CA1270717A - Phenylene mono - and diester peracid precursors - Google Patents

Abstract

Abstract of the Invention The invention provides novel peracid precursors representative of which is the structure:

wherein R1 is alkyl of 1 to 20 carbon atoms; R2 is OH, -O-R3, or -O-?-R4; and X1, X2, Y and Z are individually selected from H, SO?, CO?, NO2,-NR?+, halogen, R6 and mixtures thereof;
wherein R3 of -O-R3 is alkyl of 1 to 20 carbon atoms;
R4 of -O-?R4 is alkyl of 1 to 20 carbon atoms; R5 of NR?+ is selected from H, alkyl of 1 to 24 carbon atoms and mixtures thereof; and R6 is alkyl of 1 to 20 carbon atoms.

In one embodiment of the invention, the novel peracid precursors are combined with a source of hydrogen peroxide and sufficient quantities of buffer to impart an alkaline pH when the composition is placed in aqueous solution. Preferred embodiments of the invention include wherein R2 is hydroxy, and R1 is alkyl of 1 to 20 carbon atoms (monoester); and wherein R2 is -O-?-R4, and R1 and R4 are alkyls of 1 to 20 carbon atoms (diester) and may be either symmetrical (i.e., R1=R4) or mixed (i.e., R1?
R4). The mixed diester embodiment appears to provide benefits of mixed hydrophobic/hydrophilic peracid generation to oxidize both hydrophobic and hydrophilic soils. Various detergent adjuncts known to those skilled in the art may be added, such as surfactants, builders, fragrances, antimicrobial compounds and the like.

Description

'; ' , ~,~t~ 7~ , PHENYLE~ MONO - AND DIESTER
PERACID PRECURSORS

Field of the Invention .

This relates to novel peracid precursors and the in situ generation of peracid in aqueous solution by combining a source of hydrogen peroxide, and the novel peracid precursor, exemplary of which are phenylene mono - and diesters, in water, said precursors being of the general structure:

O-C-R
~~,,~Xl wherein Rl, R2, Xl, X2, Y and z are defined within the specification.

Background of the Invention . _ Peroxygen bleaching compounds, such as hydrogen peroxide, sodium percarbonate, so~ium perborate monohydrate or tetrahydrate are useful for bleaching fabrics, textiles and other materials.

Unfortunately, these sorts of pecoxygen bleaches appear less effective when bleaching temperatures o less than 70 C are utilized. Thus, the low wash temperatures found in American washing machines make the use of these bleaches less effective than in European-type washing machines, which typically use water temperatures above 70C. Therefore, attempts have been made to use activators in combination with these peroxygen bleaches. It may be more accurate to call these activators peracid precursors, ' ~7~7~7 since it is generally accepted that when a molecule of a compound such as sodium acetyloxy benzene sul~onate (rNABS~) is combined with a source of hydrogen peroxide, such as sodium perborate monohydrate, in aqueous solution (as indicated in GB 864,798), the result is production of peracetic acid, O

CH3C~O-However, nothing within the prior art shows, discloses, orsuggests that di-substituted benzenes, more specifically, phenylene diesters, may be appropriate for use as peracid precursors.

, Summary of the Invention The invention provides a compound of the general structure o O -C~R
" Z ~ Xl wherein Rl is alkyl of l to 20 carbon atoms; R is OH, -O-R , or -O-C-R ; and X , X , Y and Z are individually selected from H, SO3, CO2, NO2,.
NR4-,- halogen,-R and mi-xtures~ hereo~-Oherein ~3 of -o-R3 is alkyl of l to 20 carbon atoms;
R4 of -o-C-R4 is~alkyl---of l-to 20 carbon atoms; R5 of NR5 is selected from H, alkyl of 1 to 24 carbon atoms and 0 mixtures thereof; and R6 is alkyl of l to Z0 carbon atoms;
wherein when R2 is OH, Rl has m8re than about 3 carbon atoms.; and wherein when RZ is -o-c-R4 t and Rl and R comprise individually alkyls of less than 3 carbon atoms, R ~ R .

~2--7~
The invention also provides a 501id or liquid bleaching composition comprising:

(a) A hydrogen peroxide source; and (b) A bleach effective amount of a precursor of the general structure:

O-C-R

y ~x2 wherein Rl is alkyl of 1 to 20 carbon atoms; R2 is OH -o-R3 or O C R4 and Xl x2 Y d individually selected from H, S03, CQ2, N02, 0 NR4 , halogen, R6 and mixtures thereof; ~o wherein R3 of -o~R3 is alkyl of 1 to 20 carbon atoms;
R4 of ~o-C-R4 is alkyl o~ 1 to 20 carbon-atoms; R of NR4~ is selected from H, alkyl of 1 to 24--carbon atoms--and mixtures thereof; and R6 is alkyl of 1 to 20 carbon atoms.

Preferred embodiments include phenylene ~onoesters wherein R is OH and Rl is straight chain alkyl of 1 toOll carbon atoms; and phenylene diesters wherein R2 is ~o-C-R4, bot~ R2 and R4 straight chain comprislng alkyls of L to 11 carbon atoms.

Selected adjuncts can be added to these bleaching compositions, such as surfactants, stabilizers, buffers and builders. The invention also includes a method for synthesizing the above noted precursor compounds and a method of bleaching.

~7~7~L~

Detailed DescriptiOn o:E the Invention The invention generally relates to novel peracid precursors ~ypical precursors are esters, imide or enol ester compounds which are combined with a source of peroxygenr such as hydrogen peroxide, sodium percarbonate or sodium perborate. These particular types of precursors are commonly used in Europe where washing temperatures are generally higher than is prevalent in the United States. Washing temperatures of up to 100C are common in Europe.

However, there remains a need to provide peracid precursors which are effective to promote good bleaching in wash temperatures below 70 C, more preferably-below 60 C, and most--preferably below 50C.

The preferred peracid precursors of this invention have the general structure:
O-C-R

~R2 wherein ORl is alkyl of 1 to 20 carbon atoms; R2 is OH, -O-R , or -O-C-R ; and X , X , Y and Z are individually selected from H, SO3, CO2, NO2, 0 NR45+, halogen, ~6 and mixtures thereof;

wherein R3 of -o-R3 is alkyl of l to 20 carbon atoms;
R of -O-C-R is alkyl of 1 to 20 carbon atoms; R of NR4 is selected from H, alkyl of 1 to 24 carbon atoms and 7~7 mixtures thereof; and R6 is alkyl of 1 to 20 carbon atorns;
wherein when R is OH, R has more than about 3 carbon atoms; and wherein when R2 is -o-C-R4, and Rl and R comprise individually alkyls of less than 3 carbon atoms, Rll R4 The embodiments of this general structure include:

O -C-Rl ~,~ X

wherein Rl, Xl, X2, Y and Z are defined as above;

O--C--E'~l (II) ~ X

wherein Rl, R3, Xl, X2, Y and Z are defined as above;
and O
I i 1 (III) ~ ~ x2 ~1 4 O-C-R

wherein Rl, R4, Xl, X2, Y and Z are defined as above.

The substituents ~1, R4 and R6, all being alkyls o~ 1 to 20 carbon atoms, may additionally be either straight chain, branched chain, have some unsaturation ~for example, if Rl, R4 or R is derived from natural oils or fatty acids, e.g , oleic acid), and may be substituted at various positions on the carbon chain. substituents of R , R and R may include halogen (Cl , Br , T ), NO2, NR4 ~R5 defined as in the foregoing, and representing, e.g., NH4 and other quaternary ammonium compounds), SO4, CO2, and OH.

With respect to the ring substituents X , X2, Y and Z, which are selected from H, S03, CO2, NO2, NR4 , halogen, R6 and mixtures thereof (wherein R5 of NR4+ is selected from H, alkyl of 1-24 carbon atoms, and mixtures thereof;
and R6 is alkyl of l to 20 carbon atoms~, any combination of these substituents may be present in the precursors of this invention. When the substituents are charged moieties, e.g.
SO3, appropriate counterpart ions (counterions) may be present. With respect to SO3, CO2, Cl , Br , and F , appropriate counterions may be chosen from H , alkali metal salts (Na , Li , K ), although alkaline earth salts (calcium, magnesium, barium) or even - 20 ammonium salts may be possible. With respect to a quaternary ammonium substituent, i.e., NR4 , appropriate counterions can include halides, (CI , Br , I ), methosulfates~ sulfates and nitrates. These aforementioned counterions may also be present with respect to the substituted Rl, R4 and R6 groups, as appropriate.

When compounds of (I), i.e., phenylene monoesters, are considered, it is preferred that R comprise alkyl of l to 20, more preferably l to 15, and ~nost preferably l to ll carbon atoms. Particularly preferred are phenylene monoesters of about 6-ll carbon atoms in length, which appear to provide surface active peracids when combined with a hydrogen peroxide source in ~X~717 -aqueous solution. As exemplified below, in EXPERIMENTAL, E~ample II, these particular compounds were found to be excellent in perhydrolysis, giving good yields of the desired peracid, with surprisingly low levels of diacyl peroxide, which, as described in Chung it al, U.S. 4,412,934, may be problematic.

Compounds of ~II), i.e., phenylene esters with an ether substituent, -o-R5, wherein R5 is alkyl of 1 to 20, more preferably 1 to 10, and most preferably 1 to 6, carbon atoms, may be very reactive compounds. Especi~lly preferred may be when R
= CH3. As with the substituents R , R and R , R may be straight chain, branched, unsaturated or substituted.

With compounds of (III), i.e., phenylene diesters, wherein R is -O-C-R , R and R are preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 11 carbon atoms.
These particular compounds have the advantages of containing two potential sites for perhydrolysis and thus appear to greatly increase peracid yields over prior art precursors when the same amount of precursors, based on molar equivalents, is used~
Additionally, unexpected salutary benefits appear when R and R are unequal, i;e., the compound is a mixed diester. In particular when R or R is less than 5 carbons, and the other is greater, it is believed that both hydrophobic and hydrophilic peracids are generated. Therefore, if used in aqueous media with a source of hydrogen peroxide ~e.g., sodium perborate monohydrate), for example, as an all fabric bleach, two different oxidizing species appear to be present which can attach to different types of soils, i.e., hydrophilic soils such as tea and wine, and oily soils, such as sebum.

The phenylene diesters of ~III) include ortho, meta and Dara substituted phenylene diesters, such as diacetate, dihexanoate, dioctanoate and mixed (i.e., wherein Rl T R4) ester derivatiVes of resorcinol, hydroquinone and catechol, which S are exemplified below: OH

-Hydroquinone (1,4-benzenediol; 1,4-dihydroxybenzene;
p-dihydroxybenzene) is a white crystalline compound which can be obtained by dry distillation of quinic acid or by reduction of 1~ quinone. OH

Resorcinol (1,3 benzenediol; 1,3-dihydroxybenzene;
m-dihydroxybenzene) is a crystalline compound with a faint aromatic odor, and a sweet/bitter taste. It may be produced by the alkali fusion of galbanum and asafetida resins.

~ OH

Catechol (1,2-benzenediol; 1,2-dihydroxybenzene;
o~dihydroxybenzene) is a crystalline compound with a phenolic odor and a sweet and bitter taste. It may be obtained by dried distillation of catechin which is found in the aqueous extract of catechu, which is an extract of an East Asian acacia plant.

7~

A11 three oE these dihydroxybenzene startiny materials are commercially available.

The dihydroxybenzenes are weak acids with two dissociation constants. They are generally classified as antioxidant agents and are useful analytical reagents. Their structures, uses and chemistries are more thoroughly explored in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., vol 13, pages 39-69 ( 19~

., The diesterified derivatives of these dihydroxybenzene compounds are generally produced by reacting them with an appropriate acid anhydride in the presence of a strong acid. The general procedures for making these precursors are set forth below in EXPERIMENTAL. Additionally, the preferred phenylene monoesters are depicted below in EXPERIME~TAL.

15It is believed that in situ peracid generation occurs when these novel precursors are combined with a source of hydrogen peroxide in aqueous solution as follows: O- !

+ OOH ~ Rl OOH +

~ O-C-R O-C-R

Step II ~ ~ + 0O~_ > R4Coo~ +

20wherein the phenylene diester precursors revert back to the appropriate dihydroxybenzene compound.

_9_ ~'7~7~L7 While the foregoing is believed to occur, in fact, the mechanism behind peracid generation may occur simultaneously, or in rapid sequence, or a combination of these reactions.

~ hatever the mechanism, it was surprisingly discovered that when the novel precursors were combined with hydrogen peroxide in aqueous solution, high yields of peracid were produced, even at low temperatures such as those found in U.S. wash water temperatures.
It was even move surprising to see these high yie~ds given that the byproducts of reaction, dihydroxybenzenes, are noted antioxidants which one would expect to consume the peracids thus produced.

Applicants have found these particular substituted phenylene diesters to be particularly effective in low temperature bleaching applications. It was surprising that, given the large number of carbons on the disclosed compositions, the reactivities thereof lS were suitable for low temperature bleaching applications. Large alkyl groups ar~'hydrophobic, hence solubility or dispersibility in cold water was assumed to be problema-tic. While enhanced bleaching activity occurs when vari.ous solubili-ing ~roups are added to these composl.tions, sufficient pero~yacid generation for 20 bleach applications has béen observed even in their''abs'ence.

Addtionally, applicants observed that with increasing chain lengths of the phenylene diester'precursors, decreasing bleaching performance may be observed due to decreasing solubility or dispersibility. Therefore, solubility~dispersibility and hence performance can be improved by the addition of solubilizing groups such as SO3, CO2, NR43 . Placement of these solubilizing groups may have different effects on the precursor compositions. For example, if the solubil-izing groups are placed 07~7 on the aromatic rinq or at or near the end of the alkyl groups of the esters, increased solubility may be observed. Placing the solubilizing groups next to the carbonyl carbon on the ester group or electron withdrawing substituents on the aromatic leaving group may increase the perhydrolysis rate. These theories are by way of explanation and not intended to thereby restrict the invention herein.

Addition of the above described substituent groups can be accomplished by ways known to thosë skilled in the art. For example, halogen groups may be added by typical halogenation reactions, in which a typical source of halogen is combined with the selected dihydroxybenzene starting material in the presence of a Lewis Acid. Nitration, on the other hand, occurs when the dihydroxybenzene is reacted with nitric acid in the presence of sulfuric acid. Sulfonation occurs when the dihydroxybenzene is reacted with concentrated sulfuric acid. on the other hand, amination will generally be produced by reacting a source of amino with the dihydroxybenzene in the presence of liquid ammonia.
Further, as with typical benzene-derived compounds, acylation and

2~ al~.ylation can occur via Friedel-Crafts reactions.

Especially preferred are solubilizing groups, such as sulfonate (-S03) or carboxylate (~C02) groups. These - appear to impart good solubilit~/dispersibility properties to the peracid precursors of this invention. Additionally, it is preferred that a counterpart ion (counterion) to the sulfonate or carbonate group be chosen from H~ or an alkali metal ion selected from sodium, potassium or lithium, although alkaline earth counterions and even ammonium counterions may be appropriate.

The precursors can be incorporated into a liquid or solid matrix for use in liquid or solid detergent bleaches by dissolving L'7 into an appropriate solvent or surfactant or b~ dispersing onto a substrate material. Examples of appropriate solvents include acetone, non-nucleophilic alcohols, ethers or hydrocarbons. Other more water-dispersible or -miscible solvents may be considered.
As an example of affixation to a substrate material, the precursors of the present invention could be incorporated onto a non-particulate substrate such as disclosed in published European Patent Application EP 98 129 In a further embodiment of the phenylene diesters of this invention, it has ~en found that precursors containing mixed chain lengths, i.e., a shorter carbon chain length of at least one ester functionality, and a longer carbon length at the second ester functionality, provides extremely proficient bleaching For example, it is believed that when one of the ester functionalities has an alkyl straight chain length of less than 5, e.g., wherein R or R is CH3, and the other alkyl group's chain length is greater than 5 carbon atoms, peroxyacids which are, respectively, hydrophilic and hydrophobic are generated. The believed advantage thereof is that particulate soils, e.g~, clay soil/ and hydrophilic stains, e.g., tea and wine, can be attacked with a hydrophilic peroxyacid bleach while oily soils, e.g., sebum, can be attacked with a hydrophobic peroxyacid bleach Different pre-formed hydrophobic and hydrophilic peroxyacid bleaches were combined in published European Patent Application EP 68 547 Pre-formed peracids appear, however, to have storage stability problems and may lose significant amounts of active oxygen (A.O) upon prolonged storage. EP 98 129, mentioned above, discloses in one embodiment, separate peracid precursors which are impregnated on a fabric substrate. Problematic to this approach are the added manufacturing steps to producing different peracid precursors and 7~'~

using slurrying, emulslfyiny or other techniques to bind the different precursors to the substrate. A particularly preferred combination of the present invention is when one ester is an acetate te.g., Rl is CH3) and the other is an hexanoate, heptanoate, octanoate or nonanoate (e.g, R is -(CH2)4CH3 to -(CH2)7CH3). In a preferred embodiment, the total number of backbone carbons of Rl plus R4 should be in the range of 2-20, more preferably 5-20, most preferably 7-14.

Additionally, it was surprisingly found that while the positioning of the ester groups with respect to each other on the phenyl ring is significant, it is not critical. This was surprising since some references had suggested that activators which comprise a substituted phenyl ring must have the active substituent in para configuration with respect to other substituents, likely, it is assumed, to avoid steric hindrance.

~ nder wash conditiorls and at temperatures below 70C, it has been surprisingly found that any dihydroxybenzene, whether catechol, hydroquinone or resorcinol, can be used as perhydrolysis leaving groups, and that the resul-ting antioxidant does not appreciably or rapidly consume the oxidant formed, i.e., the peroxyacid(s). Resorcinol and catechol may be the preferred leaving groups because, of the byproducts of perhydrolysis of ortho, meta and para phenylene diesters, hydroquinone may be the most readily oxidizable.

In the disclosure of Chung, et. alO, U.S. 4,412,934, it is contended that the molar ratio of hydrogen peroxide to bleach activator must exceed 1.5 or else a competing reaction is favored wherein peracid generated reacts with the bleach activator itself to form diacyl peroxide. In contrast to the Chung, et. al. bleach activator, the present invention has ~een surprisingly discovered t~".

~ 7~
form low levels of diacyl peroxi~e. This is further depicted below in EXPERIME~TALi Examples II and IV. Although it is not definitely understood why this phenomenon occurs, it appears that the phenylene diester precursors may have different surface active properties. And, because of two reactive sites, which provides two equivalents of peracid per equivalent of precursor, lower concentrations of precursor are needed. There also is no need for a hydrogen peroxide/precursor ratio of greater than 1.5, as rnandated in the Chung, et. at. disclosure. ~ased on two reactive sites, i.e., the ester equivalents of the phenylene diester precursors, a ratio of l:l hydrogen peroxide: ester is possible, although ratios greater than this are also within the invention.
It is preferred that the molar ratio of hydrogen peroxide: ester be from about 1:20 to 20:1, more preferably about 1:10 to 10:1, most preferably about 1:1 to 5:1.

While it has been disclosed by applicants that substituting solubilizing groups on the phenyl ring will improve the solubility and enhance the reactivity of these precursors, an alternate mode and preferred embodiment is to combine the precursors with a 20 -surfactant. Particularly effective surfactants appear to be nonionic surfactants. Preferred surfactants of use include linear ethoxylated alcohols, such as those sold by shell Chemical Company under the brand name Neodol. Other suitable nonionic surfactants can include other linear ethoxylated alcohols with an average length of 6 to 16 carbon atoms and averaging about ~ to 20 moles of ethylene oxide per ~ole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average length of about 6 to 16 carbon atoms and averaginy 0-10 moles of ethylene oxide and about l-to 10 moles of propylene oxide per mole of alcohol; linear and branched alkylphenoxy (polyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, with an average chain length of 8 to 16 carbon atorns and averaging 1.5 to ~7~7~.J7 30 moles of ethylene oxide per mole of aleohol; arld mixtu~es thereof.

Further suitable nonionic surfactants may inelude polyoxyethylene earboxylie aeid esters, fatty aeid glyeerol esters~ fatty aeid and ethoxylated fatty aeid alkanolamides, certain bloek copolymers of propylene oxid~e and ethylene oxide, and block polymers of propylene oxide and ethylene oxide with propoxylated ethylene diamine. Also ineluded are such semi-polar nonionic surfactants like amine oxides, phosphine oxides, sulfoxides, and their ethoxylated derivatives.

Anionic surfactants may also be suitable. Examples of such anionie surfactants may inelude the ammonium, substituted ammonium ~e.g., mono-di-, and triethanolammonium), alkal; metal and alkaline earth metal salts of C6-C20 fatty acids and rosin acids, linear and branehed alkyl benzene sulfonates, alkyl sulfates, alkyl ether sulfates, alkane sulfonates, ole~in sul~onates, hydroxyalkane sulfonates, fatty aeid monoglyceride sulfates, alkyl glyeeryl ether sul~ates, aeyl sarcosinates and acyl N-methyltaurides.

Suitable eationic surfactants may include the quaternary ammonium eompounds in whieh typically one o~ the groups linked to the nitrogen atom is a C12-C18 alkyl group and the other three groups are short chained alkyl groups which may bear inert substituents such as phenyl groups.

Further, suitable amphoterie and zwitterionie sur~aetants which contain an anionic water-solubilizing group, a cationic group and a hydrophobic organie group may inelude amino earboxylic acids and their salts, amino diearboxylic acids and their salts, ~7~37~7 alkylbetaineS, alkyl aminopropylbetaines, sulfobetaines, alkyl imidazolinium derivatives, certain quaternary ammonium compounds, certain quaternary phosphonium compounds and certain tertiary sulfonium compounds. other examples of potentially suitable 5 zwitterionic surfactants can be found described in Jones, U.S.
4,005,029, at columns 11-15.

Further examples of anionic, nonionic, cationic and amphoteric surfactants which may be suitable for use in this invention are 10 depicted in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 22, pages 347w387, and McCutcheon's Detergents and EmulsifierS, North American Edition, 1983.

As mentioned hereinabove, other common detergent adjuncts may 15 be added if a bleach or detergent bleach product is desired. If, for example, a dry bleach cornposition is desi.red, the ollowing ranges (weight %) appear practicable:

0.5-50.0% Hydrogen Peroxide Source 0.05~25.0% Precursor 1.0-50.0~ Surfactant 1.0-50.0% Buffer 5.0-99.9% Filler, stabilizers, dyes, Fragrances, brighteners, etc.

The hydrogen peroxide source may be selected from the alkali 25 metal salts of percarbonate, perborate, persilicate and hydrogen peroxide adducts and hydrogen peroxide. Most preferred are sodium percarbonate, sodium perborate mono- and tetrahydrate, and hydrogen peroxide. other peroxygen sources may be possible, such as monopersulfates and monoperphosphates. In liquid applications, 30 liquid hydrogen peroxide solutions are preferred, but the precursor may need to be kept separate therefrom prior to combination in aqueous solution to prevent premature decomposition.

7~

The buffer may be selected Erom sodium carbonate, sodium bicarbonate, sodium borate, sodium silicate, phosphoric acid salts, and other alkali metal/alkaline earth metal salts known to those skilled in the art. organic buffers, such as succinates, 5 maleates and acetates may also be suitable for use. It appears preferable to have sufficient buffer to attain an alkaline pH, i.e., above at least about 7Ø

The filler material, which, in a detergent bleach application, may actually constitute the major constituent, by weight, of the 10 detergent bleach, is usually sodium sulfate. SodiUm chloride is another potential filler. Dyes include anthraquinone and similar blue dyes. Pigments, such as ultramarine blue (UMB), may also be used, and can have a-bluing effect by depositing on fabrics washed with a detergent bleach containing ~MB. Monastral colorants are 15 also possible for inclusion. Brighteners, such as stilbene, styrene and styrylnapthalene brighteners (fluorescent-whit-ening agents), may be included. Fragrances used for esthetic purposes are commercially available from Norda, Irlternational FlaVors and Fragrances and GiVaudon. Stabilizers include hydrated salts, such 20 as magnesium sulfate, and boric acid.
!

In one of the preferred embodiments in which a monoester compound such as in (I) above is the precursor, a preferred bleach composition has the following ingredients:

15.5% Sodium Perborate Tetrahydrate 11.93 Resorcinol Monooctanoate 7.0% Nonionic surfactant 15.0% Sodium Carbonate 50.6~ Sodium Sulfate 100 . 0%--The above composition is ormulated to deliver, desirably, 14 30 parts per million total available oxygen (ppm A.O.), at a pEI of about 10.5 ~.~ 7~
In another one of the preferred embodiments, in which a mixed diester compound as in (III) above is the precursor, a preferred bleach composition has the following ingredients:

15.5% Sodium Perborate Tetrahydrate 7.0% Resorcinol octanoate Acetate 7.0% Nonionic Surfactant 15.0~ Sodium Carbonate 55.5% Sodium Sulfate 100 . 0%

The above composition is formulated to deliver, desirably, about 14 ppm A.O. at a pH of about 10.5. Other peroxygen sources, such as sodium perborate monohydrate or sodium percarbonate are suitable. If a more detergent-type product is desired~ the amount of filler can be increased and the precursor halved or further decreased.

The novel precursocs of this invention are synthesized by the methods which are disclosed below. Additionally, perforrnance results are showri below in the EXPERIMENTAL section.

~18-EXPERI MRNTAL

I synthesis of 1 Octanoyloxy-3-Hydroxy Benzene O
-~-C7E~15 /\

~ 1 OH
Adapting the method of synthesis disclosed .in D. Johnston, 5 ~Preparation of Hydroquinone Monoacetate, n Chemistry & Industry 24:1000 ~lg82),it i~ .
expected that resorcinol may be combined with about an equimolar amount of dioctanoic acid anhydride, and ethyl acetate solvent, a non-nucleophilic solvent, in the presence of 4-dimethylaminopyri-10 dine, a catalyst, and a base, such as triethylarnine, at roomtemperature, to produce the desired 1 octanoyloxy-3-hydroxy benzene (resorcinol monooctanoate).

Therefore, the followinq procedure was performed:

~esorcinol (2.75 g, 0.025 mole), 4~dimethylaminopyridine (0.3 15 g, 0.0025 mole), triethylamine (2~5 g, 0.025 mole) were dissolved in 50 ml of ethyl acetate in a 100 ml round bottom flask equipped with a magnetic stir bar. Dioctanoic acid anhydride (6.76 g, 0.025 mole) was added dropwise, via an addition funnel, to the stirred solution over a 100 minute time period~

The resulting solution was stirred ~or an additional 30 minutes, at which time the solvent was removed via rotary vacuum evaporation The remaining oil was dissolved in 200 ml of ethyl ether and extracted with a 200 ml portion of 3g HCl to remove the 4-dimethylaminopyridine catalyst, and four 100 ml portions of 5 25 NaHCO3 were used to remove the octanoic acid byproductO

After drying the organic phase with ~0 grams of Na2S0~, the ether was removed by rotary vacuum evaporation and the remaining oil was redissolved in 15 ml of chloroform. The sample was then chromatographed in a column on 200 grams of silica gel G
5 with chloroformJpetroleum ether (1:2 vol/vol ratio) and pure resorcinol monooctanoate (2.36 g) was collected. Yields of the desired monoester were typically about 40%~wt.).

Surprisingly, unlike in the synthesis described in Johnston's report, the~ high yields of desired monoester, resorcinol 10 monooctanoate, were not achieved. However, beneficially, -symmetrical diesters, resorcinol dioctanoate, were co-produced in a slightly greater portion (about 50~(wt.)) and available for use in the present invention.

In the foregoing synthesis, and in those depicted in III and 15 IV, it is believed that any of the dihydroxybenzenes are suitable for use as starting materials. If non nucleophilic solvents are required, as in base catalysis, acetone tdimethyl ketone), ethyl or methyl acetate, tetrachloromethane, dichloromethane, ethylene chloride, chloroform, and others appear appropriate to the 20 synthesis. The catalyst, 4-dimethylaminopyridine, appears to promote transesterification by acting to for~ a reactive intermediate. other suitable catalysts may include pyridine-and other tertiary aliphatic and aromatic amines. The base, which may act to tie up any carboxylic acid moieties formed in the reaction, 25 may include triethylamine, tetramethyl piperidine, NaHCO3, Na2C03, and suitable tertiary amines. In the selection of suitable bases, care must be taken to insure solubility of the ingredients in the reaction. Similarly, if acid catalysis is the chosen route of synthesis, concentrated sulfuric acid, 30 hydrochloric acid, and methanesulfonic acid are among the catalysts of choice known to those skilled in the art.

~'7~71>7 II. Comparison of Diacyl Peroxide Formatlon In order to ascertain the amounts of diacyl peroxide formed when less than a 1.5: 1 H2O2: precursor ratio are used, applicants compared the levels of diacyl peroxide formed when two peracid precursors were separately combined with H2O2, namely, resorcinol monooctanoate (representing a mono ester functionality of one of the embodiments of the present invention, 7 15 .

~0~

and sodium octanoyloxy benzene sulfonate (NABSl, 10 [~ ' a+SO

which is one of the activators shown in U.S. 4,412,~34.

The two precursors were subjected to the following conditions:

H2O2: 1.25 X 10 M
(a) precursor~ 1.25 X 10 3~ predissolved in surfactant) buffer: 0.02M NaHCO3/NaOH
pH: 10.5 temperature: 25C

~7~

(b) all conditions in (a), but H~02 at 2.5 X 10 3M. ~J. :~

The results were:

H202/~ster equiv. Diacyl Peroxide Content(M) Monooctanoate NABS
(a) 1:1 0.3X10-4 Z.OX10-4 (b) 2:1 - b.3X10-4 1 OX10-4 The results show that at lower than 1.5:1 H202:precursor ratios, the inventive precursors will maintain low amounts of 10 diacyl peroxide. The activators of U.S. 4,412,934, on the other hand, will form significantly higher levels of diacyl peroxide.
Comparing the results, it should be noted that the activators of U.S. 4,412,934 produce several times more diacyl peroxide as the precursors of the present invention.

III. Synthesis of 1,3 Dihexanoyloxybenzene O-~-C5~

o-c-cs~ll In a reaction vessel, resorcinol is placed with an equimolar amount of hexanoic acid anhydride (from Aldrich Chemicals~.
Concentrated sulfuric acid (98~) is added to the solution and 20 heated at 100C for 3 hours. A crude reaction product was obtained from this acid catalysis containing the 1,3 dihexanoyloxybenzene (resorcinol dihexanoate) and hexanoic acid.

-22~

~ ~ 7 ~7 ~

The reaction mixture is diluted with diethyl ether and the hexanoic acid removed by extraction with 5~ NaHCO3. The ether phase is dried under Na2SO4 and rotary evaporated to remove the solvent. For hydroquinone dihexanoate, the resulting solid is 5 recrystallized with EtOH/H2O to give a pure solid (m.pt.
56-57C). For resorcinol dihexanoate, the liquid is distilled and the product fraction collected at 175-180/0.5~m Hg. Isolated yields are generally 903 for either synthesis.

IV. Synthesis of 1 octanoyloxy-3~acetoxy benzene O-II-C H

10 ~ \ o-~o-c~3 An acetoxylated resorcinol is obtained through commercial sources (from American Hoechst). It is placed in a reacti.on vessel with an equimolar amount of dioctanoic acid anhydride (from Aldrich Chemicals), in the presence of rnethanesulEonic acid to lS promote acid catalysis, and reacted at room temperature (21C) for one hour. A 95% yield of the 1 octanoyloxy 3-acetoxy benzene (resorcinol acetate octanoate) and octanoic acid as a by-product results.

The purpose of the next experiment was to see if a greater 20 than 1.5 molar ratio of H2O2: precursor as contended by U.S.
4,412,934 was actually necessary for the precursors of~this invention to give good yields of desired peracids.

~27(g7~7' V. Yield of 1 Octanoyloxy-3-Acetoxy Benzene -a. The compound synthesi~ed in IV (resorcinol acetate octanoate) was combined in aqueous solution with sufficient hydrogen peroxide to yield a hydrogen peroxide: precursor ratio (based on ester equivalents) of about 1.4:1. The reaction conditions were pH 10.5 (based on 0.02M NaHCO33, temperature 25 C, and lg/l liter of a nonionic surfactant, Neodol 25-12 (which is a linear ethoxylated alcohol with predominant chain length of 12-15 carbon atoms, averaging about 12 moles of ethylene oxide per mole of alcohol). The concentration of II (resorcinol acetate octanoate) was 4.375 X 10 M, H2O2 was about 1.225 X
M, to result in an H2O2: precursor (based on ester equivalents) ratio of about 1.4:1. Yields of about 7s% peracid were obtained Low levels of diacyl peroxide were detected consistent with the high peeacid yield.

b. Repeating the above experiment, with the compound of IV
~resorcinol acetate octanoate) at 4.375 X 10 M, but with 1.75 X
10 3M H2O2, to result in-a ratio of H2O2: precursor of about 2:1, the~ resulting yield was about 78%. Thé reason for the absence of substantial diacyl peroxide formation in a competing side reaction as posited by U.S. 4,412,934 are presently unknown.
It is speculated that there is a lack of interaction between the recently formed peracid and that portion of unreacted-precursor.
This theory is-for purposes of explanation- and not meant to restrict the scope of the invention. It is also believed that any acetyl octanoyl diacyl peroxide formed may be rapidly re-perhydrolyzed, i.e., converted back into peracid, without the need for a large excess of hydrogen peroxide. Further experiments appear to bear out the low diacyl peroxide formation in the inventive compositions.

Perforrnance tests for the inventive precursors have also been conducted. The pcecursors have been found to exhibit siynificant improvements in bleaching performance over a commercial dry perborate bleach:

VO % Stain Removal of crystal Violet stained Cotton Swatches o~ L, 3 Dihexanoyloxy Benzene Composition % Stain Removal H2O2+ resorcinol dihexanoatel/
Neodol 25-12 90.45~+1.26 10 H22 + Neodol 25-12 76.77+1.24 H22 + resorcinol dihexanoatel 69.85+2.84 Neodol 25-12 80.45+1.05 Commercial Blea-ch ~sodium, perborate, brighteners, builders) 73.45+2.39 H2O2 - 2.50 X 10 M

Resorcinol dihexanoate = 6O25 X 10 M
pH 10.5, 0.02M carbonate buffer, 38C
10 minutes wash time Average of 5 swatches in 200 ml wash water 1 1,3 Dihexanoyloxy Benzene ~25 VI. ~ Stain ~emoval of Crystal Violet/Cotton swatches of 1 Octanoyloxy-3-Acetoxy Benzenel Composition % Stain Re~oval Buffer only 29.7 5.7 H22 + Neodol 25-12 65.8+1.4 C2/C~ 1(7 ppm A.O. theoretical) 76.5_1.5 + H2O2+ Neodol 15-12 C2/C8 1(10 ppm A.O. theoretical) 79.0+1.1 ~H2O2+ Neodol 25-12 C2/Cg 1(14 ppm A.O. theoretical) 82.0+0.4 +H2O2+ Neodol 25-12 -Peracetic acid (7 ppm A.O.) 50.4_3.0 Peroctanoic acid (7 ppm A.O.) 83.8_1.9 H2O2= 1.75x10 M
pH 10.5 0.02M carbonate buffer 22 C
10 minutes wash time Average of 5 swatches in 200 ml wash water 1 ~esorcinol Acetate octanoate . .

-~6 ~'~'70~
The foregoing description and embodiments of the invention have been presented for purposes of illustration and not intended to restrict the scope of the invention. other non-limiting embodiments of the invention are possible~ For example, standard 5 bleaching and detergent adjuncts may be added to the compositions disclosed. Exemplary of such adjuncts are builders (sodium carbonate, sodium tripolyphosphate, etc.), fille~s (e.g., sodium sulfate), brighteners, enzymes ~e.g., alkaline proteases), defoaming agents, and the like known to those skilled in the art.
10 Additionally, further esterification of the phenylene diesters may be possible, for example, resulting in tri- and quaternary-, substituted phenylene precursors. The claims hereto further llustrate the invention.

Claims (21)

WHAT IS CLAIMED IS:

1. A bleaching composition comprising:
(a) A source of hydrogen peroxide; and (b) A bleach effective amount of a peracid precursor of the general structure Wherein R1 is an alkyl of less than 5 carbon atoms; and X1, X2, Y and Z are individually selected from H, SO?, CO?, NO2, NR?+, Halogen, R6, and mixtures thereof;
Wherein R4 of -O-?-R4 is alkyl of about 5 to 11 carbon atoms; R5 of NR?+ is selected from H, alkyl of 1 to 24 carbon atoms and mixtures thereof; R6 is alkyl of about 1 to 20 carbon atoms.

2. A method of removing soils from fabrics comprising contacting said fabrics with a bleaching composition which comprises:
(a) A source of hydrogen peroxide; and (b) A bleach effective amount of a peracid precursor of the general structure Wherein R1 is an alkyl of less than 5 carbon atoms; and X1, X2, Y and Z are individually selected from H, SO?, CO?, NO2, NR?+, Halogen, R6, and mixtures thereof;
Wherein R4 of -O-?-R4 is alkyl of 5 to 11 carbon atoms;
R5 of NR?+ is selected from H, alkyl of 1 to 24 carbon atoms and mixtures thereof; R6 is alkyl of about 1 to 20 carbon atoms.

3. The composition of claim 1 wherein R1 is CH3 and R4 is C5-11 alkyl.

4. The composition of claim 3 wherein R4 is C5-8 alkyl.

5. The composition of claim 4 wherein the precursor is a phenylene monoacetate monohexanoate.

6. The composition of claim 4 wherein the precursor is a phenylene monoacetate monoheptanoate.

7. The composition of claim 4 wherein the precursor is a phenylene monoacetate monooctanoate.

8. The composition of claim 4 wherein the precursor is a phenylene monoacetate monononanoate.

9. The composition of claim 1 further comprising (C) sufficient quantities of buffer to yield an alkaline pH when the composition is placed in aqueous solution.

10. The composition of claim 1 wherein -O-?-R1 and -O-?-R4 of the precursor are para in relationship to each other.

11. The composition of claim 1 wherein -O-?-R1 and -O-?-R4 of the precursor are ortho in relationship to each other.

12. The composition of claim 1 wherein -O-?-R1 and -O-?-R4 of the precursor are meta in relationship to each other.

13. The composition of claim 1 wherein at least one of X1, X2, Y and Z are SO? with a counterpart ion which is H+ or an alkali metal cation selected from the group consisting essentially of sodium, potassium or lithium.

14. The composition of claim 1 further comprising (d) a surfactant which will not react with the precursor.

15. The composition of claim 14 wherein the surfactant is selected from the group consisting essentially of anionic, nonionic, zwitterionic, cationic, amphorteric surfactants and mixtures thereof.

16. The composition of claim 15 wherein the surfactant is nonionic.

17. The composition of claim 1 wherein the hydrogen peroxide source is selected from the alkali metal salts of percarbonate, perborate, persilicate and hydrogen peroxide adducts.

18. The composition of claim 17 wherein the hydrogen peroxide source is selected from sodium perborate monohydrate or tetrahydrate, sodium percarbonate and hydrogen peroxide.

19. The composition of claim 18 wherein the ratio of hydrogen peroxide yielded by the hydrogen peroxide source to the precursor is greater than about 1:1 of hydrogen peroxide to ester equivalent.

20. The composition of claim 1 wherein at least one of R1, R4 or R6 is substituted at the carbon adjacent the carbonyl group of the ester groups with at least one substituent selected from the group consisting essentially of SO?, CO?, NR?+, halogen, R6 and mixtures thereof, wherein R5 of NR?+ is further defined as H, alkyl of about 1 to 24 carbon atoms and mixtures thereof and R6 is alkyl of about 1 to 20 carbon atoms.

21. The composition of claim 1 wherein at least one of R1, R4 or R6 is substituted at the terminal carbon of the ester groups with at least one substituent selected from the group consisting essentially of SO?, CO?, NR?+, halogen, R6 and mixtures thereof, wherein R5 of NR?+ is further defined as H, alkyl of about 1 to 24 carbon atoms and mixtures thereof and R6 is alkyl of about 1 to 20 carbon atoms.