US2238487A - Azine compounds and materials colored therewith - Google Patents

Description

Patented Apr. 15, 1941 AZINE COMPOUNDS AND MATERIALS COLORED THE-REWITH Joseph B. Dickey and James G. MoN-ally, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. .Application July 24,

Serial No. 347,219

6 Claims.

The present invention relates to azine compounds and to materials colored therewith. More particularly, it relates to ,azine compounds having the general formula:

wherein Z1 represents the non-metallic atoms necessary to complete a benzene nucleus, Z2 represents the non-metallic atoms necessary to complete an aryl nucleus selected from the group consisting of a benzene nucleus, a naphthalene nucleus, and a phenanthrene nucleus, and X represents a member selected from the group consisting of an oxygen atom, a sulphur atom, a nitrogen atom, and an imide group, and wherein Z1 contains at least one alkylamino group, and Z1 and Z2 together contain at least one acid ester of phosphorus group joined to the omega carbon atom of anon-cyclic organic sidechain. These compounds are usually prepared in the form of their quaternary salts such as the chloride, sulfate, chlorate, sulfonate, and the like. While they are considered mostly as having the p quinonoid structure, it will be understood that they are subject to tautomeric change to the oquinonoid form.

More specifically, the acid ester of phosphorus group can be represented by the ganeral formula:

wherein ,n. represents zero or the numeral 1. R1 and R2 each represents an amino group, an alkylamino group such as methylamino, ethylamino, propylamino, butylamino, cetylamino, methoxyethylamino for example, and the group OZ, wherein Z represents hydrogen, an alkyl group such as methyl, ethyl, propyl, butyl, cetyl, an alkali forming metal such as sodium, potassium, calcium, barium, a nitrogen containing basic group such as an ammonium radical, and organic amine salts of the free acid such as the dimethylamine salt, the ethanolamine salt, the diethanolamine salt for example, and X representsan atom of oxygen or an atom of'sulphur. The sidechain can be represented by the radicals such as.

and other similar kind of radicals. Further, the "nuclei Z, and Z2, in addition to Z1 containing at least one al'kylamino group and Z1 and Z2 together containing at least one acid ester of phosphorus group in a sldeehain, can also contain other mcnovalent substituent groups such as methyl, ethyl, propyl, methoxy, ethoxy, amino, methyl- 'amino,-ethylamino, hydroxyl, and atoms such as chlorine and bromine. 1

We have found that the azine compounds above described form a valuable series of coloring agents for textile materials such as organic derivatives of cellulose, wool, silk and mordanted cottons, as well as dyes for anti-halation backing compositionsfor photographic films. The tinting power of our new dyes range in color from green to blue. The materials colored by these dyes exhibit good stability to light and atmospheric exposure. The water-soluble feature of our new dyes is particularly advantageous in the case of anti-halation backings, since the dyes can be removed quiteeasily during the process of development and fixation of the photographic film.

It is an object of our invention, therefore, to prepare the compounds described. A further object is to color textile materials therewith. Another object is to prepare backing compositions containing our new dyes.

The azine compounds of the invention can be prepared by starting initially with the dye nucleus already formed and containing one or more substituent groups having a hydroxyl roup, or, groups such as amino which can be converted to ah'ydroxyalkylamino group by reaction with an alkyleneoxide such as ethylene oxide, or, nuclear hydroxylgroups which can be converted to a hydroxyalkoxygroup by reaction with'an alkylene chlorhydrin, and phosphating the hydroxyl groupsuitable phosphating agents include compounds such as phosphorus oxychloride,

phosphorus sulfochloride, phosphorus trichloride, phosphoric acid, tetraphosphoric acid, thiophosphoric acid, phosphoric anhydride, phosphorus oxydichloride, methoxy phosphorus oxymonochloride, amino phosphorus oxydichloride, methylamino phosphorus oxydichloride and various other alkoxy and substituted amino phosphorus compounds. The phosphating intermediates may be prepared as described in McNally and Dickey U. S. Patent No. 2,183,998, December 19, 1939. Another method of preparing the dye compounds of the invention is to start with intermediates such as a paranitrosoaniline and con dense it with a compound such as a 2,6-diphenyl naphthylene diamine, a dialkyl-m-amino-p-cresol, and the like, or, start with a para-alkylaminodiphenylamine and condense it with a compound such as phenanthrene for example. The phosphorus acid ester groups can be present originally in one or both of the starting materials or such acid ester groups can be formed by simple esterification of nuclear hydroxyl groups or hydroxyl groups contained as substituents on the omega carbon atom of non-cyclic organic sidechains.

The following examples further illustrate the compounds of our invention, their methods of preparation and their applications. It will be understood that these examples are not intended to limit our invention.

Example 1 1 mole of 3-hydroxy-7-amino-paraphenothiazine chloride is treated with approximately 2 molar equivalents of ethylenchlorhydrin, and the product obtained is dissolved in pyridine and condensed with 2 molar equivalents of methoxy phosphorus oxydichloride dissolved in pyridine or dimethylaniline. The reaction is completed by warming, after which the halogen remaining on the phosphorus is hydrolyzed with aqueous sodium carbonate, from which the ammonium salt may be prepared. The dye obtained has the probable formula:

and colors cellulose acetate blue shades from an aqueous solution which may contain salt.

In place of methoxy phosphorus oxydichloride there can be substituted an equivalent amount of methoxy phosphorus dichloride, in which case there is obtained the trivalent phosphorus dye- 3 9-methylphosphitoethoxy-7-p-methylphospitoethyllamino-phenothiazine chfloride. Various other phosphating agents may be used including phosphorus trichloride.

Example 2 1 mole of 1-methylcarboxy-3,4-dihydroxy- 7 (di-p-hydrozq ethyl) amino-paraphenoxazlne chloride is dissolved in pyridine and treated in the cold with approximately 1.1 moles of phosphorus oxychloride. The reaction is completed by warming, after which the halogen remaining on the phosphorus atom is hydrolyzed with aqueous sodium carbonate. The dye obtained has the formula:

COOCH:

and colors cellulose acetate and mordanted cotton blue shades from an aqueous solution of the dye. Any desired basic salt such as anmionium, piperidine, methylamine, calcium, and the like, can be prepared. In place of the phosphorus oxychloride exployed in the above example, there may be substituted phosphorus sulfochloride, in

which case there is obtained the corresponding thiophosphoric acid ester derivative.

Example 3 In a manner similar to that described in Example 2, there is condensed together approximately equal molar proportions of l-methylcarboxy- 3,4-dihydroxy- 7 cetyl p hydroxyethylaminoparaphenoxazine chloride and phosphorus trichloride, the compound obtained being a phosphorus acid ester having the formula:

COOCH:

and coloring cellulose acetate and mordanted cotton blue shades from an aqueous solution or the dye.

Example 4 1 mole of gallocyanine is reacted in the cold, in the presence of an oxidizing agent such as air, with approximately 1 mole of amino-ethyl phosphate. After the initial reaction is complete, the product is deoarboxylated by heating at C. The dye obtained has the probable formula:

(C ozN 0 and colors cellulose acetate blue shades from an aqueous solution which may contain salt.

Example 5 I Cl CHaO and colors cellulose acetate blue shades from an aqueous suspension of the dye.

In place' of 4-nitroso-l-ethyl-fl-dimethyl phosphatoethylamino-benzene, there can be substituted. an equivalent amount of 4-nitroso-1-(di- 5 phenyl phosphitoethyl) amino-benzene, the product obtained having the probable formula:

and coloring cellulose acetate, Wool and silk blue and the dye allowed to crystallize from. solution. The dye obtained has the formula:

CzHs I CH \N shades. l5 Example 6 I I O 1 mole of 2-(N-di-c-hydroxyethyl) phenylene- N I I v p-diamino-B-amino-l-(di-fi-hydroxyethyl) amino-phenazine chloride is treated in pyridine with 2 molar equivalents of phosphorus oxychloride. 110 The resulting chloro compound is hydrolyzed with O C H N 2 4 01 sodium carbonate, neutralized with mmeral acid 11 cans and 'the'diethanolamine salt prepared. The dye NHZ 0 obtained has the probable formula: Cellulose acetate is colored green shades from N /C2H,OH 8 9 40 l 2 NH-C N OH.HN(CzHlOH)z Ho-o2Hl 7 oaHr-O-P (HOC2H4)QNH.HO N= 6 5 4 NH:

. v N ounmmmom,

P-O-O2HA 01 1 and colors cellulose acetate violet shades from an aqueous solution which may contain salt.

Example 7 v 1 mole of 2-amino--ethyl-fl-disodium phosphatoethylamino-diphenylamine is heated with approximately 1 mole of phenanthrenequinone in 6000 c. c. of acetic acid on a water bath untila portion of the reaction mixture boiled with an excess of water and acidified with hydrochloric acid shows no increase in intensity of color. The melt is thenboiled with 6000 c. c. of water, acidified with hydrochloric acid and salted out. The dye obtained has the probable formula:

Similar dye compounds can be prepared by employing other phosphorus ester derivatives. For example, the condensation of molar equivalents of 2-amino--butyl-p-dimethyl phosphitoethyl-amino-diphenylamine and phenanthrenequinone gives the dye compound 9-phenyl-12- butyl-fl-dimethyl phosphitoethylamino-a, 'y-dibenzophenazine chloride which colors silk, wool and mordanted cotton orange shades.

Example 8 1 mole of 4-nitroso-1-ethyl-[3-(diethylamino) phosphorus oxyethylaminobenzene hydrochloride is heated in alcohol with approximately 1 mole of 2,6-diphenyl-naphthalene diamine. When the reaction is complete, the alcohol is concentrated an aqueous solution which may contain saltq Wool is also colored green shades from an acid bath.

Cellulose acetate is colored blue shades from an aqueous solution of the dye which may contain salt.

onml 0 Cellulose acetate is colored green shades from an aqueous solution which may contain salt.

/OCH3 0112-0-1 v Cellulose acetate, wool and silk are colored blue shades from an aqueous solution of the dye.

The new dye compounds of our invention can r ordinarily be applied to the textile material to be colored directly from an aqueous solution 01' the dye which may contain salt. As textile materials there can be employed organic derivatives of cellulose such as cellulose acetate, and natural fibers such as wool, silk and cotton. In some cases where the particular dye compound is only moderately water-soluble, it will be found that the addition of a dispersing agent such as a soap, a sulfonated oil or a fatty acid glyceryl sulfate is advantageous. More specifically, the dyeing operation can be conducted as follows:

2.5 parts by weight of the dye, prepared according to any of the examples described, are dissolved in 230 parts of water and the'mixture heated to about 80-85" C. at which point it is maintained throughout the entire dyeing operation. Then 100 parts of a textile material such as cellulose acetate, for example, is immersed in the dye solution and worked until the color acquired is considered satisfactory. Salt may be added during the dyeing operation to promote exhaustion of the dye bath. The material is then removed from the bath, washed with soap, rinsed and dried. It will be colored green to blue shades depending on the particular dye compound employed.

While our invention has been illustrated more particularly in connection with cellulose acetate, wool and silk, it will be understood that our new phosphated azine compounds are likewise applicable as dyes for other cellulosic derivatives including the hydrolyzed as well as the unhydrolyzed organic acid esters of cellulose and mixed organic acid esters of cellulose such as cellulose formate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose phthalate, cellulose acetate-propionate, cellulose acetate-butyrate and cellulose ethers such as methyl cellulose, ethyl cellulose, benzyl cellulose, and the like.

We claim:

1. The azine compounds selected from the group consisting of a phenothiazine nucleus, a

phenoxazine nucleus, a phenazine nucleus, and an a, -dibenzophenazine nucleus, each of said nuclei containing as nuclear carbon atom substituents at least one alkylamino group and at least one acid ester of phosphorus group joined to the omega carbon atom of a non-cyclic organic sidechain.

2. The azine compounds having the general formula:

wherein Z1 represents the non-metallic atoms necessary to complete a benzene nucleus, Z2 represents the non-metallic atoms necessary to complete an aryl nucleus selected from the group consisting of a benzene nucleus, a naphthalene nucleus, and a phenanthrene nucleus, and X represents a member selected from the group consisting of an atom of oxygen, an atom of sulphur, an atom of nitrogen, and an imide group, and wherein Z1 contains .at least one alkylamino group, and Z1 and Z2 together contain at least one acid ester of phosphorus group joined to the omega carbon atom of a non-cyclic organic sidechain.

3. The azine compounds selected from the group consisting of a phenothiazine nucleus, 9. phenoxazine nucleus, 2. phenazine nucleus, and an a, y-dibenzophenazine nucleus, each of said nuclei containing as nuclear carbon atom substituents at least one alkylamino group and at least one acid ester of phosphorus group having the general formula:

wherein n is selected from the group consisting of zero and the numeral 1, R1 and R2 each represents a member selected from the group consisting of an amino group, an alkylamino group, and the group -OZ, wherein Z represents a member selected from the group consisting of hydrogen, an alkyl group, and an alkali forming metal, the said acid ester group being joined to the omega carbon atom of a non-cyclic organic sidechain.

4. The azine compounds selected from the group consisting of a phenothiazine nucleus, a phenoxazine nucleus, a phenazine nucleus, and an a, 'y-dibenzophenazine nucleus, each of said nuclei containing as nuclear carbon atom substituents at least one alkylamino group and at least one acid ester of phophorus group joined to the omega carbon atom of an alkylamino group.

5. An organic derivative of cellulose textile material colored with a dye selected from the group of azine compounds consisting of a phenothiazine nucleus, a phenoxazine nucleus, a phenazine nucleus, and an a, -dibenzophenazine nucleus, each of said nuclei containing as nuclear substituents at least one alkylamino group and at least one acid ester of phosphorus group joined to the omega carbon atom of a non-cyclic organic sidechain.

6. A cellulose acetate textile material colored with a dye selected from the group of azine compounds consisting of a phenothiazine nucleus, a phenoxazine nucleus, a phenazine nucleus, and an a, 'y-dibenzophenazine nucleus, each of said nuclei containing as nuclear substituents at least one alkylamino group and at least one acid ester of phosphorus group joined to the omega carbon atom of a non-cyclic organic sidechaln.

JOSEPH B.'DIC'KEY. JAMES G. MCNALLY.