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Publication numberUS3657231 A
Publication typeGrant
Publication dateApr 18, 1972
Filing dateMar 24, 1970
Priority dateSep 30, 1968
Also published asDE1949137A1
Publication numberUS 3657231 A, US 3657231A, US-A-3657231, US3657231 A, US3657231A
InventorsGary E Booth
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Oligomeric optical brightening compounds
US 3657231 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent Olfice 3,657,231 OLIGOMERIC OPTICAL BRIGHTENING COMPOUNDS Gary E. Booth, Oxford, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Continuation-impart of application Ser. No.

763,944, Sept. 30, 1968. This application Mar. 24, 1970,

Ser. No. 24,468

Int. Cl. C07d 55/20 US. Cl. 260-440 B 3 Claims ABSTRACT OF THE DISCLOSURE Oligomeric optical brightening compounds having a molecular weight in the range of 200 to 24,000 and containing from 2-24 fluorescent moieties being separated by inorganic or organic chemical linkages derived from a condensation reaction. The optical brighteners, which are useful in admixture with detergent compositions, are prepared by a reaction between a difunctional fluorescent compound and a difunctional linking compound.

CROSS REFERENCE TO RELATED CASES This application is a continuation-in-part application of copending application Ser. No. 763,944, filed Sept. 30, 1968, now abandoned.

BACKGROUND This invention relates to oligomeric optical brightening compounds. More particularly, it relates to optical brightening compounds for use in laundry detergent formulations containing an organic detergent and an alkaline builder salt. In recent years the use of optical brightening agents, sometimes referred to as optical bleaches, fluorescers, or whitening agents, has grown considerably. The reason for their general acceptance is due to the fact that these compounds are capable of adding additional light (brightness) by means of fluorescence. These compositions which are colorless dyestuffs 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 (400-500 nm.). This fluorescence tends to mask the natural yellowing of textile fabrics and results in a highly desirable blue-white appearance on white goods and a brighter cleaner appearance on colored goods. For practical purposes, particularly for use in laundry detergent formulations, a neutral blue fluorescence is generally preferable.

Generally, optical brighteners contain aromatic condensed ring systems and have a unique conjugated, planar molecular configuration.

- Patented Apr. 18, 1972 Optical brighteners suitable for laundry application must have the following attributes: fabric substantivity; alkaline stability; water solubility or satisfactory dispersibility; a high degree of fluorescence; fabric aflinity in presence of detergent compositions; satisfactory build-up but not discolor; chemically stable; preferably bleach stable; satisfactory exhaust rate; homogeneous leveling effect on fabrics; pH stability, and light fastness. Moreover, an optical brightener compound should desirably be compatible with the usual ingredients found in modern day built and unbuilt detergent compositions.

A major disadvantage of most optical brighteners in current use is that the fluorescent moiety, or that portion of the molecule which contributes the desired brightening effect, actually represents a relatively minor portion of the molecule in terms of molecular weight. The nonchromophoric or non-fluorescent portion is the major portion of the molecule.

By way of illustration, one of the most widely used optical brighteners is dis0dium-4,4'-bis(4-anilino-6-morpholino-s-triazine-2-yl-amino) 2,2 stilbene disulfonate having the following formula:

a .l ii i. Q OaNa Oa a 1 In the above formula the fluorescent moiety is represented primarily by the central stilbene portion of the molecule which constitutes a molecular weight of only about 300. However, the entire molecule has a molecular weight of about 1,000. The primary purpose of the bulky non-fluorescent portion of the molecule is to render the compound substantive to the fabric being treated. Numerous similar examples could be given, all of which emphasize this disadvantage of currently used optical brighteners. No one has heretofore conceived of a way of reducing the amount of non-fluorescent material without the necessity of adding other bulky substantivity-conferring groups.

A primary object of the present invention is to provide a completely new class of optical brightener compounds which are free of the aforementioned disadvantages. Optical brightener compounds are provided which have an unusually high fluorescent chromophore/weight ratio. Another object is to reduce the amount of non-fluorescent material without the necessity of adding other bulky substantivity-conferring groups. Still another object is to confer substantivity to a relatively non-substantive fluorescent compound by oligomerizing the non-substantive monomer. The oligomerization condensation reaction for achieving this unique elfect is also an object of this invention.

These objects are achieved according to the present invention by building up an oligomeric molecule in which nearly bare fluorescent moieties are joined together by short organic or inorganic connecting groups, In this way, the substantivity of fluorescent compounds which are either nonsubstantive or only slightly substantive to such fabrics as cotton (cellulosic materials), wool, rayon and such synthetic fabrics such as nylon, polyamides, orlon (polyesters), and the like and blends of synthetic and natural fibers is increased. As used herein the term nonsubstantive or relatively or slightly nonsubstantive means that the degree of substantivity falls short of being sufiicient to be considered a candidate for wide scale commercial use.

SUMMARY OF THE INVENTION The above and other objects of this invention are achieved by providing an oligomeric optical brightener compound having a. molecular weight in the range of from about 200 to about 24,000 and containing from about 2 to about 24 repeating fluorescent moieties which are characterized by ultraviolet absorption in the range of about 325 to about 420 nm. and fluorescence in the range of about 400 to about 475 nm., said fluorescent moieties being separated by inorganic or organic chemical linkages derived from a condensation reaction between a difunctional fluorescent compound and a difunctional linking compound.

The invention in its broadest terms is unlimted as respects the chemical structure of the fluorescent moiety, provided that the prescribed absorption-emission spectrum is met. The starting fluorescent moiety should be a difunctional compound. Accordingly, the following list of fluorescent moieties is merely representative of the classes which are contemplated by the present invention:

S O Na S OgND- disodium 4,4'-diamino-2,2'-stilbenedisulfonate S O N OzN s 02 C1 s 0101 4,4-diacetamido-2,2-stilbenedisulfonylchloride S 0201 g 0201 4,4'-diamino-2,2'-stilbenedisulfonylchloride 2,6-dichloropyrazine 4,4'-bis[3-hydroxyethylbenzimidazol-Z"-yl]stilbene 4,4'-p-distyryl benzene dicarboxylic acid chloride a,;3-bis- [hydroxyethylbenzimidazol-2-yl] ethylene I /N\ G t CH;

2-[3'-methyl-5,6'-dicarbomethoxybenzimidazol-2'-yl]- 5-phenylthiophene H C-O CH1 sodium fl-[5-aminobenzoxyazol-2-yl]-4-amino-2- styrenesulfonate HO OH SJ-bis-[5-hydroxvybenzoxazol-2'-yl]p-divinylenephenylene 0 0 H3 0 C H3 4,4-chlorocarboxyl-2,2-dimethoxystilbene 0 OH: OH:

4,4-dihydroxy-2,2-dimethoxystilbene 16) o 0 ll 4-acetamido-1,8-naphthalenedicarboxylic acid wherein R is hydrogen, a saturated or unsaturated, branched or straight chain alkyl group containing from one to about six carbon atoms, an aryl group, or a substituted aryl group; R is selected from the group consisting of alkoxy having from one to six carbon atoms, alkyl having from one to six carbon atoms, and alkylamine having from one to six carbon atoms; and x has a value of from 1 to about 10.

It has now been discovered that a fluorescent moiety of the type listed above can be rendered substantive or substantially more substantive to a broad spectrum of natural and synthetic fabrics by building them up to oligomers. It is an essential embodiment of the present invention that the linking groups be of such a character that they electronically insulate the repeating fluorescent moiety. While the linking groups have as a primary role converting a relatively unsubstantive fluorescent moiety to a substantive optical brightener compound, they also serve the additional purpose of electronically insulating the fluorescent moieties and preventing them from interfering, masking or destroying the inherent absorption emission properties of each fluorescent moiety.

The molecular weight of the oligomeric optical brightener compounds prepared by this invention are in the range of from about 200 to about 24,000 and preferably from about 200 to about 10,000. The number of repeating fluorescent moieties has a bearing on the molecular weight of any specific compound which comes within the scope of the present invention. In some cases dimers of a fluorescent monomer are satisfactory for a given brightening purpose. On the other hand, trimers or higher oligomers are more satisfactory. In most cases it has been found that the number of repeating fluorescent moieties should be in the range of from about 2 to about 12. Such compounds have molecular weights on the lower end of the permissible molecular weight range. The size of a given linking group also has a bearing upon the spectral energy of a given compound. This will be apparent to one skilled 'in the art.

The repeating fluorescent moieties in the oligomers contemplated by this invention can be the same or they can be different. Moderated or varied optical brightening effects (shifted spectral absorption-emission profiles) can be achieved by selecting the fluorescent moieties in preparing the oligomeric compounds. Similarly, the organic or inorganic linkages can be varied in the linear oligomeric optical brightening compounds of the present invention.

The oligomeric compounds of the present invention constitute a basic departure from anything known heretofore in the area of optical brightener compounds.

The oligomerization condensation reactions are generally effected by placing the difunctional fluorescent moiety of the type described above in a polar, aprotic solvent such as dimethylformamide, dimethylacetamide, cyclic ethers such as tetrahydrofuran and dioxane, acetonitrile, pyridine, dimethylsulfoxide, aromatic hydrocarbons such as benzene, and the like along with a difunctional linking agent of the type described above. The solutions are stirred at -150 C. from 1 to 50 hours, preferably at 20-120 C. for 2 to 30 hours. If an acid is produced during the condensation reaction it is desirable to have a base such as triethylamine, tributylamine, sodium carbonate, sodium bicarbonate or their equivalent present in the reaction mixture. Similarly, if the condensation reaction produces water, it is desirable to have a material such as molecular sieves present or their equivalent that will remove water from the reaction medium. The reactions can be monitored and can be stopped by cooling, removing the reaction solvent, or by adding an excess of some material such as water or methanol that will react with one of the functional groups participating in the condensation reaction. The condensation reactions also can be effected by heating a dry solid mixture of the fluorescent moiety and the linking agent thus avoiding the use of a solvent for the reaction. Both reaction systems can be used, i.e., with or without a solvent.

In order to provide the inorganic and organic chemical linkages described above, suitable difunctional linking compounds can be used. The following classes of compounds are given as being merely illustrative of the type which can be used. This list will suggest numerous equivalent difunctional compounds to persons skilled in the art of condensation reactions. Illustrative examples are:

wherein R can be NH and alkyl having one to ten carbons, OR where R can be lower alkyl having one to ten carbons, NR R where R" and -R"' can each be H, NH or R H(CHOH) H HO CH -OH Normally equimolar amounts of the fluorescent moiety and the linking agent are employed in the reactions. Oligomer compounds are obtained, however, when either of the reactants is present in excess. Mixtures of fluorescent moieties and/or linking agents are acceptable for these condensation reactions as is illustrated in the examples given below.

The amount of solvent employed, if desired, is not critical. If one is used it should be in an amount suflicient to readily dissolve the reactants. Normally, a minimum amount of about five times the weight of the fluorescent compound is suflicient, particularly in the case of nonionic fluorescent compounds. The maximum amount of solvent employed is not subject to limitation, the amount of thirty times the weight of the fluorescent compounds being satisfactory from an economic standpoint.

The present invention is illustrated by the following examples. The condensation reaction described in each of the examples below is terminated to provide an oligomeric optical brightener compound having a molecular weight in the range from about 200 to about 24,000 and containing about 2 to about 24 repeating fluorescent moieties. To provide more meaning to the description in the example, an equation for the reaction has been included. In addition, a magnitude of the fluorescence intensity is given for most of the examples. This measurement was obtained in the following manner. Fluorescent free cloths as specified in each example were washed in 200 ml. of washing solution in a pint jar in a Landerometer for 30 minutes at F. The washing solutions contain 0.15% of the detergent composition given below.

DETERGENT COMPOSITION The water contained 7 grains hardness per gallon. The concentration of the brightener was at the parts per million figure in the examples. A concentration of brightener of 2 parts per million in an aqueous solution of 0.15% of the detergent composition is another way of reciting the use of 0.133 of the brightener in the complete detergent composition. After being washed, the fabrics were dried and then graded by means of a Galvanek-Morrison Fluorimeter. This instrument is a device for measuring fluorescence intensity. It operates by exciting a treated fabric with ultraviolet light and recording the intensity of emitted visible light from the cloth by means of a photoelectric cell. The magnitude of the emitted visible light is given in the examples in terms of a GM unit. Larger numbers indicate better brightening results.

The magnitude of the improvement made possible by the olegomeric optical brightening agents of this invention was totally unexpected. The fact that any improvement in substantivity was noted at all was surprising. As an indication of the order of magnitude of improvement provided by the compounds of the present invention, it is noted that the fluorescent monomer diaminostilbene has a GM rating of about 7. When this monomer is transformed into an oligomer according to the teachings of the present invention, GM ratings on the order of 190 are obtained. A GM rating of about 30 represents a level of fluorescence intensity which can be appreciated by ordinary visual inspection (such as would be observed in an average household laundry situation).

The oligomeric optical brightener compounds of the present invention have been described above as containing from 2 to about 24 repeating fluorescent moieties and preferably 2 to about 12 fluorescent moieties. It should be noted that the degree of oligomerization (D is usually an average within these prescribed ranges. In other words, in the following examples it will be seen that a range of fluorescent moieties is given in each case. The degree of oligomerization can be a single integer within the prescribed ranges, if desired.

EXAMPLE 1 A solution of 3.64 gms. (0.01 mole) of 4,4-diamino- 2,2-stilbenedisulfonamide in 50 ml. of dry dimethylformamide (DMF) was added to a solution of 1.59 gms. (0.01 mole) of succinic chloride in 50 ml. dry DMF contained in a 250 ml. round-bottom flask equipped with a condenser and magnetic stirring bar. The resulting solution was heated at 80 for 3 hours after which the DMF was removed by evaporation under reduced pressure and the remaining solid crystallized from ethanol. The resulting oligomer exhibited carbonyl bonds in the infrared at 1690 cm.- The ultraviolet spectrum demonstrated a A at 349 nm. The insoluble, dispersible oligomer shown in the equation below produced a GM reading of 80 on cotton and 60 on nylon after a standard wash test using 50 p.p.m. brightener.

S OzNHz S OzNHs OzNHz S O NHg EXAMPLE 2 A solution obtained by adding 4.1 gms. (0.01 mole) of disodium 4,4'-diamino-2,2'-stilbenedisulfonate and 1 ml. triethylamine to 400 ml. of dry dimethylformamide (DMF) was added to a 1 l. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser and addition funnel. The stirred solution was then heated to 50 C. and 1.8 gms. (0.01 mole) of 2,4-dichloro-6-methoxy-s-triazine dissolved in 50 ml. of dry DMF was added over a minute period. The stirred solution was then heated at 60 C. for 3 hours and at 90 C. for 4 hours. After moving the solvent with a rotary evaporator, the resulting solids were crystallized from water. The oligomer shown below thus obtained 12 produced a GM reading of on cotton cloths after a standard wash test utilizing 4 p.p.m. brightener.

N 01% W-Cl mN- -o= --NH C 2+ N L SO Na SO Na l 0on1 n n n H SO;Na SO Na OCH; 2-12 EXAMPLE 3 A solution obtained by adding 4.1 parts (0.01 mole) of disodium 4,4'-diamino-2,2'-stilbenedisulfonate and 1 ml. triethylamine to 400 ml. of dry dimethylformamide (DMF) was added to a 1 l. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser and addition funnel. The stirred solution was then heated to 70 C. and 1.65 parts (0.01 mole) of 2- amino-4,6-dichloro-s-triazine dissolved in 50 ml. of dry DMF was added over a 30 minute period. The stirred solution was then heated at 80 for 6 hours. After the solvent was removed by evaporation under reduced pres sure, the oligomer was crystallized from water. This oligomer shown below produced a GM reading of on cotton cloths after a standard wash test using 5 p.p.m. brightener.

I it A solution of 3.64 gms. (0.01 mole) of 4,4-diamino- 2,2'-stilbenedisulfonamide in 50 ml. of dry dimethylformamide (DMF) was added to a solution of 1.59 gms. (0.01 mole) of succinic chloride in 50 ml. dry DMF contained in a 250 ml. round-bottom flask equipped with a condenser and magnetic stirring bar. The DMF was removed by evaporation under reduced pressure and the remaining solid crystallized from ethanol. The resulting oligomer exhibited carbonyl bonds in the infrared at 1690 cmr The ultraviolet spectrum demonstrated a A at 349 nm. The insoluble, dispersible oligomer shown below produced a GM reading of 80 on cotton and 60 on nylon after a standard wash test using 5 p.p.m. brightener.

l S OZNIIZ S OZNIIZ EXAMPLE A solution obtained by adding 3.64 gms. (0.01 moles) of 4,4-diamino-2,2-stilbenedisulfonamide and 1 ml. triethylamine to 200 ml. of dry dimethylformamide (DMF) was added to a 500 ml. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser, and additional funnel. The stirred solution was then heated to 60 and 1.8 grns. (0.01 mole) of 2,4-dichloro-6-methoxy-s-triazine dissolved in 150 ml. of dry DMF was added over a period of minutes. The stirred solution was then heated at 75 C. for 4 hours. The resulting oligomer was precipitated by adding the reaction solution to water. The oligomer shown below produced a GM reading of 70 on cotton cloths and 85 on nylon cloths after a standard wash test utilizing 4 p.p.m. brightener.

A mixture obtained by ading 4.67 grns. (0.01 mole) of 4,4'-diacetamido-2,2'-stilbenedisulfonylchloride to l l.

H H H N i i C1/ C1 0mm somm OCH};

r a H N 1 OzNHn O2NH2 EXAMPLE 6 A solution obtained by adding 3.64 gms. (0.01 mole) of 4,4-diamino-2,2-stilbenedisulfonamide and 1 ml. pyridine to 200 ml. dry dimethylformamide (DMF) is added to a 500 ml. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser and additional funnel. The stirred solution is then heated to 40 C. and 2.07 gms. (0.01 mole) of Z-ethylmethylamine- 4,6-dichloro's-triazine dissolved in 150 ml. of dry DMF is added over a minute period. The stirred solution is then heated at 60 C. for 4 hours. The resulting oligomer is precipitated by adding the warm reaction mixture to 1 l. of water. The oligomer shown below produces a GM reading of 60 on cotton cloths and 80 on nylon cloths after a standard test utilizing 4 p.p.m. brightener.

2-10 of benzene was added to a solution of 1.16 grns. (0.01 mole) of hexamethylenediamine contained in 200 ml. of benzene contained in a 2 l. round-bottom flask equipped with a magnetic stirring bar and a heating mantle. The resulting mixture was allowed to stir at 50 for 8 hours. The benzene was removed by distillation under reduced pressure and the residue crystallized from ethanol. This oligomer shown below was insoluble but dispersible in water. A standard performance test utilizing 5 p.p.m. brightener produced GM readings of on cotton and 60 on nylon.

EXAMPLE 8 A solution of 3.04 gms. (0.01 moles of 4,4'-stilbenedicarboxylicacid chloride dissolved in l l. of carbontetrachloride was added to a solution of 1.16 gms. (0.01 mole) of hexamethylenediamine dissolved in 200 ml. of 40% NaOH contained in a Waring Blendor. The twophase system was stirred vigorously at room temperature for two hours and the solid material thus obtained filtered with a sintered glass filter. The resulting white oligomer exhibited an ultraviolet A at 325 A and a amide canbonyl bond at 1690 cm? in the infrared. This oligomer shown below was substantive to cellulose and produced a GM reading of on cotton after a standard wash test utilizing 5 p.p.m. brightener.

15 EXAMPLE 9 A solution obtained by adding 2.1 gms. 0.01 mole) of 4,4 diamino stilbene and 1 ml. of pyridine to 50 ml. of dry dimethylformamide (DMF) was added to a 250 ml. 3-necked round-bottom flask equipped wit-h a magnetic stirring bar, heating mantle, condenser, and addition funnel. A solution of 1.59 gms. (0.01 mole) of succinic chloride in dry DMF was added to the flask over a ten minute period while stirring was maintained at room temperature. The solution was then warmed to 40 C. and allowed to stir for 12 hours. The resulting oligomer was crystallized from ethanol after the DMF was removed by distillation. The oligomer shown below produced a GM reading of 50 on cotton cloths and 50 on nylon cloths after a standard wash test utilizing 4 ppm. brightener.

C a P l mN--o=o- N ol-d-omonrb-ci A solution obtained by adding 2.1 gms. (0.01 mole) of 4,4 diamino stilbene to 50 ml. of dimethylformamide (DMF) was added to a 500 ml. 3-necked, roundbottom flask equipped with a magnetic stirring bar, heating mantle, condenser and addition funnel containing 1.8 gms. (0.01 mole) of 2 methoxy 4,6 dichloro-s-triazine, 2 ml. triethylamine and 100 ml. dry DMF. The stirred solution was heated at 90 C. for 8 hours. The resulting oligomer was precipitated by adding the hot reaction mixture to 1 l. of cold water. After filtration the resulting oligomer was crystallized from ethanol. The oligomer shown below produced a GM reading of 120 on cotton cloths and 85 on nylon cloths after standard wash test utilizing 4 p.p.m. brightener.

HlL aA i QC.

| OCH;

EXAMPLE 11 A solution obtained by adding 1.55 gms. (0.01 mole) of 2,6-dichloropyrazine to 50 ml. of dry dimethylformamide (DMF) was added over a period of 30 minutes to a solution of 1.16 gms. (0.01 mole) of hexamethylenediamine dissolved in 20 ml. of dry DMF contained in a 125 ml. round-bottom flask equipped with a magnetic stirring bar. The resulting solution was heated at 75 C. for 8 hours. After removing the DMF with a rotary evaporator the resulting solids were crystallized from water. The oligomer shown below thus obtained was substantive to cellulose and produced a GM reading on cotton of 35 after a standard wash test utilizing ppm. brightener.

EXAMPLE 12 A solution obtained by adding 3.24 gms. (0.01 mole) of 1,2-bis-[N,N-di(2-hydroxyethyl)benzimidazol 2 yl] ethylene and 1 ml. pyridine to 600 ml. of dimethylformamide (DMF) to a l l. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser, and an addition funnel. The stirred solution was then heated to 50 C. and 2.4 gms. (0.01 mole) of sebacoyl chloride in 50 ml. dry DMF was added over a 30 minute period. The resulting solution was heated to C. and allowed to stir overnight. The oligomer shown below was precipitated by adding the hot liquid reaction to 2 liters of water. The crude reaction product produced a GM reading of 140 on cotton cloths and on nylon cloths after a standard wash test utilizing 5 ppm. brightener.

A solution obtained by adding 4.14 gms. (0.01 mole) of disodium 4,4-diamin0-2,2'-stilbenedisulfonate to 1 l. of dry dimethylformamide (DMF) was added over a period of 10 minutes to a solution of 3.1-8 gms. (0.02 mole) of succinic chloride in 250 ml. dry DMF contained in a 2 l. round-bottom flask equipped with a magnetic stirring bar and a heating mantle. After the resulting solution had been heated at 80 for 6 hours 7.38 gms. (0.02 mole) of 4,4-diamino-2,2'-stilbenesulfonamide in 100 ml. of dry DMF was added over a twenty minute period. After the resulting solution was heated at 80 for three hours, the DMF was removed by distillation under reduced pressure. The resulting solid was crystallized from water. The product was shown by thin-layer chromatog- 3,657,231 17 18 raphy to be primarily the oligomer of structure III. The cm.- The ultraviolet spectrum demonstrates a A at ultraviolet A was 350 nm. The oligomer shown below 349 nm. The insoluble, dispersible oligomer shown below produced a GM reading of 70 on cotton cloths after a standard wash test utilizing p.p.m. brightener.

1'1 H o o 0 i) 1'1 H H H o 0 HN-O=0--NH 2Cl- J-CHiOH2-( J-Cl Cl -CHzCHz-N= --l x-i omc c S O Na SIO3NB S 0;Na O3Nt3 0 0 H H H I o 0 H H C1= -CH2CHz N-(!7=()Ni-CH2CHz- -Cl 2NHr('J=(B-NH1 S Oa Ii B 3 n S OzNHa SIO2NH1 1'1 E 1'1 0 0 III E H Ill 0 (I) H H H HzN-=o=b--N-i s-0Ht0Ht- -N--o= -N-ii-om0Ht- J-I I--( NH,

s ozNHg SO2NH2 B OzNfl S O Na B ORNHI B OgNHi (III) produces a GM reading of 80 on cotton and 60 on nylon EXAMPLE 14 after a standard wash test using 5 p.p.m. brightener. Al bdbdd 11 (27l)f 1 i I i so ution o taine y a ing g. mo es 0 the diacid chlorides of 1,4-bis-(para-carboxystyryl)ben- HN Q C NH+C1 (CH) 'C1 zene and 0.49 g. (2.7 moles) of sorbitol to 40 ml. of dry dimethylformamide (DMF) was added to a 100 ml. 802m" 802m" round-bottom flask equipped with a magnetic stirring bar 1 and a condenser. The stirred solution was heated at 130 H H H H 0 O C. for 3 hours. The resulting oligomer was precipitated 4} I I g g by adding the reaction solution to diethyl ether. The 30 =0 N- .(CH2)4 0H oligomer shown below produced a GM reading of 190 l- J on cotton cloths after a standard wash test utilizing 4 N z 2-a p.p.m. brightener and the brightening efi'ect was also noted EXAMPLE 17 under tungsten lighting conditions. A solution of 3.64 gms. (0.01 mole) of 4,4-diamino- EXAMPLE 15 2,2-stilbenedisulfonamide in 50 m1. of dry dimethylform- A solution obtained by adding 1.1 g. (2.7 moles) of amide is added to a Solution of g (0.01 the diacid chloride of 1,4-bis-(para-carboxystyryl)benmole) of sebacoyl chloride in ml. dry DMF contained zene and 0.15 g. (2.7 moles) of glycerol to 40 ml. of dry in a 250 roundbottom flask equipped with a com d h if d DMF dd d 110 a 100 ml. 53 33 zg g gg f euippe g aamaegnefic stirring bar denser and magnetic sttrnng bar. The resulting solution and a condenser. The stirred solution was heated at 130 15 heated at 800 for 3 hours after Whlch the DMF 18 C. for 3 hours. The resulting oligomer was precipitated 50 moved by evaporation under reduced pressure and the y adding the reaction Solution to diellhyl ether- The remaining solid crystallized from ethanol. The resulting oligomer shown below produced a GM reading of 200 on cotton cloths after a Standard wash test utilizing 4 ppm. oligomer exhibits carbonyl bonds m the infrared at 1690 brightener and the brightening etfect was also noted under elm-1' The ultraviolet spectrum demonstrates a max at tungsten lighting conditions. 55 349 nm. The insoluble, dispersible oligomer shown below produces a GM reading of 80 on cotton and on nylon EXAMPLE 16 after a standard wash test using 5 p.p.m. brightener.

A solution of 3.64 gms. (0.01 mole) of 4,4-diaminog E 0 2,2'-stilbenedisulfonamide in 50 ml. of dry dimethylform- N 1a 1- -(CHi)a 1 amide (DMF) is added to a solution of 1.83 grams .(0.01 g mole) of adipoyl chloride in 50 ml. dry DMF contained 301N111 OzNH: in a 250 ml. round-bottom flask equipped with a condenl ser and magnetic stirring bar. The resulting solution is heated at for three hours after which the DMF is I' H H H 0 0' removed by evaporation under reduced pressure and the 1 1; g g remaining solid crystallized from ethanol. The resulting 7 oligomer exhibits carbonyl bonds in the infrared at 1690 5 o NH H2 3,657,231 19 20 EXAMPLE 18 structure III. The ultraviolet A is 350 nm. The oligomer A solution obtained by adding 4.14 gms. (0.01 mole) shown below produces a GM reading of 70 on cotton of disodium 4,4'-diamino-2,2-stilbenedisulfonate to 1 1. cloths after a Standard Wash test utilizing p-pof dry dimethylformamide (DMF) is added over a period 5 brightener.

H H I? I I II i t? I II I HzN--C=dJ-NHZ 2c1-ocH2).-d-c1 oi-dcnm- -N--c=o--N-oom)i(I-or l I S O Na S O Na SO Na SO Na O O H r r O a H CI-Ii- CHm-I J-I I-Q-c=o-NIi(oHm-h-or 2NH,-- ;=o--NH,

S O Na SOQNQ SIO2NHI SOzNH:

H H H 0 o H H H H 0 0 H H H I I I II I; I l I I II I] I l I H2N- C=C N -(GHz)s N G=C N (CH1)5 -N-- -C=C- NII;

I s orNHi S OzNH1 S OaNQ SO3N3 SIOZNHI SOQNH:

(III) of minutes to a solution of 3.66 gms. (0.02 mole) of 5 EXAMPLE adipoyl chloride in 250 ml. dry DMF contained in a 2 1. round-bottom flask equipped with a magnetic stirring bar A solution obtained by adding 4.1 gms. (0.01 mole) d a h g mantle- After the resulting solllfiOIl is of disodium 4,4'-diamino-2,2-stilbenedisulfonate and 1 heated at 80 for 6 hours 7.38 gms. 2 m l f ml. triethylamine to 400 ml. of dry dimethylformamide diarnino-2,2'-stilbenesulfonamide in 100 ml. of dry DMF (DMF) i added to a 1 l. 3-necked round-bottom flask is added over a twenty minute period. After the resulting equipped with a magnetic stirring bar, heating mantle, consolution is heated at 80 for three hours, the DMF is denser and addition funnel. The stirred solution is then removed by distillation under reduced pressure. The reheated to C. and 1.92 gms. (0.01 mole) of 2,4-disulting solid is crystallized from water. The product is chloro-6-ethoxy-s-triazine dissolved in 50 ml. of dry DMF shown by thin-layer chromatography to be primarily the 35 is added over a 15 minute period. The stirred solution is oligomer of structure III. The ultraviolet A is 350 then heated at C. for 3 hours and at 90 C. for 4 nm. The oligomer produces a GM reading of 70 on cotton hours. After removing the solvent with a rotary evapocloths after a standard wash test utilizing 5 p.p.m. brightrator, the resulting solids are crystallized from water. The

ener. oligomer shown below thus obtained produces a GM H H 0 0 0 o H H H H 0 0 I I II II II I5 I I I I II II HQN- C=C -NH, 2Cl- (CH2)4CC1 01- (CH2)A N -0=c- -N-c-(CH1)i-c-oi SO3N3 SIOQNSA SIOQNH s ogNi) 0 I? I? H i re c1-IioHi i-o-N-o=o--N-cclrz)i-c-cl 2NH,-c=o-NH,

S O Na SO Na SOZNH] s ozNHfl H H H 0 0 H H H H 0 0 H H H I l I g I I I I 5 II I I I HzN- C=C- N -(CH2)4- -N C=C N- (OH1)4 N C=C- -NH,

S|O:NH7 SOzNHz SOaNB s ogNB SIOZNHI S OzNIh reading of 140 on cotton cloths after a standard wash EXAMPLE 19 60 test utilizing 4 p.p.m. brightener.

H H Cl\ N Cl -A solution obtained by adding 4.14 gms. (0.01 mole) of HN I NHZ T disodium 4,4'-diamino-2,2'-stilbenedisulfonate to 1 l. of N dry dimethylformamide (DMF) is added over a period of soaNa SIOSNa 10 minutes to a solution of 4.78 gms. (0.02 mole) of sebacoyl chloride in 250 ml. dry D'MF contained in a 2 1. 091mm round-bottom flask equipped with a magnetic stirring bar and a heating mantle. After the resulting solution is heated I at 80 for 6 hours 7.38 gms. (0.02 mole) of 4,4-diamino- H H H 2,2'-stilbcnesu1fonamide in 100 ml. of dry DMF is added I I I over a twenty minute period. After the resulting solution -N- 01 is heated at 80 for three hours, the DMF is removed by I distillation under reduced pressure. The resulting solid is SOQNa SOSNQ crystallized from water. The product is shown by thin- I layer chromatography to be primarily the oligomer of 0 2 2 Ii 21 EXAMPLE 21 A solution obtained by adding 3.64 gms. (0.01 mole) of 4,4'-diamino-2,2-stilbenedisulfonamide and 1 ml. triethylamine to 200 ml. of dry dimethylformamide (DMF) is added to a 500 m1. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser, and addition funnel. The stirred solution is then heated to 60 C. and 1.64 gms. (0.01 mole) of a 2,4-dichloro-6-methyl-s-triazine dissolved in 150 ml. of dry DMF is added over a period of 20 minutes. The stirred solution is then heated at 75 C. for 4 hours. The resulting oligomer is precipitated by adding the reaction solution to water. The oligomer shown below produces a GM reading of 70 on cotton cloths and 85 on nylon cloths after a standard wash test utilizing 4 p.p.m. brightener.

OH; l s

F i i i N 'I I 502N112 OzNHz H: 2-1: EXAMPLE 22 A solution obtained by adding 3.64 gms. (0.01 mole) of 4,4'-diamino-2,2'-stilbenedisulfonamide and 1 ml. triethylamine to 200 ml. of dry dimethylformamide (DMF) is added to a 500 ml. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser, and addition funnel. The stirred solution is then heated to 60 C. and 1.94 gms. (0.01 mole) of 2,4-dichloro-6-ethoxy-s-triazine dissolved in 150 ml. of dry DMF is added over a period of 20 minutes. The stirred solution is then heated at 75 C. for 4 hours. The resulting oligomer is precipitated by adding the reaction solution to water. The oligomer shown below produces a GM reading of 70 on cotton cloths and 85 on nylon clothes after a standard Wash test utilizing 4 p.p.m. brightener.

| 1 I 01 -o1 HN- =o- -NHz U somm somm OCHzCHa ii. E E

S OZNHQ OCHgCHa 2-12 EXAMPLE 23 22 is substantive to cellulose and produces a GM reading of 45 on cotton after a standard wash test utilizing 5 p.p.m. brightener.

EXAMPLE 24 A solution of 3.04 gms. (0.01 mole) of 4,4-stilbenedicarboxylicacid chloride dissolved in 1 l. of carbontetrachloride is added to a solution of .60 gm. (0.01 mole) of ethylenediamine dissolved in 200 ml. of 40% NaOH contained in a Waring Blendor. The two-phase system is stirred vigorously at room temperature for two hours and the solid material thus obtained filtered with a sintered glass filter. The resulting white oligomer exhibited an ultraviolet A at 325 nm. and an amide carbonyl band at 1690 cm. in the infrared. This oligomer shown below is substantive to cellulose and produces a GM reading of 45 on cotton after a standard wash test utilizing 5 p.p.m. brightener.

A solution obtained by adding 4.1 parts (0.01 mole) of disodium 4,4'-diamino-2,2-stilbenedisulfonate and 1 ml. triethylamine to 400 ml. of dry dimethylformarnide (DMF) is added to a l 1. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser, and addition funnel. The stirred solution is then heated to 70 C. and 2.07 parts (0.01 mole) of 2- ethylmethylamino-4,6-dichloro-s-triazine dissolved in 50 ml. of dry DMF is added over a 30 minute period. The stirred solution is then heated at for 6 hours. After the solvent is removed by evaporation under reduced pressure, the oligomer is crystallized from water. This oligomer shown below produces a GM reading of on cotton cloths after a standard wash test using 5 p.p.m. brightener.

H CI c1 mN- o= --Nnl L L 0 Na some /N CH: CH, (RH.

11 H H H are t a. l O.

l SO Na OaN! CH2 CH3 H2 in.

EXAMPLE 26 A solution obtained by adding 4.1 parts (0.01 mole) of disodium 4,4'-diamino-2,2'-stilbenedisulfonate and 1 ml. triethylamine to 400 ml. of dry dimethylformamide (DMF) is added to a 1 l. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser, and addition funnel. The stirred solution is then heated to 70 C. and 1.93 parts (0.01 mole) of 2- dimethylamino-4,6-dichloro-s-triazine dissolved in 50 ml. of dry DMF is added over a 30 minute period. The stirred solution is then heated at 80 for 6 hours. After the solvent is removed by evaporation under reduced pressure, the oligomer is crystallized from water. This oligomer shown below produces a GM reading of 160 on cotton cloths after a standard wash test using p.p.m. brightener.

HaC CH;

EXAMPLE 27 A solution obtained by adding 3.64 gms. (0.01 mole) of 4,4-diamino-2,2'-stilbenedisulfonamide and 1 ml. pyridine to 200 ml. of dry dimethylformamide (DMF) is added to a 500 ml. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser and addition funnel. The stirred solution is then heated to 40 C. and 1.93 gms. (0.01 mole) of 2-dimethylamino-4,6-dichloro-s-triazine dissolved in 150 mi. of dry DMF is added over a 30 minute period. The stirred solution is then heated at 60 C. for 4 hours. The resulting oligomer is precipitated by adding the warm reaction mixture to 1 l. of water. The oligomer shown below produces a GM reading of 60 on cotton cloths and 80 on nylon cloths after a standard wash test utilizing 4 p.p.m. brightener.

l or o1 -o=o- -NH ll I SOzNHz OZNHI solNm somH, N

EXAMPLE 28 oligomer is crystallized from ethanol. The oligomer shown below produces a GM reading of 120 on cotton cloths and 85 on nylon cloths after standard wash test utilizing 4 p.p.m. brightener.

EXAMPLE 29 A solution obtained by adding 2.1 gms. (0.01 mole) of 4,4'-diaminostilbene to ml. of dimethylformamide (DMF) is added to a 500 ml. 3-necked, round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser and addition funnel containing 1.64 gms. (0.01 mole) of 2-methyl-4,6-dichloro-s-triazine, 2 ml. triethylamine and 100 ml. dry DMF. The stirred solution is heated at 90 C. for 8 hours. The resulting oligomer is precipitated by adding the hot reaction mixture to l l. of cold water. After filtration the resulting oligomer is crystallized from ethanol. The oligomer shown below produces a GM reading of 120 on cotton cloths and on nylon cloths after standard wash test utilizing 4 p.p.m. brightener.

A solution obtained by adding 4.1 gms. (0.01 mole) of disodium 4,4-diamino-2,2'-stilbenedisulfonate and 1 ml. triethylamine to 400 ml. of dry dimethylformamide (DMF) is added to a l l. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser and addition funnel. The stirred solution is then heated to 50 C. and 1.64 gms. (0.01 mole) of 2,4-dichloro-6-methyl-s-triazine dissolved in 50 ml. of dry DMF is added over a 15 minute period. The stirred solution is then heated at 60 C. for 3 hours and at C. for 4 hours. After removing the solvent with a rotary evaporator, the resulting solids are crystallized from water. The oligomer shown below thus obtained produces a GM 25 26 reading of 140 on cotton cloths after a standard wash 50 on cotton cloths and 50 on nylon cloths after a standtest utilizing 4 p.p.m. brightencr. ard wash test utilizing 4 p.p.m. brightener.

H H H 0 H H HN aa L 01.45-)... to. H2N=-NHg I if 5 2 2 5 N B0: S OaNa l CH3 H H H EH 0 0 Fl @l I I II If H-N 0:0- --NC(CH2)5=(,OH l J2-.. H H H I EXAMPLE 33 1 1 J 01 A mixture obtained 'by adding 4.67 gms. (0.01 mole) i of 4,4'-diacetamido-2,2-stilbenedisulfonylchloride to 1 1. SOaNa SOBNB N 19 of benzene is added to a solution of .74 gm. (0. 01 mole) of '1,3-propanediamine containing 200 ml. of benzene E M2 contained in a 2 l. round-bottom flask equipped with a EXAMPLE 31 magnetic stirring bar and heating mantle. The resulting mixture is allowed to stir at 50 for 8 hours. The benzene A solution obtained by adding 2.1 gms. (0.01 mole) is removed by distillation under reduced pressure and the of 4,4-diaminostilbene and 1 ml. of pyridine to 50 residue crystallized from ethanol. This oligomer shown ml. of dry dimethylforrnamide (DMF) is added to a 250 below is insoluble but dispersible in water. A standard ml. 3-necked round-bottom flask equipped with a magperformance test utilizing 5 p.p.m brightener produces netic stirring bar, heating mantle, condenser, and addi- GM readings of 40 on cotton and 60 on nylon.

0 Eli III H H o om-b-rrcab-@JrJL-om HzN(CH2)aNHg O H H 1?: I? O H0--S0 III III L S 0zN' (C H2) 3-N H J2-l2 a i HOS02 111 I? l- S OflN-'(CHz) 3-N H tion funnel. A solution of 1.83 gms. (0.01 mole) of adiiEXAMPLLE 34 poyl chloride in dry DMF is added to the flask over a ten minute period while stirring is maintained at room temperature. The solution is then warmed to 40 C. and allowed to stir for 12 hours. The resulting oligomer is crystallized from ethanol after the DMF is removed by distillation. The oligomer shown below produces a GM reading of on cotton cloths and 50 on nylon cloths 50 after a standard wash test utilizing 4 p.p.m. brightener.

A solution obtained by adding 1.55 gms. (0.01 mole) of 2,6-dichloropyrazine to 50 ml. of dry dimethylformamide (:DMF) is added over a period of 30 minutes to a solution of .60 gms. (0.01 mole) of ethylenediamine dissolved in 20 ml. of dry DMF contained in a 125 ml. round-bottom tflask equipped with a magnetic stirring bar. The resulting solution is heated at 75 C. for 8 hours. After removing the DMF with a rotary evaporator the H H Hz 0 0 resulting solids are crystallized from Water. The oligomer g g shown below thus obtained is substantive to cellulose and produces a 'GM reading on cotton of 35 after a standard wash test utilizing 5 p.p.m. brightener. Thinl layer chromatographic analysis of this oligomer indicates that the degree of polymerization (DP) was 5-9. I-H H H H 0 0'] IR spectra indicates the presence of N-H bonds the l ultraviolet A 1s 318 nm.

L J -li! N iEXAMPLE 32 l H2N(CH2)2 NH2 A solution obtained by adding 2.1 gms. (0.01 mole) 01 N 01 of 4,4'-diaminostilbene and 1 m1. of pyridine to 50 m1. of l dry dimethylformamide (DMF) is added to a 250 ml. 3- necked roundbottom flask equipped with a magnetic stirring bar, heating mantle, condenser, and addition funnel. H H A solution of 2.39 gms. (0.01 mole) of sebacoyl chlo- 01 l; l ride in dry DMF is added to the flask over a ten minute L N period while stirring is maintained at room temperature. The solution is then warmed to 40 C. and allowed to EXAMPLE 35 stir for 12 hours. The resulting oligomer is crystallized from ethanol after the DMF is removed by distillation. A solution obtained by adding 1.55 gms. (0.01 mole) The oligomer shown below produces a GM reading of of 2,6-dichloropyrazine to 50 ml. of dry dimethylformamide (DMF) is added over a period of 30 minutes to a solution of 74 gms. (0.01 mole) of 1,3-propanediamine dissolved in 20 ml. of dry DMF contained in a 125 ml. round-bottom flask equipped with a magnetic stirring bar. The resulting solution is heated at 75 C. for 8 hours. After removing the DMF with a rotary evaporator the resulting solids are crystallized from water. The oligomer shown below thus obtained is substantive to cellulose and produces a GM reading on cotton of after a standard Wash test utilizing 5 p.p.m. brightener. Thin-layer chromatographic analysis of this polymer indicates that the degree of polymerization (DP) is 5-9. IR spectra indicates the presence of N-H bonds the ultraviolet A is 318 nm.

EXAMPLE 36 A solution obtained by adding 3.24 gms. (0.01 mole) of 1,2-bis-[N,N-di(2" hydroxyethyl)benzimidazol-2-yl] ethylene and 1 ml. pyridine to 600 ml. of dimethylformamide (DMF) is added to a 1 l. 3-necked round-bottom flask equipped with a magnetic stirring bar, heating mantle, condenser, and an addition funnel. The stirred solution is then heated to 50 C. and 1.83 gms. (0.01 mole) of adipoyl chloride in 50 ml. dry DMF is added over a 30 minute period. The resulting solution is heated to 80 C. and allowed to stir overnight. The oligomer is precipitated by adding the hot liquid reaction to 2 liters of water. The crude oligomeric reaction product shown below produces a GM reading of 140 on cotton cloths and 100 on nylon cloths after a standad wash test utilizing 5 p.p.m. brightener.

28 EXAMPLE 37 A solution obtained by adding 3.24 gms. (0.01 mole) of 1,2 bis[N,N di(2" hydroxyethyl)benzimidazol- 2'-yl] ethylene and 1 ml. pyridine to 600 ml. of dimethylformamide (DMF) is added to a 1 l. 3-necked roundbottom flask equipped with a magnetic stirring bar, heating mantle, condenser, and an addition funnel. The stirred solution is then heated to 50 C. and 1.59 grns. (0.01 mole) of succinyl chloride in 50 ml. dry DMF is added over a 30 minute period. The resulting solution is heated to C. and allowed to stir overnight. The oligomer is precipitated by adding the hot liquid reaction to 2 liters of Water. The crude oligomeric reaction product shown below produces a GM reading of 140 on cotton cloths and on nylon cloths after a standard wash test utilizing 5 p.p.m. brightener.

glam

The invention is further illustrated by the following equations which show the preparation of oligomeric optical brighteners having substantially improved substantivity over the fluorescent monomer. Each of the reaction products can be effectively used in admixture with detergents and builders as described above to brighten synthetic fabrics, cellulosic fabrics and blends of such materials.

EXAMPLE 38 COCl In this example, as in Example 40 below, amidation reactions using analogous chlorides, e.g., ortho, meta para, or other electrophilic functional groups such as an acid in positions other than those illustrated also produce useful oligomers. Similarly, the diamine can be any diamine containing from two to ten carbon atoms, e.g.,

Positional isomers of the 7-amino3 [P-aminophenyl] coumarin can also be used in the above displacement reaction to form oligomer optical brightener compounds. The 6 position on the triazine ring can have any lower alkoxy, amino, alkylamino, or dialkylamino group containing from 1 to about 10 carbon atoms.

EXAMPLE 40 Analogous amidation reactions using acid chlorides or other electrophilic functional groups in positions other than those illustrated will also produce useful oligomers. Similarly, the diamine can be any diamine containing from two to ten carbon atoms.

EXAMPLE 41 Positional isomers of the 2,5-bis[diaminophenyl]furan may also be used in the condensation reaction to prepare useful oligomers. The :,0: diacidchlorides may contain from three to twelve carbon atoms.

EXAMPLE 42 i N i 011,00 coon, f

CH N HCHa The aliphatic diamine used in the above arninolysis reaction can contain from 2 to 10 carbon atoms. The methylamino groups on the pyrazine can be replaced with any lower alkylamino group, C

NHCH; 0-10 The aliphatic diol used in the above alcoholysis can be any aliphatic diol containing from 2 to 10 carbon atoms. The methylamino groups on the pyrazine ring can be replaced with any lower-alkylamino group having from 1 to 10 carbons.

EXAMPLE 44 COOCH NH 0/ 3+ 3H2 3 2 1 among E-NI-P-CH CH -3 U \o 3- a H Analogous amidation reactions using acid chlorides or other electrophilic functional groups in positions other than those illustrated will also produce useful oligomers. Similarly, the diamine can 'be any diamine containing from two to ten carbon atoms.

31 32 EXAMPLE 45 N N NH H H o-c n=c z-o 0 omoii ii-ocn: 1 1m N N CCH=CHC CH3Oii -h-N-oHzoH2N H L 0 0 .JH

Analogous amidation reactions using acid chlorides or other electrophilic functional groups in positions other l than those illustrated will also produce useful oligomers.

Similarly, the diamine can be any diamine containing from two to ten carbon atoms. H0--N-O EXAMPLE 46 H H l O C(|3== /N H H N\ O H H H 1'; H01 \O/ I T-(CH2)s-'1 I-H HI l NH 13-1 Analogous amidation reactions using acid chlorides or other electrophilic functional groups in positions other than those illustrated will also produce useful oligomers. Similarly, the diamine can be any diamine containing 1 from two to ten carbon atoms.

EXA L HH MP E49 0 o-e= 'J-o H O 0 Positional isomers of the a,}8-bis[6-aminobenzoxazol- NH,

2-yl]ethylene may also 'be used in the condensation reaction to prepare useful oligomers. The a,w-diacidchlo- 1 I ride may contain from three to twelve carbon atoms. 40 I EXAMPLE 47 I F i N N H0 e 4' N o 0 HO s on ii-oi -o s s A; s 11 H N CN(CHz);N-H on, n J

A) 50 OH: 0 a Analogous amidation reactions using acid chlorides or other electrophilic functional groups in positions other than those illustrated will also produce useful oligomers. Similarly the diamine can be any diamine containing from two to ten carbon atoms.

|' 0. :l EXAMPLE so 0 H LO 1'1 0 g 2-1: EN III (g-Cl Positional isomers of the 2,5-bis[6-hydroxybenzthiazol- E 2-yl]thiophene may also be used in the condensation N Na H1 reaction to prepare useful oligomers. The new diacida L chlorides may contain from three to twelve carbon atoms. l The sulfur moiety can be oxygen or nitrogen also. i

EXAMPLE 48 N 0001 f 0 r w H r O /oo=o (ones L /0-c=o -i JCHzCHni JOH NH o 0001 1 N some i l Positional isomers of the sodium a-[5-aminobenzoxazol- 2-yl]-4-aminostyrenesulfonate may also be used in the con- 34 densation reaction to prepare useful oligomers. The a,w-di- Analogous amidation reactions using acid derivatives in acidchlorides may contain from three to twelve carbon positions other than those illustrated also produce useful atoms. oligomers. Similarly, the diamine can be any diamine con- EXAMPLE 51 taining from two to ten carbon atoms.

Positional isomers of the B,}8'-bis [fi-hydroxybenzoxazol- EXAMPLE 55 2-yl]-p-phenylenedivinylene may also be used in the con- H H densation reaction to prepare oligomers. The a,w-diacid- C CHZGH2COQH chlorides may contain from three to twelve carbon atoms.

EXAMPLE 52 SOQNa SOK a 0 H H 0 NH: 1 oil 1 l'l-Gl ((bH 111 H 0 OCHQ CH3 2 .N b=o -omoml I. S O Na S oaNa 15-20 0 H H O H H The homo-condensation illustrated above will also pro- F& 5 l a duce useful oligomers when positional isomers are used as HO =o- -N(GH2)a-' the starting monomers.

I. $0113 $0113 L 3? EXAMPLE 56 0 Analogous amidation reactions using acid chlorides on 01 other electrophilic functional groups in positions other 2 than those illustrated will also produce useful oligomers. HzN Similarly, the diamine can be any diamine containing from two to ten carbon atoms. l

EXAMPLE 53 o [H S 0z--- 0 H b-el 11:

E g 5 L HO- OH H Q C} e a The self-condensation illustrated above will produce H3 H304) useful oligomers if positional isomers are used as the -Cl starting monomers. g EXAMPLE 5? l H2NC H H o o I ll 3 a t il H- o= -0- -0H2GHP OH N l L J a OCH: OCHa -1 H1 -01 Positional isomers of the 4,4'-dihydroxy-2,2'-dimethoxystilbene also may be used in the condensation reaction to prepare useful oligomers. The cc,w-diaCidCh10Iid6S can con- SOSNQ tain from three to twelve carbon atoms. l

EXAMPLE 54 n 0 NH 0 o H HlgI-O'4} 2 I" H A]; 13'' 5 ILL H O o F lTI l n n HO (C|H2)0 N''-'(CHZ)6 "N-CCHzCHr-COH NHg I NE NH I 0 F-O soaNa 2-12 L 1 Positional isomers of the above diamine can also be H3 used in the condensation reaction to prepare useful oligomers. The a,w-diacidchlorides can contain from three to twelve carbon atoms.

Detergent (laundering and brightening) compositions illustrative of those contemplated by this invention are exemplified by the following examples which show different built formulations in which Oligomeric optical brighteners are employed. These compositions provide pHs in the range of 8-12. The invention is not limited by these examples, however; they are merely illustrative.

EXAMPLE 58 Percent Sodium soap of :80 coconutttallow fatty acids Sodium silicate 10 Tetrasodium pyrophosphate Sodium chloride 6 The oligomeric optical brightener prepared in Example 1 0.05 Water Balance This composition launders well and exhibits good brightening properties on cotton fabrics.

EXAMPLE 59 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 Sodium sulfate 14 Sodium carboxymethylcellulose 0.5 Sodium silicate 7 The oligomeric optical brightener prepared in Example 2 0.10 Water Balance Substantially similar results are obtained when the oligomeric optical brighteners prepared in Examples 3- 10 are employed in lieu of that recited above. They impart effective fluorescence effects without interfering with the cleaning of soiled fabrics.

EXAMPLE 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 Tetrasodium methylene diphosphonate 10 Sodium tripolyphosphate 60 Sodium carboxymethyl cellulose 0.5 Sodium silicate 10 Oligomeric optical brightener prepared in Example l1 0.20 Water 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.

EXAMPLE 61 The following granular composition performs very well Disodium. 4,4 bis(4 anilino-6-morpholino-s-triazin-2-yl-amino)-2,2-silbene disulfonate 0.05 Water Balance 36 EXAMPLE 62 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 Oligomeric optical brightener prepared in Example 1 0.05 Oligomeric optical brightener prepared in Example 2 0.05 Water Balance EXAMPLE 63 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 This detergent composition is effective in laundering and brightening resin-treated cotton wash and wear fabrics.

EXAMPLE 64 A household laundering composition can contain the H following ingredients:

Percent Sodium salt of SO -sulfonated tetradecene 10 Dimethyl coconut alkyl ammonio acetate 10 Trisodium ethane-hydroxy triphosphonate 60 Sodium carbonate l0 Oligomeric optical brightener prepared in Example l0 0.10 4,4'-bis(4-anilino 6 ethanolamine-s-triazin-2-ylamino-2,2-stilbene disulfonic acid 0.20 Water Balance This composition brightens as it cleans and can be usefully employed in laundering nylon fabrics.

EXAMPLE 65 An effective graunlar detergent composition has the following formulation:

Percent Sodium linear dodecylbenzenesulfonate 7.5 Sodium tallow alkyl sulfate 2 Hydrogenated marine oily fatty acid suds depressant 2.2 Sodium tripolyphosphate 40 Trisodium nitrilotriacetate 20 Sodium silicate (ratio SiO :Na O of 22d) 10 Sodium sulfate l3 Oligomeric optical brightener prepared in Example Water Balance 37 EXAMPLE 66 Another effective granular detergent has the following composition:

Percent Sodium linear dodecylbenzenesulfonate Condensation product of 1 mole of nonyl phenol with 12 moles of ethylene oxide 10 Sodium tripolyphosphate 10 Trisodium ethane-l-hydroxy-1,1-diphosphate Trisoduim nitrilotriacetate 10 Sodium silicate (ratio of SiO :Na O of 2: 1) 6 Trisodium phosphate 10 Sodium carboxymethyl cellulose 0.5 Oligomeric optical brightener prepared in Example 32 0.1 Oligomeric optical brightener prepared in Example Water Balance EXAMPLE 67 A laundering-brightening composition, especially effective on cotton fabrics at cool water temperatures, has the following composition:

Percent Sodium tallow alkyl sulfate 5 3 (N,N-dimethyl-N-dodecylammonio)-2-hydroxy-propane-l-sulfonate 12 Sodium salt of SO -sulfonate a tridecene 5 Sodium tripolyphosphate 30 Trisodium nitrilotriacetate 20 Sodium silicate (SiO :Na O=1.6:1) 10 Sodium sulfate 10 Sodium carboxymethyl hydroxyethyl cellulose 0.2 l ,Z-bis 5-methyl-2-benzoxazolyl) ethylene 0.=1 Sodium 4-methyl 4' (3-chlorophthalimidyl)-2-stilbenesulfonate 0.1 Oligomeric optical brightener compound prepared in Example 9 0.1 Water Balance EXAMPLE 68 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) -propane-1- sulfonate 5 Dimethyldodecylphosphine oxide 10 Trisodiurn ethane-l-hydroxy-l,l-diphosphonate 5 Trisodium nitrilotriacetate 10 Sodium tripolyphosphate Sodium silicate (Na O:SiO =7:2.5) 10 Sodium carboxymethyl cellulose 0.3 Sodium sulfate 110 3-phthalimidyl-2,S-di-m-aminophenylfuran 0.15 Oligomeric optical brightener prepared in Example 14 0.15 Water Balance When used in conjunction with detergent compositions the oligomeric brightener compounds of this invention are used in an effective amount to achieve the desired brightening effect. Usually this amount is in the range of from about .001% to about 5% by weight of the detergent composition, preferably 0.5% to about 3%. It is understood that these compounds can be used in admixture with each other as well as with other brightening agents.

In addition to these optical brightener compounds laundry detergent compositions of this invention comprise at least about 10% of a mixture of an organic detergent and an alkaline builder in a ratio in the range of about 5:1 to about 1:20, preferably 2:1 to about 1:10. Such a mixture of a detergent and a builder can represent the balance of a detergent composition, especially a laundry composition. Detergent compositions are contemplated also which comprise the optical brighteners descrbied herein mixed with the detergent compounds (or mixtures of such compounds) described below. The organic detergent compound and alkaline builder salts are more fully disclosed 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) Anion 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 0 0,, 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 12-14 carbons; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher acohols 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 derived from coconut oil; sodium and potassium salts of SO -sulfonated C -C a-olefins.

(c) Noniom'c 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 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 semipolar 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 80% 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 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 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 long chain tertiary phosphine oxides corresponding to the followng general formula RR'R"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-(2-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 O to about 5 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 10 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 S-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 compounds falling within this definition are 3-(N,N-dimethyl- N-hexadecylammonio) propane-l-sulfonate and 3-(N,N- dimethyl-N-hexadecylammonio) 2 hydroxy propane-lsulfonate which are preferred for their cool water detergency characteristics. See for example, Snoddy et al., 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 carbonates, borates, phosphates, polyphosphatcs, bicarbonates, silicates and sulfates. Specific examples of such salts are sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, 0rthophosphates and hexametaphosphates.

Examples of suitable organic alkaline detergency bullder salts are: (l) Water-soluble aminopolyacetates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(Z-hydroxyethyl)-nitrilo diacetates; (2) Water-soluble salts of phytic acid, e.g., sodium and potassium phytatessee U.S. Pat. 2,739,942; (3) Watersoluble polypho'sphonates, including specifically, sodium, potassium and lithium salts of ethane-l-hydroxy-l,l-diphosphonic acid, sodium, potassium and lithium salts of methylene diphosphonic acid, sodium, potassium and lithium salts of ethylene diphosphonic acid, and sodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid. Other examples include these alkali metal salts of ethane-2-carboxy-1, l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethanel-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-l,1, 2-triphosphonic acid, propane 1,1,3,3 tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propanel,2,2,3tetraphosphonic 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

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3849155 *Jun 8, 1972Nov 19, 1974Ciba Geigy AgBrightening of polyacrylonitrile wet tow
US3951960 *Jun 18, 1969Apr 20, 1976Sterling Drug Inc.Novel crystalline forms of optical brighteners
US3959277 *Feb 20, 1974May 25, 1976E. I. Du Pont De Nemours And CompanyDiimidazopyrazines and tetracarboxamidopyrazines
US4166176 *Mar 20, 1978Aug 28, 1979Bayer AktiengesellschaftFluorescent dyestuffs
US6171715 *Jul 30, 1998Jan 9, 2001Fuji Photo Film Co., Ltd.Organic electroluminescent element
US20080146482 *Dec 6, 2006Jun 19, 2008The Procter & Gamble CompanyLiquid laundry detergent having improved brightener stability
US20140020257 *Jan 11, 2012Jan 23, 2014Electrolux Home Products Corporation N.V.Household Appliance For Drying Objects
Classifications
U.S. Classification544/193.2, 427/158, 544/83, 544/86, 549/496, 548/143, 562/60, 548/305.7, 548/220, 564/82, 548/379.7, 252/301.23, 549/288, 560/89, 544/357, 548/306.1, 548/304.7, 548/217, 562/831, 548/305.4, 549/491, 548/379.1, 162/162, 564/83, 544/406
International ClassificationC07D235/20, C07K1/00, C07D263/62, C07D241/20, C11D3/37, C07D241/26, C07D307/52, C11D3/42, C07D231/06
Cooperative ClassificationC07D241/20, C07D307/52, C07D235/20, C11D3/3715, C11D3/3719, C11D3/42, C07D231/06, C07D263/62, C07D241/26, C07K1/006
European ClassificationC11D3/42, C07D235/20, C07K1/00B, C07D307/52, C07D241/20, C11D3/37B4, C11D3/37B8, C07D241/26, C07D231/06, C07D263/62