CA1120472A

CA1120472A - Process for the production of vat dyes and use thereof

Info

Publication number: CA1120472A
Application number: CA000307288A
Authority: CA
Inventors: Athanassios Tzikas
Original assignee: Individual
Current assignee: BASF Schweiz AG
Priority date: 1977-07-15
Filing date: 1978-07-13
Publication date: 1982-03-23
Also published as: FR2397441A1; GB2001093B; BR7804544A; LU77773A1; ES471713A1; JPS5420040A; FR2397441B1; DE2830881A1; BE868990A; GB2001093A; IT7850258A0; CH637413A5

Abstract

ABSTRACT OF THE DISCLOSURE
A process for which the production of vat dyes of the formula (1) , wherein R is an alkylene radical of 1 to 6 carbon atoms which can be substituted by halogen, hydroxy or phenyl, an alkenylene radical of 1 to 6 carbon atoms or a phenly-lene radical, and the radical R can form 1 to 3 ring members between the two oxygen atoms, which process com-prises reacting the compound of the formula

Description

The present i.nvention relates to a process for the production of vat dyes of the formula ~: "' '`', ' t)~3 ' 1~~

wherein R is an alkylene radical o~ 1 to 6 carbon atoms which can be substituted by halogen, hydroxy or phenyl~ an alkenylene radical of 1 to 6 carbon atoms or a phenylene radical, and the radical R can form l to 3 ring members~
between the two oxygen atoms, which process comprises reacting the compound of the formula . ., . , , . . , . . .. , .. , . . .. ...... , .. . .. . , , . , . .. . , ., . , .. , ., ,. .:, , .. , .. ,.,.. ,., ., ., ., ,. ,. ._, .... .. . .............
' ` ' ' '' 7~

' 1~o~l, ~ ', o~3 in aprotic dipolar solvellts selected from the group con-sisting of sulfolane, N-methyl-2-pyrrolidone, hexamethyl-phosphoric triamide, dimethyl sulphoxide, dimethyl forma-mide, dimethyl acetamide, diethyl acetamide, acetonitrile and tetramethyl urea, with compounds o~ the formula X - R - X (3), wherein X is halogen and R is as defined in formula (I), in the presence of bases, at elevated temperature.
The alkylene radicals R can be straight~chain or bran~hed. If R is substituted by halogen, possible halogen substituents are fluorine, chlorine and bromine atoms. Preferably R is the ethylene radical.
. - As examples of R there may be cited:

-CH2-~ -CF2-, CC12-, -CBr~-, -CH~CH2-,-CH2-CH-, -CH - CH-, ~H~ CH3 CH3 -~=C-, -CH2-C-CH2~ -CH2-cH2-c~2 , ~H2 CH 2 ~ H
-CH~-CH2-CH~

¢~ .

()4~'~

Halogen atoms in the compo-mds of the formula (3) can be fluorine, chlorine and bromine atoms.
The starting compound of the formula (2), dihy-droxyviolanthrone, is known . Compounds of the form~lla (3), wherein R has the above meanings, are also known. Examples of such compounds are: dichloromethane, tr:ichloromethane, tetrachloromethane, 1,1 dichloroethane, 1,2-dichloro-ethane~ 1,1,2-trichloroethane, 1,2-dichloroethylene, 1,1-, 1;2-, 1,3- and 2,2-dichloropropane a 1,2,3-trichloropropane, 1,3-dichloro-1 propene, 2,3-dichloro-1-propene, 1,1-, 1,2-, 1,3-, 2,2- and 2,3-dichlorobutane, 3,4 dichloro-l-butene,

2,2-dichloroethanol, 2,3-dichloro l-propanol, 1,3-dichloro-2-propanol, dibromomethane, chlorobromomethane, tribromo-methane, te~rabromomethane~ dichlorodibromomethane, tri-chlorobromomethane, l,l-dibromoethane, 1,2-dibromoethane, l,l-, 1,2- and 1,3-dibromopropane, 1,1-, 1,2-, 1,3-~ 2,2-and 2,3-dibromobutane, 1,2-dibromoethanol, 2,2-dibromo-ethanol, 1,3-dibromo-2-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-2-butanol, 2,3-dibromo-l-butanol, 3,4-dibromo-l-butanol, difluoromethane, tri1uoromethane, tetrafluor-methane, trifluorochlormethane, dichlorodifluoromethanc, chlorotrifluoromethane, dichlorofluoromethane, chloro-difluoromethane, trifluorobromomethane, difluorochloro-bromomethane, l,l-difluoroethane, penta1uoroethane, hexa-fluoroethane, tetrachloro-1,2-difluoroe~hane, 1,2~dichloro-l,l-di-fluoroethane, tetrafluoroethylen, a,a-dichlorodi-phenylmethane, 1,2-dichloro-1,2-diphenylethane, 1,2-dibro-mo-1,2-diphenylethane, benzal chloride, benzal bromide, 1~2-dichlorobenzene, 1,3-dichlorobenzene, 1,2-dibromo-benzene and 1,3-dibromobenzene.
Sulpholane, N-methyl-2-pyrrolidone or hexa-methylphosphoric triamide are preferably used as ap.rotic dipolar solvents.

. . .
:

9L7~:

.

As bases there may be mentioned: sodium hydro-xide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, potassium hydrogen carbonate, potassium formiate, sodium propionate, potassium phosphate etc. Pre-ferred bases are sodium carbonate, potassium carbonate or sodium acetate.
To shorten the reaction times, the reaction of the present invention is carried out at elevated te~peratu-re, i.e. above room temperature. Preferably the reaction is carried out in the temperatu~ range between 100 and The reaction is carried out in a manner which is in itself known in closed reaction vessel and under re-1ux etc., if necessary~ under pressure in an autoclave.
The working up of the reaction mixture also is effected in a manner which is in itsel known.
Ethylene chloride is preferably used as compound of the formula (3).
The vat dyes of the formula (1) give blue (navy blue) shades; but if R is a methylene or substituted methy-lene group, the shades are red, and if R has 3 ring members (e.g. propylene, methylpropylene), greenish shades are obtained The dyes have a very good build-up and exhaustion capacity and the dyeings obtained with them are distin-guished by good fastness properties.
The preferred vat dye of the formula (1), wherein R is ethylene, gives a clear unitary navy blue shade. It is also distinguished by a good build-up and exhaustion capaci-ty and, in particular, by the very good fastness to water-spotting of the dyeings obtained with it.
Compared with the prior art (~IOS 987, 70, US
patent specifications 1,531,261, 1,761,624, 1,950~366, 2,218,663, 2~318,663, 2,318,266, 2,662,892 and 3,036,095~, ,, , . ,~. , . ,.. . . ,.. .......... ,.. ,.. - ....

.

the process of the present inventlon is distinguished by the fact that it makes possible shorter reaction times, the use of simpler apparatus, and lower reaction temperatures.
The process of the present invention, which is carried out with dihydroxyviolanthrone and ethylene chlo-ride as starting materials, constitutes the simplest and cheapest method of obtaining the preferred vat dye of the formula (1~ (C.I. Vat Blue 16).
The invention is illustrated by the following Examples, in which the parts are by weigbt, .. ... . .

; ~...,., ..~.... ..

,:

Example 1 ~

1~1 o~ CH2 ~0~ 2 (4) o~

A mixture of 20 parts of dihydroxyviolanthrone and 20 parts of potassium carbonate is suspended in 150 parts of sulpho-lane. To the suspension are added 20 parts of ethylene chloride and the resulting reaction mixture is heated. The temperature is kept for 1 hour at 130 C, then raised to 150-155C, and the mixture is stirred for 5 hours. I'hen the reaction mixture is allowed to cool to room temperature and filtered. The product is washed with sulpholane, then suspended in water, washed neutral, and dried at 100C.
Yield: 20 parts (94.9 % of theory).
Analysis: Cl~ 0.3%.
A vat dye which is virtually identical with the product of this Example is obtained by using ethylene bromide as starting material instead of ethylene chloride.
The same vat dye is also obtained in good,,yield by using the corresponding amount of dimethyl sulphoxide, dimethyl formamide, dimethyl acetamide~ diethyl acetamide, acetonitrile or tetramethyl urea instead of sulpholane as solvent, and carrying out the reaction in a manner analogous to that described in this Example or, if necessary, under pressure in an autoclave.

. _ . _ .. . . . ... .. .... . .. . .. . . . . . . .

.
.~ ' . ' z 20 parts of dihydroxyviolanthrone and 20 parts of potas-sium carbonate are suspended in 150 parts of N-methyl-2-pyrrolidone. To the suspension are added 20 parts of ethylene chloride, then the mixture is heated and the temperature is kept for 1 hour at 130C. The temperature is then raised to 145-150C and the mixture is stirred for S hours at this temperature. The reaction mixture is then allowed to cool to room temperature, filtered, and the residue is washed with N-methyl-2-pyrrolidone. The resulting product is suspended in water, washed neutral and dried at 100C.
Yield: 19.8 parts (94.5% of theory).
Analysis: Cl~ 0.3%.
The resulting vat dye is identical with that of Example L.

Example 3 '. 0~
~L
- - ~ C~:~ (5) '. o~3 15 parts of dihydroxyviolanthrone and 15 parts of potassium carbonate are suspended in 100 parts of N-methyl-2-pyrro-.

.. , . , .. . . , . . ... . . . . . . . .. , .. . ... .... ., .. , . " .. . . ... ., ,,.. ~"_ . . .... ~ .
..

0~7Z

lidone. Then 15 parts of methylene bromide are added to thesuspension. The reactivn mixture is heated and stirred for 6 hours at 140-145C, ~hen cooled to room ~emperature and poured into water. The precipitated product is collected by filtration 9 washed neutral with water and dried at 100C.
Yield: 15.5 parts ~100% of theory).
Analysis: Br~ 0.3%.

Example 4 15 parts of dihydroxyviolanthrone and 15 parts of sodium carbonate are suspended in 100 parts o N-methyl-2 pyrro-lidone. Then 15 parts of ethylene bromide are added to the suspension. The reaction mixture is heated and stirred for 6 hours at 140-145C, then cooled to room temperature and poured into water. The precipitated product is collected by filtration, washed neutral with water aIId dried at 100C.
Yield: 15 parts.
Analysis: Br ~ 0.3%.
The resulting vat dye is identical with that of Example 1.
Instead of using 15 parts of sodium carbonate, it is also possible to use 15 parts of a mixture of sodium carbonate and potassium carbonate in the ratio 1:1.

20 parts of dihydroxyviolanthrone and 20 parts of potas-sium carbonate are suspended in 150 parts of hexamethyl-phosphoric triamide. To the suspension are added 20 parts of ethylene chloride and the mixture is then heated and kept for 1 hour at 130C. The temperature is subsequently raised to 145-150C and the reaction mixture is stirred for 5 hours at this temperature, then cooled to room temperature and filtered. The residue is washed with hexa-methylphosphoric triamide and the resulting product is :

suspended in water, washed neutral and dried at 100 C.
Yield: 19.8 parts (94.5% of theory).
Analysis ClS 0.3%.
The resulting vat dye is identical with that of Example 1.

Example 6 lS parts of dihydroxyviolanthrone and lS parts of potas-sium carbonate are suspended in 100 parts of sulpholane.
To the suspension are then added 15 parts of methylene bromide and the mixture is heated and stirred for 6 hours at 140-145C. The react:ion mixture is then cooled to room temperature and poured into water. The precipitated product is collected by filtration~ washed neutral with water and dried at 100C.
Yield: 15 parts.
Analysis: Br ~0.3%.
The resulting vat dye is identical with that of Example 3.

15 parts of dihydroxyviolanthrone and 15 parts of sodium carbonate are suspended in 100 parts of N~methyl-2-pyrro-lidone. Then 15 parts of methylene bromide are addecl to the suspension. The mixture is heated and stirred for 6 hours at 140-145C. The reaction mixture is subsequently cooled to room tem~erature and poured into water. The precipitated product is collected by filtration, washed neutral with water and dried at 100C.
Yield: 15.2 parts.
Analysis: Br~ 0.3~/0.
The resulting vat dye is identical with that of Example 3.

Example 8 20 parts of dihydroxyviolanthrone and 20 parts of a mixtu-re of 10 parts of sodium carbonate and 10 parts of potas-sium carbonate are suspended in lS0 parts of N-methyl-2-pyrrolidone. Then 20 parts of methylene bromide are added to the suspension and the mixture is heated and stirred for 6 hours at 140-145C. The reaction mixture is subse-quently cooled to room temperature and poured into water.
The precipitated product is collected by filtration, washed neutral with water and dried at 100C.
Yield: 20.7 parts Analysis: Br~ 0.3%.
The resulting vat dye is identical with that of Example 3.

E mple 9 o~
(~Lo~
~ 0/C ~ (6) 0~

30 parts of dihydroxyviolanthrone and 30 parts o~ potas-siwm carbonate are suspended in 200 parts of N-methyl-2-pyrroLidone. Then 20 parts of dichlorodiphenylmethane arP
added to the suspension and the mixture is heated and stir-red for 6 hours at 140-145C. The reaction mixture is subsequently cooled to room temperature and poured into water. The precipitated product is collected by filtration, washed neutral with water and dried at 100C.
The resulting vat dye colours cotton in navy blue shades.
Yield: 36.7 parts (92% of theory).

.
, 47;~

Analysis: Cl~ 0.3%.

Example 10 ~', ' ' .

~--O--CH2 ~ ~ C 3 0~

15 parts of dihydroxyviolanthrone and 15 parts of potas-sium carbonate are suspended in 100 parts of N-~lethyl-2-pyrrolidone. Then 15 parts of 1,2-dibromopropane are added to the suspension and the mixture is heated and stirred for 6 hours at 140-145C. The reaction mixture is subsequently cooled to room temperature and poured into water. The preci-pitated product is collected by filtration, washed neutral with water and dried at L00C. The resulting vat dye co-lours cotton in navy blue shades.
, Yield: 15.8 parts (98% of theory).
Analysis: Br G 0~.3%.
: :
Exampl-e 11 15 parts of dihydroxyviolanthrone and lS parts of potas-sium carbonate are suspended in 100 parts of sulpholane~
Then 15 parts of 1,2-dibromopropane are added to the suspen-sion and the mixture is heated and stirred for ~ hours at 140-145C. The reaction mixture is subsequently cooled to room temperature and poured into water. The precipitated product is collected by filtration, washed neutral with ` ' , .

4~

water and dried at 100C.
Yield: 15.6 parts ~97% of theory)~
Analysis: Br~ 0.37/0.
The resulting vat dye is identi.cal with that of Example 10.

Example 12 0~

~L O-CH2 _ O_~H2/ 2 t8) 0~

20 parts of dihydroxyviolanthrone and 20 parts of potas-sium carbonate are suspended in lS0 parts of N-methyl-2-pyrrolidone. Then 20 parts of 1,3-dibromopropane are added to the suspension and the mixture is heated and stirred for 10 hours in an autoclave at 140-145C and under a pres-sure of 5 to 9 bar. The reaction mixture is then cooled to room temperature and poured into water. The precipita~ed product is collected by filtration, washed neutral with water and dried at 100C. The resulting vat dye colours cotton in bluish-green shades.
Yield: 22 parts (~J100% of theory).
Analysis: Br ~ 0.3%, l~Z~g~7Z

Example 13 ~3 ' o-CH2~1 (9 ) O~CH
~ ~ CH3 :: 0 ~
~: :
20 parts of dihydroxyviolanthrone~ and 20 parts of potas-sium carbonate are suspended in 150 parts of N-methy'L-2-pyrrolidone. The 20 parts of 1,3-dibromopropane are added to the suspension and the mixture is heated and stirred ~or 6 hours at 140-145C. The reaction mixture is then cooled to room temperature and poured into water. The pre-cipitated product is collected by filtration, washed neu-~ral with water and dried at 100C. The resulting vat dye colours cotton in bluish-green~shades.
Yield: 22 parts (99% of theory) - Analysis: Br~ 0.3%.

DyeLn~ Procedure .
1 part of dye is stirred at 50-70C with 10 parts by vo-lume of sodium hydroxide having a specific gravity of 36 Bé and 5 parts of sodium hydrosulphite in 200 parts of water. The above stock vat is aflded to a dyebath which con-tains, in 2000 parts of water, 5 parts by volume of sodium hydroxide solution with a specific gravity of 36 Bé and

3.7 parts of sodium hydrosulphite. 100 parts of cotton are put into thls batb at 40C. After L0 m~nutes, 15 parts of ~ , , ' ' :

' ' ' sodium chloride are added and after 20 minutes a further 15 parts are added and dyeing is performed for ~5 m.inutes at 40 C~ The cotton is squeezed out, oxidised, and finished in the usual manner.

Pigment Colouration 5 parts of dye are mixed with 95 parts o~ dioctyl phthalate and the mixture is ground in a ball mill until the dye particles are smaller than 3 ~I
0~8 part of this dioctyl phthalate paste are mixed with 13 parts of polyvinyl chloride, 7 parts of dioctyl phthalate and 0 1 part of càdmium stearate and this mixture is rol-led for 5 minutes on a two roll mill at 140C to a colou-red sheet having good migration properties and good light-fastness.

Lacquer Colouration 10 g of titanium dioxide and 2 g o dye are ground for 48 hours in a ball mill with a mixture of 26.4 g of coconut alkyd resin, 24 g of melamine/formaldehyde resin (50% so-lids content), 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene. The resulting lacquer is sprayed onto an aluminium sheet, predried for 30 minutes at room tempe-rature and then stoved for 30 minutes at 120C, to give a finish which has very good colour strength and is dis-tinguished by good fastness to overstripe bleeding, out-standing lightfastness and good resistance to atmospheric influences.

~;
: .

Claims

What is claimed is:

1. A process for the production of vat dyes of the formula (l), wherein R is an alkylene radical of 1 to 6 carbon atoms which can be substituted by halogen, hydroxy or phenyl, an alkenylene radical of 1 to 6 carbon atoms or a pheny-lane radical, and the radical R can form 1 to 3 ring members between the two oxygen atoms, which process com-prises reacting the compound of the formula (2), in aprotic dipolar solvents selected from the group con-sisting of sulpholane, N-methyl-2-pyrrolidone, hexamethyl-phosphoric triamide, dimethyl sulphoxide, dimethyl forma-mide, dimethyl acetamide, diethyl acetamide, acetonitrile and tetramethyl urea, with compounds of the formula X - R - X (3), wherein X is halogen and R is as defined in formula (1), in the presence of bases, at elevated temperature.

2. A process according to claim 1, wherein sulpho-lane, N methyl-2-pyrrolidone or hexamethylphosphoric triami-de are used as aprotic dipolar solvents.

3. A process according to claim 1, wherein sodium carbonate, potassium carbonate or sodium acetate are used as bases.

4. A process according to claim 1, wherein the reaction is carried out in the temperature range between 100° and 200°C

5. A process according to claim 1, wherein ethy-lene chloride is used as compound of the formula (3)