US3864366A - Novel acylamidophenol photographic couplers - Google Patents

Abstract

Cyan dye-forming phenolic or Alpha -naphtholic coupler compounds having a p-hydroxy-alkylphenoxy-alkylcarbonamido substituent in a non-coupling ring position thereon; a silver halide emulsion containing at least one of such couplers; a color photographic element comprising a support and at least one silver halide emulsion containing the above coupler applied thereto; and a method for preparing a cyan photographic dye by reacting one of the above defined couplers with oxidized color developing agent.

Description

United States Patent Lau et a1. 1 1 Feb. 4, 1975 [54] NOVEL ACYLAMIDOPHENOL 2,423,730 7/1947 Salminen et a1. 96/100 2,772,162 11/1956 Salminen et al. 96/100 X PHOTOGRAPH: COUPLERS 2,895,826 7/1969 Salminen et al. 96/100 X In ento s: Philip u; llmari Salminen; 2,908,573 10/1959 Bush et a1. 96/100 Leo E. Beavers, all of Rochester, 2,920,961 l/1960 Bush et al. 96/100 NY. 3,227,554 1/1966 Barr et al 96/56.5 3,781,328 12/1973 Witte et al. 260/404 X [73] Assignee: Eastman Kodak Company,

R 11 t N.Y. I CC es er Primary Exammer-Lew|s Gotts Flledi J 1973 Assistant Examiner-Ethel G. Love [2]] Appl NO: 3709111 Attorney, Agent, or Firm-J. T. Lewis Related US. Application Data 57 ABSTRACT [62] Division of Ser. No. 213,812, Dec. 29, 1971, 1

abandoned. Cyan dye-forming phenolic or a-naphtholic coupler compounds having a p-hydroxy-alkylphenoxy- 1 Cl /307 D, alkylcarbonamido substituent in a non-coupling ring 2 D, 260/4045, 0/ position thereon; a silver halide emulsion containing at 0/ 260/555 260/556 260/556 least one of such couplers; a color photographic ele- 260/558 60/5 59 B, 2 0/562 ment comprising a support and at least one silver hal- [51] int. Cl. C07c 103/30 ide emulsion containing the above coupler applied [58] Field of Search 260/4045, 404 thereto; and a method for preparing a cyan photographic dye by reacting one of the above defined cou- [56] References Cited piers with oxidized color developing agent.

UNITED STATES PATENTS 12 Claims, No Drawings 2,367,531 1/1945 Salmmen et al. 96/100 NOVEL ACYLAMIDOPHENOL PHOTOGRAPHIC COUPLERS This is a division of application Ser. No. 213.812, filed Dec. 29. 1971. now abandoned.

This invention relates to a novel group of phenolic and a-naphtholic coupler compounds. More specifically. the present invention relates to a group of new color photographic couplers which are usefully incorporated into a photographic element or cmtllsion layer thereof to obtain cyan dye images having increased D values.

Colored images are customarily obtained in the photographic art by coupling the development product (i.e., oxidized aromatic primary amino developing agents) with a color-forming or coupling compound in para position. The subtractive process of color formation is ordinarily employed in multicolor photoelements and the resulting image dyes are usually cyan, magenta or yellow dyes which are formed in silver halide layers sensitive to complementary light.

A majority of such color photographic couplers are known and described as four-equivalent couplers, which are characterized in requiring the development of four light-exposed silver halide molecules in order to ultimately produce one molecule of dye. Also widely used, are so-called two equivalent couplers in which a non-chromophoric coupling-off group is substituted in coupling position. Couplers of this type of functionally characterized by requiring the development of two exposed silver halide molecules during development to obtain one molecule of dye. Known two-equivalent couplers have coupling-off groups such as halo, alkoxy. acyloxy, aryloxy, arylthio, cyclooxy or thiocyano groups substituted in p-position in the case of phenolic or a-naphtholic couplers. Additional couplers of this type are demonstrated, for instance, in U.S. Pat. Nos. 3,458,315 and 3,227,155.

Suitability of an organic compound as a color photographic coupler, however, depends upon more than general reactivity. Consideration is also given to the color balance, contrast, grain size and general sharpness of the dye images obtained. A coupler should be stable and produce stable photographic dyes having precise spectral absorption characteristics when reacted with oxidized developer.

such as wetting agents and color components, and these changes can directly affect the coating characteristics of a photographic emulsion. This problem is suggested, for instance, on page 250 of the text by Zelikman and Levi, entitled Making and Coating Photographic Emulsions" The Focal Press (l964).

Including antihalation and gelatin interlayers, up to eight or more separate layers may be applied to a film base to obtain a modern color photographic element (ref. Kirk-Othmer, Vol. 5, pages 8l2-845, Encyclopedia of Chemical Technology (1950). For this reason any induced changes in the physical properties of an emulsion coating may well be as important as coupler reactivity with oxidized developer.

The above-listed characteristics are not necessarily complete and are often incompatible since the color photographic technology of recent years is complex and functionally interrelated. In fact, some coupler characteristics considered advantageous in earlier photographic art may now even be considered undesirable.

For the above reasons. it is necessary and desirable to discover new coupler compounds.

It is an object of this invention to obtain a new class of cyan dye-forming couplers inclusive of the 2- and 4- equivalent type suitable for modern color photographic purposes.

It is a further object of this invention to provide new coupler compounds which will readily and efficiently react with oxidized color developer to obtain cyan dye images having substantially improved D,,,,,, values.

It is a still further object of this invention to obtain novel photographic elements and photographic emulsions utilizing couplers of this invention for color photographic purposes.

These and other objects of the invention are obtained by utilizing a phenolic or a-naphtholic cyan dyeforming coupler compound having a p-hydroxy-malkylphenoxy-alkylcarbonamido substituent group substituted on a ring position of the phenolic or a-naphtholic nucleus of the coupler. The alkylcarbonamido moiety in the above substituent group is replaced with an alkylcarbamyl moiety when the substituent group is attached to an a-naphthol coupler ring in the No. 2 position.

Particularly useful couplers of the invention have the formulae ALK (I) o O-L-C-NHQ (II) HO or l (ALK) Successful color photographic couplers also possess wherein: a number of important ancillary characteristics. It is dem is 0-3;

sirable, for instance, for a non-diffusible coupler to be soluble in minimal amounts of high-boiling coupler solvent in order to obtain thinner and more durable photographic elements. It is also important that nondiffusible couplers be capable of precise incorporation into a silver halide emulsion with no adverse effects on emulsion viscosity. adhesion characteristics, or the unity of an emulsion layer during modern high-speed multilayer application onto a film backing.

Undesirable changes may also be caused by additives L is a divalent alkylene group, such as an alkylene group having 1-20 carbon atoms, including a branched chain alkylene group;

ALK is an alkyl group of l-l5 carbon atoms, particularly an alkyl group of l-8 carbon atoms, such group including a branched alkyl such as a secondary or tertiary alkyl group of 4-8 carbon atoms, and exemplified by methyl, isopropyl, tert. butyl and pentadecyl;

Q is a phenolicor anaphtholic-cyan dye-dorming coupler moiety having 1-3 of the above-described phydroxy-alkylphenoxy-alkylcarbonamido or phydroxy-dialkylphenoxy-alkylcarbonamido substituent groups attached on a ring position of the phenolic or a-naphtholic nucleus of the coupler, the alkylcarbonamido moiety of the substituent group being replaced as above with an alkylcarbamyl moiety when the substituent group is attached to an a-naphtholic coupler in the No. 2 ring position.

Suitable dye-forming coupler moieties of the above- (7) an acyloxy group of the formula wherein R is an alkyl group of l-2O carbons or an aryl group such as a phenyl or a naphthyl group inclusive of ha|o-, alkoxyor alkyl-substituted aryl groups; (8) a thiocyano group; or (9)'a heterocyclic radical having a 5-6 membered heterocylic nucleus with at least one nidefined types (i.e., Q) are exemplified, for instance in m trogcn, oxygen, or sulfur atom, the heterocyclic nuthe U.S. Pat. Nos. 2,275,292 2,367.53], 2,423,730.

3,458,315 and 3,476,563.

Illustrative compounds within the scope of the present invention are more specifically described in formulae cleus being attached to the ring by a bridging -O or -S- group.

T is (I) a halo group, such as a chloro or fluoro group; (2) an alkyl group inclusive of an alkyl group of 5 lcarbon atoms such as methyl. isopropyl and eicosyl; or (3) an alkoxy group inclusive of an alkoxy group of l-20 carbon atoms such as methoxy, isopropoxy, or eicosyloxy.

Z is individually defined as in T.

IOll [\LK and (ail) LUNllCO-L-OQ (IV) Am NHCO-Rl (ALlO X wherein: R, is (l an aryl group such as a phenyl or a naphthyl L is defined as above, and is preferably a branched group exemplified by a fluorophenyl such as pdivalent alkylene group of 10-20 carbon atoms;

ALK represents an alkyl group as defined above; n is 0-1; X is defined as (1) hydrogen; (2) a halo group such fluorophenyl or pentafluorophenyl, as an alkylphenyl such as p-methylphenyl or trifluoromethylphenyl; or (2) NHR wherein R is hydrogen, an alkyl group of 1-20 carbon atoms, or an aryl group such as a phenyl as fluoro or chloro; (3) an aryloxy group such as a phe- 40 or a naphthyl group.

noxy group; (4) a thioaryl group such as a phenylthio or a naphthylthio group; (5) an alkoxy group of l-20 carbon atoms inclusive of cycloalkoxy of 4-8 carbon atoms exemplified by methoxy, isopropoxy, octyloxy,

eicosyloxy, and cyclohexyloxy groups; (6) a thioalkyl group of l-20 carbon atoms inclusive ofcycloalkylthio;

Coupler compounds of the invention can be prepared, for example, from the corresponding psubstituted phenol by nitration and hydrogenation to obtain an o-amino, m-nitro precursor which is then reacted with an acid chloride. A suitable reaction mechanism is described as follows:

a H a v H I 2 Pd/C I 32804 x X X CH3C(OC2H5) 3 11x0 (D) 2 H 9 H2804 3 A I O (E) n 0 on A N11 g (F) NH R R C1 p NO w.

C, 0 on i 0 H M (G) NHdR ll (H) 0 NB 1 ClCCll-C H ll N13 l (3 11 CHCNH it o l O -T 4 9 ccn 4 9 t p) CCH o (J) 0H l OH NBC R C H -(IZHJNH wherein: are exemplified, for instance. in Tables lll below with X and R, are defined as above. reference to formulae V and ll: Where the o-substituent radical of the coupler moi- 35 ety in formula IV is a ureido group such as a phenyl H, I ureido, steps (A) through (E) may be followed by reac- I ECO-R tion with an aryl isocyanate to obtain a corresponding o'ureido substituted intermediate. I

Compounds within the scope of the present invention 40 RZ-CONH l I TABLE I Coupler Ho. 3% X 1 H OCH- 4 llO- OCH- F (III) H z HCO-L-O-QOH T Alk TABLE. II

p No. x T z L ALK 1 01- cu 01- CH 1; c a

3- c1- cH -on CH3(CH2)6CH2 c1- (CH I.

5 n Cl8il5 CH3- (:H

7 O-CH 3. o c n 01 on (t)C H 8 o CMH9 u u u 9 c H -o cn -o- -CHCH A v u 9 3 2 CH3 c H /Q 11 2 l N: N

C1130 Cl- H (t) u 9 The ballasted non-diffusible type cyan couplers of the present invention are usefully incorporated into light-sensitive photographic silver halide emulsion layers and applied onto an emulsion support or film base in a single-or multi-layer color photographic material by known methods (example: the solvent and Fisher fat-tail methods)) as described, for instance, in Mannes et al. in U.S. Pat. Nos. 2,304,939- and Jelley et al. in U.S. Pat. No. 2,322,027, in which high-boiling organic solvents are used to dissolve the coupler. Further useful procedures are described, for instance, in Vittum et al. U.S. Pat. No. 2,80l,l; Fierke et al. U.S. Pat. No. 2,801,171 (July 57); and Julian U.S. Pat. No. 2,479,360 (August 1960), whereby low-boiling 0r water-soluble organic solvents are used with or in place of a high-boiling solvent. In the case of multi-layer photographic materials or elements, the non-diffusible coupler compounds are generally incorporated into the red-sensitive silver halide emulsion layer and preferably utilize minimal amounts of high-boiling solvents.

Generally speaking, a useful coupler concentration will vary from about 25-200 mg/ft of coated material, a range of 30-50 mg/ft" being generally satisfactory for use in photographic paper, with overlapping and higher concentrations found useful in color photographic films.

A variety of color coupler-containing photographic materials and elements are obtainable utilizing the above family of cyan dye-producing couplers. Generally speaking, however, such photographic materials and elements will comprise the following main components:

A. A support layer such as cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, poly (ethylene terephthalate) film, polyethylene film, polypropylene film and related films of resinous materials as well as paper, polyethylene coated paper, glass, and others.

B. An antihalation layer such as a dye-containing gelatin, starch, etc., as described, for instance, in Glafkides Photographic Chemistry, Volume 1, pages 470-471, Arrowsmith Ltd. 1958',

C. One or more, preferably three light-sensitive and differently sensitized color coupler-containing silver halide emulsion layers coated onto the support. optionally with one or more gelatin spacer layers between. The support is conveniently coated in succession with a red-sensitive layer containing one or more of the above-defined class of cyan-dye-producing coupler, a green-sensitive layer and a blue-sensitive layer, either with or without a Carey-Lea filter layer between the blueand greensensitive layers. The three differently color-sensitized layers can also be arranged in any other order over one another that is desirable, with the exception that a Carey-Lea filter layer cannot be placed over a blue-sensitive layer.

The light-sensitive silver halide emulsions can include coarse, regular, or fine grain silver halide crystals or mixtures thereof such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide. silver chlorobromoiodide and mixtures thereof; such emulsions are described, for instance, in The Photographic Journal, Volume LXXIX, May 1939, pages 330-338; Journal of Photographic Science, Volume 12, No. 5, September/October 1964, pages 242-251, and also in US. Pat. Nos. 2,184,013, 2,456,953, 2,541,472, 2,563,785, 3,367,778 and 3.501.307. Such silver halide emulsions typically are gelatin emulsions although other hydrophilic colloids can be used in accordance with usual practice.

D. One or more gelatin or hydrophilic spacer layers between the light-sensitive emulsion layers or the emulsion layers and Carey-Lea filter layer as above described; and

E. A protective water-permeable overcoat layer, such as gelatin or other hydrophilic colloids. The overcoat may conveniently contain aldehyde scavenger such as described, for instance, in US. Pat. No. 3,236,652, 3,287,135, 3,220,839, 2,403,927, and British Pat. No. 623,448, and other ingredients such as buffering agents (e.g., an acidic or basic material), and

ultra-violet light absorbers such as 2,2'-di-hydroxy 4.4-dimethoxyb'enzophenone, 4.4-dimethoxybenzophenone. 4,4diazidostilbene-2,2'-disulfonic acid sodium salt, and sodium-(a-phenylhydrazone.

In addition, photographic materials and elements utilizing the present cyan-dye-forming couplers can usefully contain brighteners such as stilbenes, triazines, 0xazoles and coumarins as described, for instance, in German Pat. Nos. 972,067, 115,024, and in US. Pat. No. 2,933,390; they may also contain spectral sensitizing dyes to impart additional sensitivity to light-sensitive silver halide emulsion layers.

This invention is further described, although not limited, by the following examples. Example V-Vll include couplers not of the invention for purposes of comparison.

EXAMPLE I 2-Acylamido-5-aminophenol A solution of 0.1 mole of 2-amino-5-nitrophenol and 0.2 mole of quinoline in 300 m1 of dioxane is admixed with a solution of 0.1 mole of acid chloride in 50 ml of dioxane. The resulting reaction mixture is stirred at room temperature for 1 hour, then poured into 1 liter of ice water containing 10-15 ml of concentrated hydrochloric acid. The solid product then is collected, washed with water and recrystallized from aqueous ethanol solvent. 0.05 Mole 2-acy1amido-S-nitrophenol in termediate product is dissolved into 200 ml of dioxane containing a teaspoonful of palladium-on-charcoal. This mixture is then placed in a Parr bottle and reduced under hydrogen (40 psi) at 40 C. After about 30 min. the reaction mixture is filtered; a solution of the 2- acylamido-S-amino product (intermediate G) can be used directly for preparation of desired couplers.

EXAMPLE ll (Coupler 2 of Table l) 200 Ml of a dioxane containing 11.4 g (0.05 mole) of 2-benzamido-5-aminophenol prepared by the general procedure described above on page 6 and in Example 1 is admixed with 13 g (0.1 mole) ofquinoline and 22.7 g (0.05 mole) of (3-tert-butyl-4-acetoxyphenoxy) tetradecanolyl chloride. The mixture is stirred at room temperature for 2 hours, then poured onto 500 ml of ice-water containing 10-15 ml of concentrated HCl. The resulting resinous solid is then collected, triturated with petroleum ether and recrystallized from cyclohexane; (m.p. l 19-120C). The above acetoxy intermediate is then dissolved in 200 ml of ethanol and treated with 50 ml of 2% alcoholic potassium hydroxide. After stirring for 0.5 hour, the mixture is pured onto 500 ml of ice-water and then acidified with concentrated hydrochloric acid. The resulting viscous oil is separated out, and triturated with petroleum ether until it solidifies. Upon recrystallization from CHC1 -petroleum ether there is obtained a product identified as coupler No. 2 (mp. 133-135 C).

EXAMPLE lll (Couplers l, 3 and 4 of Table l) Couplers 1, 3 and 4 are prepared as in Example ll from the corresponding 2-(4-fluoro-benzamido)-5- aminophenol, 2-(4-trifluoromethylbenzamido)-5- aminophenol, and 2-pentafluorobenzamido-4-fluoro-5- aminophenol respectively. The couplers have melting points of 84-86, 147-149, and 1181 19 C.

EXAMPLE 1V (Coupler 1 of Table ll) To a solution of 5.8 g (0.03 mole) of 2-amino-4, 6- dichloro-S-methyl phenol in 500 ml of acetic acid is added with stirring 2.5 g of sodium acetate and 13.6 g (0.03 mole) of (3-tert-butyl-4-acetoxyphenoxy) tetradecanoyl chloride. The mixture is stirred for 1 hour, poured onto 1 liter of ice-water. and the resulting gummy solid collected and dissolved in diethyl ether. After drying over Na SO the diethyl ether solvent is removed under reduced pressure and triturated with petroleum ether until it solidifies. The solid obtained is then dissolved in 300 ml of ethanol and treated with 50 ml of 2% alcoholic potassium hydroxide. After stirring under a blanket of nitrogen for 0.5 hour, the mixture is drowned in ice-water and strongly acidified with HCl. The resulting gelatinous solid is collected, triturated with petroleum ether, and recrystallized from acetonitrile to obtain 8.5 g of product hydroxide. After stirring under a blanket of nitrogen for 0.5 hour, the mixture EXAMPLE V (Related Couplers For Comparison, See Table 111) Using the general reaction mechanism demonstrated in Example 11 and otherwise disclosed in US. Pat. Nos. 2,322,027 and 2,801,171, five 2,5-disubstituted phenoliccompounds are prepared from phenol, pfluorophenol or o,p-dichloro-m-methyl phenol to obtain coupler products structurally distinguishable from the above-described compounds within the present invention. The couplers obtained are identified as l-Vll and found to have melting points at 166167 C., 155-156 C., 184-185 C., 133-134 C., 194-195 C., 112l 13 C., and 122-123 C.. These compounds are structurally identified, below with respect to foris drowned in ice-water and strongly acidified with HCl. 20 mula V and Table [I],

I H NH-CO-R R2-CON TABLE III Compound No. H R' X I 'fi Cs Cll- @F H II 'H C OC{l1- c 11 CFHH 11 5" CF3 H Iv Otlili- F F F 0 x c 11 F 'll cocn- F F F V 11 5 4 9 F c u TABLE II -Continued Compound No R R3 X 7 VI Oiil- F F F ll F c H t 12 25 and as C1 NHCOCHO c li l s n EXAMPLE Vl Color Developing Solution BCntinued Twenty-four photographic test film strips respectively as l A, lB-SB, IA, lB-VllB, are prepared by coating a transparent cellulose acetate support with lightsensitive gelatinous silver bromo-iodide emulsion coating to obtain 136 mg silverlft 450 mg gelatinlft and 78 mg/ft of one of coupler l and IVll. and A and B strips containing equal molar amounts of the same coupler dissolved into 39 mg/ft of di-n-butyl phthalate with B-ethoxy ethyl acetate as auxiliary solvent, then dispersed into an aqueous gelatin solution. etc.. in the manner described, for instance, in Example l of US. Pat. No. 2,949,360. The ratio ofcoupler solvent to coupler for this purpose is l 1%. The coated strips are sensitometrically exposed through a graduated-density test object and processed in the usual manner at C., one duplicate being treated with Color Developing Solutions A and B, as hereinafter described. The strips are then stop-fixed, washed, silver bleached. washed, fixed, wash-ed, stabilized and dried in the usual manner, thereafter tested as explained below, and evaluated to determine their maximum image dye density, and light and heat fading characteristics. The results set forth in Table IV.

Color Developing Solution A 4-Amino'3methyI-N-cthyl-N-,B( methanesulfonamide)-ethylaniline sesqui- Light Fading Tests The extent to which the image dyes fade under the influence of light is determined by subjecting processed coatings to a simulated 21-day north skylight exposure (SANS) and determining the resulting decrease in dye density in an area having an initial dye density of approximately l.2. The resulting Light Fade" is recorded as density units.

The extent to which. unreacted coupler causes unwanted stain under the influence of light is determined by exposing processed coatings to SANS, as above described, and recording the resulting increase in density to blue light (420 nm) in a D,,,,,, area of the coating. This increase is termed PrintOut" (PO) and is recorded in terms of percent density increase.

Heat Fading Tests The extent to which the image dyes fade under the influence of heat and humidity is determined by subjecting coatings to a temperature of C at a relative humidity of for l week. The resulting decrease in TABLE IV Coupler Coupler No. Dev. I),,,,, A LP 71 P HF '71 Yell. M.P.C.

2 A 2.85 662 0.08 l 0 3 l33-I 35 5 A 3.03 072 0.05 0 +0.15 4 x1- 82 B 3.48 051 0.00 1 +0.10 7

iv A 3.20 054 0.011 0 40.03 5 133-134 v1 A 3.110 001 0.10 2 +0.03 '7 112-1 13 B 3.15 040 0.07 2 +0.03 7

VII A 3.45 004 0.03 40.00 5 122-123 B 3.27 055 0.03 +0.04 7

Based on the above data, it is apparent that a substantially higher D value is obtained when using the coupler compounds of the present invention (Arabic number) with analogous compounds outside of the present invention (Roman numerals) without substantial disadvantage with respect to other important coupler char- EXAMPLE VII The experiment described in Example Vl is repeated with the exception that the coupler used is initially dissolved in the low-boiling removable auxiliary solvents without using the retained higher boiling coupler solvent (i.e., the di-n-butyl phthalate).

After exposure, development and testing as in Example Vi, the results are evaluated and reported in Table actenstlcs. TABLE V Coupler Coupler No. Dev. m, A LF 7( Po HF 72 Yell. M.P. C.

1 A 2.36 673 0.34 l 0 7 84-86 B 2.65 655 0.30 0 +0.02 9

2 A 2.17 673 0.44 l 0 2 133-135 B 246 653 0.35 2 0 3 3 A L54 659 0.35 0 0 4 l47-I49 l A .98 665 0.25 3 +0.05 6 l66-l67 II A .56 No values recorded l-l56 B .85 No values recorded ii A .98 659 0. I 2 0 +0.06

194-]15 A 1.48 668 0.22 5 +007 7 B 1.92 l 0.25 7 +0.01 8

Couplers l-4 of the invention have D,,,,, cyan dye image values which are photographically satisfactory and possess the additional advantages associated with systems having no retained high boiling coupler solvent (Le. increased durability and better image resolution).

This invention has been described in detail with particular reference to certain preferred embodiments thereof. but it will be understood that variations and modilications can be effected within the spirit and scope of the invention.

We claim:

I. A compound of the formula L is a divalent alkylene group of l-20 carbon atoms;

ALK is an alkyl group of I-8 carbon atoms;

X is (1) hydrogen, (2) a halo group, (3) an alkoxy group, or (4) a phenylthio group,

T is (l) a halo group, (2) an alkyl group or (3) an alkoxy group; and

Z is individually defined as in T.

2. A compound of claim 1 wherein:

L is a divalent branched alkylene group of l0-20 carbon atoms;

X is hydrogen or a halo group;

T is an alkoxy group of l-20 carbon atoms; and

Z is individually defined as an alkyl group, an alkoxy group, or a halo group.

3. A compound of claim 1 wherein:

L is a divalent branched alkylene group of l0-20 carbon atoms;

X is a hydrogen or a halo group;

T is an alkyl group, an alkoxy group or a halo group;

and

Z is an alkoxy group of l-20 carbon atoms.

4. A compound of claim 1 wherein:

ALK is a tertiary alkyl group of 4-8 carbon atoms. 5. A compound of the formula I NHCO -R R -CONH wherein:

X is hydrogen, fluoro, chloro, alkoxy of l-8 carbon atoms, phenoxy, thiophenyl or cyclohexyloxy,

R, is phenyl, p-fluorophenyl, trifluoromethyl phenyl,

or pentafluorophenyl: and

R, is a p-hydroxy-alkylphenoxy-alkylene or a p-hyd roxy-dialkylphenoXy-alkylene group, wherein the alkylene group has from 10-20 carbon atoms.

. 22 6. A compound of claim 5 wherein:

R, is phenyl, p-fluorophenyl. pentafluorophenyl, or

trifluoromethylphenyl; 5 X is hydrogen. fluoro, or chloro; and

R, is a substituent of the formulae c, u i

9 c n n) 7. A compound of claim 6 wherein:

R, is p-fluorophenyl; and

R z is o o-cu- C12H25 25 OM1 4 -8. A compound of claim 6 wherein: g phenyl; and

OH o-ca- Q l2 25 c a fl 9. A compound of claim 6 4() wherein:

R, is p-trifluoromethyl phenyl; and R, is

O-CH- 10. A compound of claim 5 wherein:

X is a halo group;

R, is pentafluoro phenyl; and

tridecylcarbonamido]-2-(pentafluorophenylcarbonamido )-phenol.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,864,366 DATED February 4, 1975 lNvENroRrs) Philip T. Lau, Ilmari F. Salminen and Leo E.

. Beavers It rs certrfred that error appears rn the above-Identified patent and that sald Letters Patent are hereby corrected as shown below:

Column 1, line 29, second occurrence, "of" should read --are--.

Column 2, line 66, "dorming" should read -forming---.

Column 20, Table V, "Coupler No. 4" under the heading "LF" "10.75" should read -v-0.l7-; the line dividing "A" and "B" of "Coupler No. 4" should divide "B" of "Coupler No. 4" and "A" of "Coupler No. I"; under "%Yell." "Coupler No. II"

"2" should be preceded by a "3"; under "Coupler M.P.C." for "Coupler No. II" for "A" insert --l84-l85-- "A" of "Coupler No. IV" delete "194-195" in the first column and insert --l94-l95--- under the column headed "Coupler M.P.C.".

Signed and sealed this 10th day of June 1975.

(SEAL) Attest: V

. C. MARSHALL DANN RUTH C MASON I Commissioner of Patents Attesting Officer I and Trademarks

Claims (12)

1. A COMPOUND OF THE FORMULA

2. A compound of claim 1 wherein: L is a divalent branched alkylene group of 10-20 carbon atoms; X is hydrogen or a halo group; T is an alkoxy group of 1-20 carbon atoms; and Z is individually defined as an alkyl group, an alkoxy group, or a halo group.

3. A compound of claim 1 wherein: L is a divalent branched alkylene group of 10-20 carbon atoms; X is a hydrogen or a halo group; T is an alkyl group, an alkoxy group or a halo group; and Z is an alkoxy group of 1-20 carbon atoms.

4. A compound of claim 1 wherein: ALK is a tertiary alkyl group of 4-8 carbon atoms.

5. A compound of the formula

6. A compound of claim 5 wherein: R''1 is phenyl, p-fluorophenyl, pentafluorophenyl, or trifluoromethylphenyl; X'' is hydrogen, fluoro, or chloro; and R''2 is a substituent of the formulae

7. A compound of claim 6 wherein: R''1 is p-fluorophenyl; and R''2 is

8. A compound of claim 6 wherein: R''1 is phenyl; and R''2 is

9. A compound of claim 6 wherein: R''1 is p-trifluoromethyl phenyl; and R''2 is

10. A compound of claim 5 wherein: X'' is a halo group; R''1 is pentafluoro phenyl; and R''2 is

11. 4,6-Dichloro-5-methyl-2( Alpha (p-hydroxy-m-tert. butylphenoxy) tridecylcarbonamido) phenol.

12. 4-Fluoro-5( Alpha (p-hydroxy-m-tert. butylphenoxy) tridecylcarbonamido)-2-(pentafluorophenylcarbonamido)-phenol.