Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
'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
/ 1 1
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
NH2
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
R4-
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 -
.
CN NH2
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
~ ~ '
-- 4 --
CH3
,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~ ',
CN CH2
N = ~ - N~CH2CH3)2
11 1
O ~ .
The dyestuff dyes polyester golden yellow with good fastness to light and
sublimation.
5 -
,' ~
.
';
-~ . . , ~ -
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
CN NCH3
\ 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
~` _ ... .. _ ._ . _ _ .: .
;.
. .. .
'~
.. ... .... ~. . .......... ..... - ....... . .. ,.. , ~ . ...... ...
