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Publication numberUS3717630 A
Publication typeGrant
Publication dateFeb 20, 1973
Filing dateSep 11, 1968
Priority dateNov 1, 1967
Also published asDE1806256A1
Publication numberUS 3717630 A, US 3717630A, US-A-3717630, US3717630 A, US3717630A
InventorsG Booth
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Mono-and diphthalimidyl derivatives
US 3717630 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent US. Cl. 260-240 CA 5 Claims ABSTRACT OF THE DISCLOSURE The provision of monoand diphthalimidyl derivatives of fluorescent, aromatic amines and their use in (1) laundry detergent compositions which contain an organic detergent and an alkaline builder salt and (2) in aqueous and granular hypochlorite bleach compositions.

This application is a continuation-in-part of US. Pat. application, Ser. No. 679,661 filed Nov. 1, 1967, and now abandoned.

BACKGROUND This invention relates to optical brightening agents. More particularly, it relates to optical brightening agents for use in laundry detergent formulations containing an organic detergent active and an alkaline builder salt and for use in aqueous and granular bleach compositions.

In recent years, the use of optical brightening agents,

oftentimes termed optical bleaches or fluorescers, has grown enormously. These compositions which are colorless dyestutfs exhibiting substantivity to fabrics function by absorbing light in the ultraviolet invisible range (300- 400 nm.) such as is contained in natural daylight and remitting this as visible, blue-white light (400500 nm.). This fluorescence masks the natural yellowing of textile fibers and results in a highly desirable blue-white glow on white goods and a fresher, cleaner appearance of colored goods. The fluorescence of optical brightening agents, while in the blue range, varies somewhat in dominant wavelength. Where the dominant wavelength is longer, the blue fluorescence is considered to have a slightly greenish tinge. A shorter dominantwavelength near the violet end of the spectrum results in blue fluorescence which is slightly reddish. For practical purposes, particularly for use in laundry detergent formulations, a neutral blue fluorescence is generally preferable. Optical brighteners suitable for laundry application must have fabric substantivity, alkaline stability, water solubility and a high degree of fluorescence. In addition, it is particularly advantageous if an' optical brightener is resistant to the destructive effect of hypochlorite bleaches. Hypochlorite and similar oxidizing bleaches are generally known to decompose or quench the fluorescent properties of conventional optical brighteners employed in detergent compositions. Since many of the deeply embedded soils and stains encountered in the laundering of textile fabrics may be efflciently removed only by the action of chemical bleaching, the use of chemical bleaching, as a practical matter, may not be eliminated. Consequently, a great effort has been expended in the search for optical brighteners which are compatible with hypochlorite bleach and which are susceptible of use in laundering operations where contact with hypochlorite bleaches is encountered.

Accordingly, it is an object of this invention to provide optical brighteners having fabric substantivity, alkaline stability, water solubility and a high degree of fluorescence.

3,7116% Patented Feb. 20, 1973 Another object of this invention is to provide optical brighteners compatible with and resistant to the destructive effects of hypochlorite bleaches.

A further object of this invention is to provide laundry detergent compositions containing an organic detergent, an alkaline builder salt and an optical brightener.

Still another object of this invention is to provide laundry detergent compositions containing an organic detergent, an alkaline builder salt, a hypochlorite bleach and an optical brightener.

Still another object of this invention is to provide aqueous and granular hypochlorite bleach compositions containing an optical brightener.

Other objects of this invention will become apparent from consideration of the detailed description of the invention which appears hereinafter.

comprises the provision of monoand diphthalimidyl optical brightener derivatives of the formula:

wherein each a is an integer from 1 to 4; x is an integer 0 to 1; each A is hydrogen; alkyl of 1 to about 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, octyl, decyl), preferably of 1 to 4 carbon atoms; halogen (e.g., chlorine, bromine); alkoxy of 1 to about 10 carbon atoms (e.g., methoxy, butoxy, hexoxy, decoxy); aryl of from 6 to about 12 carbon atoms (e.g., phenyl, biphenyl, naphthyl); alkylsulfonyl of from about 1 to 4 carbon atoms (e.g., methylsulfonyl, octylsulfonyl, decylsulfonyl); alkoxyalkyl of from 2 to about 10 carbon atoms (e.g., methoxymethyl, butoxymethyl, ethylhexyloxymethyl); polyethylenoxy of the formula H(CH CH O) where n is an integer from 1 to 10 (e.g.,

CH CH O (CH CH O or haloalkyl of from 1 to about 10 carbon atoms (e.g., trifluoromethyl, perfluoroethyl, dichloroethyl); alkanoyl of from 2 to about 10 carbon atoms (e.g., aeetyl, propionyl, hexanoyl, octanoyl, decanoyl); cyano; polyhydroxyalkyl of from 1 to about 10 carbon atoms (e.g., 1,2,3-trihydroxypropyl, sorbityl); and Z is, when x is zero, a monovalent radical derived by abstraction of a primary amino group of a fluorescent aromatic monoor diamine characterized by ultraviolet absorption in the 325 to 400 nanometer (nm.) range and fluorescence in the 400 to 475 nm. range; and, when x is one, a bivalent 3 DETAILED DESCRIPTION OF THE INVENTION The monoand diphthalimidyl derivatives of the present invention having the formula wherein A, a and x have the hereinbefore described definitions are characterized as monoand diphthalimidyl derivatives depending upon the value of x. When at is zero in the generic formula, monophthalimidyl compounds are contemplated whereas diphthalimidlyl compounds are contemplated when x is one.

The monophthalirnidyl optical brighteners of the present invention are derived from fluorescent aromatic primary monoor diamines characterized by ultraviolet absorption in the 325 to 400 nanometer range and fluoroescence in the 400 to 475 range. There fluorescent amines can be represented by the formula (H N) --Z, wherein Z represents the residue of the fluorescent amine, i.e. the entire molecule exclusive of the amino group and n is one in the case of a monoamine and two in the case of a diamine. The equimolar reaction of a monoamine with an aromatic ortho-dialdehyde to form a monophthalimidyl compound is represented as follows:

In a like reaction, one amino group of a diamine as defined hereinbefore can be reacted with an aromatic orthodialdehyde to form a monophthalimidyl compound wherein an unreacted amino group is present on the 3 moiety.

Similarly, fluorescent aromatic diamines having the same spectral characteristics and represented as,

undergo reaction with aromatic ortho-dialdehydes according to the following scheme:

The radical, Z, where employed herein is used to represent the radical derived by abstraction of one or two primary amino groups from a fluorescent aromatic amine described hereinbefore. It will be understood that this radical is considered as being derived by abstraction for convenience only and that the characterization of the amine residue in such terms is not intended toimply that abstraction in a chemical sense is actually involved in the formation'of the brightener compounds of the present invention.

The aldehydes employed in the preparation of optical brighteners of the present invention and represented by the formula CHO wherein A and ahave the definitions hereinbefore described, are aromatic ortho-dialdehydes and include, for example,

phthalaldehyde, 4-tert-butyll ,Z-phth alaldehyde, 3-chloro- 1 ,Z-phthal aldehyde,

4,5 -dimethoxy- 1,2-phthalaldehyde, 4-naphthyll ,Z-phth alaldehyde, 3methylsulfonyll,2-phthalaldehyde, 4-ethoxyethyll ,Z-phthalaldehyde, 3-trifluoromethyl-1,2-phthalaldehyde, 3 -phenyll ,2-phthalaldehyde, 4-chlorornethyl-1,Z-phthalaldehyde, 3-cyano- 1 ,2-phthalaldehyde and 4- 1,2-dihydroxyethyl -l,2-phthalaldehyde.

A preferred ortho-dialdehyde is phthalaldehyde, which undergoes reaction with facility and is readily available.

The amines which can be employed to prepare the optical brighteners of the present invention are any of those fluorescent aromatic primary monoand diamines characterized by ultraviolet absorption in the range of 325 to 400 nm. and fluorescence in the 400-475 nm. range. These compounds are conventional brightener chromophores known to those skilled in theart. Examples of fluorescent amines having the prescribed spectral characteristics and their monovalent and/or bivalent radicals (3) derived by abstraction of one or more amino groups include the following preferred structures:

(l) 7-aminocoumarine of the formula:

wherein each p is l or 2 and each A is as hereinbefore defined;

(2) S-amino-1,8-naphthalenecarboximides of the, formula;

where each p'an'd A is defined as above; and ,R is hydrogen; alkyl of l to 4; carbon atoms; or and. of 6'to about 12.carbon atoms; 1 Y i p: (3) 4-arninostilbenes of the formula:

where each a is as defined above and each B is defined as A above or SO OM or i R I SOzN I where M is hydrogen or an alkali metal (e.g., sodium, p0- tassium,lithiurn); and R and R are each hydrogen or alkyl of 1 to about 4 carbon atoms; or part'ofaring structure (e.g., morpholine);

(4) 4,4'-diaminostilbenes of the formula:

where each a is as defined above and each B is defined the same as A above or SO OM or where M is hydrogen or an alkali metal (e.g., sodium, potassium, lithium); and R and R are each hydrogen or alkyl of l to about 4 carbon atoms; or part of a ring structure;

(5) 2-aminonaphthalenes of the formula:

where each p is defined as above and each B is the same as A defined above or 40 0M or where M is hydrogen or an alkali metal (e.g., sodium, potassium, lithium); and R and R are each hydrogen or alkyl of 1 to about 4 carbon atoms; or part of a ring structure;

(6) 3-amino-2,5-diaryl heterocyclics of the formula:

srgr

where X is 0 or NCH each ar is phenyl, naphthyl sulfonate or phenyl having a substituent at the meta, para or both meta and para positions selected from the group consisting of chlorine, methoxy, sulfonate and dialkylamino wherein each alkyl has from 1 to about 4 carbon atoms.

Especially preferred amines for reasons of facility in undergoing the desired reaction with aromatic orthodialdehydes are the 3-amino-2,5-diarylfurans wherein each ar has the above described definition (e.g., 3-amino-2,5 diphenylfuran); the 7-aminocoumarins (e.g., 4-methyl-6-methoxycoumarin); the aminostilbenes (e.g., 4-amino-4'-methoXy-2,2'-stilbenedisulfonic acid,

i SOzOH SOzOH the disodium salt thereof, 4-amino-4'-methoXy-2,2'-stilbenedisulfonamide,

| S OzNHz S OzNHB 4,4'-diamino-2,2'-stilbenedisulfonic acid,

SOZOH SOzOH the disodium salt thereof; and 4,4'-diamino-2,2'-stilbenedisulfonamide) It will be understood, of course, that the specific amine chromophores described above are described by way of example only and are not intended as limiting the scope of the invention as defined in the appended claims. Inasmuch as the precise nature of the fluorescent amine employed during reaction is believed to be secondary to the presence of the essential phthalimidyl moiety SOzOM SOzOM and The monoand diphthalimidyl compounds of the present invention can be prepared according to methods known in the art. For example, they can be prepared in the manner described in Yakugaku Zasshi 85 (l2), 1042- 49 (1965). A convenient method involves reaction of a dialdehyde and a suitable amine hereinbefore described. The reaction can be carried out at a temperature in the range of about -20 C. to about 150 C. by reacting an aromatic ortho-dialdehyde with a fluorescent aromatic primary amine having the aforedescribed spectral characteristics. The proportions of ortho-dialdehyde to fluorescent primary amine which can be employed are generally in the range of about 0.8:1 to 3: Ion a molar basis. In the case of the preparation of compounds of the type wherein x is zero, a. range of about 0.8:1 to 31.5 :1 is employed. Since the ortho-dialdehyde employed in the course of reaction can be more readily removed from the reaction vessel than can the fluorescent primary amine, it is preferable to employ a slight excess of the orthodialdehyde over a molar proportion of fluorescent primar amine. Accordingly a molar proportion of about 1.1 to 1 of ortho-dialdehyde to fluorescent primary amine is especially preferred. In the case of the preparation of compounds having a bis-structure, i.e., those wherein x in the above described formula is one, the molar proportion of ortho-dialdehyde to fluorescent primary amine employed is from about 1.8:1 to about 3: 1, the ratio of 2.2 to 1 being especially preferred. When asymmetrical diphthalimidyl derivatives are desired, any mixture of two or more dissimilar ortho-dialdehydes may be employed, the only limitation being that the molar proportion of admixed ortho-dialdehyde to fluorescent primary amine be in the range of about 1.321 to about 3:1.

The reaction of the ortho-dialdehyde of the present invention with the aforedescribed fluorescent, amine chromophores can be conducted by adding a solution of the amine to a solution of the aromatic ortho-dialdehyde. Conversely, an amine solution can be added to a solution of ortho-dialdehyde, the latter sequence being preferred. While the reaction can be effected by reacting at a temperature of from 20 C. to 150 C., a preferred temperature range is about 10 C. to about C. Reactions conducted at the lower temperature of the suitable range, i.e., at about 0 C. normally are eil'ected in a period of time of about 24 hours. Conversely, reactions at about 100 C. require less time and may be elfected in good yield in about 30 minutes. Especially preferred is reaction at about 0 C. to about 60 C.

Generally, the process of the present invention is effected in a polar organic solvent which is essentially nonreactive to either the ortho-dialdehyde or fluorescent amine employed in the reaction. The amount of solvent employed is not critical so long as an amount suflicient to readily dissolve the fluorescent amine is employed. Normally, a minimum amount of about five times the weight of amine employed is suflicient particularly in the case of nonionic fluorescent amines. The maximum amount of solvent employed is not subject to limitation, the amount of thirty times the weight of the Weight of the fluorescent amine being satisfactory from an economic standpoint. Examples of suitable essentially non-reactive solvents which may be employed are N,N-dialkyl low molecular weight amides such as dimethylformamide, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene and certain organic solvent-Water mixtures such as dimethylformamide-water, dimethylformamide containing from about 1 to about 60% water on a volume/volume basis.

Specific examples of the brightener compounds employed in the laundry detergent composition of this invention are the following:

( 1 3-phenyl-7-phthalimidylcoumarin (2) 2-(p-chlorophenyl)-7-phthalimidylcoumarin (3) 3-phenyl-7-(Z-methylphthalirnidyl)coumarin (4) 3-phenyl-5-methoxy-7-phthalimidylcoumarin (5) 3(p-phenylsulfonic acid)-7-phthalimidylcoumarin (6) N-methyl-S-phthalimidyl-1,8-naphthalene carboxamide (7) 4-phthalimidyl-4'-methylstilbene (8) 4-phthalimidyl-4'-methoxystilbene (9) sodium 4-phthalimidyl-4'-stilbenesulfonate acid (10) 4-phthalimidyl-4'-phenylstilbene l l) 4-phthalimidyl-3-methoxy-4-methylstilbene (l2) 4-(2-chlorophthalimidyl)-4'-(Z-methylphthalimidyl)-stilbenedisulfonic acid (13) disodium 4,4-diphthalimidyl-2,2'-stilbenedisulfon-ate (l4) 4,4-diphthalimidyl-2,2'-stilbenedisulfonamide l5 4phthalimidyl-4'-(2-chlorophthalimidyl)-2,2-

stilbenedisulfonamide (l6) disodium 4,4-diphthalimidyl-6,6'-dichloro-2,2'-

stilbenedisulfonate (17) sodium 6-phthalimidyl-2-naphthalenesulfonate l8) 6-phthalimidyl-2-naphthalenesu1fonamide (19) sodium 4-ch1oro-6-phthalimidyl-2-naphthalenesulfonate (20) 2,5-diphenyl-3-phthalimidylfuran (21) disodium 2,5-(p-phenylsulfonate)-3-phthalimidylfuran 9 (22) 2,5 -di (p-chlorophenyl -3-phthalimidylfuran (23) 2- (p-methoxyphenyl -3-phthalimidyl-5- (p-chlorophenyl) -furan (24) N-methyl-Z,S-diphenyl-3-phthalimidylpyrrole (25 2,5 -dim-methoxyphenyl -3 -phthalimidylfuran The brightener compounds of the present invention are alkali-stable and have a high degree of fluorescence and substantivity to cellulosic, nylon and acetate fabrics, particularly with respect to cotton fabrics. The water solubility of these brightener compounds is also satisfactory.

These brightener compounds are employed at a level ranging from about 0.01% to about 3% of the laundry detergent composition. A preferred amount of brightener is about 0.5 to about 1.5%. In addition to these brightener compounds, the laundry detergent compositions of this invention comprise at least about 10% of a mixture of an organic detergent and an alkaline builder salt in a ratio in the range of about 5:1 to about 1:20, preferably about 2:1 to about 1:10. This mixture can be as much as the balance of the composition. The organic detergent compounds and alkaline builder salts are more fully described below.

ORGANIC DETERGENTS The organic detergent compounds which can be utilized in the detergent compositions of this invention are the following:

(a) Water-soluble soaps.-Examples of suitable soaps for use in this invention are the sodium, potassium, ammonium and alkanolammonium (e.g., mono-, di-, and triethanolammonium) salts of higher fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.

(b) Anionic synthetic non-soap detergents.A preferred class can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic, sulfuric acid reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of these anionic synthetic detergents are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group can be a straight or branched chain and contains from about 9 to about 15 carbon atoms, preferably about 1214 carbons; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium alkyl phenol ethylene oxide ether sulfates, with 1 to 10 units of ethylene oxide per molecule and wherein the alkyl radicals contain from 8 to 12 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl tauride in which the fatty acids, for example, are derievd from coconut oil; sodium and potassium salts of SO sulfonated C -C u-olefins.

(c) Nonionic synthetic detergents-One class of nonionic detergents can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be alip-hatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophoblc group can be readily adjusted to yield a watersoluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. A second class of nonionic detergents comprises higher fatty amides. A third class of nonionic detergents has semi-polar characteristics. These three classes can be defined in further detail as follows:

(1) One class of nonionic synthetic detergents is marketed under the trademark of Pluronic. These detergent compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility, has a molecular weight of from about 1500 to 1800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point Where the polyoxyethylene content is about 50% of the total weight of the condensation product.

(2) Alkylphenol-polyethylene oxide condensates are condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.

(3) Nonionic synthetic detergents can be derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine and include compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000. Such compounds result from the reaction of ethylene oxide with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000.

(4) Other nonionic detergents include condensation products of aliphatic alcohols having from 8 to 22 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide; e.g., a coconut alcohol ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol.

(5) The ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms are useful nonionic detergents. These acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fishcher-Tropsch process.

(6) Semi-polar nonionic detergents include long chain tertiary amine oxides corresponding to the following general formula wherein R is an alkyl radical of from about 8 to about 18 carbon atoms, R and R are each methyl, ethyl or hydroxyethyl radicals, R is ethylene, and n ranges from 0 to about 10. The arrow in the formula is a conventional representation of a semi-polar bond. Specific examples of amine oxide detergents include dimethyldodecylamine oxide and bis-(2-hydroxyethyl) dodecylamine oxide.

(7) Other semi-polar nonionic detergents include long chain tertiary phosphine oxides corresponding to the following general formula RRR"P+O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical containing from 10 to 20 carbon atoms and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are found in U.S. Pat. 3,304,263 which issued Feb. 14, 1967, and include: dimethyldodecylphosphine oxide and dimethyl-(Z-hydroxydodecyl) phosphine oxide.

'(8) Still other semi-polar nonionic synthetic detergents include long chain sulfoxides having the formula wherein R is an alkyl radical containing from about 10 to about 28 carbon atoms, from to about ether linkages and from 0 to about 2 hydroxyl substituents, at least one moiety of R being an alkyl radical containing 0 ether linkages and containing from about to about 18 carbon atoms, and wherein R is an alkyl radical containing from 1 to 3 carbon atoms and from one to two hydroxyl groups. Specific examples of these sulfoxides are: dodecyl methyl sulfoxide and 3-hydroxy tridecyl methyl sulfoxide.

(d) Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical can be straight chain or branched alkyls and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono. Examples of compounds falling within this definition are sodium 3 dodecylaminopropionate and sodium-S-dodecylaminopropane sulfonate.

(e) Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic radical can be straight chain or branched alkyl, and wherein one of the aliphatic substituents contains from about 8 to 24 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato or phosphono. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylammonio) propane-l-sulfonate and 3-(N,N-dimethyl N-hexadecylarnmonio)-2-hydroxy propane-l-sulfonate which are preferred for their cool water detergency characteristic. See for example, Snoddy et 111., Canadian Pat. 708,148.

These soap and non-soap anionic, nonionic, ampholytic and zwitterionic detergent compounds can be used singly or in combination. The above examples are merely illustrations of the numerous suitable detergents. Other organic detergent compounds can also be used.

BUILDER SALTS The detergent compositions of this invention also contain water-soluble, builder salts either of the organic or inorganic types.

Examples of suitable water-soluble, inorganic alkaline detergency builder salts are alkali metal carbonate, borates, phosphates, polyphosphates, bicarbonate, silicates and sulfates. Specific examples of such salts are sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, pyroprosphates, orthophosphates and hexametaphosphates.

Examples of suitable organic alkaline detergency builder salts are: (1) Water-soluble aminopolyacetates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N(2-hydroxyethyl)-nitrilo diacetates; (2) Water-soluble salts of phytic acid, e.g., sodium and potassium phytatessee U.S. Pat. 2,739,942; (3) Water-soluble polyphosphonates, including specifically, sodium, potassium and lithium salts of ethane-l-hydroxy-l,l-diphosphonic ac sodium, po as ium and lithium salts of methylene diphosphonic acid, sodium, potassium and lithium salts of ethylene diphosphonic acid, and sodium, potassium and lithium salts of ethane-l,1,2-triphosphonic acid. Other examples include these alkali metal salts of ethane-2- carboxy-l, 1-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy- 1,1,2-triphosphonic acid, ethane-Z-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,2,23- tetraphosphonic acid; (4) Water-soluble salts of polycarboxylate polymers and copolymers as described in the patent of Francis L. Diehl, U.S. Pat. 3,308,067 issued Mar. 7, 1967. Specifically, a detergent builder material comprising a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about calculated as to acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; .(d) the site of attachment to the polymer chain of any carboxy-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical. Specific examples are polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other compatible monomers usch as ethylene.

Mixtures of organic and/ or organic builders can be used and are generally desirable. One such mixture of builders is disclosed in Canadian Pat. 755,038 of Burton H. Gedge, e.g., ternary mixtures of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane-1-hydroxy-1,1- diphosphonate. The above described builders can also be utilized singly in this invention.

The preferred builders are sodium tripolyphosphate and sodium nitrilotriacetate, alone or in admixture. The preferred organic detergents are the anionic sulfate and sulfonates. The detergent compositions preferably provide pHs in the range of about 8.5 to about 11.5.

The laundry detergent compositions of this invention can contain, if desired, in addition to the brightener, organic detergent and builder, any of the usual additives for such compositions which make them more attractive or eifective. For example, perfumes, dyes, proteolytic enzymes, corrosion inhibitors, oxygen and chlorine bleaches, soil redeposition agents and other brighteners can be used. Diluents such as water, moisture and sodium sulfate can also be used to make up any balance of a composition comprising brightener, organic detergent and alkaline builder salt.

The monoand diphthalimidyl optical brighteners of the present invention are stable to attack by hypochlorite compounds. Thus this stable class of brighteners is advantageously employed in laundry compositions which contain from about 0.5% to about 25%, usually 3-17 of an active-chlorine containing bleaching compound. Example of such compounds are: dichlorocyanuric acid; 1,3- dichloro-5,5-dimethyl hydantoin; N,N'-dichlorobenzoylene urea; paratoluene sulfondichloroamide; trichloromelamine; N chloroammeline; N chlorosuccinimide; N,N dichloroazodicarbonamide; N-chloroacetyl urea; N,N'- dichlorobiuret; chlorinated dicyandiamide; sodium hypochloride; calcium hypochlorite; lithium hypochlorite; chlorinated trisodium phosphate. Preferred compounds are dichlorocyanurates, i.e., dichlorocyanuric acid and the sodium and potassium salts thereof.

In other embodiments of the present invention the monoand diphthalimidyl optical brighteners are employed in aqueous and granular bleach Compositions. In

general, aqueous bleach compositions are prepared by dissolving or dispersing an optical brightener in an aqueous solution of alkali metal hypochlorite bleach. The optical brighteners of the present invention are readily soluble in aqueous hypochlorite solution and remain stable over an extended period of time so that they can be successfully packaged, shipped and stored Without rendering inefiective the whitening action of the optical brightener or the oxidizing action of the bleach. Liquid bleach compositions prepared in accordance with the present invention are characterized by a pH ranging from about 10.5 to about 13.0 and consist essentially of from about 1.0% to about 10% alkali metal hypochlorite bleach and from about 0.002 to about 2% of the optical brightener.

Preferred hypochlorite bleach-containing compositions contain the alkali metal hypochlorite bleach component in amount of about 1 to 10%, preferably about 3 %to 7%, with about 5.2% being especially preferred.

The bleach component can be any one of the alkali metal hypochlorites. Examples of such useful bleaches are sodium hypochlorite, potassium hypochlorite, lithium hypochlorite, and the like. However, sodium hypochlorite is highly preferred because of its superior properties and its ready availability.

The optical brightener is present in the liquid bleach compositions of this invention in an amount ranging from 0.002% to about 2.0%, preferably from about 0.01% to about 0.1% with about 0.05% being especially preferred.

The bleach stable brighteners of the present invention are capable of retaining their whitening and brightening effects even after exposure to aqueous 110% hypochlorite-containing bleach solutions for extended periods of time, e.g., several weeks of storage. The bleach stability which is normally ascribed to conventional optical brighteners is commonly understood to mean that these optical brighteners are not ineffective when exposed to dilute solutions of bleach for limited periods of time, e.g., at washing machine conditions where the hypochlorite bleach is present in aqueous solutions at about 0.02% hypochlorite level for up to 20 to 30 minutes. In contradistinction to the bleach compatibility commonly understood in the art, the compatibility of the presently claimed optical brighteners retain their desirable effects after exposure to hypochlorite bleach concentrations not normally found in the course of the laundering process.

The desirable bleach compatibility of the optical brighteners of the present invention is employed to advantage in the use of these brighteners in solid hypochlorite bleach containing compositions. These compositions normally comprise about 1% to about 99% of an active chlorine-containing bleaching compound which is capable of evolving hypochlorite upon contact with water and from about 0.005% to 10% of the optical brightener of the present invention. Preferably the granular bleaching compositions of the present invention contain from 1% to 80% of the active chlorine-containing bleaching compound, about 2% to 25% of an organic detergent and about to 60% of an alkaline builder salt, said bleaching compounds and builder salts being of the type hereinbefore described.

The granular-bleach compositions of this invention can contain, if desired, in addition to the bleaching compound, any of the usual additives for such compositions Which make them more attractive or effective, for example, perfumes, dyes, proteolytic enzymes, corrosion inhibitors, other chlorine bleaches, soil redeposition agents and other brighteners may be used.

These granular bleach compositions have a pH ranging from about 8 to 12 and upon dissolution in water evolve active hypochlorite chlorine for the elfective bleaching of cellulosic fabrics.

Preparations of exemplary optical brighteners of this invention are described as follows, with Roman numerals designating the compounds in Table I below.

14 EXAMPLE I Preparation of disodium 4,4-diphthalimidyl-2,2'- stilbenedisulfonate (I) l SOzONa SOzONa The solution obtained by dissolving 4.14 grams (.01 mole) of disodium 4,4'-diamino-2,2-stilbenedisulfonate in 1 liter of dimethylformamide (DMF) was added over a period of one hour to a stirred solution of 2.94 grams (.022 mole) of phthalaldehyde dissolved in 200 ml. of DMF and maintained at 60. The reaction was conducted in a 2 liter flask equipped with a magnetic stirring bar and dropping funnel. After stirring for one additional hour at 60 C. the DMF was removed by a rotary evaporator. The disodium 4,4'-diphthalimidyl-2,2'-stilbenedisulfonate was then crystallized from water (yield 5.78 grams). The ultraviolet absorption lambda max was 349 nm. and the fiuorescense lambda max was 429 nm. Elemental analysis indicated the followinng:

Calcd. (percent): C, 52.9; H, 3.52; N, 4.11. Found (percent): C, 53.3; H, 4.23; N, 4.05.

Infrared spectra (IR) indicated carbonyl absorption at 5.97 aromatic absorption at 6.25;]. and 6. 67;; and sulfonate absorption at 8.35;]. and 9.70 1. Nuclear magnetic resonance spectra (NMR) indicated a methylene singlet at 4.97 and an aromatic multiple from 1.61- to 2.97".

Substantially similar results are obtained when the following compounds are substituted for phthalaldehyde in the above example in that the correspondingly substituted phthalimidyl compounds are formed:

EXAMPLE II Preparation of 4,4'-diphthalimidyl-2,2'-stilbenedisulfonamide (II) S OzNHz S OzNHa The solution obtained by adding 3.68 grams (0.1 mole) of 4,4'-diamino,2,2'-stilbene disulfonamide to 200 ml. of DMF (dimethyl formamide) was added over a period of 1 hour to a stirred solution of 2.94 grams (0.022 mole) of phthalaldehyde dissolved in 200 ml. of DMF and maintained at 60. The reaction was conducted in a one liter flask equipped with a magnetic stirrer and dropping funnel. After stirring for one additional hour, the DMF was removed by a rotary evaporator and the 4,4- diphthalimidyl-Z,2'-stilbenedisulfonamide was then recrystallized from ethanol (yield 4.01 grams). The ultraviolet absorption lambda max was 357 nm.; the fluorescence lambda max was 438 nm.; IR and NMR spectra were consistent with the above structure.

Analysis.-Calcd. (percent): C, 62.6; H, 3.47; N, 9.72. Found (percent): C, 62.0; H, 3.37; N, 9.90.

Substantially similar results are obtained when the above reaction is conducted in the following solvents in place of dimethylformamide: dimethylacetamide; dimethylisopropamide; tetrahydrofuran; dioxane, morpholine; benzene; toluene; Xylene and petroleum ether.

EXAMPLE III Preparation of 2,5-di(p-chlorophenyl)-3- phthalimidylfuran cumen-- (ii-0611.01

The solution obtained by adding 4.52 gms. (.01 mole) of 2,5 di(p-chlorophenyl) 3 aminofuran to 300 ml. of dimethylformamide (DMF) is added over a period of two hours to a stirred solution of 1.47 grams (.011. mole) of phthalaldehyde dissolved in 100 ml. of DMF and maintained at 60 C. The reaction is conducted in a 500 ml. flask equipped with a magnetic stirrer and a dropping funnel. After stirring for three additional hours at 60 C., the DMF is removed by evaporation under reduced pressure. The 2,5-di(p-chlorophenyl)-3-phthalimidylfuran is recrystallized from ethanol to provide a yield of approximately 4.8 grams.

Substantially similar results are obtained when the following compounds are substituted for 2,5-di(p-chlorophenyl-3-aminofuran in the above reaction in that phthalimidyl compounds are formed:

EXAMPLE IV Preparation of 4-methyl-4-phthalimidylstilbene The solution obtained by adding 2.09 grams .01 mole) of 4-amino-4'-methylstilbene (I) to 100 m1. of dimethylformamide (DMF) is added over a period of 45 minutes to a stirred solution of 1.47 grams (.011 mole) of phthalaldehyde dissolved in 100 ml. of DMF and maintained at 85 C. The reaction is conducted in a 250 ml.

actinic round bottomed flask equipped with a magnetic stirrer and a dropping funnel. After stirring for fifteen additional minutes at 85 C. the DMF is removed by distillation under reduced pressure. The 4 methyl 4'- phthalimidylstilbene is obtained in a yield of approximately 3 grams after recrystallization from benzene.

1 6 EXAMPLE v Preparation of sodium 6-phthalimidyl-Z-naphthalene sulfonate oj I A solution of 2.45 grams (.01 mole) of sodium 6- amino-Z-naphthalenesulfonate in 100 ml. of a 1:1 mixture of waterzdimethyl formamide (DMF) is added over a period of one hour to a solution of 1.47 grams (.011 mole) of phthalaldehyde dissolved in 100 ml. of DMF and maintained at 45 C. The reaction is conducted in a 250 ml. round bottomed flask equipped with a magnetic stirring bar and dropping funnel. After stirring for five additional hours at 45 C., the solvents are removed by evaporation under reduced pressure. The sodium 6-phthalimidyl-2- naphthalenesulfonate is crystallized from Water and obtained in approximately 2.87 grams yield.

EXAMPLE VI Preparation of S-phthalimidylnaphthalimide o3 =o T l The solution obtained by adding 2.02 grams .01 mole) of S-aminonaphthalimide to 100 ml. of dimethylformamide (DMF) is added over a period of one hour to a stirred solution of 1.47 (.011 mole) of phthalaldehyde dissolved in 100 ml. of DMF and maintained at C. The reaction is conducted in a 500 ml. round bottom flask equipped with a magnetic stirrer and a dropping funnel. After stirring for 40 additional minutes at C., the DMF is removed by distillation under reduced pressure. The 5-phthalimidylnaphthalimide is obtained in a yield of approximately 2.8 grams after crystallization from benzene.

EXAMPLE VII Preparation of 3-phenyl-7-phthalimidylcoumarin C'HS imidylcoumarin is obtained in good yield (approximately 3 grams) after crystallization from ethanol.

1 7 Substantially similar results are obtained when the following compounds are used in place of 7-amino-3-phenyl coumarin in that phthalimidyl compounds are formed:

7-amino-4-phenyl coumarin;

7-amino-3(sodium p-phenylsulfonate) coumarin; 7-amino-3 (m-methoxyphenyl) coumarin; 7-amino-S-chlorocoumarin; 7-amino-3-phenyl-S-methoxycoumarin; 7-amino-3-methyl coumarin; 7-amin0-3,5,8-trimethoxycoumarin; 7-amino-3,S-diphenylcoumarin; 7-amino-3-phenyl-5-chloromethylcoumarin; 7-amino-5-(3,5,7'-trioxanonyl)-3-phenylcoumarin.

BRIGHTENER TESTS Table I contains data obtained by Washing unsoiled, fluorescer-free cloths of the fabrics indicated in 200 ml. of washing solution in a pint jar in a laundrometer for 30 minutes at 130 F. The'washing solutions were composed of 0.15% of the detergent composition as outlined below, water of 7 grain per gallon hardness, and the specified brightener compound (I or II) in the concentrations indicated. The bleach stability of the brighteners of Table II, where tested, was tested under conditions normally encountered in the home laundering process. This test involved incorporating 0.3 ml. of an aqueous 5.25 sodium hypochlorite-containing solution into the 200 ml. laundrometer jar solution containing 0.15% of the detergent composition below and brightener at the specified level indicated in Table I. The aqueous hypochlorite solution was added to the laundrometer jar maintained at 130 F. six minutes prior to the addition of fluorescerfree cloth to be laundered. The brighteners bleach-tested in this manner as so indicated by an asterisk next to the GM reading. Tests were run at 2 parts per million of the brightener; however, Table I below also contains data at 4, 5, and 6 p.p.m. The numbers are recorded under each fabric type in GM (Galvanek-Morrison Fluorimeter) units, with the larger numbers indicating better brightening results.

Detergent composition Percent Sodium linear dodecyl benzene sulfonate 7.8 Sodium tallow alkyl sulfate 9.5 Sodium tripolyphosphate 49:4 Sodium silicate 5.9 N3-2S04 Sodium carboxymethylcellulose 0.2 Nonionic suds controlling agents 2.2 Moisture Balance 2 p.p.m. brighteners in an aqueous solution of 0.15 of this composition is another way of reciting the use of 0.133 of the brightener in the full formulation listed above.

TABLE I Brightener GM units concentra- Brightener compound tion, p.p.m Cotton Nylon Acetate 1 Bleach-tested.

taining approximately 5.25% sodium hypochlorite and 0.1% of compound II, i.e., disodium 4,4-diphthalimidyl- 2,2-stilbenedisulfonate was formulated by dissolving the optical brightener in the aqueous hypochlorite-containing solution. The resulting solution was visually examined periodically under ultraviolet light for fluorescence. The solution continued to exhibit strong fluorescence after a storage period of two months indicating a high degree of stability under extremely adverse hypochlorite degradative conditons.

The detergent (laundering and brightening) compositions of this invention are exemplified by the following examples which show different built formulations in which the monoand diphthalimidyl optical brighteners can be employed. These compositions provide pHs in the range of -115. The invention is not limited by these examples, however, which are merely illustrative.

EXAMPLE 1 Percent Sodium soap of 20:80 coconutztallow fatty acids 35 Sodium silicate 10 Tetrasodium pyrophosphate 40 Sodium chloride 6 Disodium 4,4'-diphthalimidyl 2,2 stilbenedisulfonate 0.05 Moisture Balance This composition launders well and exhibits good brightening properties on cotton fabrics.

EXAMPLE 2 A granular built synthetic detergent composition having the following formulation can be prepared with the brightening agents of this invention incorporated therein. The composition, in addition to performing well in its cleaning capacity, imparts effective fluorescence to fabrics cleaned in the solution.

Percent Sodium linear dodecyl benzene sulfonate 17.5 Sodium tripolyphosphate 50 Sodium sulfate 14 Sodium carboxymethylcellulose 0.5 Sodium silicate 7 4,4'-diphthalimidyl-2,2'-stilbenedisulfonamide 0.10 Moisture Balance An excellent granular laundering and brightening composition has the following formula:

Percent Dimethyldodecylphosphine oxide 5 Condensation product of 11 moles of ethylene oxide with 1 mole of coconut fatty alcohol 10 Tetrasodium methylene diphosphonate 10* Sodium tripolyphosphate 60 Sodium carboxymethyl cellulose 0.5 Sodium silicate 10 3-phthalimidyl-2,S-diphenylfuran 0.20 Moisture Balance A water solution containing 0.15%, 0.3% and 0.45% concentrations of the above formula provides very good cleaning and brightening results in household laundering of cotton fabrics.

19 EXAMPLE 4 The following granular composition containing an effective chlorine bleaching agent performs very well in cleaning, whitening and brightening:

Percent Sodium tallow alkyl sulfte 7 Sodium linear dodecylbenzenesulfonate 7 Sodium tripolyphosphate 50 Sodium carbonate 10 Sodium sulfate 10 Potassium dichlorocyanurate l5 7-phthalimidyl-3,-6-dimethylcoumarin 0.5 7-phthalimidyl-4,S-dichlorocoumarin 0.05 Moisture Balance EXAMPLE 5 A built liquid laundering composition which brightens as it cleans and which is suitable for laundering household fabrics can have the following composition:

Percent Sodium-3-dodecylaminopropionate 6 Sodium linear dodecylbenzenesulfonate 6 Potassium pyrophosphate 20 Potassium toluene sulfonate 8 Sodium silicate 3.8 Carboxymethyl hydroxyethyl cellulose 0.3 4,4'-diphthalimiclyl-Z,2'-stilbenedisulfonic acid 0.05 Water Balance EXAMPLE 6 Another built liquid detergent composition according to this invention has the following composition:

Percent Sodium linear dodecylbenzenesulfonate 6 Dimethyldodecylamine oxide 6 Trisodium ethane-l-hydroxy-l,l-diphosphonate Tripotassium nitrilotriacetate 10 Potassium toluene sulfonate 8 Sodium silicate (ratio SiO :Na O of 2:1) 3.8 Sodium carboxymethyl cellulose 0.3 2,5-diphenyl-3-phthalimidyl-N-methylpyrrole 0.20 Water Balance This detergent composition is effective in laundering and brightening resin-treated cotton wash and wear fabrics.

EXAMPLE 7 A household laundering composition can contain the following ingredients:

Percent Sodium salt of S0 -sulfonated tetradecene 10 Dimethyl coconut alkyl ammonio acetate l0 Trisodium ethane-hydroxy triphosphonate 60 Sodium carbonate 10 2,5-di(p-phenylsulfonamide)-3-phthalimidylfuran 0.10 Mixture Balance This composition brightens as it cleans and can be usefully employed in laundering nylon fabrics.

EXAMPLE 8 An effective granular detergent composition has the following formulation:

Percent Sodium linear dodecylbenzenesulfonate 7.5 Sodium tallow alkyl sulfate 2 Hydrogenated marine oil fatty acid suds depressant 2.2

Sodium tripolyphosphate 40 Trisodium nitrilotriacetate 20 Sodium silicate (ratio SiO :Na O of 2:1) 10 Sodium sulfate 13 4-phthalimidyl-4'-methoxy 2,2 stilbene-disulfonic acid 0.5 Water g Balance following composition:

20 EXAMPLE 9 Another effective granular detergent has the following composition:

EXAMPLE 10 A laundering-brightening composition, especially effective on cotton fabrics at cool water temperatures, has the Percent Sodium tallow alkyl sulfate 5 3(N,N-dimethyl N dodecylammonio)-2-hydroxypropane-l-sulfonate Sodium salt of SO -sulfonate a. tridecene 5 Sodium tripolyphosphate 30 Trisodium nitrilotriacetate 20 Sodium silicate (SiO :Na O=1.6:l) 10 Sodium sulfate 10 Sodium carboxymethyl hydroxyethyl cellulose 0.3 Sodium 4,4'-di-(3 chlorophthalimidyl)-2-stilbenedisulfonate 0.1 Sodium 4-methyl 4' (3-chlorophthalimidyl)-2-stilbenesulfonate 0.1

EXAMPLE 1 1 Another effective cool water built granular composition according to this invention, particularly useful with resin-treated cotton fabrics, has the following composition:

Percent Sodium tallow alkyl sulfate 5 3(N,N-dimethyl N hexadecylammonio)-propanel-sulfonate Dimethyldodecylphosphine oxide 10 Trisodium ethane-l-hydroxy-1,1-diphosphonate 5 Trisodium nitrilo triacetate 10 Sodium tripolyphosphate 40 Sodium silicate (Na O:SiO =l:2.5) 10 Sodium carboxymethyl cellulose 0.3 Sodium sulfate 10 3-phthalimidyl-2,5-di-m-aminophenylfuran 0.3 Moisture Balance The aqueous and granular bleach compositions of this invention are exemplified by the following examples which show different formulations in which the monoand diphthalimidyl optical brighteners can be employed. The invention is not, however, limited by these examples which are merely illustrative.

EXAMPLE 12 An excellent aqueous bleach composition which improves the whitening of bleached textiles can have the following composition:

Percent Sodium hypochlorite 5.2 Disodium 4,4 diphthalimidyl-2,2-stilbenedisulfonate 0.2

Water "gun---" Balance 21 EXAMPLE 13 An aqueous bleach composition effective in improving the appearance of white and colored fabrics can have the following composition:

Percent Potassium hypochlorite 3.5

4,4-diphthalimidyl-Z,2-stilbenedisulfonamide 0.05

Water Balance EXAMPLE 14 An aqueous bleach having advantageous bleaching and whitening can have the composition:

Percent Sodium hypochlorite 5.2 3-phenyl-7-phthalimidylcoumarin 0.05 Water Balance EXAMPLE 15 The following granular bleach composition which dissolves readily in a household automatic washing machine can have the following composition:

Percent Potassium dichlorocyanurate 65 Sodium linear dodecylbenzenesulfonate 6 Potassium pyrophosphate 25 Sodium 4-phthalimidyl 4' methyl-Z-stilbenesulfonate 3 Moisture 0.3 Sodium sulfate Balance EXAMPLE 16 A granular bleach formulation which improves the appearance of bleached textiles can have the following composition:

Percent Sodium dichlorocyanurate 40 Sodium tallow alkyl sulfate Potassium tripolyphosphate 25 N,N'-s0dium 4 phthalimidyl-4'-methoxy-2-stilbenesulfonate 1 Sodium sulfate Balance The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.

22 What is claimed is: 1. A compound having the formula 1 i VMQBEEECH BQAIV wherein each B is selected from the group consisting of SO OM where M is hydrogen or alkali metal; and

3. The compound of claim 2 wherein each B is SO2ONa.

4. The compound of claim 2 wherein each B is SO OH.

5. The compound of claim 1 wherein each B is SO NH References Cited FOREIGN PATENTS 1,091,976 10/1958 Germany 260'240 OTHER REFERENCES ,lWanag, Ber. Deut. Chem. vol. 75, pp. 719 to 725 (1942).

Chemical Abstracts (abstract of Artico et al., Farmaco,

Ed. Sci. 22, pp. 272-86 (1967), vol. 67, page 8500 to 8501 (Nov. 6, 1967).

Amano et al., Chem. Abstracts 64: 8178a.

HENRY R. JILES, Primary Examiner G. T. TODD, Assistant Examiner U.S. Cl. X.R.

106-193 D; 117-335 R, 138.8 N, 144; 25230l.2 W; 26037 NP, 281, 325

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Classifications
U.S. Classification548/460, 548/472, 252/301.24, 548/465, 548/463, 546/100, 544/144
International ClassificationC07D209/46, C11D3/395, C11D3/42
Cooperative ClassificationC11D3/3955, C11D3/42, C07D209/46
European ClassificationC07D209/46, C11D3/395F, C11D3/42