Polyglycolate compounds are provided having the general structure: ##STR1## wherein n is an integer from 2 to about 10; R is C.sub.1-20 linear or branched alkyl, alkoxylated alkyl, cycloalkyl, aryl, alkylaryl, substituted aryl; R' and R" are independently H, C.sub.1-20 alkyl, aryl, C.sub.1-20 alkylaryl, substituted aryl, and NR.sub.3.sup..alpha.+, wherein R.sup..alpha. is C.sub.1-30 alkyl; and L is a leaving group displaceable in a peroxygen bleaching solution by perhydroxide anion. When this compound is combined with a source of peroxygen in aqueous solution, then a plurality of stain removing peracids are formed. Such peracids are formed substantially sequentially beginning with the carbonyl adjacent to the leaving group L. Thus, a first stain removing peracid having the structure ##STR2## will be formed in amounts approaching quantitative yield.

TECHNICAL FIELD 
This invention generally relates to peracid bleaching, and more 
particularly to peracid precursors having the general formula 
##STR3## 
where n is 2 to about 10 and L is a leaving group that is displaced in a 
peroxygen bleaching solution by perhydroxide anion. 
BACKGROUND OF THE INVENTION 
Peroxy compounds are effective bleaching agents, and compositions including 
mono- or diperoxyacid compounds are useful for industrial or home 
laundering operations. For example, U.S. Pat. No. 3,996,152, issued Dec. 
7, 1976, inventors Edwards et al., discloses bleaching compositions 
including peroxygen compounds such as diperazelaic acid and 
diperisophthalic acid. 
Peroxyacids (also known as "peracids) have typically been prepared by the 
reaction of carboxylic acids with hydrogen peroxide in the presence of 
sulfuric acid. For example, U.S. Pat. No. 4,337,213, inventors Marynowski 
et al., issued June 29, 1982, discloses a method for making diperoxyacids 
in which a high solids throughput may be achieved. 
However, granular bleaching products containing peroxyacid compounds tend 
to lose bleaching activity during storage, due to decomposition of the 
peroxyacid. The relative instability of peroxyacid presents a problem of 
storage stability for compositions consisting of or including peroxyacids. 
One approach to the problem of reduced bleaching activity of peroxyacid 
compositions has been to include "activators" for or precursors of 
peroxyacids. U.S. Pat. No. 4,283,301, inventor Diehl, issued Aug. 11, 
1981, discloses bleaching compositions including peroxygen bleaching 
compounds, such as sodium perborate monohydrate or sodium perborate 
tetrahydrate, and activator compounds such as isopropenyl hexanoate and 
hexanoyl malonic acid diethyl ester. However, these bleach activators tend 
to yield an unpleasant odor under actual wash conditions. U.S. Pat. No. 
4,486,327, inventors Murphy et al., issued Dec. 4, 1984, and U.S. Pat. No. 
4,536,314, inventors Hardy et al., issued Aug. 20, 1985, disclose certain 
alpha substituted derivatives of C.sub.6 -C.sub.18 carboxylic acids which 
are said to activate peroxygen bleaches and are said to reduce malodor. 
U.S. Pat. No. 4,539,130, inventors Thompson et al., issued Sept. 3, 1985 
(and its related U.S. Pat. No. 4,483,778, inventors Thompson et al., 
issued Nov. 20, 1984) disclose chloro, methoxy or ethoxy substituted on 
the carbon adjacent to the acyl carbon atom. U.S. Pat. No. 3,130,165, 
inventor Brocklehurst, issued Apr. 21, 1964, also discloses an 
.alpha.-chlorinated peroxyacid, which is said to be highly reactive and 
unstable. 
U.S. Pat. No. 4,681,952, inventors Hardy et al., issued July 21, 1987, 
discloses peracids and peracid precursors said to be of the general type 
RXAOOH and RXAL, wherein R is said to be a hydrocarbyl group, X is said to 
be a hetero-atom, A is said to be a carbonyl bridging group, and L is a 
leaving group, such as an oxybenzene sulfonate. C.sub.6 through C.sub.20 
alkyl substituted aryl are said to be preferred as R, with C.sub.6 
-C.sub.15 alkyl said to be especially preferred for oxidative stability. 
Chung et al., U.S. Pat. No. 4,412,934, issued Nov. 1, 1983, discloses 
bleaching compositions containing a peroxygen bleaching compound and a 
bleach activator of the general formula 
##STR4## 
wherein R is an alkyl group containing from about 5 to about 18 carbon 
atoms, and L is a leaving group, the conjugate acid of which has a 
pK.sub..alpha. in the range of about 6 to about 13. 
Nakagawa et al., U.S. Pat. No. 3,960,743, issued June 1, 1976, discloses an 
activating agent represented by the formula 
##STR5## 
wherein R stands for an alkyl group having 1 to 15 carbon atoms, a 
halogen- or hydroxyl-substituted alkyl group having 1 to 16 carbon atoms 
or a substituted aryl group, B designates a hydrogen atom or an alkyl 
group having 1 to 3 carbon atoms, M represents a hydrogen atom, an alkyl 
group having 1 to 4 carbon atoms or an alkali metal, and n is an integer 
of at least 1 when M is an alkyl group or n is an integer of at least 2 
when M is a hydrogen atom or an alkali metal. However, perhydrolysis of 
this activating agent substantially does not occur at the carbonyl 
adjacent the M substituent and the overall perhydrolysis that does occur 
tends to occur relatively slowly. 
U.S. Pat. No. 4,778,618, Fong et al., issued Oct. 18, 1988 provides novel 
bleaching compositions comprising peracid precursors with the general 
structure 
##STR6## 
wherein R is C.sub.1-20 linear or branched alkyl, alkylethoxylated, 
cycloalkyl, aryl, substituted aryl; R' and R"are independently H, 
C.sub.1-20 alkyl, aryl, C.sub.1-20 alkylaryl, substituted aryl, and 
NR.sub.3.sup..alpha.+, wherein R.sup..alpha. is C.sub.1-30 alkyl; and 
where L is a leaving group which can be displaced in a peroxygen bleaching 
solution by perhydroxide anion. The present invention is related to the 
Fong et al. glycolate ester peracid precursors in that precursors of the 
present invention are polyglycolates of the Fong et al. monoglycolate 
precursors. Further, compositions of the invention preferably include 
admixtures of the polyglycolate and glycolate precursors. 
SUMMARY OF THE INVENTION 
In one aspect of the present invention, a bleaching composition comprises a 
peracid precursor having the general structure: 
##STR7## 
wherein n is 2 to about 10; R is C.sub.1 -C.sub.20 linear or branched 
alkyl, alkylethoxylated, cycloalkyl, aryl, substituted aryl; R' and R" are 
independently H, C.sub.1-20 alkyl, aryl, C.sub.1-20 alkylaryl, substituted 
aryl, and NR.sub.3.sup..alpha.+, wherein R.sup..alpha. is C.sub.1-30 
alkyl, more preferably where one of R' and R" is methyl or H and the 
other is H; and L is a leaving group displaceable in a peroxygen bleaching 
solution by perhydroxide anion. When this peracid precursor is combined 
with a source of peroxygen in aqueous solution, then a plurality of stain 
removing peracids are formed. Such peracids are formed substantially 
sequentially beginning with the carbonyl adjacent to the leaving group L. 
Thus, when a peracid precursor is dissolved in aqueous solution and is in 
the presence of sufficient peroxygen source, then a first stain removing 
peracid having the structure 
##STR8## 
will be formed in amounts approaching quantitative yield. Subsequent stain 
removing peracids then form in solution so that there is a high level of 
bleaching capacity maintained over a typical wash cycle. 
In another aspect of the present invention, the just described peracid 
precursor is admixed with a monoglycolate peracid precursor having 
substantially the same general structure, but wherein n is 1. This 
admixture provides a mixture of soluble peracids and surface active 
peracids during the wash cycle. Soluble peracids are believed to assist in 
reducing dye transfer. Commercial preparation of the admixture is also 
easier and less expensive than preparing either substantially pure 
monoglycolate peracid precursor or peracid precursor that is substantially 
entirely polyglycolate.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
Compounds of the invention are peracid precursors having the general 
structure: 
##STR9## 
wherein n is 2 to about 10, preferably an average of about 4; R is C.sub.1 
-C.sub.20 linear or branched alkyl, alkylethoxylated, cycloalkyl, aryl, 
substituted aryl; R' and R" are independently H, C.sub.1-20 alkyl, aryl, 
C.sub.1-20 alkylaryl, substituted aryl, and NR.sub.3.sup..alpha.+, wherein 
R.sup..alpha. is C.sub.1-30 alkyl, preferably where one of R' and R" is 
methyl or H and the other is H; and L is a leaving group displaceable in a 
peroxygen bleaching solution by perhydroxide anion. 
When this peracid precursor is combined with a source of peroxygen in 
aqueous solution, then a plurality of stain removing peracids are formed. 
Such peracids are formed substantially sequentially down the carbon chain 
at the carbonyls, beginning with the carbonyl adjacent to the leaving 
group L. Thus, when a peracid precursor is dissolved in aqueous solution 
and is in the presence of sufficient peroxygen source, then a first stain 
removing peracid having the structure 
##STR10## 
will be formed in amounts approaching quantitative yield. Subsequent stain 
removing peracids then form in solution so that there is a high level of 
bleaching capacity maintained over a typical wash cycle. Among the 
peracids formed are both soluble and surface active peracids. Soluble 
peracids are believed to assist in preventing dye transfer during 
laundering of colored fabrics. 
A particularly preferred peracid precursor and the "cascade" of bleaching 
compounds formed in aqueous solution in the presence of perhydroxide 
anions therefrom, are illustrated by Reaction Scheme I. 
##STR11## 
As illustrated by Reaction Scheme I, the peracid precursor designated 
OOAOAPS (where R=C.sub.7, R' and R" are H, L is --O--.phi.--SO.sub.3 Na 
and n=2) can give almost quantiative production of the first peracid in 
the cascade. This first peracid is designated POOAOAA and provides stain 
removal. Proceeding down the cascade (Route B), another good stain 
removing peracid is formed. This second peracid is designated POOAA. In 
yet another stage of the cascade, the peracid designated POA (i.e., 
peroctanoic acid) is formed, which is a stain removing peracid. These 
sequentially formed peracids together maintain a high level of total 
peracid available for bleaching over a twenty minute period, as is 
illustrated by FIG. 1 (where the initial OOAOAPS compound and peroxide 
were in a 1:2molar ratio and the species were monitored at room 
temperature by HPLC with an iodometric detector). The peracid designated 
PGA is water soluble while the POOAA and POA are surface active peracids. 
Reaction Scheme I indicates that minor amounts of the compound PDGA are 
probably formed, along with POA, and then to PGA. 
As may be seen from Reaction Scheme I, the peracid precursor has n=2. Where 
the polyglygolates are in a mixture, for example so that the average of n 
is 4, then the reactions are much more complicated than shown by Reaction 
Scheme I since there are many more reactive sites and the "cascade" 
formation of peracids appears to occur even more rapidly. Table I 
illustrates the species formed where R=C.sub.7, R' and R" are H, L is 
--O--.phi.--SO.sub.3 Na and n is an average of 4 (hydrogen peroxide being 
the limiting reagent). The pH was 10.5, temperature was 23.degree. C., 
precursor was in 1:2 molar ratio with respect to H.sub.2 O.sub.2, and the 
initial precursor concentration was 0.8 mM. 
TABLE I 
______________________________________ 
Peracid Species.sup.1 (mM) 
Elasped 
Time Per- 
(min) glycolic.sup.2 
n = 0 n = 1 n = 2 n = 3 n = 4 
______________________________________ 
2 0.640 0.017 0.126 0.076 0.015 0.004 
5 0.724 0.020 0.156 0.027 0.001 -- 
10 0.589 0.053 0.130 0.031 -- -- 
______________________________________ 
##STR12## 
.sup.2 The sum of poly or monoperglycolic acid species 
Turning to FIG. 2, the OOAOAPS inventive polyglycolate is shown to provide 
significantly better stain removal of crystal violet on cotton when 
dissolved as a theoretical A.O. of 14 ppm (for phenol sulfonate ester) 
solution with 28 ppm A.O. H.sub.2l 0.sub.2 present than is provided with 
28 ppm hydrogen peroxide by itself at 23.degree. C. Similarly, another 
inventive polyglycolate (where n averages 4) designated "OOPOAPS" also 
provides good stain removal. For comparison, two comparative (prior art) 
compounds were also tested for crystal violet stain removal on cotton at 
23.degree. C. as theoretical A.O. of 14 ppm solutions with 28 ppm A.O. 
H.sub.2 O.sub.2 present. These two comparative compounds are designated 
"prior art (1)" and "prior art (2)", respectively. As can be seen from 
FIG. 2, both of the inventive precursors provided better stain removal 
than both of the comparative compounds. All solutions were tested at pH 
10. These two comparative compounds had the structures shown below 
(disclosed by U.S. Pat. No. 3,960,743, supra). 
##STR13## 
Turning to FIG. 3, the two embodiments of the invention described in 
connection with FIG. 2 are again shown for crystal violet stain removal, 
but at 5.degree. C. Hydrogen peroxide is shown as control (at 28 ppm A.O. 
rather than the 14 ppm of the precursors), and another two prior art 
comparative compositions (designated as "prior art (3)" (disclosed by U.S. 
Pat. No. 4,412,934, suora) and "prior art (4)") having the structures 
shown below are shown for stain removal under the same conditions. 
##STR14## 
As is seen by the above comparative structures, prior art (3) is a peracid 
precursor while prior art (4) is a preformed peracid. The similar stain 
removal performance of the inventive precursors with respect to prior art 
(4), that is, peroctanoic acid, or "POA", is quite surprising and means 
that formulations of the invention intended for use in cold or cool water 
washes (such as, for example, from about 5.degree. C. to about 15.degree. 
C.) should provide as good stain removal as would a peracid such as 
peroctanoic acid; without, however, the well-known stability and handling 
problems of such preformed peracids. This surprising performance in cold 
or cool water can be explained by the high reactivity of the inventive 
compounds when compared to prior art precursors. This is illustrated in 
Table II, which presents the peracid generation of inventive embodiments 
(1) and (2) in comparison with peracid generation of prior art compound 
(3) at 5.degree. C. 
TABLE II 
______________________________________ 
Comparative Peracid Generation at 5.degree. C.* 
A.O. (ppm) Generated by Precursor at 5.degree. C. 
Inventive Inventive Prior 
Time (min) 
Embodiment (1) 
Embodiment (2) 
Art (3) 
______________________________________ 
1 9.4 9.2 4.7 
2 10.0 9.7 6.0 
3 10.3 9.9 6.7 
6 10.7 10.3 7.7 
8 10.8 10.6 8.0 
10 10.7 10.6 8.2 
______________________________________ 
*[H.sub.2 O.sub.2 ]:[precursor] = 2:1 
[precursor] = 8.75 .times. 10.sup.-4 M 
pH = 10.0 (.02M CO.sub.3.sup.= buffer) 
FIG. 4 illustrates another comparison between the prior art (1) compound 
discussed for FIG. 2 (where n=2) and the inventive compound OOAOAPS (where 
n=2). Thus, perhydrolysis % yield over 14 minutes at pH 10.5.degree. and 
25.degree. C. is illustrated, where H.sub.2 O.sub.2, and tested compounds 
were in a 2:1 mole ratio. As can be seen, the inventive OOAOAPS provided 
significantly greater yield of peracid over the 14 minute period 
(representing the usual maximum wash cycle) than did the prior art (1) 
compound. This indicates that peracid precusors of the invention achieve 
and maintain superior levels of bleaching capacity over a typical wash 
cycle. 
FIG. 5 is similar to FIG. 4, but illustrates a comparison between the 
inventive precursor OOPOAPS (where n averages 4) and the prior art (2) 
compound and was conducted at pH 10. Again, the inventive precursor 
provided significantly greater yield of peracid over the 14 minute period. 
Both FIGS. 4 and 5 were conducted with a precursor concentration of 
8.75.times.10.sup.-4 M (i.e., 14 ppm A.O. theoretical). 
Preparation of particularly preferred embodiments of the invention and 
additional experimental details will be described in the Experimental 
section of this specification, following a brief review of definitions and 
a detailed description of suitable leaving groups and delivery systems for 
precursors of the invention. 
By peracid precursors are meant reactive esters which have a leaving group 
substituent. During perhydrolysis the leaving group cleaves off at the 
acyl portion of the ester. 
By perhydrolysis is meant the reaction that occurs when a peracid precursor 
is combined in a reaction medium (aqueous solution) with an effective 
amount of a source of hydrogen peroxide. 
As may be seen, the leaving group is a substituent which is attached via an 
oxygen bond to the acyl portion of the ester and which can be replaced by 
a perhydroxide anion (-OOH) during perhydrolysis. 
In the Formula I structure of the invention, R is defined as being 
C.sub.1-20 linear or branched alkyl, alkoxylated alkyl, cycloalkyl, aryl, 
substituted aryl or alkylaryl. 
It is preferred that R is C.sub.1-20 alkyl or alkoxylated alkyl. More 
preferably, R is C.sub.1-14, and mixtures thereof. R can also be 
mono-unsaturated or polyunsaturated. If alkoxylated, ethoxy and propoxy 
(branched or unbranched) groups are preferred, and can be present per mole 
of ester from 1-30 ethoxy or propoxy groups, and mixtures thereof. 
It is especially described for R to be from 4 to 17, most preferably 6 to 
12, carbons in the alkyl chain. Such alkyl groups provide surface activity 
and are desirable when the precursor is used to form surface active 
peracids for oxidizing soils and stains affixed to fabric surfaces at 
relatively low temperatures. 
It is further highly preferred for R to be aryl and C.sub.1-20 alkylaryl. A 
different type of bleaching compound results when aromatic groups are 
introduced onto the ester. 
Alkyl or alkanoyl groups are generally introduced onto the ester via an 
acid chloride synthesis discussed further below, although acid anhydrides 
may also be used. Fatty acid chlorides such as hexanoyl chloride, 
heptanoyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl 
chloride and the like provide this alkyl moiety. Aromatic groups can be 
introduced via aromatic acid chlorides (e.g., benzoyl chloride) or 
aromatic anhydrides (e.g., benzoic acid anhydride). 
R' and R" are independently H, C.sub.1-20 alkyl, aryl, C.sub.1-20 
alkylaryl, substituted aryl, and NR.sub.3.sup..alpha.+, wherein 
R.sup..alpha. is C.sub.1-30 alkyl. When R' and R" are both alkyl, aryl, 
alkylaryl, substituted alkyl or mixtures thereof, preferably the total 
number of carbons of R'+R" does not exceed about 20, more preferably does 
not exceed about 18. Alkyls of about 1-4 are preferred. If substituted 
aryl, OH-, SO.sub.3 -, and CO.sub.2 -; NR.sub.3.sup..alpha.+ 
(R.sup..alpha. is C.sub.1-30 carbons, and preferably, two of R.sup..alpha. 
is a long chain alkyl (C.sub.6-24). Appropriate positive counterions 
include Na.sup.+, R.sup.+, etc. and appropriate negative counterions 
include halogen (e.g., Cl-), OH- and methosulfate. It is preferred that at 
least one of R' and R" be H, and most preferably, both (thus forming 
methylene). 
The leaving group, as discussed above, is capable of being displaced by 
perhydroxide anion in aqueous medium. 
The preferred leaving groups include: phenol derivatives, halides, 
oxynitrogen leaving groups, and carboxylic acid (from a mixed anhydride). 
Each of these preferred leaving groups will now be more specifically 
described. 
Phenol Derivatives 
The phenol derivatives can be generically defined as: 
##STR15## 
wherein Y and Z are, individually H, SO.sub.3 M, CO.sub.2 M, SO.sub.4 M, 
OH, halo substituent, --OR.sup.2, R.sup.3, NR.sub.3.sup.4 X, and mixtures 
thereof, wherein M is an alkali metal or alkaline earth counterion, 
R.sup.2 of the OR.sup.2 substituent is C.sub.1-20 alkyl, R.sup.3 is 
C.sub.1-6 alkyl, R.sup.4 of the NR.sub.3.sup.4 substituent C.sub.1-30 
alkyl, X is a counterion, and Y and Z can be the same or different. 
The alkali metal counterions to sulfonate, sulfate or carboxy (all of which 
are solubilizing groups) include K.sup.+, Li.sup.+ and most preferably, 
Na.sup.+. The alkaline earth counterions include Sr.sup.++, Ca.sup.++, and 
most preferably, Mg.sup.++. Ammonium (NH.sub.4.sup.+) and other positively 
charged counterions may also be suitable. The halo substituent can be F, 
Br or most preferably, Cl. When --OR.sup.2, alkoxy, is the substituent on 
the phenyl ring, R.sup.2 is C.sub.1-20, and the criteria defined for R on 
the acyl group apply. When R.sup.3 is the substituent on the phenyl ring, 
it is a C.sub.1-10 alkyl, with preference given to methyl, ethyl, N- and 
isopropyl, N-, sec- and tertbutyl, which is especially preferred. When 
NR--.sub.3.sup.4 X (i.e. quaternary ammonium) is the substituent, it is 
preferred that two of R.sup.4 be short chain alkyls (C.sub.1-4, most 
preferably, methyl) and one of the R.sup.4 alkyls be longer chain alkyl 
(e.g., C.sub.8-30), with X, a negative counterion, preferably selected 
from halogen (Cl-, F-, Br-, I-), CH.sub.3 SO.sub.4 - (methosulfate), 
NO.sub.3 -, or OH-. 
Especially preferred are phenol sulfonate leaving groups. A preferred 
synthesis of phenol sulfonate esters which could be adapted for use herein 
is disclosed in U.S. Pat. No. 4,735,740, inventor Alfred G. Zielske, 
entitled "Diperoxyacid Precursors and Method" issued Apr. 5, 1988. 
Preferred phenol derivatives are: 
##STR16## 
Halides 
The halide leaving groups are quite reactive and actually are directly 
obtained as the intermediates in the synthesis of the phenyl sulfonate and 
t-butylphenol esters. While halides include Br and F, Cl is most 
preferred. 
Oxynitrogen 
The oxynitrogen leaving groups are especially preferred. In the co-pending 
application entitled "Acyloxynitrogen Peracid Precursors", inventor Alfred 
G. Zielske, commonly assigned to The Clorox Company, Ser. No. 928,065, 
filed Nov. 6, 1986, incorporated herein by reference, a detailed 
description of the synthesis of these leaving groups is disclosed. The 
oxynitrogen leaving groups are generally disclosed as --ONR.sup.6, wherein 
R.sup.6 comprises at least one carbon which is singly or doubly bonded 
directed to N. Thus, --ONR.sup.6 is more specifically defined as: 
##STR17## 
wherein R.sup.7 and R.sup.8 are individually H, C.sub.1-20 alkyl, (which 
can be cycloalkyl, straight or branched chain), aryl, or alkylaryl and at 
least one of R.sup.7 and R.sup.8 is not H. Preferably R.sup.7 and R.sup.8 
are the same or different, and range from C.sub.1-6. Oximes are generally 
derived from the reaction or hydroxylamine with either aldehydes or 
ketones. 
Examples of oxime leaving groups are: oximes of aldehydes (aldoximes), 
e.g., acetaldoxime, benzaldoxime, propionaldoxime, butylaldoxime, 
heptaldoxime, hexaldoxime, phenylacetaldoxime, P-tolualdoxime, 
anisaldoxime, caproaldoxime, valeraldoxime and p-nitrobenzaldoxime; and 
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, acetophenone oxime, 
benzophenone oxime and cyclopentanone oxime. 
Particularly preferred oxime leaving groups are: 
##STR18## 
wherein R.sup.9 and R.sup.10 can be the same or different, and are 
preferably straight chain or branched C.sub.1.degree. alkyl, aryl, 
alkylaryl or mixtures thereof. If alkyl, R.sup.9 and R.sup.10 can be 
partially unsaturated. It is especially preferred that R.sup.9 and 
R.sup.10 are straight or branched chain C.sub.1-6 alkyl, which can be the 
same or different. R.sup.11 is preferably C.sub.1-20 alkyl, aryl or 
alkylaryl, and completes a heterocycle. For example, a preferred structure 
is 
##STR19## 
wherein R.sup.12 can be an aromatic ring fused to the heterocycle, or 
C.sub.1-6 alkyl (which itself could be substituted with water solubilizing 
groups, such as EO, PO, CO.sub.2 - and SO.sub.3 -). 
The esters of imides can be prepared as described in Greene, Protective 
Groups in Organic Synthesis, p. 183, and are generally the reaction 
products of acid chlorides and hydroxymides. 
Examples of N-hydroxyimides which will provide the hydroxyimide leaving 
groups of the invention include: N-hydroxysuccinimide, 
N-hydroxyphthalimide, N-hydroxyglutarimide, N-hydroxynaphthalimide, 
N-hydroxymaleimide, N-hydroxydiacetylimide and N-hydroxydipropionylimide. 
Especially preferred examples of hydroxyimide leaving groups are: 
##STR20## 
In the first preferred structure for amine oxides, R.sup.13 and R.sup.14 
can be the same or different, and are preferably C.sub.1-20 straight or 
branched chain alkyl, aryl, alkylaryl or mixtures thereof. If alkyl, the 
substituent could be partially unsaturated. Preferably, R.sup.13 and 
R.sup.14 are C.sub.1-4 alkyls and can be the same or different. R.sup.15 
is preferably C.sub.1-30 alkyl, aryl, alkylaryl and mixtures thereof. This 
R.sup.15 substituent could also be partially unsaturated. It is more 
preferred that R.sup.13 and R.sup.14 are relatively short chain alkyl 
groups (CH.sub.3 or CH.sub.2 CH.sub.3) and R.sup.15 is preferably 
C.sub.1-20 alkyl, forming together a tertiary amine oxide. 
Further, in the second preferred amine oxide structure, R.sup.16 can be 
C.sub.1-20 alkyl, aryl or alkylaryl, and completes a hetercxycle. R.sup.16 
preferably completes an aromatic heterocycle of 5 carbon atoms and can be 
C.sub.1-6 alkyl or aryl substituted. R.sup.17 is preferably nothing, 
C.sub.1-30 alkyl, aryl, alkylaryl or mixtures thereof, with g=0 or 1. 
R.sup.17 is more preferably C.sub.1-20 alkyl if R.sup.16 completes an 
aliphatic heteroxycle. If R.sub.16 completes an aromatic heterocycle, 
R.sup.17 is nothing. 
Examples of amine oxides suitable for use as leaving groups herein can be 
derived from: pyridine N-oxide, trimethylamine N-oxide, 4-phenyl pyridine 
N-oxide, decyldimethylamine N-xoide, dodecyldimethylamine N-oxide, 
tetradecyldimethylamine N-oxide, hexadecyldimethylamine 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-xoide and 2-picoline N-xoide. 
Especially preferred amine oxide leaivng groups include: 
##STR21## 
Carboxylic Acids from Mixed Anhydrides 
Carboxylic acid leaving groups have the structure 
##STR22## 
wherein R.sup.18 is C.sub.1-10 alkyl, preferably C.sub.1-4 alkyl, most 
preferably either CH.sub.3 or CH.sub.2 CH.sub.3 and mixtures thereof. 
When R.sup.18 is C.sub.1 and above, it is believed that the leaving groups 
will form carboxylic acids upon perhydrolytic conditions. Thus, when 
R.sup.18 is CH.sub.3, acetic acid would be the leaving group; when 
CH.sub.2 CH.sub.3, propionic acid would the leaving group, and so on. 
However, this is a possible explanation for what may be a very complicated 
reaction. 
Examples of mixed anhydride esters include 
alkanoyl-oxyacetyl-oxyacetyl-oxyacetic or 
alkenyl-poly[oxyacetyl]-xoyacetic/acetic or propionic mixed anhydride. 
Delivery Systems 
The precursors 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 onto a substrate material, such as 
an inert salt (e.g., NaCl, Na.sub.2 SO.sub.4) or other solid substrate, 
such as 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 incorporated onto a 
non-particulate substrate such as disclosed in published European patent 
application EP No. 98 129. 
While substituting solubilizing groups may improve the solubility and 
enhance the reactivity of these precursors, an alternate mode and 
preferred embodiment is to combine the precursors with a surfactant. 
For example, the inventive precursors with oxynitrogen leaving groups are 
apparently not as soluble in aqueous media as compared to phenyl 
sulfonates. Other precursors may be similarly somewhat less soluble than 
phenyl sulfonate esters. 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.degree. C. A melt of 
surfactant may be simply admixed with peracid precursor, cooled and 
chopped into granules Exemplary surfactants for such use are illustrated 
in Table I below. 
TABLE I 
______________________________________ 
Commercial Name 
m.p. Type Supplier 
______________________________________ 
Pluronic F-98 
55.degree. C. 
Nonionic BASF Wyandotte 
Neodol 25-30 47.degree. C. 
Nonionic Shell Chemical 
Neodol 25-60 53.degree. C. 
Nonionic Shell Chemical 
Tergitol-S-30 
41.degree. C. 
Nonionic Union Carbide 
Tergitol-S-40 
45.degree. C. 
Nonionic Union Carbide 
Pluronic 10R8 
46.degree. C. 
Nonionic BASF Wyandotte 
Pluronic 17R8 
53.degree. C. 
Nonionic BASF Wyandotte 
Tetronic 90R8 
47.degree. C. 
Nonionic BASF Wyandotte 
Amidox C5 55.degree. C. 
Nonionic Stepan 
______________________________________ 
The precursors, whether coated with the surfactants or not so coated, could 
also be admixed with other surfactants to provide either bleach additive 
or detergent compositions. 
Particularly effective surfactants appear to be non-ionic surfactants. 
Preferred surfactants 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 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 ethylene oxide and 
about 1 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 
atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; 
and mixtures thereof. 
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 or propylene oxide 
and ethylene oxide with propoxylated 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 C.sub.6 -C.sub.20 fatty acids and rosin acids, linear and 
branched alkyl benzene sulfonates, alkyl sulfates, alkyl ether sulfates, 
alkane sulfonates, alpha 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 compounds 
in which typically one of the groups linked to the nitrogen atom is a 
C.sub.12 -C.sub.18 alkyl group and the other three groups are short 
chained alkyl groups which may bear inert substituents such as phenyl 
groups. 
Suitable amphoteric and zwitterionic surfactants containing an anionic 
water-solubilizing group, a cationic group or a hydrophobic organic group 
include amino carboxylic acids and their salts, amino dicarboxylic acids 
and their salts, alkyl-betaines, alkyl aminopropylbetaines, sulfobetaines, 
alkyl imidazolinium derivatives, certain quaternary ammonium compounds, 
certain quaternary phosphonium compounds and certain tertiary sulfonium 
compounds. 
As mentioned above, other common detergent adjuncts may be added if a 
bleach or detergent bleach product is desired. If, for example, a dry 
bleach 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, brighteners, 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 monoperphosphates. In 
liquid applications, 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. 
The range of peroxide to peracid precursor is preferably determined as a 
molar ratio of peroxide to precursor Thus, the range of peroxide to each 
precursor is a molar ratio of from about 0.1:1 to 10:1, more preferably 
about 1:1 to 10:1 and most preferably about 2:1 to 8:1. This peracid 
precursor/peroxide composition should provide about 0.5 to 100 ppm A.O., 
more preferably about 1 to 50 ppm peracid A.O. (active oxygen), and most 
preferably about 1 to 20 ppm peracid A.O., in aqueous media. 
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 medium) and liquid hydrogen peroxide in a container such as 
described in Beacham et al., U.S. Pat. No. 4,585,150, issued Apr. 29, 
1986. 
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. It is especially advantageous to have an amount of 
buffer sufficient to maintain a pH in the range of about 8.5 to about 
10.5. 
The filler material (which 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 styrylnaphthalene 
brighteners (fluorescent whitening agents), may be included. Fragrances 
used for aesthetic purposes are commercially available from Norda, 
International Flavors and Fragrances and Givaudon. Stabilizers include 
hydrated salts, such as magnesium sulfate, and boric acid. 
EXPERIMENTAL 
Example I describes the synthesis of 
sodium-p-(n-octanoyl-di[oxyacetyl]-oxy)-benzene sulfonate [OOAOAPS]. 
Example II describes the synthesis of 
sodium-p-(n-octanoyl-poly[oxygen]-oxy)-benzene sulfonate (with the average 
value of n=4). Example III describes another synthesis where an admixture 
of polyglycolate precursors are formed but with a lower degree of 
oligomerization than in Example II. Example IV describes the synthesis of 
another precursor embodiment of the invention, where the leaving group is 
an oxime. Example V describes the procedure for the crystal violet 
diagnostic stain removal determinations illustrated by FIGS. 2 and 3 with 
the compounds prepared from Examples I and II. 
EXAMPLE I 
Synthesis of Benzyl Glycolate 
A 500 ml round bottom flask, equipped with a Dean-Stark apparatus and 
heated by an oil bath, was charged with 25 g (0.329 mole) glycolic acid, 
which had been recrystallized from ethyl acetate, 40 g (0.378 mole) benzyl 
alcohol, 150 ml benzene and 15 drops concentrated sulfuric acid. This 
mixture was heated to reflux while stirring with a magnetic stir bar, and 
water was removed by azeotrope. After two hours, 5.9 ml (approx. 0.328 
mole) of water had been removed, and the reaction was cooled to room 
temperature. The reaction was diluted with 250 ml of diethyl ether and 
extracted with: 3.times.200 ml 4% aqueous NaHCO.sub.3 saturated with NaCl. 
The organic layer was dried over MgSO.sub.4, filtered, and rotary 
evaporated to an oil (wt=50 g), which was approximately 64% product by 
G.C.. This material was chromatographed on silica gel using ethyl 
acetate/hexane as mobil phase, yielding 20 g of product that was 95% in 
purity by G.C.. .sup.1 H NMR confirmed the structure to be that of benzyl 
glycolate (t at 3.2 ppm, 1 H; d at 4.0 ppm, 2 H; s at 5.0 ppm, 2 H; and m 
at 7.2 ppm, 5 H. All shifts downfield from TMS). IR shows v.sub.-OH at 
3420 cm.sup.-1 and V.sub.-C.dbd.0 at 1748 cm.sup.-1. 
Synthesis of Benzyl (octanoyl-oxyacetyl-oxyacetate) 
1) Octanoyl-oxyacetyl Chloride: 
9.7 g (0.048 mole) octanoyl-oxyacetic acid was suspended in 50 ml hexane at 
room temperature, and 5.4 ml oxalyl chloride (approx. 0.05 mole) was added 
in one portion with stirring. A CaSO.sub.4 drying tube was attached, and 
the reaction was stirred overnight at room temperature. The clear reaction 
solution was then gradually warmed to 60.degree. C. in an oil bath. A 
distillation head and condenser was attached, and the excess oxalyl 
chloride was distilled off along with the hexane solvent. This left 10.6 g 
of light straw colored oil that had no v.sub.-OH and strong v.sub.-C.dbd.0 
at 1812 cm.sup.-1 and 1755 cm.sup.-1. 
2) Benzyl (octanoyl-oxyacetyl-oxyacetate) 
A round bottom flask was charged with 8.0 g 0.048 mole) benzyl glycolate, 
8.0 g (0.101 mole) pyridine, and 30 ml anhydrous diethyl ether. This was 
cooled in an ice-water bath while stirring with a magnetic stirring bar. 
An addition funnel containing the acid chloride from reaction 1 above in 
30 ml ether was attached, and this was added dropwise to the 
alcohol/pyridine solution (a white ppt. formed upon addition) over 30 
minutes. The reaction was then stirred for 1 and 1/8 hours at room 
temperature, filtered and extracted with: 2.times.200 ml 4% aqueous HCl, 
4.times.200 ml 10% aqueous NaHCO.sub.3, and 1.times.200 ml saturated NaCl. 
The ether layer was dried over MgSO.sub.4, filtered and rotary evaporated 
to an oil. Vacuum drying left 14.9 g of material. This was chromatographed 
on 150 g of flash grade silica gel with 10% ethyl ether in hexane 
(vol/vol). The combined product fractions yielded 11 g of 94% (G.C.) 
product. IR shows no v.sub.--OH and a strong, broad v.sub.-C.dbd.0 
centered at 1760 cm.sup.-1, with aromatic C-H stretch at 3040 and 3060 
cm.sup.-1 and aliphatic C-H stretches at 2955, 2925 and 2860 cm TLC (20% 
ethyl ether in hexane on silica GF) indicates one component (I.sub.2 
stain) with an R.sub.f of 0.38. 
Hydrogenolysis of Benzyl (octanoyl-oxyacetyl-oxy-acetate) 
1.3 g 10% Pd/C was weighed into a 500 ml parr hydrogenation flask. 9.96 g 
(0.028 mole) Beneyl(octanoyl-oxyacetyl-oxyacetate) dissolved in 100 ml 
ethyl acetate was added to the catalyst under a nitrogen blanket. The 
flask was attached to the hydrogenation apparatus, and after a series of 
evacuations and fillings with hydrogen, the mixture was shaken for 6 hours 
under hydrogen pressure (P.sub.o =14.9 psig, P.sub.6hrs,=12.0 psig). The 
reaction was filtered through celite under a nitrogen blanket, and solvent 
removed by rotary evaporation. Vacuum drying left 7.4 g of an oil which 
crystallized upon standing. G.C. of the TMS ester of this material 
indicates it to be approximately 84% in purity. IR shows an acid v.sub.-OH 
at 3400-2500 cm.sup.-1 and a broad v.sub.-c.dbd.o centered at 1740-1780 
cm.sup.-1. .sup.13 C NMR exhibits three carbonyl resonances at 167.4, 
171.9 and 173.2 ppm downfield from TMS, as well as the two glycolic 
methylenes at 60.1 and 60.5 ppm (spectrum run in CDCl.sub.3) 
Synthesis of Octanoyl-oxyacetyl-oxyacetyl Chloride 
5.6 g (0.022 mole) octanoyl-oxyacetyl-oxyacetic acid, 50 ml hexame were 
placed in a 250 ml round bottom flask. 2.9 ml (0.03 mole) oxalyl chloride 
was added in one portion and the reaction stirred at room temperature for 
6 hours. The reaction was then heated to 80.degree. C., a distillation 
head attached with condenser and receiver, and the excess oxalyl chloride 
and solvent removed at reduced pressure. There remained 4.5 g of light 
yellow oil. IR spectrum reveals no free -OH and a broad v.sub.-c.dbd.o 
absorbance, with maxima at 1815, 1780 and 1755 cm.sup.-1. 
Synthesis of Sodium-p-(n-octanoyl-di-[oxyacetyl]-oxy)-Benzene Sulfonate 
A 250 ml round bottom flask with magnetic stirrer was charged with 4.5 g 
n-octanoyl-oxyacetyl-oxyacetyl chloride (approx. 0.022 mole), 4.8 g (0.025 
mole) anhydrous sodium-p-phenol-sulfonate, and 75 ml DMF. The reaction was 
chilled with stirring in an ice-water bath, and 3.5 g (0.35 mole) 
triethylamine was added dropwise over 20 minutes. The reaction thickened 
upon the amine addition, as a precipitate formed. After stirring an 
additional 1 hour the slurry was diluted with 200 ml diethyl ether and 
filtered on a paper filter overnight. There remained 9 g of waxy solid on 
the filter paper. Two recrystallizations from 50/50 methanol/water yielded 
3.8 g of shiny light brown flakes that were determined by HPLC, 
saponification and .sup.13 C NMR to be the desired phenol sulfonate ester 
in 97% wt. purity. (NMR: three carbonyl resonances at 173, 168 and 166.5 
ppm in 1:1:1 ratio; four aromatic carbon resonances at 121, 127.5, 146 and 
150 ppm in 2:2:1:1 ratio; two glycolate ethylene resonances at 60.5 and 62 
ppm in 1:1 ratio; and the expected C.sub.7 H.sub.15 - alkyl chain 
resonances (all downfield from TMS)). 
EXAMPLE II 
Glycolic Acid Condensation 
305 g (2.8 mole) of 70% aqueous glycolic acid and 150 ml benzene were 
combined in a round bottom flask equipped with a magnetic stirrer, oil 
bath heater, and Dean-Stark apparatus. The resulting two phase mixture was 
heated to reflux and water removed by azeotropic distillation. After 20 
hours of heating with the oil bath at 120.degree. C. a total of 120 ml of 
water had been removed (this amounts to approximately a 57 mole% excess 
beyond the water of solvation) the solvent was distilled off, and the 
reaction cooled to room temperature and dried in vacuo. To the pasty 
residue was added 250 ml of DMF, and this was stirred with warming for 3 
hours, cooled and filtered on a paper filter. The solid filtrate was 
extracted with two portions of acetone, filtered and these were combined 
with the DMF solution. Solvent removal by rotary evaporation and drying in 
vacuo left 150 g of soluble glycolic acid n-mers, with n=1 to 11 
(determined by LC, GC of TMS esters, and MS), and a maximum in the n=3 to 
5 domain. This material was used "as is" for the subsequent acylation 
reaction. 
Acylation of Glycolic Acid Oligomers 
A 500 ml round bottom flask was charged with 31 g (approx. 0.124 mole for 
n.sub.avg. =4) of n-meric glycolic acid, and 100 ml DMF. A clear solution 
was obtained upon warming on an oil bath with stirring by magnetic stir 
bar. 25 g (0.34 mole) Li.sub.2 CO.sub.3 and 20 g (0.17 mole) MgSO.sub.4 
were then added and thoroughly dispersed by stirring. An addition funnel 
containing 75 ml (0.44 mole) octanoyl chloride was attached and the 
contents added dropwise over 3 hours. A moderate level of CO.sub.2 
evolution was observed through a bubbler during the addition. The reaction 
was then stirred 56 hours, at which time 5.6 g (0.076 mole) more Li.sub.2 
CO.sub.3 was added. While stirring for 2 hours more, little gas evolution 
was seen. 20 ml methanol was added to quench the residual acid chloride, 
and after 1 hour more stirring the reaction was diluted with 200 ml 
CHCl.sub.3 and filtered to remove salts. Solvent was removed by rotary 
evaporation and the oily residue extracted with 3.times.250 ml hexane 
leaving a gummy residue weighing 67 g after drying in vacuo. 39.3 g of 
this material was dissolved in 500 ml of 0.5 N NaHCO.sub.3. This was then 
acidified to pH 2 with aqueous HCl and the resulting precipitate isolated 
by filtration, redissolved in CH.sub.3 CN, dried over MgSO.sub.4, filtered 
and rotary evaporated to a waxy material. Vacuum drying left 8.4 g of 
material that was clean by HPLC and .sup.13 C NMR, giving a distribution 
of acylated glycolic acid n-mers with n=1 to 10 and an n.sub.avg 32 4.0 to 
4.5 on a mole basis. 
Octanoyl-poly[oxyacetyl]-oxyacetyl chloride 
In a 250 ml round bottom flask 5.0 g (approx. 0.013 mole for n.sub.avg. =4) 
of C.sub.8 acylated glycolic acid n-mers was dissolved in 25 ml 
CHCl.sub.3, followed by the addition of 2.0 ml oxalyl chloride. This was 
stirred under a CaSO.sub.4 drying tube overnight at room temperature. The 
reaction was gradually heated to 70.degree. C. on an oil bath and a 
distillation apparatus was attached. The excess oxalyl chloride and 
solvent were removed by distillation leaving 2.5 g of a light yellow 
colored oil. IR of this material shows no free -OH and a broad 
v.sub.-c.dbd.o with a distinct peak at 1810 cm.sup.-1. 
Sodium-p-(octanoyl-poly[oxyacetyl]-oxy)-Benzene Sulfonate 
To 5.2 g (0.013 mole) octanoyl-poly(oxyacetyl)-oxyacetyl chloride 
(n.sub.avg. =4) in a 250 ml round bottom flask was added 3.6 g (0.018 
mole) anhydrous sodium-p-phenol sulfonate and 40 ml anhydrous ethylene 
glycoldimethyl ether (glyme) This slurry was stirred with a magnetic stir 
bar and chilled in an ice water bath while 2.0 ml triethylamine (TEA) in 
8.0 ml glyme was added dropwise with stirring over 10 minutes. The 
resultant thickened slurry was stirred at 4.degree. C. for 15 minutes, 
then at room temperature for 45 minutes, diluted with 300 ml diethyl ether 
and filtered on a paper filter. Vacuum drying of the filtrate left 10.5 g 
of tan waxy material. Recrystallization from 25 ml of 70/30 (vol/vol) 
IPA:water yielded 3.4 g of product that was 85-90% pure by HPLC. A second 
recrystallization provided 97.sup.+ % material. .sup.13 C NMR confirmed 
the proposed structure (in d.sup.6 -DMSO: multiple C=O resonances at 166.0 
to 167.3 ppm and a single resonance at 172.3 ppm; aromatic resonances at 
149.7, 146.1, 127.0, and 120.7 ppm; multiple glycolate methylene 
resonances at 62.0 to 60.2 ppm; and the characteristic C-7 alkyl chain 
resonances, with all shifts downfield from TMS), and HPLC showed it to be 
a mixture of the desired esters of the acylated glycolic n-mers, with n=2 
to 10 and a maximum in the distribution at n=3 to 5 (n.sub.avg. =4-4.5 by 
NMR and HPLC). 
EXAMPLE III 
Glycolic Acid Condensation 
150 g (1.38 moles) of 70% aqueous glycolic acid and 150 ml benzene were 
combined in a 500 ml round bottom flask, equipped with a hot oil bath, a 
magnetic stirrer, and a Dean-Stark apparatus. This mixture was heated to 
reflux and water removed by azeotropic distillation. After 10 hours, 54 g 
of water had been removed, and the solvent was stripped off at reduced 
pressure, leaving behind 97 g of a tan liquid which crystallized upon 
cooling. G.C. analysis of the TMS esters of this material showed it to be 
a mixture of glycolic acid n-mers in a ratio of 47 (n=1): 32 (n=2): 16 
(n=3): 5 (n=4). The average n value of this mixture was calculated to be 
1.8. 
The material so formed in Example III is then used "as is" for the 
subsequent acylation reaction as described in Example II, and illustrated 
by Reaction Scheme III. This procedure is a particularly preferred method 
of preparing an admixture of monoglycolate and polyglycolate precursors of 
the invention. 
EXAMPLE IV 
Methyl-Ethyl-Ketoxime Ester of n-Octanoyl-poly[oxyacetyl]-oxyacetic Acid 
The methyl-ethyl ketoxime ester of the C.sub.8 -acyl-poly glycolic acid 
(n.sub.avg =4) was prepared as follows. 4 g (0.046 mole) methyl ethyl 
ketoxime, 5 ml (0.06 mole) pyridine, and 50 ml anhydrous THF were placed 
in a 500 ml round bottom flask. This solution was chilled in an ice water 
bath while stirring. An additional funnel containing 12 g (0.027 mole) 
n-octanoyl-poly[oxyacetyl]-oxyacetyl chloride, prepared as described 
previously, in 50 ml THF was attached to the reaction vessel, and its 
contents were added dropwise over 40 minutes to the chilled 
ketoxime/pyridine solution. After 2 hours of additional stirring at 
4.degree. C. the reaction was filtered to remove the precipitated pyridine 
hydrochloride, and the clear filtrate was diluted with 300 ml diethyl 
ether. The ether solution was washed with: 2.times.200 ml 0.5% aqueous 
HCl, 1.times.200 ml D.I. water, and 1.times.200 ml saturated aqueous NaCL. 
The ether layer was dried over MgSO.sub.4, filtered and rotary evaporated 
to a yellow oil weighing 11.8 g (12.0 g theo.). Purified material was 
obtained by chromatography on an amino-bonded silica gel column. IR 
(V.sub.c.dbd.o (s) at 1760 cm.sup.-1 and no V.sub.OH and .sup.13 C NMR 
(multiple C.dbd.O resonances at 165.6 to 168.5 ppm and at 172.8 ppm, 
glycolate CH.sub.2 resonances at 59.9 to 60.6 ppm) confirmed the structure 
of this material. 
EXAMPLE V 
Procedure for Crystal Violet Diagnostic Stain Removal Determination 
a) Staining of Swatches: 
100 2".times.2"100% scoured cotton swatched (Test Fabrics Inc.) were soaked 
overnight in a solution of 0.125 g crystal violet in 1250 ml deionized 
water. The swatches were rinsed with water until the rinse was nearly free 
of dye, and then air dried. The HunterLab colorimeter Y value, from the 
tri-stimulus XYZ reading, was then determined for each swatch. 
b) Stain Removal Procedure: 
To a solution of 192 ml pH 10.0, 0.02 M carbonate buffer, and 2.53 ml 
(2.51.times.10.sup.-4 Mole) of 0.1386 M H.sub.2 O.sub.2 in distilled water 
was added 1.75.times.10.sup.-4 Mole of peracid precursor dissolved in 5.0 
ml of 70:30/IPA:water, and timing is begun. At t.dbd.30 sec. four stained 
swatches were added to the solution and stirred at the desired temperature 
for 13.5 minutes. The swatches are then removed from the perhydrolysis 
solution and thoroughly rinsed with deionized water. After air drying, the 
post-treatment HunterLab Y value was determined and %SRY was calculated by 
the Kubelka-Munk equation. 
Although the present invention has been described with reference to 
specific examples, it should be understood that various modifications and 
variations can be easily made by those skilled in the art without 
departing from the spirit of the invention. Accordingly, the foregoing 
disclosure should be interpreted as illustrative only and not to be 
interpreted in a limiting sense. The present invention is limited only by 
the scope of the following claims.