CA1061784 A CA 1061784A CA 313664 A CA313664 A CA 313664A CA 1061784 A CA1061784 A CA 1061784A
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- Canada
- Prior art keywords
- parts
- formula
- volume
- cyano
- filtered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Abstract of the Disclosure The present invention pertains to novel intermediates useful in the preparation of novel dyestuffs. The novel intermediates of the present invention are 2-cyano-3-amino-benzanthrones of the formula
Description
'7~
The present patent application is a divisional from copending Canadian application serial number 203,450 filed June 26, 1974 which discloses dyestuffs of the formula (I) _ _ IR ~Rl F _ N=C N (I) R2 n wherein F represents a ring system with at least 3 rings which are angularly condensed with one another, n is 1, 2 or 3, and R, Rl and R2 represent option-ally substituted alkyl groups which can be interrupted by heteroatoms and also represent cycloalkyl, aralkyl, aryl or heterocyclic radicals, R and Rl can also represent hydrogen atoms, Rl and R2, together with the nitrogen atom, are able to form a ring with 5 or 6 members, and R and R2 can combine to form a nitrogen-containing heterocycle.
~, ,.
The dyestuffs according to copending Canadian application serial number 203,450 can be manufactured a) from the amidinium salts of the formula p~ N~ I (anion)D
wherein F, R, Rl, R2 and n have the same meanings as given hereinbefore, by reaction with a base to yield the dyestuffs of the formula r I Rll F ~ R2 ¦ n or b) by reaction of dyestuffs containing primary amino groups of the formula F ~NH2)n ~ :
', , ~, ~;'' .
. . .- - . . . . .. . . . . . . . .
., . . . : . , .. "
. .. ,. . :, .
~1~61'7~4 with n moles of an amidacetal of the formula R~O 7 /Rl C N
R'O R2 according to the reaction scheme R'O\ IR ~ 1 -~~ 2)n C - N >
R'O R2 F t N=C N\ ~ ~ 2n R'OH
As starting materials for the manufacture of the amidine dyes it is possible to use e.g. the dyestuffs with amidinium groups which are de~
scribed in Belgian patent 657 303.
The present invention provides a starting material useful in the above noted reaction for the preparation of the novel dyestuffs disclosed 10 and claimed in copending Canadian application serial no. 203,450 filed June `t 26, 1974.
.~ .
The present invention provides 2-Cyano-3-amino-benzanthrones of the formula CN
4 ~ ~ ~
', .
~herein R4 represents a halogen atom, a lower alkyl group or a hydrogen atom; 2-cyano-3-amino-benzanthrone beinB particularly preferred.
' .
:' .
- ~ , . , . :,,, : ., : :
. ., .. , . , : .: . : : .
:: : . .
7~
The compounds of this invention may be rnanufactured by reacting a vinylidene compound of formula CHCN)2 with a Friedel-Crafts reagent.
In a preferred embodiment, the vinylidene compound is of formula C(CN)2 CH
~3 such that 2-cyano-3-amino-benzanthrone is formed as product.
The present invention will be more fully illustrated by the follow-ing example, wherein the parts and percentages are by weight unless other-wise specified.
Manufacture of 2-c~ano-3-amino-benzanthrone 927 parts of anthracene-9-aldehyde are suspended in 4.2 litres of ethanol. The suspension is treated with 10 parts by volume of piperidine - and at about 45C over the course of one hour with 310 parts of malonic acid , dinitrile in 400 parts by volume of ethanol.
The orange suspension is stirred for 2 hours at 70 C and subse-quently cooled to 5 - 10 C. The suspension is ~iltered with suction and the residue is washed with 500 parts by volume of ethanol and dried in vacuo at 90 - 100 C to yleld 1077 parts of the intermediate of the formula CH=C(CN)2 @~
~ .
:~, X
. .
- - ,. . . ", . , , - : , - - . , , , , , . , , ' ", .: ',.. .. : : :, , ,, : ' :
- . . ~ ............ . , ; . : : .
7~
254 parts of the resulting interrnediate are finely suspended in ~,75 litres of dry benzene. At room temperature, 320 parts of anhydrous a,luminium chlo-ride are added thereto over the course of about 2 hours. The green suspen-sion is heated to 80 C over the course of 45 minutes, stirred for 15 minutes at this temperature and then allowed to cool to 10 C. The benzene is de-canted off from the viscous mass and the residue is poured onto 7 kg of ice.
The agueous suspension is stirred for 8 hours at room temperature. The suspension is filtered off and the residue is washed neutral with about 2 litres of water and dried in vacuo at 105C to yield 254 parts of 2-cyano-3-aminobenzanthrone.
The compounds of the formula '' ~ - 3a -.
R4 ~
wherein R4 represents a halogen atom, a lower alkyl group or hydrogen, are ordinarily accessible by reaction of the vinylidene compounds of the formula C(CN)2 4 i = ~
~ith Friedel-Crafts reagents, wherein treatment is effected in inert solvents such 8S benzene, nitrobenzene or carbon disulphide at -20C to 150C, prefer-ably at 0C to 100C, with ferric trichloride, boron trifluoride, boron tri-fluoride etherate or preferably aluminium chloride, and processing is carried ` out in the conventional manner. -The compounds of the present invention are characterized by prepar-ing the following derivatives having the specified characteristics.
Reference Example 1 3 parts by volume of phosphoroxy chloride are added dropwise to a suspension of 2.7 parts of 2-cyano-3-aminobenzanthrone in 10 parts by volume of N,N-diethylbutyric acid amide. The mixture is then stirred for 80 minutes at 60C, cooled, and treated with 100 parts by volume of benzene. The result-ing precipitate is filtered off with suction, washed with benzene and dried.
The amidine hydrochloride is given to a 10% ammonia solution, and the mixture is thoroughly stirred, then filtered with suction and the residue is dried.
Recrystallisation from ethanol yields 2.2 parts of dyestuff (melting point 170&) of tho for ulu ~ ~ ' ,H2 , .
CN N = C - N ~ 2 3 ~ ~/ ~CH2CH3 which dyes polyester fibres golden yellow with good light fastness.
Reference Example 2 3 parts by volume of phosphoroxy trichloride are added dropwise at room temperature to a suspension of 4.1 parts of 2-cyano-3-aminobenzanthrone in 15 parts by volume of phenylacetic acid diethyl amide. The mixture is then heated to 60& , stirred for 80 minutes at this temperature, then cooled, treated with 80 parts by volume of benzene and the resulting crystalline pre-cipitate is filtered off with suction. The precipitate is washed with benzene 10and then dried by suction. The residue is given to 100 parts by volume of 10%
ammonia solution, the mixture is thoroughly stirred and filtered with suction.
Recrystallisation from ethanol yields 4.4 parts of dark crystals which melt at 212& and constitute the dyestuff of the formula ' ' `` 1~ ', N = ~ - N~CH2CH3)2 O ~ .
The dyestuff dyes polyester golden yellow with good fastness to light and sublimation.
,' ~
.
';
-~ . . , ~ -Reference Examplé 3 6 parts by volume of phosphoroxy trichloride are added dropwise at room temperature to a suspension of 5.4 parts of 2-cyano-3-aminobenzanthrone in 20 parts by volume of N-methylpyridone. The mixture is subsequently stirred for 1 hour at 35C, then treated with 100 parts by volume of benzene and sub-sequently filtered with suction. The residue is washed with benzene and dried.
The greenish amidine hydrochloride is given to 100 parts by volume of 10%
ammonia, the mixture is thoroughly stirred, filtered with suction and the resi-due is washed with water. Recrystallisation from ethanol yields 5.4 parts of a light brown powder which melts at 233 - 234C and has the formula \ CH2 ~ 2 ~0~
The dyestuff dyes polyester fibres golden yellow with good fastness to light.
Refe~è~ce Examplè 4 0.9 part of 1-formyl-1,2,3,4-tetrahydroquinoline is added at room temperature to 1.4 parts of 2-cyano-3-aminobenzanthrone in 40 parts by volume of thionyl chloride. The mixture is stirred for 2 hours, then filtered off at room temperature and the residue is washed with benzene. The dried residue is given to 10% ammonia solution, the mixture is thoroughly stirred, filtered with suction and the residue is dried, yielding 1.7 parts of a dyestuff of the fo~mula - .. .. . : . - .: .
10ti1~7~
CN ~) ~ N=CH-N~
which dyes polyester fibres yellow with very good fastness to light.
Reference Example 5 1.1 parts of 1-formyl-2,3,3-trimethylindoline are added at room temperature to 1.4 parts of 2-cyano-3-aminobenzanthrone in 40 parts by volume of thionyl chloride. The procedure as described in Example 5 is carried out.
Yield: 2.2 parts of a dyestuff of the formula ` ~ ,' ~"' " ~ ~CH
O
which dyes polyester fibres yellow with good fastness to light.
Rèfcrc~o Ex~nplè 6 5 parts by volume of phosphoroxy chloride are added dropwise to a suspension of 2.7 parts of 2-cyano-3-amimo-benzanthrone and 2.7 parts of acetanilide in 50 parts by volume of toluene. The mixture is stirred at loo&
for 30 minutes, then cooled, filtered, and the product is washed with toluene.
The residue is given to 10% ammonia solution, thoroughly stirred filtered with suction and dried. Recrystallisation from dimethyl formamide yields 1.8 parts of a dyestuff of the formula .
~, .
., '. ' ~ - . - . - , . : -CN U=C-NH ~
~S~
which dyes polyester fibres greenish yellow.
The dyestuffs listed in the following Table la of the general formula CN R
' O
; are obtained in analogous manner.
TABLE la No. _ 2 Shade on polyester ~ ~ ~ :
1 C2H5 C6H5 greenish yellow ~ -
The present patent application is a divisional from copending Canadian application serial number 203,450 filed June 26, 1974 which discloses dyestuffs of the formula (I) _ _ IR ~Rl F _ N=C N (I) R2 n wherein F represents a ring system with at least 3 rings which are angularly condensed with one another, n is 1, 2 or 3, and R, Rl and R2 represent option-ally substituted alkyl groups which can be interrupted by heteroatoms and also represent cycloalkyl, aralkyl, aryl or heterocyclic radicals, R and Rl can also represent hydrogen atoms, Rl and R2, together with the nitrogen atom, are able to form a ring with 5 or 6 members, and R and R2 can combine to form a nitrogen-containing heterocycle.
~, ,.
The dyestuffs according to copending Canadian application serial number 203,450 can be manufactured a) from the amidinium salts of the formula p~ N~ I (anion)D
wherein F, R, Rl, R2 and n have the same meanings as given hereinbefore, by reaction with a base to yield the dyestuffs of the formula r I Rll F ~ R2 ¦ n or b) by reaction of dyestuffs containing primary amino groups of the formula F ~NH2)n ~ :
', , ~, ~;'' .
. . .- - . . . . .. . . . . . . . .
., . . . : . , .. "
. .. ,. . :, .
~1~61'7~4 with n moles of an amidacetal of the formula R~O 7 /Rl C N
R'O R2 according to the reaction scheme R'O\ IR ~ 1 -~~ 2)n C - N >
R'O R2 F t N=C N\ ~ ~ 2n R'OH
As starting materials for the manufacture of the amidine dyes it is possible to use e.g. the dyestuffs with amidinium groups which are de~
scribed in Belgian patent 657 303.
The present invention provides a starting material useful in the above noted reaction for the preparation of the novel dyestuffs disclosed 10 and claimed in copending Canadian application serial no. 203,450 filed June `t 26, 1974.
.~ .
The present invention provides 2-Cyano-3-amino-benzanthrones of the formula CN
4 ~ ~ ~
', .
~herein R4 represents a halogen atom, a lower alkyl group or a hydrogen atom; 2-cyano-3-amino-benzanthrone beinB particularly preferred.
' .
:' .
- ~ , . , . :,,, : ., : :
. ., .. , . , : .: . : : .
:: : . .
7~
The compounds of this invention may be rnanufactured by reacting a vinylidene compound of formula CHCN)2 with a Friedel-Crafts reagent.
In a preferred embodiment, the vinylidene compound is of formula C(CN)2 CH
~3 such that 2-cyano-3-amino-benzanthrone is formed as product.
The present invention will be more fully illustrated by the follow-ing example, wherein the parts and percentages are by weight unless other-wise specified.
Manufacture of 2-c~ano-3-amino-benzanthrone 927 parts of anthracene-9-aldehyde are suspended in 4.2 litres of ethanol. The suspension is treated with 10 parts by volume of piperidine - and at about 45C over the course of one hour with 310 parts of malonic acid , dinitrile in 400 parts by volume of ethanol.
The orange suspension is stirred for 2 hours at 70 C and subse-quently cooled to 5 - 10 C. The suspension is ~iltered with suction and the residue is washed with 500 parts by volume of ethanol and dried in vacuo at 90 - 100 C to yleld 1077 parts of the intermediate of the formula CH=C(CN)2 @~
~ .
:~, X
. .
- - ,. . . ", . , , - : , - - . , , , , , . , , ' ", .: ',.. .. : : :, , ,, : ' :
- . . ~ ............ . , ; . : : .
7~
254 parts of the resulting interrnediate are finely suspended in ~,75 litres of dry benzene. At room temperature, 320 parts of anhydrous a,luminium chlo-ride are added thereto over the course of about 2 hours. The green suspen-sion is heated to 80 C over the course of 45 minutes, stirred for 15 minutes at this temperature and then allowed to cool to 10 C. The benzene is de-canted off from the viscous mass and the residue is poured onto 7 kg of ice.
The agueous suspension is stirred for 8 hours at room temperature. The suspension is filtered off and the residue is washed neutral with about 2 litres of water and dried in vacuo at 105C to yield 254 parts of 2-cyano-3-aminobenzanthrone.
The compounds of the formula '' ~ - 3a -.
R4 ~
wherein R4 represents a halogen atom, a lower alkyl group or hydrogen, are ordinarily accessible by reaction of the vinylidene compounds of the formula C(CN)2 4 i = ~
~ith Friedel-Crafts reagents, wherein treatment is effected in inert solvents such 8S benzene, nitrobenzene or carbon disulphide at -20C to 150C, prefer-ably at 0C to 100C, with ferric trichloride, boron trifluoride, boron tri-fluoride etherate or preferably aluminium chloride, and processing is carried ` out in the conventional manner. -The compounds of the present invention are characterized by prepar-ing the following derivatives having the specified characteristics.
Reference Example 1 3 parts by volume of phosphoroxy chloride are added dropwise to a suspension of 2.7 parts of 2-cyano-3-aminobenzanthrone in 10 parts by volume of N,N-diethylbutyric acid amide. The mixture is then stirred for 80 minutes at 60C, cooled, and treated with 100 parts by volume of benzene. The result-ing precipitate is filtered off with suction, washed with benzene and dried.
The amidine hydrochloride is given to a 10% ammonia solution, and the mixture is thoroughly stirred, then filtered with suction and the residue is dried.
Recrystallisation from ethanol yields 2.2 parts of dyestuff (melting point 170&) of tho for ulu ~ ~ ' ,H2 , .
CN N = C - N ~ 2 3 ~ ~/ ~CH2CH3 which dyes polyester fibres golden yellow with good light fastness.
Reference Example 2 3 parts by volume of phosphoroxy trichloride are added dropwise at room temperature to a suspension of 4.1 parts of 2-cyano-3-aminobenzanthrone in 15 parts by volume of phenylacetic acid diethyl amide. The mixture is then heated to 60& , stirred for 80 minutes at this temperature, then cooled, treated with 80 parts by volume of benzene and the resulting crystalline pre-cipitate is filtered off with suction. The precipitate is washed with benzene 10and then dried by suction. The residue is given to 100 parts by volume of 10%
ammonia solution, the mixture is thoroughly stirred and filtered with suction.
Recrystallisation from ethanol yields 4.4 parts of dark crystals which melt at 212& and constitute the dyestuff of the formula ' ' `` 1~ ', N = ~ - N~CH2CH3)2 O ~ .
The dyestuff dyes polyester golden yellow with good fastness to light and sublimation.
,' ~
.
';
-~ . . , ~ -Reference Examplé 3 6 parts by volume of phosphoroxy trichloride are added dropwise at room temperature to a suspension of 5.4 parts of 2-cyano-3-aminobenzanthrone in 20 parts by volume of N-methylpyridone. The mixture is subsequently stirred for 1 hour at 35C, then treated with 100 parts by volume of benzene and sub-sequently filtered with suction. The residue is washed with benzene and dried.
The greenish amidine hydrochloride is given to 100 parts by volume of 10%
ammonia, the mixture is thoroughly stirred, filtered with suction and the resi-due is washed with water. Recrystallisation from ethanol yields 5.4 parts of a light brown powder which melts at 233 - 234C and has the formula \ CH2 ~ 2 ~0~
The dyestuff dyes polyester fibres golden yellow with good fastness to light.
Refe~è~ce Examplè 4 0.9 part of 1-formyl-1,2,3,4-tetrahydroquinoline is added at room temperature to 1.4 parts of 2-cyano-3-aminobenzanthrone in 40 parts by volume of thionyl chloride. The mixture is stirred for 2 hours, then filtered off at room temperature and the residue is washed with benzene. The dried residue is given to 10% ammonia solution, the mixture is thoroughly stirred, filtered with suction and the residue is dried, yielding 1.7 parts of a dyestuff of the fo~mula - .. .. . : . - .: .
10ti1~7~
CN ~) ~ N=CH-N~
which dyes polyester fibres yellow with very good fastness to light.
Reference Example 5 1.1 parts of 1-formyl-2,3,3-trimethylindoline are added at room temperature to 1.4 parts of 2-cyano-3-aminobenzanthrone in 40 parts by volume of thionyl chloride. The procedure as described in Example 5 is carried out.
Yield: 2.2 parts of a dyestuff of the formula ` ~ ,' ~"' " ~ ~CH
O
which dyes polyester fibres yellow with good fastness to light.
Rèfcrc~o Ex~nplè 6 5 parts by volume of phosphoroxy chloride are added dropwise to a suspension of 2.7 parts of 2-cyano-3-amimo-benzanthrone and 2.7 parts of acetanilide in 50 parts by volume of toluene. The mixture is stirred at loo&
for 30 minutes, then cooled, filtered, and the product is washed with toluene.
The residue is given to 10% ammonia solution, thoroughly stirred filtered with suction and dried. Recrystallisation from dimethyl formamide yields 1.8 parts of a dyestuff of the formula .
~, .
., '. ' ~ - . - . - , . : -CN U=C-NH ~
~S~
which dyes polyester fibres greenish yellow.
The dyestuffs listed in the following Table la of the general formula CN R
' O
; are obtained in analogous manner.
TABLE la No. _ 2 Shade on polyester ~ ~ ~ :
1 C2H5 C6H5 greenish yellow ~ -
2 C3H7 _ " .. " .
3 C2H5 -CH2-C6H5 ., .l ~` _ ... .. _ ._ . _ _ .: .
;.
. .. .
'~
.. ... .... ~. . .......... ..... - ....... . .. ,.. , ~ . ...... ...
;.
. .. .
'~
.. ... .... ~. . .......... ..... - ....... . .. ,.. , ~ . ...... ...
Claims (2)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. 2-Cyano-3-amino-benzanthrones of the formula wherein R4 represents a halogen atom, a lower alkyl group or a hydrogen atom.
2. 2-Cyano-3-amino-benzanthrone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA313,664A CA1061784A (en) | 1973-06-29 | 1978-10-18 | Disperse dyestuffs |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH950373A CH572083A5 (en) | 1973-06-29 | 1973-06-29 | |
| CA203,450A CA1051426A (en) | 1973-06-29 | 1974-06-26 | Disperse dyestuffs |
| CA313,664A CA1061784A (en) | 1973-06-29 | 1978-10-18 | Disperse dyestuffs |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1061784A true CA1061784A (en) | 1979-09-04 |
Family
ID=27163523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA313,664A Expired CA1061784A (en) | 1973-06-29 | 1978-10-18 | Disperse dyestuffs |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1061784A (en) |
-
1978
- 1978-10-18 CA CA313,664A patent/CA1061784A/en not_active Expired
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