CA1340039C - Acyloxynitrogen peracid precursors - Google Patents

Abstract

The invention provides novel bleaching compositions comprising peracid precursors having oxynitrogen leaving groups. Peracid precursors containing these leaving groups provide new, proficient and cost-effective compounds for fabric bleaching.

These compounds have the general structures:

wherein R is a straight or branched chain C1-20 alkyl, alkoxyl, cycloalkyl and mixtures thereof; R1 contains at least one carbon atom which is singly bonded directly to N; n is an integer from 1 to 6 and X is methylene or a heteroatom; or wherein n is the same as in (I); but R2 contains a carbon atom doubly bonded directly to N, and, either X
is a heteroatom, R is C4-17 alkyl or both.

Description

134003~
ACYLOXYNITROGEN ~ERACID PRECURSORS
Backqround of the Invention 1. Field of the Inve~tion This invention relates to novel peroxygen bleach activator compounds that aid in providing efficient peroxygen bleaching of fabrics over a wide temperature range when combined with a source of hydrogen peroxide in aqueous media. These compounds have the general structures:

1~l (I) R-X-(CH2)nC-O-N-R', wherein R is a straight or branched chain C120 alkyl, alkoxyl, cycloalkyl and mixtures thereof; R1 contains at least one carbon atom which is singly bonded directly to N; n is an integer from 1 to 6 and X is methylene or a heteroatom; or o ( I I ) R-X-(CH,~nC-O-N-R2, wherein n is the same as in (I); but R2 contains a carbon atom doubly bonded directly to N, and, either X
is a heteroatom, R is C417 alkyl or both.

X~

2. Brief Statement on the Prior Art 13 ~ ~ ~ 3 3 It is well known that peroxygen bleaches are effective in removing stains and/or soils from textiles.
They can be used on a wide variety of fabrics and colored garments. However the efficacy of peroxygen bleaches can vary greatly with temperature of the wash water in which they are used and they are usually most effective when the bleaching solution is above 130~F. Below this temperature, it has been found that peroxide bleaching efficacy can be greatly increased by the simultaneous use of activators, otherwise known as peracid precursors. It has widely been accepted that in aqueous media, precursors and peroxygen combine to form peracid species. However, efficacy of most precursors, such as tetracetylethylene diamine (TAED), is also dependent on high wash water temperature. However, there is a need for bleach activator or peracid precursor compounds which are able to react with peroxide efficiently at low temperatures (70-100~F) to form peracids in good yields for proper cleaning performance.

Peracids themselves can be hazardous to make and are particularly prone to decomposition upon long-term storage. Thus it is advantageous to prepare the more stable peracid precursor compounds, which in alkaline water solution will react with peroxide anion to form the desired peracid in situ. As can be seen from the Xj ~ 13~0~33 extensive literature in this area, many such peroxygen activators (peracid precursors) have been proposed.
However, no reference appears to have taught, disclosed or suggested the advantages of leaving groups containing nitrogen in perhydrolysis.

Various compounds have been disclosed in the prior art that contain nitrogen as part of the leaving group of the peroxygen precursors. Murray, U.S. 3,969,257, Gray, U.S. 3,655,567, Baevsky, 3,061,550, and Murray, U.S.

3,928,223 appear to disclose the use of acyl groups attached to nitrogen atoms as leaving groups for activators. In all these examples, the acyl carbon atom is directly attached to the nitrogen atom. The nitrogen can in turn be attached to other carbonyl carbon groups.

In Finley et al, U.S. 4,164,395, a sulfonyl group is attached to the nitrogen atom of the leaving group. The activator structure is thus a sulfonyl oxime.

Dounchis et al, U.S. 3,975,153 teaches the use of only isophorone oxime acetate as a bleach activator. It is claimed that this isophorone derivative results in an activator of low odor and low toxicity. In Sarot et al, U.S. 3,816,319, the use of diacylated glyoximes are taught. The use is restricted to diacylated dialkylglyoximes wherein the alkyl group contains one to i 1340~
.~, ..

four carbon atoms. In neither reference is it disclosed, taught or suggested that it is surprisingly necessary to provide a heteroatom alpha to the carbonyl of the acyl group if a peracid precursor contains oxime as a leaving group. Additionally, neither reference discloses the unique advantages conferred by surface active peracid precursors which contain about 4-14 carbons in the acyl group.
Summary of the Invention The present invention comprises, in one embodiment, a bleaching composition comprising:
a bleaching composition comprising:
(a) a peracid precursor having the general structure:

1~l (I) R-X-(CH.~nC-O-N-R' wherein R is a straight or branched chain C120 alkyl, alkoxyl, cycloalkyl and mixtures thereof; R1 contains at least one carbon atom which is singly bonded directly to N; n is an integer from l to 6 and X is methylene or a heteroatom; or (II) R-X-(CH.~nC-O-N-R
wherein n is the same as in (I); but RZ contains a carbon atom doubly bonded directly to N, and either X is a heteroatom, R is C~ ,7 alkyl or both, and X

1, 1~00533 (b) a bleach-effective amount of a source of hydrogen peroxide.

In another aspect, the present invention provides a bleaching composition comprising: (a) a bleach activator selected from: (i) oxime esters having the structure:

1~l R-C-O-N=RI; or 1~l R-X-CH2-C-O-N=R', wherein R is Cs to C9 alkyl and wherein the substituent -O-N=R1 is a leaving group which contains a carbon atom doubly bonded directly to N; X is -O-, -N-, -S- or quaternary ammonium; (ii) oxyimide esters having the structures:

1~l R-C-O-N=R'; or 1~l R-X-CH2-C-O-N=R' wherein R is C5 to Cy alkyl; R1 has at least one carbon atom singly bonded directly to N; X is -O-, -N-, -S- or quarternary ammonium; wherein -O-N-R1 ie either O o Il 11 C-R3 ~ C ~

-O-N or -O-N R5 and \C-R4 'C ~
Il 11 O O
- 4a -X~

1 3 ~

wherein R3 and R4 are the same or different, and are separately straight or branched chain Cl20 alkyl, aryl, alkylaryl or mixtures thereof; and Rs is straight or branched chain ClzO alkyl, aryl, or alkylaryl and completes a heterocycle; and (iii) an amine oxide ester having the structures:

R-C-O-N-RI; or R-X-CHz-C-O-N-RI.
wherein R is a straight or branched chain C120 alkyl, alkoxyl, cycloalkyl; X is -O-, -N-, -S- or quaternary ammonium; and the substituent -O-N-Rl is selected from the group comprising;

~ R~ ~ C ~ ~ .C ~
-O-N-R'~ , -O-N-R'2 R" and -O-N Rq R9 C ~ \ C ~
and wherein R8 and R9 are the same or different and are separately straight or branched chain C~20 alkyl, aryl, alkylaryl or mixtures thereof; R10 is C130 alkyl, aryl, alkylaryl or mixtures thereof; R11 is C120 alkyl, aryl, alkylaryl and completes a heterocycle; and R12 is Cl20 alkyl, aryl, alkylaryl or mixtures thereof; and (b) a bleach effective amount of a source of hydrogen peroxide.

- 4b -X~' i 3 -~ fJ d 3 ~

Detailed Description of the Invention The complete precursor (an ester) is o (I) R-X-(CH~nC-O-N-R' wherein R is a straight or branched chain C120 alkyl, alkoxyl, cycloalkyl and mixtures thereof; R1 contains at least one carbon atom which is singly bonded directly to N; n is an integer from l to 6 and X is methylene or a heteroatom; or (II) R-X-(CH~nC-o-N-R2, wherein n is the same as in (I); but R2 contains a carbon atom doubly bonded directly to N, and, either X
is a heteroatom, R is C417 alkyl or both.

It is preferred that R is C1zo alkyl or alkoxylated alkyl. More preferably, R is C4 ~7, and mixtures thereof.
R can also be mono-unsaturated or polyunsaturated. If alkoxylated, ethoxy (EO) -(-OCH2CH2) and propoxy (PO) -(OCH2CH2CH2) groups are preferred, and can be present, per mole of ester, from 1-30 EO or PO groups, and mixtures thereof.

It is preferred for R to be from 4 to 17, and especially 6 to 12, carbons in the alkyl chain. Such alkyl groups would be surface active and would be desirable when the precursor is used to form surface I

~--' 13 ~- i? J~

active peracids for oxidizing fat or oil based soils from substrates at relatively low temperatures.

These alkyl groups are generally introduced onto the ester via an acid chloride synthesis discussed further below. Fatty acid chlorides such as hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride and the like provide this alkyl moiety.
When it is desired to introduce an aryl group, an aromatic acid chloride can be used, such as phenoxyacetyl chloride, although this is the subject of Canadian Patent Application, Serial No. 549,746 entitled "Phenoxyacetate Peracid Precursors and Perhydrolysis System Therewith", inventors Alfred G. Zielske et al, filed October 20, 1987 and commonly assigned to The Clorox Company.

Also, in the above generic structures for the precursors of the invention, when n is 1, X is at the alpha-position to the terminal carbonyl group. In the present invention, under certain circumstances, such as when the nitrogen of the oxynitrogen bond is itself double bonded to a carbon atom (structure (II)), forming on oxime, X is O, oxygen. X, however, could also be another electronegative atom, such as -S-(sulfide), -N-(amine) or even -NH+~ (quaternary ammonium). In the invention, however, it is most preferable that X is O (oxygen), or methylene.

~ ~ , -' l3la~3~

As mentioned, n = 1 to 6 carbylene substituents, but n= 1 to 3 is more preferred, and most preferably n does not exceed about 2.

When n = 1 to 2, the base carbonyl is a acetic acid or propionic acid derivative. The acetic acid derivatives have been found surprisingly effective and are discussed in two Canadian applications commonly assigned to The Clorox Company, namely, "Glycolate Ester Peracid Precursors," inventors Ronald A. Fong et al, Canadian Application Serial No. 550,479, filed October 28, 1987, and Canadian Application Serial No. 549,746 referred to above.

When the heteroatom, X is O (oxygen), and n is 1, the effect of an electronegative substituent alpha to the terminal carbonyl enhances the reactivity of the inventive precursors.

The electronic effect of this modification at the proximal methylene group (when n=1) appears to make the carbonyl group more susceptible to nucleophilic attack by a perhydroxide anion. The resulting enhanced reactivity results in higher peracid yields at low temperatures (e.g., 70~F), across a broader pH range, and makes the perhydrolysis reaction to generate peracids less susceptible to critical activator to H2Oz ratios.

V

I

~ 131U~33 However, in another embodiment, when the leaving group of the precursor is structure (I), -ONR1, it is preferred that X is methylene. As a representative example, the octanoyl group, o C,H,5C-o-, does not contain any heteroatoms within the alkyl chain.

In the following discussion, certain definitions are utilized:

Peracid precursor is equivalent to bleach activator.
Both terms generally relate herein to reactive esters which have a leaving group substituent, which during perhydroly~is, actually cleave off the acyl portion of the ester.

Perhydrolysis is the reaction which occurs when a peracid precursor or activator is combined in a reaction medium (aqueous medium) with an effective amount of a source of hydrogen peroxide.

The leaving group is basically a substituent which is attached via a oxygen bond to the acyl portion of the ester and which can be replaced by a perhydroxide anion (OOH-) during perhydrolysis.

A l The basic reaction is:
O

R-C-O-(CH2)n-C-L+ OoH-O o Il 11 R-C-O-(CH2)n-C-OOH + L-The present invention provides, in particular, novel oxynitrogen leaving groups having the general structures (I) -ON R' and (II) -ON 5 R2 o are attached to an acyl, R-C-, group to form the peracid precursors of this invention. These leaving groups have an oxygen atom attached to nitrogen which in turn can be attached to carbon atoms in a variety of structural configurations. The oxygen of the leaving group is attached directly to the carbonyl carbon to form the intact precursor.

When aonsidering the activator structures below O o Il 11 (I) R-X-(CHQ)nC-O-N-R' and (II) R-X-(CH~"C-O-N = R2, there are at least two different types of structure for the Rl group and there is at least one type of structure for the R2 group.

X' 1, ~

- ~~ 13i~ ~033 The first preferred structure for R1 is where the nitrogen atom is attached to two carbonyl carbon groups.
The leaving group then would be an oxyimide group:

o o ~-R3 C ---ON or -ON R5 \ C-R4 C ~
Il 11 O o wherein R3 and R4 can be the same or dif~erent, and are preferably straight chain or branched C~20 alkyl, aryl, aklylaryl or mixtures thereof. If alkyl, R3 and R4 can be partially unsaturated. It is especially preferred that R3 and R4 are straight or branched chain C~6 alkyls, which can be the same or different. Rs is preferably C120 alkyl, aryl or alkylaryl, and completes a heterocycle. R5 includes the preferred structure o wherein R6 can be an aromatic ring fused to the heterocycl~, or C~6 alkyl.

X~l ,_~ 1340033 Thus, these leaving group structures could contain an acyclic or cuclic oxyimide moiety. The above precursor can be seen as a combination of a carboxylic acid and a hydroxyimide compound:

o C-R
Il /
R-C-OH HO-N
\ IR~

~arboxylic acid Hydroxyimi~e These esters of imides can be prepared as described in Greene, Protective Groups in Orqanic Synthesis, p. 183, and are generally the reaction products of acid chlorides and hydroxyimides.

Non-limiting examples of N-hydroxyimide which will provide the oxyimide leaving groups of the invention include:

N-hydrooxysuccinimide, N-hydroxyphthalimide, N-hydroxyglutarimide, N-hydroxynaphthalimide, N-hydroxymaleimide, N-hydroxydiacetylimide and N-hydroxydipropionylimide.

Especially preferred examples of oxyimide leaving groups are:

13~ 3~

-O-N ~ -O-N = ~ O

Oxysu~cinimide Oxypht~alimide When treated with peroxide anion, a peracid is formed and the leaving group departs with oxygen attached to nitrogen and a negative charge on the oxygen atoms. The pKa (about 6) of the resulting hydroxyimides is quite low, making them excellent leaving groups.

The second preferred structure for R1 is where the nitrogen atom is attached to at least two carbons. These are amine ~xide leaving groups, comprising:
/ R~ + / ~
-o-N-R'~ or -O-N-RI2 R"

Rg C J
In the first preferred structure for amine oxides, R8 and R9 can be the same or different, and are preferably C~20 straight or branched chain alkyl, aryl, alkylaryl or mixtures thereof. If alkyl, the substituent could be partially unsaturated. Preferably, R8 and R9 are C~ 4 alkyls and can be the same or different. R10 is preferably C130 alkyl, aryl, alkylaryl and mixtures thereof. This R10 substituent could also be partially unsaturated. It is most preferred that R8 and R9 are relatively short chain alkyl groups (CH3 or CH2CH3) and Rl~ is preferably C120 Xl, 13~0033 ~.

alkyl, forming together a tertiary amine oxide.

Further, in the second preferred amine oxide structure, R11 can be C120 alkyl, aryl or alkylaryl, and completes a heterocycle. R11 prefereably completes an aromatic heterocycle of 5 carbon atoms and can be C16 alkyl or aryl substituted. R12 is prefereably C130 alkyl, aryl, alkylaryl or mixtures thereof. R1Z is more preferably C120 alkyl if R11 completes an aliphatic heterocycle. If R11 completes an aromatic heterocycle, R12 is nothing.

In the case where R12 is nothing, structure of the second preferred amine oxide is as follows:

/c --O-N Rll This type of structure is really a combination of a carboxylic acid and an amine oxide:

o R

R-C-OH -o-N R

Carboxylic acid Amine oxide - 12a -X

l340a~
f--~

Amine oxides can be prepared as described in March, Advance Organic Chemistry, 2d Ed., 1977, p.l,lll.

- 12b -13~0033 ,~
Non-limiting examples of amine oxides suitable for use as leaving groups herein can be derived fro~: pyridine N-oxide, trimethylamine N-oxide, 4-phenyl pyridine N-oxide, decyldimethylamine N-oxide, dodecyldimethylamine N-oxide, tetradecyldimethylamine N-oxide, hexadecyldimethylamine N-oxide, octyldimethylamine N-oxide, di (decyl) methylamine N-oxide, di (dodecyl) methylamine N-oxide, di (tetradecyl) methylamine N-oxide, 4-picoline N-oxide, 3-picoline N-oxide and 2-picoline N-oxide.

Especially preferred amine oxide leaving groups include:

-O-N~ -O-N~

PYridinium N-oxidePhenylpyridinium N-oxide When the precursor is attacked by peroxide anion, a peracid is formed and the leaving group leaves as an amine oxide, again with oxygen attached to nitrog~n and the negative charge on the oxygen.

When the oxynitrogen leaving group is structure (II) -ON=R2, preferred examples thereof are oximes.

' X;

~ 13~03~

In these oxime leaving groups, the nitrogen atom is combined to a carbon atom via a double bond.

-ON=C
\ R'4 wherein R13 and R14 are individually H, C120 alkyl, (which can be cycloalkyl, Straight or branched chain), aryl, or alkylaryl. Preferably R13 and R14 are the same or different and range from C16; and at least one of R13 and R14 is not H.

The structure of an oxime ester of a carboxylic acid and can be broken down into two parts:

R-C-OH HO-N=C(R)2 CarboxYlic acid Oxime of a Carbonyl Cpmpound As mentioned since R2 is carbon double directly to the nitrogen of the oxynitrogen bond, either (a) the R
group of the acyl is preferably C4l7, more preferably C612, alkyl (resulting in a surface active ester) or (b) X, the heteroatom is oxygen and the carbylene number, n, is 1, or (c) both conditions may occur.

An example of (a) is octanoyloxy dimethyl oxime ester, 13'10~33 H3C(CH~6-C-O-N=C(CH3).
An example of (b) is hexanoxy acetyl dimethyl oxime ester, 1~l H3C(CH~6-O-CH2C-O-N=C(CH3)~
Oximes are generally derived from the reaction of hydroxylamines with either aldehydes or ketone~ (Allinger et al, Orq~nic ChemistrY, 2d Ed., p.562 (1976), both of which are within the scope of this invention.

Non-limiting examples of an oxime leaving group are:
(a) oximes of aldehydes (aldoximes), e.g., acetaldoxime, benzaldoxime, propionaldoxime, butylaldoxime, heptaldoxime, hexaldoxime, phenylacetaldozime, p-tolualdoxime,anisaldoxime,caproaldoxime,valeraldoxime and p-nitrobenzaldoxime; and (b) oximes of ketones (ketoximes), e.g., acetone oxime (2-propanone oxime), methyl ethyl ketoxime (2-butanone oxime), 2-pentanone oxime, 2-hexanone oxime, 3-hexanone oxime, cyclohexanone oxime, ac~tophenone oxime, benzophenone oxime, and cyclopentanone oxime.

Particularly preferred oxime leaving groups are:

V

I

13 l ~ G ~ 9 ~ CH3 / CH3 -ON = C -ON = C
\ CH3 CH2CH3 Acetone Oxime Methylethyl Ketoxime When attacked by peroxide anion, the oxime ester forms a peracid and the oxime becomes the leaving group.
It is rather surprising that the oximes are such good leaving groups since their pKa values (about 12) are rather high for a good leaving group. Previous experience teaches that leaving groups with pKa values for their conjugate acids in the 8-10 range make the best leaving groups. Although there are examples in the prior art of oxime esters (U.S. 4,164,395, U.S. 3,975,153), in fact, no mention is made of the fact that a heteroatom alpha to the carbonyl group on the acyl portion of the ester is necessary for good perhydrolysis yields; or that if the R
group of the acyl is C4l7 alkyl, more preferably C612 alkyl, surface active peracid precursors giving rise to surface active peracids will result.

The precursors of the invention can be incorporated into a liquid or solid matrix for use in liquid or solid detergent bleaches by dissolving into an appropriate solvent or surfactant or by dispersing liquid or liquefied precursors onto a substrate material, such as an inert salt (e.g. NaCl, NazSO~) or other solid substrate, such as ~3~0~1)33 , zeolites, sodium borate, or molecular sieves. 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 incorporate onto a non-particulate substrate such as disclosed in published European Patent Application EP98 129.

The inventive precursors with oxynitrogen leaving groups are apparently not as soluble in aqueous media as compared to phenyl sulfonates. Thus, a preferred embodiment of the invention is to combine the precursors with a surfactant. It is particularly preferred to coat these precursors with a nonionic or anionic surfactant that is solid at room temperature and melts at above about 40~C. A melt of surfactant may be simply admixed with peracid precursor, cooled and chopped into granules.
Exemplary surfactants for such use are illu6trated in Table I below:
Tab~e I
Co~mercial Name m.p. Type Su~plier Pluronic F-98 55~C Nonionic BASF ~yandotte Neodol 25-30 47~C Nonionic Shell Chemical Neodol 25-60 53~C Nonionic Shell Chemical Tergitol S-30 41~C Nonionic Union Carbide *Trade Mark xl~

~ 3 ~

Tergitol S-40 45~C Nonionic Union Carbide Pluronic 10R8 46~C Nonionic BASF Wyandotte Pluronic 17R8 53~C Nonionic BSAF Wyandotte Tetronic 90R8 47~C Nonionic BASF Wyandotte Amidox C5 55~C Nonionic Stepan The precursors, whether coated with the surfactants with melting completion temperatures above about 40~C or not so coated, could also be admixed with other surfactant$ to provide, depending on formulation, either bleach addltive or detergent compositions.

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 na~e Neodol .
Other suitable nonionic surfactants can include other linear ethoxylated alcohols with an average length of 6 to 16 carbon atoms and averaging about 2 to 20 moles of ethylene oxide per mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average length of about 6 to 16 carbon atoms and averaging 0-10 moles of propylene oxide pqr mole of alcohol; linear and ~ranched alkylphenoxy (polyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, with an average chain length of 8 to 16 carbon atoms and *Trade Mark ~ I

~ 134û033 averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures therof.

Further suitable nonionic surfactants may include polyoxyethylene carboxylic acid esters, fatty acid glycerol esters, fatty acid and ethoxylated fatty acid alkanolamides, certain block copolymers of propylene oxide and ethylene oxide, and block polymers of propylene oxide and ethylene oxide with propoylated ethylene diamine.
Also included 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 anionic surfactants may include the ammonium, substituted ammonium (e.g., mono-, di-, and triethanolammonium), alkali metal and alkaline earth metal salts of C6-CzO fatty acids and rosin acids, linear and branched alkyl benzene suffonates, alkyl sulfates, alkyl ether sulfates, alkane sulfonates, olefin sulfonates, hydroxyalkane sulfonates, fatty acid monoglyceride sulfates, alkyl glyceryl ether sulfates, acyl sarcosinates and acyl N-methyltaurides.

Suitable cationic surfactants may include the quaternary ammonium co~pounds in which typically one of the groups linked to the nitrogen atom is a Cl2-C~8 alkyl X, 3 ~

group and the other three groups are short chained alkyl groups which may bear inert substituents such as phenyl groups.

Further, suitable amphoteric and zwitterionic surfactants which contain an anionic water-solubilizing group, a cationic group and a hydrophobic organic group may include amino carboxylic acids and their salts, amino dicarboxylic acids and their salts, alkylbetaines, alkyl aminopropylbetaines, sulfobetaines, alkyl imidazolinium derivatives, certain quaternary ammonium compounds, certain quaternary phosphonium compounds and certain teritary sulfonium compounds. Other examples of potentially suitable 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 depicted in Kirk-Othmer, En~yclopedia of Chemical Technoloqy, Third Edition, Volume 22, pages 347-387, and McCutche~n's ~eter~ents and Em~lsifiers, North American Edition, 1983, which are incorporated herein by reference.

As mentioned hereinabove, other common detergent adjuncts may be added if a bleach or detergent bleach product is desired. If, for example, a dry bleach ~X

13~0iD39 , ~

composition is desired, the following 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, brighten~rs, etc.

The hydrogen peroxide source may be selected from the alkali 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 monoperpho~phates. In liquid applications, liquid hydrogen peroxide solutions are preferred, but the precursor nay need to be kept separate therefr~m prior to combination in aqueous solution to prevent premature decomposition.

The range of peroxide to peracid precursor is preferably determined as a molar ratio of pleroxide to ester groups contained in the precursor. Thus, the range of peroxide to each ester group is a molar ratio of from about 0:5 to 10:1, more preferably about 1:1 to 5:1 and most preferably about 1:1 to 2:1. It is preferred that this peracld precursor/peroxide composition provide preferably about 0.5 to 100 ppm A.O., and most preferably ~X

13~ 0'~3 ,,._ about 1 to 50 ppm A.O., and most preferably about 1 to 20 ppm A.O., in aqueous media.

A description of, and explanation of, A.O.
measurement is found in the article of Sheldon N. Lewis, "Peracid and Peroxide Oxidations," In: Oxidation, 1969, pp.213-258.

Determination of the peracid can be ascertained by the analytical techniques taught in Organic Pe~acid, (Ed.
by D. Swern), Vol. 1, pp. 501 et seq. (Ch. 7) ~1970).

An example of a practical execution of a liquid delivery system is to dispense separately metered amounts of the precursor (in some non-reactive fluid ~edium) and liquid hydrogen peroxide in a container such a$ described in Beacham et al. U.S. Patent 4,585,150, commonly assigned to The Clorox Company.

The buffer may be selected from 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, 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 7.0, more preferably above about pH

X '~

9.0, and most preferably above about pH 10Ø

The filler material, which, in a detergent bleach application, may actually constitute the major constituent, by weight, of the 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 UMB.
Monastral colorants are also possible for inclusion.
Brighteners, such as stilbene, styrene and styrylnapthalene brighteners (fluorescent whitening agents), may be included. ~ragrances used for esthetic purposes are commercially available from Norda, International Flavors and Fragrances and Givaudon.
Stabilizers include hydrated salts, such as magnesium sulfate, and boric acid.

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

12.8% Sodium Perborate Tetrahydrate 8.3% Octanoyloxy dimethyl oxime ester 7.0% Nonionic Surfactant 15.0% Sodium Carbonate 56.9% Sodium Sulfate 100 . 0%

In another one of the preferred embodiments, in which a compound as in (II) below is the precursor, a preferred bleach composition has the following ingredients:

12.8% Sodium Perborate Tetrahydrate 10.0% Octanoyloxy succinimide 7.0% Nonionic Surfactant 15.0% Sodium Carbonate 55.2% Sodium Sulfate 100. 0%

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.

X~

13~003g ~~

EXPERIMENTAL

The oxime esters can be prepared by treatment of an oxime with the acid chloride of the corresponding carboxylic acid. In order to have a liquid reaction medium, a non-reactive solvent is added, and a base.

The oximes can be purchase or prepared by treatment of a carbonyl compound with hydroxylamine. Two oximes, acetone oxime and methyl ethyl ketone oxime are readily available from commercial sources and are inexpensive.

EXAMPLE I
Preparation of Acetone Oxime Ester of Octanoic Acid O o ¦ pyrldine ll CH,(CH2)6-C-CI+ HO-N=C(CH3)2 >cH3(cH~)6-c-o-N=c(cH3)2 THF
A 500 ml three-neck flask was fitted with a paddle stirrer, condenser and dry tube, and lowered into an oil bath. To the flask was added THF (100 ml), acetone oxime (15g, .21 mole), pyridine (16.5 ml, .21 mole), and then oxtanoyl chloride (35 ml, .21 mole) in THF (50 ml), dropwise, with rapid stirring. A white solid (pyridine hydrochloride) precipitated from the solution. The reaction was allowed to stir in an oil both at a temperature of 50~C for three hours. The reaction mixture was filtered and the solvent therein removed via rota-evaporator to give an orange oil (38.8g).

! Xl 13~033 Thin layer chromatography analysis (silica gel, HX-ETAC*, 80-20) of the crude product showed one mail spot (I2 visualization) at Rf= . 47, a small spot at Rf= . 90 and a spot at the origin, probably pyridine hydrochloride. The crude product was placed on a column of silica gel (125g, 230-400 mesh, 4cm D X 25 cm H) and eluted with HX-ETAC*
(80-20). The fractions were monitored by TLC, the appropriate ones combined and solvent removed. In this way 37.8g of a colorless oil was obtained.

The infrared spectrum of the oil gave a very strong carbonyl at 1768 cm~~ and showed no sign of hydFoxyll acid chloride, or carboxylic acid. The 13 C-NMR (CDCl3, ppm downfield from TMS) showed only absorptions expected for the product. Using the numbering system shown, these assignments are made:

N-o-c-cH2-cH2-cH2-cH2-cH2-cH2 CH3 / \
9CH3 l~ CH3 C7(168.3), C8(160.9), C3(29.9), C6(30.8), C4(27.2), Cs(23.0), C2(20.7), C9(19.6), C1o(12.0), and C1(14.5).

The acyloxyimides can be readily prepared by the treatment of a hydroxyimide with an acid chloride. While the acid chlorides are readily, commercially available, the hydroxyimides are so commercially available.

134qo33 EXAMPLE II

Preparation of Oct~noyloxy Succinimide O O O O
Il J l pyridine CH3(CH~6-C-CI+ H-O-N ~ THF '?CH3(CHJ6--C-O-N~ ~

A 500 ml three-neck flask was fitted with paddle stirrer, condenser with drying tube, and lowered into an oil bath. To the flask was added THF (175 ml), the N-hydroxysuccinimide (9.5. g, .083 mole) and pyridine (6.7 ml, .083 mole). Octanoyl chloride (14.2 ml, .083 mole) was dissolved in THF (50 ml) and added to the reaction vessel over a period of 15 minutes. A white precipitate (pyridine hydrochloride) formed. The reaction mixture was heated at about 60~C for 3 hours, filtered, the solvent removed via rota-evaporator to give a light yellow oil (18.9g), which subsequently solidified.

Thin-layer chromotography analysis (silica gel, CH2C12) of the crude oil showed a main spot at Rf = .60 (UV
visualization), a small spot at Rf = .95 and a Spot at the origin (pyridine hydrochloride). The crude product was placed on a column of silica gel (150g, 230-400 mesh, 4 cm diameter x 30 cm tall) and eluted with methylenQ chloride.
The fractions were monitored by TLC, the appropriate ones combined, and the solvent removal. Thus a white solid (15.2g, 76% yield) of m.p. 60.5-61.0~C was obtained.

- 26a -~ X~

1340~
~,..

The infrared spectrum of this solid gave a very strong broad carbonyl at 1735 cm~1 and sharp ones at 1790 and 1822 cm~l. The 13c-nmr (CDC13) was very clean, showing only those absorptions necessary for the product. Thus it showed ester carbonyl carbon at 169.5 (ppm downfield from TMS), imide carbonyl at 170.0 and the methylene and methyl carbons at 14.0-31.6 ppm. Analysis of the solid by saponification number gave a purity of 100%.

The acyl oxy ammonium chloride type compounds can be prepared by treatment of an amine oxide with an acid chloride. Both amine oxides and acid chlorides are readily available commercially so this should provide for a large variety of practical precursors. However, the product appears to be formed as a nice solid only when certain high molecular weight amine oxides are used.
Unless care is taken in selecting the reaction conditions and the reagents, the reaction may at times form oils.

EXAMPLE III
PreParation of Octanoyloxy Ester of 4-PhenYlpyridine Oxide 11 /~ , CH,(CH.~-C-CI~ ON ~ ~CH3(CH~-C-O-N

A 500 ml three-neck flask was fitted with a paddle stirrer, drying tube, and flushed with nitrogen.

- 26b -Xll .~.

To the flask was added THF (150 ml) and 4-phenylpyridine N-oxide (5g .029 mole). A light yellow solution resulted. To this was added rapidly octanoyl chloride (5.0 ml, .029 mole) in THF (20 ml). The mixture was stirred very rapidly for 1 ~ minutes. A gelatinous precipitate formed almost immediately. When the viscous solution was diluted with ether (about 300 ml), a white solid layer separated. The mix was filtered to give a white solid which was washed with ether. The dried white solid (7.0g, 72~ yield) had a carbonyl absorption at 1822 cm~1 in the infrared spectrum. The 13C-NMR was very clean and showed only those absorptions necessary for the product. A carbonyl at 174.5 (DMS0 solvent, ppm downfield from TMS) was observed in addition to absorptions for the aromatic carbons and those for the alkyl chain.

When treated with alkaline, aqueous peroxide anion.
The precursors described form peracids in solution. The table below summarizes the perhydrolysis yields of typical precursors.

- 26c -X~

I ~ 1340U39 ,. , TAB~E 1 Item Structure ~ Peracid Yield~' 1 CH3(CH2~6-C!O-N=C(cH3)2 46%

Il / 7 2 CH3(CHz)~-C-O-N = C 3 5~o o o 3 CH3(CH2)~-C-o-N ~ 90 %

o o

4 CH3(CH.~I-C-o-N ~3 86 %

CH3(CHz)~-c-o-cHz-~ none 6 CH3(CH.~j-C-O-~ 21 %

* ph 10.5, 5 min, 70~F 2: 1 peroxide: activator molar ratio, Pluronic~L63 surfactant ( .1 wt% ) 'Trade Mark - 26d -~r t A comparison of item 5 with all the others, shows the importance of having the oxygen atom attached directly to nitrogen atom of the leaving group, in accordance with the teachings of the invention.

While the foregoing examples and discussion of the invention depict detailed embodiments thereof, it is to be understood that applicants do not limit themselves to such detailed embodiments and this application includes such variations, modifications and equivalents which would be known to those skilled in the art and do not depart from the teachings of the invention. The claims, which are appended hereto, form a similarly non-limiting part of the invention herein.

- 26e -X~ ~

Claims (21)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A bleaching composition comprising:
(a) a bleach activator selected from:
(i) oxime esters having the structures:

or wherein R is C5 to C9 alkyl and wherein the substituent -O-N-R1 is a leaving group which contains a carbon atom doubly bonded directly to N; X is -O-, -N-, -S- or quaternary ammonium;
(ii) oxyimide esters having the structures:

or wherein R is C5 to C9 alkyl;
R1 has at least one carbon atom singly bonded directly to N; X is -O-, -N-, -S- or quaternary ammonium;
wherein -O-N-R1 is either or , and wherein R3 and R4 are the same or different, and are separately straight or branched chain C1-20 alkyl, aryl, alkylaryl or mixtures thereof; and R5 is straight or branched chain C1-20 alkyl, aryl, or alkylaryl and completes a heterocycle; and (iii) an amine oxide ester having the structures:

; or , wherein R is a straight or branched chain C1-20 alkyl, alkoxyl, cycloalkyl, X is -O-, -N-, -S- or quaternary ammonium, and the substituent -O-N-R1 is selected from the group comprising:

, and and wherein R8 and R9 are the same or different and are separately straight or branched chain C1-20 alkyl, aryl, alkylaryl or mixtures thereof; R10 is C1-30 alkyl, aryl, alkylaryl or mixtures thereof; R11 is C1-20 alkyl, aryl, alkylaryl and completes a heterocycle; and R12 is C1 20 alkyl, aryl, alkylaryl or mixtures thereof, and (b) a bleach effective amount of a source of hydrogen peroxide

2 The bleaching composition of claim 1 wherein the bleach activator comprises the oxyimide esters of (a)(ii), wherein -0-N-R1 is a leaving group having the structure wherein R6 is selected from the group comprising methylene, an aromatic ring fused to the heterocycle, and C1-6 alkyl

3 The bleaching composition of claim 2 wherein the bleach activator is

4. The bleaching composition of claim 2 wherein the bleach activator is

5. The bleaching composition of claim 1 wherein the bleach activator comprises the amine oxide ester of (a)(iii), wherein -O-N-R1 is a leaving group having the structure wherein R11 completes an aromatic heterocycle.

6. The bleaching composition of claim 5 wherein the bleach activator is

7. The bleaching composition of claim 5 wherein the bleach activator is

8. The bleaching composition of claim 1 wherein the bleach activator is an oxime ester with the structure

9. The bleaching composition of claim 1 wherein the bleach activator is an oxime ester with the structure

10. The bleaching composition of claim 1 or 8 wherein the source of hydrogen peroxide (b) is selected from the group consisting essentially of hydrogen peroxide, hydroyen peroxide adducts, alkali metal and alkaline earth perborates, alkali metal salts of percarbonate, and alkali metal salts of persilicate.

11. The bleaching composition of claim 10 wherein said source of hydrogen peroxide is an alkali metal perborate selected from the mono- and tetrahydrate forms of sodium perborate.

12. The bleaching composition of claim 11 wherein the molar ratio of hydrogen peroxide source to bleach activator is 0.5:1 to 10:1, based on moles of H202 to moles of ester.

13. The bleaching composition of claim 1 or 8 further comprising (c) an adjunct selected from the group consisting essentially of surfactants, builders, fillers, enzymes, fluorescent whitening agents, pigments, dyes, fragrances, stabilizers and buffers.

14. The bleaching composition of claim 1 or 8 in which the bleach activator is coated with a surfactant having a melting completion temperature above about 40°C.

15. The bleaching composition of claim 1, wherein the bleach activator is an amine oxide ester, R is selected from the group consisting of straight and branched chain C1-20 alkyl and cycloalkyl and X is -O-.

16. The bleaching composition of claim 15 wherein -O-N-R1 is a leaving group having the structure:

wherein R11 completes an aromatic heterocycle.

17. The bleaching composition of claim 15 wherein the source of hydrogen peroxide of (b) is selected from the group consisting of hydrogen peroxide, hydrogen peroxide adducts, alkali metal and alkaline earth perborates, alkali metal salts of percarbonate, and alkali metal salts of persilicate.

18. The bleaching composition of claim 17 wherein the source of hydrogen peroxide is an alkali metal perborate selected from the mono- and tetrahydrate forms of sodium perborate.

19. The bleaching composition of claim 18 wherein the molar ratio of hydrogen peroxide to bleach activator is 0.5:1 to 10:1, based on moles of H202 to moles of ester.

20. The bleaching composition of claim 15 further comprising (c) an adjunct selected from the group consisting of surfactants, builders, fillers, enzymes, fluorescent whitening agents, pigments, dyes, fragrances, stabilizers and buffers.

21. The bleaching composition of claim 15 in which the bleach activator is coated with a surfactant having a melting completion temperature above about 40°C.