GB1601945A

GB1601945A - Process for the manufacture of naphthacene derivatives

Info

Publication number: GB1601945A
Application number: GB3253777A
Authority: GB
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1978-04-28
Filing date: 1978-04-28
Publication date: 1981-11-04

Description

(54) PROCESS FOR THE MANUFACTURE OF NAPHTHACENE DERIVATIVES (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London, SWIP 3JF, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a new chemical process for the manufacture of naphthacene derivatives.

According to the invention, there is provided a process for manufacture of compounds of the formula:

wherein X is OH or NH2 and the rings A and B may be substituted, which comprises reacting an acylated boric ester of an anthraquinone compound of the formula:

wherein X is OH or NH2 and the ring A may be substituted with 1,3-butadiene or a non-cyclic substituted buta-1,3-diene capable of taking part in the Diels-Alder reaction.

As examples of substituted buta-1,3-dienes which may be used, there may be mentioned penta-1,3-diene, hexa-2,4-diene, 2-methylbuta-l,3-diene, 2-phenylbuta 1 ,3-diene, I -methoxybuta-l .3-diene, 1-acetoxybuta-1,3-diene, 1,4-diacetoxybuta 1 ,3.diene, 1 -hydroxyhexa-2,4-diene, 2,3-dimethylbuta- I ,3-diene, 2-methoxybuta 1 ,3-diene, 1-methoxy-3-ethylbuta-1,3-diene and l-methoxy-3-trimethylsiloxybuta- I 3-diene.

As examples of compounds of formula (2) whose acylated boric esters may be used, there may be mentioned quinizarin, I - amino - 4 - hydroxyanthraquinone and 5-phenoxy-, 5-chloro-, 5-methoxy-, 5-nitro-, 5-butylthio-, 5,8-dichloro-, and 5 chloro - 8 - methoxyquinizarins, 5,8 - dichloro - I - amino - 4 hydroxyanthraquinone and 6-chloroquinizarin.

As acyl derivatives, there are preferred the lower alkanoyl, and especially the acetyl, derivatives.

The reaction may conveniently be carried out by stirring a mixture of the reactants in an inert solvent, which for example may be an excess of the 1,3butadiene compound, or a hydrocarbon, halogenated hydrocarbon, ether or carboxylic acid, for example, methylene dichloride, chloroform, toluene, dioxan, chlorobenzene and acetic acid.

Water, alkanols and organic bases decompose the boric esters and are unsuitable for use as solvents.

In many cases it is desirable or it may be necessary to heat the reaction mixture to speed up the rate of reaction.

It seems likely that formation of the naphthacene derivatives proceed by way of an intermediate Diels-Alder reaction product which is unstable and oxidises spontaneously to thq naphthacene derivative. In this connection it is noted that substituents on the reactant buta-l,3-diene are not always reproduced in the reaction product. Frequently alkoxy, hydroxy or acyloxy substituents in the I or 4 positions of the butadiene are eliminated; in the case of 2-substituents linked through an oxygen atom, these are occasionally converted to a OH group.

The compounds of formula (I) are useful as dyestuffs for acetate or polyester textiles or as intermediates suitable for use, in the dyestuffs and, possibly, the pharmaceutical industries.

The invention is illustrated by the following Examples in which parts are by weight.

Example 1 A mixture of 1 part of quinizarin diboroacetate 1 part of 2,3 - dimethylbuta 1,3 - diene and 20 parts of dichloromethane is heated under reflux in an atmosphere of nitrogen for 48 hours. The reaction mixture is evaporated to dryness under reduced pressure and the residue triturated with aqueous ethanol, the product filtered off, washed with ethanol and dried to give an orange coloured solid having the structure:

When applied to aromatic polyester textile materials from an aqueous dispersion bright orange shades are obtained.

Example 2 In place of the reactants used in Example I there are used equivalent amounts of l-methoxybuta-l,3-diene and quinizarin diboro-n-propionate. The orange product obtained has the structure

and it dyes polyester textile materials in orange shades.

Example 3 In place of the 2,3 - dimethylbuta - 1,3 - diene used in Example 1 there is used an equivalent amount of I - methoxy - 3 - trimethylsiloxybuta - 1,3 - diene. The reaction time is reduced to 3 hours and the crude product is purified by washing several times with chloroform. The product obtained which has the structure

dyes polyester textile materials in orange shades.

Examples 4 to 8 In the following Examples the general conditions given in Example I are used and appropriate reaction times are used as judged by examination of the reaction mixture by thin layer chromatography

as boroacetate derivatives.

Shade on Ex. X B substituent in product polyester 4 NH2 I -methoxy-buta- none bluish-red 1,3-diene 5 NH2 1-methoxy-3- mixture of 2 and 3-hydroxy bluish-red trimethylsiloxy buta- I ,3-diene 6 OH 2-methylbuta- 2-methyl orange 1,3-diene 7 OH 2-methoxybuta- 2-methoxy orange I ,3-diene 8 OH 1-acetoxy-buta- none orange 1 3-diene Example 9 In place of the quinizarin diboroacetate and 2,3 - dimethylbuta - 1,3 - diene used in Example I there are used equivalent amounts of 5-methoxyquinizarin diboroacetate and 2 - methylbutya - 1,3 - diene. The product obtained is a mixture having the structure

where one X=H and the other=Me.

WHAT WE CLAIM IS: I. A process for manufacture of compounds of the formula:

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

Examples 4 to 8 In the following Examples the general conditions given in Example I are used and appropriate reaction times are used as judged by examination of the reaction mixture by thin layer chromatography

as boroacetate derivatives.

Shade on Ex. X B substituent in product polyester 4 NH2 I -methoxy-buta- none bluish-red 1,3-diene 5 NH2 1-methoxy-3- mixture of 2 and 3-hydroxy bluish-red trimethylsiloxy buta- I ,3-diene 6 OH 2-methylbuta- 2-methyl orange 1,3-diene 7 OH 2-methoxybuta- 2-methoxy orange I ,

3-diene 8 OH 1-acetoxy-buta- none orange 1 3-diene Example 9 In place of the quinizarin diboroacetate and 2,3 - dimethylbuta - 1,3 - diene used in Example I there are used equivalent amounts of 5-methoxyquinizarin diboroacetate and 2 - methylbutya - 1,3 - diene. The product obtained is a mixture having the structure

where one X=H and the other=Me.

WHAT WE CLAIM IS: I. A process for manufacture of compounds of the formula:

wherein X is OH or NH2 and the rings A and B may be substituted, which comprises reacting an acylated boric ester of an anthraquinone compound of the formula:

wherein X is OH or NH2 and the ring A may be substituted with 1,3-butadiene or a non-cyclic substituted buta-1,3-diene capable of taking part in the Diels-Alder reaction.
2. A process as claimed in Claim 1, wherein the acyl group of the acylated boric ester is a propionyl group.
3. A process as claimed in Claim I, wherein the acyl group of the acylated boric ester is the acetyl group.
4. A process as claimed in Claim I substantially as herein described with reference to and as illustrated in any one of the Examples.