US3557005A

US3557005A - Detergent compositions containing 3-substituted 2,5 diphenyl-heterocycle brighteners

Info

Publication number: US3557005A
Application number: US653341A
Authority: US
Inventors: Charles D Broaddus
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1967-07-14
Filing date: 1967-07-14
Publication date: 1971-01-19
Anticipated expiration: 1988-01-19

Abstract

2,5 - DIPHENYLFURANS, 2,5 - DIPHENYLPYRROLES AND 2,5-DIPHENYLTHIOPHENES HAVING AUXOCHROMIC SUBSTITUENTS IN THE 3 POSITION ARE USEFUL BRIGHTNERS IN LAUNDRY DETERGENT COMPOSITIONS WHICH CONTAIN AN ORGANIC DETERGENT AND AN ALKALINE BUILDER SALT AND ARE PARTICULARLY EFFECTIVE IN BRIGHTENING NYLON AND ACETATE FABRICS.

Description

Int. Cl. Clld 3/28 U.S. Cl. 252-99 10 Claims ABSTRACT OF THE DISCLOSURE 2,5 diphenylfurans, 2,5 diphenylpyrroles and 2,5-diphenylthiophenes having auxochromic substituents in the 3 position are useful brighteners in laundry detergent compositions which contain an organic detergent and an alkaline builder salt and are particularly effective in brightening nylon and acetate fabrics.

BACKGROUND With the recent and current changes and improvement in fabrics employed for clothing and other household fabrics, more efiicient and less expensive chemicals are being sought to optically brighten such fabrics. Optical brightening of fabrics from detergent solutions requires fabric substantivity, alkaline stability, water solubility and a high degree of fluorescence. 2,5-diphenylheterocycle compounds: 2,5 diphenylfnran, 2,5 diphenylthiophene and 2,5 diphenylpyrrole, have been taught as optical brighteners for polystyrene and polyolefin plastics in U.S. Pat. 3,222,290, Braus et al. These materials, however, do not have desired brightening characteristics for fabrics via application from laundry detergent solutions. They are particularly deficient in proper fluorescence characteristics.

SUMMARY OF INVENTION It has been discovered that 2,5 diphenylheterocycle compounds having auxochromic substitutents in the 3 position are excellent optical brighteners for use in laundry detergents and can be synthesized very efliciently. These compounds have the general formula ar X ar wherein: A is an auxochromic substituent selected from the group consisting of (1) morpholino, (2) vinyl, (3) phenyl, (4) NR, wherein R is H or an alkyl, or hydroxyalkyl, having 1 to 3 carbon atoms, 0R wherein R is alkyl, hydroxyalkyl or NR -substituted alkyl wherein NR is as defined above and the alkyls contain 1 to 4 carbon atoms and (6) (OC H wherein n is 2 to 25; X is O, S, NH or NCH at 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 NR; as defined above.

These compounds are employed in laundry detergent compositions based on organic detergents and alkaline builder salts.

DETAILED DESCRIPTION Some of the 2,5 diphenylheterocycle compounds of this invention are known. See S. M. King et al., Journal of the American Chemical Society, vol. 73, pp. 2253-6 (1951). All of the members of the class of compounds of this invention can be synthesized by following the general procedures outlined below: I

3,557,005 Patented Jan. 19, 1971 ice In general, nucleophilic species may be added to 1,2- dibenzoylethylene or ring-substituted dibenzoylethylene to give l-substituted-l,Z-dibenzoylethane compounds or the corresponding ring-substituted dibenzoylethanes. These compounds may be cyclized to furan, pyrrole, or thiophenederivatives. As an example, addition of morpholine to 1,2-dibenzoylethylene yields l-m0rpho1ino-l,2- dibenzoylethane (I) which upon treatment with sulfuric acid in acetic anhydride produces 2,5-diphenyl-3-morpholinofuran. Treatment of I with ammonia yields the corresponding pyrrole derivative and subjecting I to P 8 gives 2,5-diphenyl-3-morpholinothiophene. Other nitrogen compounds which can be substituted for morpholine are NH or NHR; wherein R is H or an alkyl, or hydroxyalkyl, having 1 to 3 carbon atoms. The nucleophilic agent may also be varied to include oxygen compounds. For example, ethanol may be added to dibenboylethylene to prodduce l ethoxy 1,2-dibenzoylethane which can be cyclized to produce 3-ethoxy-2,5-diphenylfuran. Carbitols may also be used in this sequence to produce polyethoxylated S-derivatives. For specific descriptions of this type reaction see R. E. Lutz, P. S. Bailey, and N. H. Shearer, Jr., J. Am. Chem. Soc., 68, 2224 (1946).

Synthesis of 3-phenyl-2,S-diphenylheterocyclic deriv..- tives may be accomplished through cyclization of 1- phenyl-1,2'dibenzoy1ethane.

Another general method for the production of 3-substituted 2,5 diphenylhterocyclic derivatives of interest comes through conversion of the well-known (see Heterocyclic Compounds, vol. 1, editor R. C. 'Elderfield, John Wiley and Sons, Inc., New York, N.Y., 1950) 3-haloderivatives to organometallic compounds. For example, reaction of these compounds with magnesium produces Grignard reagents which undergo many well known reactions. (See Grignard Reactions of Nonmetallic Substances, by M. S. Kharasch and O. Reinmuth, Prentice- Hall, Inc., New York, N.Y., 1954.) As a specific example, 3-bromo-2,5-diphenylfuran may be converted to the corresponding Grignard reagent which may then be carbonated with CO to produce 3-carboxy-2,S-diphenylfuran. Reaction of the organometallic Grignard reagent with aldehydes or ketones produces alcohols which may be dehydrated to give vinyl derivatives of 2,5-diphenylfuran.

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

(1 2,5-diphenyl-3-morpholinofuran 2) 2,5-diphenyl-3-vinylfuran (3) 2,3,5-triphenylfuran (4) 2,5-diphenyl-3,N,N-diethylaminofuran (5) 2,5-diphenyI-3,N,N-diethanolaminofuran (6) 2,5-diphenyl-3-ethoxyfuran (7) 2,5-diphenyl-3-deca(oxyethylene)furan (8) 2,5-di-p-chlorophenyl-3-morpholinofuran (9) 2,5-di-p-aminophenyl-3-morpholinofuran (10) 2,S-di-m,p-dichlorophenyl-3-morpholinofuran l1 2,5-diphenyl-3-morpholinopyrrole l2) 2,5-diphenyl-3-vinylpyrrole 13) 2,3,5-triphenylpyrrole l4) 2,5-diphenyl-3-N,N-diethylaminopyrro1e (15) 2,5-diphenyl-3-N,N-diethanolaminopyrrole (16) 2,5-diphenyl-3-ethoxypyrrole (17 2,S-diphenyl-3-dicarbethoxypyrrole (l8) 2,5-di-p-chlorophenyl-3-morpholinopyrrole (l9) 2,5-di-p-aminophenyl-3-morpholinopyrrole (20) 2,5-di-m,p-dichlorophenyl-3-morpholinopyrrole (21) 2,5-diphenyl-3-morpholinothiophene (22) 2,5-diphenyl-3-vinylthiophene (23) 2,3,5-triphenylthiophene (24) 2,5-diphenyl-3-N,N-diethylaminothiophene 3 2,S-diphenyl-3-N,N-diethanolaminothiophene 2,5-diphenyl-3-ethoxythiophene 2,5-diphenyl-3-deca(oxyethylene)thiophene 2,5-di-p-chlorophenyl-3-morpholinothiophene 2,5-di-p-aminophenyl-3-morpholinothiophene (30) 2,5-di-m,p-dichlorophenyl-3-morpholinothiophene (31) 2,5 -dinaphthylsulfonate-3-morpholinothiophene It has been found that fluorescence properties desired for effective optical brightening of fabrics cannot be predicted from absorption data. In order to achieve proper fluorescence in the brightening compounds of this invention, there must be 3-position substituent other than H and it must not be one which is joined to the heterocyclic ring through a saturated carbon atom. These brightener compounds have been found to be alkali-stable and to have a high degree of fluorescence and of substantivity to cloth, particularly to nylon and acetate fabrics. It has been difficult to obtain brighteners which are substantive to such 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 1% of the laundry detergent composition. 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 alkanol-ammonium (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 carbon atoms, preferably about 12-14 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 suflates, 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 derived from coconut oil; sodium and potassium salts of So -sulfonated C -C a 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 aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble 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 trade name 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-po]yethylene 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 alcoholethylene 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 Fischer-Tropsch process.

(6) Semi-polar nonionic detergents include long chain tertiary amine oxides corresponding to the following general formula 1?: RI-(O4) ..-III 0 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-(Z-hydroxyethyl) dodecylamine oxide.

(7) Other semi-polar nonionic detergents include along chain tertiary phosphine oxides corresponding to the following general formula RR'RP- O wherein R is an alkyl, alenykl 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 oxdes are found in US. 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 sythentic 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 l8 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 sulfoxidcs 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-3-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 com pounds falling within this definition are 3-(N,N-dimethyl- N-hexadecylammonio) propane-l-sulfonate and 3-(N,N- dimethyl-N-hexadecylammonio)-2-hydroxy propane-1- sulfonate which are preferred for their cool water detergency characteristics. See, for example, Snoddy et 211., Canadian Pat. 708,148.

These soap and non-soap anionic, nonionic, ampholytic and zwitten'onic 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 as described in the patent of Francis L. Diehl, US. 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, rnesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and coplymers with themselves and other compatible monomers such as ethylene.

Mixtures of organic and/or inorganic 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-lhydroxy-l,l-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 effective. 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 2,5-diphenylfurans and 2,5-diphenylthiophenes having a non-nitrogen-containing substituent in the 3-position or in the phenyl groups comprise a special subclass of the brightener compounds of this invention which are significantly more stable to attack by hypochlorite comprising brightener, organic detergents and alkaline roles and those 2,5 diphenylthiophenes and 2,5 diphenylfurans having a nitrogen-containing group in the 3-position or in the phenyl group. Thus this stable sub-class of brighteners is advantageously employed in laundry detergent compositions which contain from about 0.5% to about 25%, usually 3-17%, of an active-chlorine containing bleaching compound. Examples of such compounds are: dichlorocyanuric acid; l,3-dichloro-5,5-di methyl hydantoin; N,N' dichlorobenzoylene urea; paratoluene sulfondichloroamide; trichloromelamine; N-chloromelamine; N-chlorosuccinimide; N,N-dichloroazodicarbonamide; N-chloroacetyl urea; N,N' dichlorobiuret; chlorinated dicyandiamide; sodium hypochlorite; calcium hypochlorite; lithium hyprochlorite; chlorinated trisodium phosphate. Preferred compounds are dichlorocyanurates, i.e., dichlorocyanuric acid and the sodium and potassium builder salt.

Preparations of exemplary 3-substituted-2,5-diphenylheterocyclic optical brighteners of this invention are described as follows, with the Roman numerals designating the compounds of Table I below:

3-amino-2,5-diphenylpyrrole (1) This compound has been prepared by two methods which are listed in order of preference:

(a) From l,2-dibenzoylethylene.-l,Z-dibenzoylethylene (6.0 g.; 0.025 m.) and 100 ml. of -40% alcoholic ammonia were placed in a vented glass liner. The liner was placed in a 500 ml. autoclave and heated for 16 hours. The temperature was varied from 60-l60 C. with no effect on yield which was of theoretical or 1.4 gm. Filtration of the reaction mixture gave 0.8 gm. and column chromatography over silica gel provided an additional 0.6 gm., M.P. 182-184 C. Elemental analysis: C=82.0 percent; H=5.8 percent; N=11.7 percent. Spectral data: t =340; s =23,00O; fluorescence max. =447. Absorption maxima (A and fluoresecence maxima are given here and subsequently in nanometers.

(b) From 2,5 diphenylpyrrole.2,5-diphenylpyrrole (2 gm.; -0.0l mole) was dissolved in 100 ml. of acetic acid and concentrated nitric acid added dropwise. The resulting solution was stirred for min. at room temperature and then poured into 20 ml. of water. This mixture was extracted with diethyl ether and the ether layer washed with 10% sodium carbonate solution. After drying with MgSO the ether layer was evaporated to give a residue which appeared to be 3-nitro-2,5-diphenylpyrrole from its infrared and ultraviolet absorption spectra. This product was dissolved in 20 ml. acetic acid-20 ml. ethanol to produce a. solution to which 4.6 gm. of zinc powder was added. The resulting mixture was stirred for 18 hr. whereupon it was filtered and the filtrate poured into 100 ml. of water. Extraction of this mixture with chloroform followed by recovery of product gave a residue with the same spectral properties as 3-amino-2,5-diphenylpyrrole.

3-amino-2,S-diphenylfuran (II) The compound was synthesized by an eight-step procedure using standard organic reaction as follows:

(1) To a suspension of 1,2-dibenzoylethylene (19.0 g.; 0.08 M) in 100 ml. of glacial acetic acid was added a solution of anhydrous HBr (10 g.; 0.12 M) dissolved in ml. of glacial acetic acid. The resulting solution was stirred for /2 hr. at room temperature and then poured into 200 ml. of water to precipitate the product which was removed by filtration. The solids were washed three times with distilled water and then recrystallized from 400 ml. of ethanol-acetone mixture. There was obtained 19.8 g. of l-bromo-1,Z-dibenbzoylethane (M.P.=l38 139 C.).

(2) l-bromo-l,Z-dibenzoylethtane (18 g.; 0.057 M) was suspended in 80 ml. of acetic anhydride and treated with 1.5 ml. of conc. H The temperature rose to 40 C. producing a red homogenous solution. The solution was stirred for /2 hour and then poured into 250 ml. of ice-water mixture. Filtration of the precipitate was followed by recrystallization from methanol. There was obtained 11 g. of 3-bromo-2,5-diphenylfuran (M.P.=83- 84 C.)

(3) A solution of 3-bromo-2,5-diphenylfuran (20 g.; 0.067 M) in ml. of tetrahydrofuran was added dropwise to magnesium metal (1.6 g.; 0.067 M) suspended in 10 ml. of tetrahydrofuran. After addition was complete the solution was refluxed for 1 hour.

(4) The resulting solution of Grignard reagent was carbonated by pouring onto -150 grams of solid C0 (Dry Ice). After the Dry Ice evaporated, the mixture was poured into water, acidified with dilute HCl and extracted with chloroform. Some solids did not dissolve in either solvent phase and were removed by filtration. These solids and the residue from the evaporation of the chloroform layer were combined and recrystallized from benzene. A yield of 12 g. of 2,5-diphenyl-3-furoic acid was realized. M.P.=22l-222 C.

(5) 2,5-diphenyl-3-furoyl chloride: A solution of 2,5- diphenyl-3-furoic acid (5.0 g.; 0.02 M) dissolved in 50 ml. of thionyl chloride was refluxed for A hr. The excess thionyl chloride was distilled off under aspirator vacuum, the last remnants being removed as an azeotrope with benzene.

(6) 2,5-diphenyl-3-furoyl isocyanate: 2,5-diphenyl-3- furoyl chloride (5.5 g.; 0.2 M) was dissolved in ml. acetone and cooled to 0 C. A solution of sodium azide (2.0 g.; 0.03 M) in 7 ml. of water was added dropwise while the reaction temperature was maintained at 0-10 C. The reaction mixture was stirred at room temperature for one hour and then poured into ml. of water. The resulting solution was extracted with ethyl ether to isolate the azide from the aqueous phase.

(7) The ether solution of the azide was dropped down an air-cooled condenser into a 500 ml. round-bottom flask containing 200 ml. of boiling benzene. The ether was allowed to distill off and the resulting benzene solution was refluxed for one hour. The benzene was stripped off under aspirator vacuum to afford 2,5-diphenyl-3-furoyl isocyanate.

(8) 3 amino 2,5 diphenylfuran: 2,5-diphenyl-3- furoyl isocyanate (4.8 g.; 0.007 M) was dissolved in 75 ml. of benzene. Concentrated HCl (10 ml.) was added to the solution which was then refluxed for 1V2 hours. The mixture was poured into water and extracted with ethyl ether to remove the unreacted isocyanate. The aqueous phase was neutralized with sodium bicarbonate and then extracted with chloroform. The evaporation of the chloroform yielded a residue which was identified by infra red and ultraviolet spectra and elemental analyses as being 3-amino-2,5-diphenylfuran.

Spectral data: A =345; e (16,000); fluorescence max.=447.

3-ethoxy-2,5-diphenylfuran (III) Triethylamine (7.5 g.; 0.075 M) was added to ml. of absolute ethanol in a 250 ml., 3-necked round-bottom flask equipped with a drying tube, magnetic stirrer, condenser and gas dispersion tube. Anhydrous hydrogen chloride was passed into the solution to attain a pH of -2-3. Addition of 1,2-dibenzoylethylene (10 g.; 0.0425 M) was followed by 18 hrs. reflux. The solution was cooled to 0 C. and the product removed by filtration. The product was dissolved in chloroform and water washed. Evaporation of the chloroform gave 3.0 gm. (percent yield=27).

Elemental analysis: C=82.1%; H=6.2%; O=l2.4%. Spectral data: M :340; e =25,700; fluorescence max.=25,400.

3-ethoxy-2,5-di-p-ch1orophenylfuran (IV) This compound was prepared in a manner analogous to that of 3-ethoxy-2,5-diphenylfuran using 1,2-di-p-chlorobenzoylethylene as starting material. The yield of material was 51%. Spectral data: A =351; e =32,000; fluorescence max.=410.

3-morpholino-2,5-di-p-chlorophenylfuran (V) 1,2-di-p chlorobenzoylethylene (10.0 g.; 0.033 M) was suspended in 100 ml. of diethyl ether in a 250 ml. roundbottom flask equipped with a reflux condenser and magnetic stirrer. Morpholine (6.0 g.; 0.066 M) was added and the reaction heated to reflux for 2 hr. The mixture was cooled to 20 C. and l-morpholino-1,2-di-p-chlorobenzoylethane, 10.7 g. (83% collected -by filtration. This product was suspended in 30 ml. of acetic anhydride and treated with 2 ml. conc. H 80 The temperature rose to 3-morpholino-2,S-diphenylfuran The compound was synthesized by the same procedure used for the corresponding dichloro compound, except that an equivalent amount of 1,2-dibenzoylethylene was used instead of l,2-di-p-dichlorobenzoylethylene.

Spectral data: A =340; e =24,0(); fluorescence max.=430.

' Brightener tests Table I contains data obtained by washing unsoiled, fiuorescer-free cloths of the fabrics indicated in 200 ml. of washing solution in a pint jar in a laundrometer for 30 min. 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-V) in the concentrations indicated. Tests were run at 3 parts per million of the brightener; however, Table I below also contains data at 6 and 9 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 Nfl SO; 13.7 Sodium carboxymethylcellulose 0.2 Nonionic suds controlling agents 2.2 Moisture Hal.

3 p.p.m. brighteners in an aqueous solution of 0.15% of this composition is another way of reciting the use of 0.2% of the brightener in the full formulation listed above.

These data in GM un its compare favorably with other available brightening compounds of different chemical types, which generally are difiicult and expensive to synthesize.

The detergent (laundering and brightening) c ompositions of this invention are exemplified by the following examples which show different built formulations in which the 3-substituted 2,5-diphenylheterocycle brighteners can be employed. These compositions provide pI-Is in the range of 8.5-11.5. The inventionis not limited by these examples, however, which are merely illustrative.

EXAMPLE 1 Percent Sodium soap of 20:80 coconut1tallow fatty acids 35 Sodium silicate l0 Tetrasodium pyrophosphate 40 Sodium chloride 6 3-amino-2,5-diphenylpyrrole 0.05 Moisture Balance This composition launders well and exhibits good brightening properties on nylon fabrics.

EXAMPLE 2 A granular built synthetic detergent composition hav ing 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 cleansed in the solution:

' Percent Sodium linear dodecyl benzene sulfonate 17.5

" Sodium tripolyphosphate Sodium sulfate 14 Sodium carboxymethylcellulose 0.5

Sodium silicate 7 3-amino-2,5-dipheny1furan 0.10

Moisture Balance EXAMPLE 3 An excellent granular laundering and brightening composition has the following formula:

Percent Dimethyldodecylphosphine oxide Condensation product of 11 moles of ethylene oxide with 1 mole of coconut fatty alcohol 10 Tetrasodium methylene diphosphonate 10 Sodium tripolyphosphate Sodium carboxymethyl cellulose 0.5 Sodium silicate 10 3-ethoxy-2,5-diphenylfuran 0.20

I Moisture Balance hold fabrics can have the following composition:

A water solution containing 0.15%, 0.3% and 0.45% concentrations of the above formula provides a very good cleaning and brightening results in household laundering of cotton, nylon and acetate fabrics.

EXAMPLE 4 The following granular composition containing an effective chlorine bleaching agent performs very well in EXAMPLE 5 A built liquid laundering composition which brightens as it cleans and which is suitable for laundering house- Percent Sodium-3-dodecylaminopropionate 6 Sodium linear dodecylbenzenesulfonate 6 Water 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 10 Tripotassium nitrilotriacetate 10 Potassium toluene sulfonate 8 Sodium silicate (ratio SiO :Na O of 2:1) 3.8 Sodium carboxymethyl cellulose 0.3 3-morpholino-2,5-diphenylfuran 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 sO -sulfonated tetradecene 10 Dimethyl coconut alkyl ammonio acetate 10 Trisodium ethane-hydroxy triphosphonate 60 Sodium carbonate l 3-morpholino-2,5-diphenylthiophene 0.10 Moisture 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 man'ne oil fatty acid suds depressant 2.2 Sodium tripolyphosphate 40 Trisodium nitrilotriacetate 20 Sodium silicate (ratio siO zNa o of 2:1) 10 Sodium sulfate 13 3-vinyl-2,S-diphenylpyrrole 0.50 Water Balance EXAMPLE 9 Another effective granular detergent has the following composition:

A laundering-brightening composition, especially effective on nylon and acetate fabrics at cool water temperatures, has the following composition:

Percent Sodium tallow alkyl sulfate 3-(N,N-dimethyl-N-dodecylammonio) 2 hydroxypropane-l-sulfonate 12 Sodium salt of SO -sulfonated-a-tridecene 5 Sodium tripolyphosphate 30 Trisodium nitrilotriacetate 20 Sodium silicate (SiO :Na O=1.61:l) 10 Sodium sulfate 10 Sodium carboxymethyl hydroxyethyl cellulose 0.3

3-deca(oxyethylene)-2,5-diphenylfuran 0.1

3-phenyl-2,5-diphenylpyrrole 0.1

EXAMPLE 11 Another effective cool water built granular composition according ot this invention, particularly useful with resintreated cotton fabrics, has the following composition:

Percent Sodiur'n tallow alkyl sulfate 5 3-(N,N-dimethyl-N-hexadecylammonio)-propane 1- sulfonate 5 Dimethyldodecylphosphine oxide l0 Trisodium ethane-l-hydroxy-1,1-diphosphonate 5 Trisodium nitrilotriacetate 10 Sodium tripolyphosphate 40 Sodium silicate (Na O:SiO =1:2.5) 10 Sodium carboxymethyl cellulose 0.3 Sodium sulfate l0 3-isopropoxy-2,5-di-m-aminophenylfuran 0.3 Moisture 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.

What is claimed is:

1. A detergent composition consisting essentially of a mixture of a water-soluble organic detergent and an alkaline builder salt suitable for use with said detergent in a ratio range of about 5:1 to about 1:20 and an optical brightener having the formula:

wherein: A is an auxochromic substituent selected from the group consisting of (l) morpholino, (2) vinyl, (3) phenyl, (4) NR wherein R is H or an alkyl, or hydroxyalkyl, having 1 to 3 carbon atoms, (5) OR wherein R is an alkyl group containing 1 to 4 carbon atoms and (6) (QC- H wherein n is 2 to 10; X is O, S, NH or NCH ar is phenyl, or phenyl having a substituent at the meta, para or both meta and para positions selected from the ggoup consisting of chlorine, methoxy and NR as defined a ove.

2. The composition of claim 1 wherein X is O.

3. The composition of claim 2 wherein the organic detergent is a water soluble anionic sulfate or sulfonate detergent and wherein the alkaline builder is sodium tripolyphosphate, sodium nitrilotriacetate or mixtures thereof.

4. The composition of claim 3 wherein the brightener is 3-morpholino-2,S-di-p-chlorophenylfuran.

5. The composition of claim 3 wherein the brightener.

9. The composition of claim 1 wherein the A, X and ar substituents are nitrogen-free and the composition con- 13 tains from about 0.5% to about 25% of an active chlorinecomaining bleaching compound selected from the group consisting of potassium dichlorocyanurate and sodium dichlorocyanurate.

10. The composition of claim 9 wherein X is O, the organic detergent is a water-soluble anionic sulfate or sulfonate detergent, wherein the alkaline builder is sodium tripolyphosphate, sodium nitrilotriacetate or mixtures thereof and the bleaching compound is a dichlorocyanurate.

14 References Cited UNITED STATES PATENTS LEON D. ROSDOL, Pyimary Examiner A. RADY, Assistant Examiner US. Cl. X.R.

252-110, 117, 137; zen-247.7, 347.7