Sulfanimines as bleach catalysts

Novel bleaches, a method for bleaching substrates using these materials and detergent compositions containing same are reported. The bleaches are sulfanimines. Substrates such as fabrics may be bleached in an aqueous solution containing the sulfanimine and a peroxygen compound.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The invention relates to bleach catalysts, compositions containing same and 
a method for using the catalysts for cleaning substrates, especially 
fabrics. 
2. The Related Art 
Many household and personal care products are formulated with an active 
oxygen-releasing material to effect removal of stain and soil. 
Oxygen-releasing materials have an important limitation; their activity is 
extremely temperature dependent. Temperatures in excess of 60.degree. C. 
are normally required to achieve any bleach effectiveness in an aqueous 
wash system. Especially for cleaning fabrics, high temperature operation 
is both economically and practically disadvantageous. 
The art has partially solved the aforementioned problem through the use of 
activators. These activators, also known as bleach precursors, often 
appear in the form of carboxylic acid esters. In an aqueous liquor, anions 
of hydrogen peroxide react with the ester to generate the corresponding 
peroxyacid which oxidizes the stained substrate. Commercial application of 
this technology is found in certain fabric bleaching detergent powders 
incorporating sodium nonanoyloxybenzene sulfonate. This activator is 
typical of a class that features a phenol sulfonate leaving group; see 
U.S. Pat. No. 4,412,934 (Chung et al.). 
While carboxylic acid ester activators and the like are often effective, 
they are not catalytic. Once the ester has been perhydrolyzed it can no 
longer be recycled. Accordingly, relatively large amounts of activator are 
necessary. Amounts as high as 8% may be necessary in a detergent 
formulation for bleaching fabrics. Cost for these relatively expensive 
activators is of major concern at such levels. 
A significant advance in catalysis was reported utilizing sulfonimines in 
U.S. Pat. No. 5,041,232, U.S. Pat. No. 5,047,163 and U.S. Pat. No. 
5,045,223 all to Batal and Madison. Only a few of the reported compounds 
have been studied in any detail. More investigation needs to be conducted 
to identify catalysts of even greater activity. 
Accordingly, it is an object of the present invention to provide novel 
bleach catalysts that can operate over a wide temperature range including 
that of under 60.degree. C. 
It is another object of the present invention to provide bleach catalysts 
which are effective at relatively low concentrations thereby achieving a 
cost effective stain removal system. 
A further object of the present invention is to provide a method for 
bleaching stained substrates such as clothes, household hard surfaces 
including sinks, toilets and the like, and even dentures. 
Other objects of the present invention will become apparent through the 
following summary, detailed discussion and examples. 
SUMMARY OF THE INVENTION 
A bleaching composition is provided including: 
(i) from 1 to 60% by weight of a peroxygen compound; 
(ii) from 0.01 to 10% of an oxygen transfer agent whose structure is: 
EQU R.sup.1 R.sup.2 C.dbd.NSO.sub.2 --XR.sup.3 
wherein: 
X is a radical selected from the group consisting of oxygen, nitrogen and 
NR.sup.1 radicals; 
R.sup.1 may be hydrogen or a C.sub.1 -C.sub.40 substituted or unsubstituted 
radical selected from the group consisting of phenyl, aryl, acyl, 
heterocyclic ring, alkyl and cycloalkyl radicals; 
R.sup.2 may be hydrogen or a C.sub.1 -C.sub.40 substituted or unsubstituted 
radical selected from the group consisting of phenyl, aryl, heterocyclic 
ring, alkyl, cycloalkyl, R.sup.1 C.dbd.NSO.sub.2 XR.sup.3, nitro, halo, 
cyano, alkoxy, keto, carboxylic and carboalkoxy radicals; 
R.sup.3 may be a C.sub.1 -C.sub.40 substituted or unsubstituted radical 
selected from the group consisting of phenyl, aryl, heterocyclic ring, 
alkyl, cycloalkyl, nitro, halo and cyano radicals; 
R.sup.1 with R.sup.2 and R.sup.2 with R.sup.3 may respectively together 
independently form a cycloalkyl, heterocyclic, and aromatic ring system; 
and 
(iii) from about 0.5 to 50% of a surfactant. 
Additionally, there is provided a method for bleaching a stained substrate 
comprising the step of applying to the stained substrate an aqueous 
solution comprising a peroxygen compound and an oxygen transfer agent 
whose structure is R.sup.1 R.sup.2 C.dbd.NSO.sub.2 --XR.sup.3, with 
radical groups as defined above, the mole ratio of peroxygen compound to 
oxygen transfer agent being from about 250:1 to about 1:2. 
Certain novel compounds are also provided whose structure is R.sup.1 
R.sup.2 C.dbd.NSO.sub.2 --XR.sup.3 having radical groups as defined above, 
with the proviso that at least one of R.sup.1, R.sup.2, R.sup.3 is 
substituted with a water-solubilizing functional group. Typical 
water-solubilizing groups include carboxylic acid, phosphoric acid, 
phosphonic acid, sulfuric acid, sulfonic acid, and, especially, their salt 
derivatives and quaternary ammonium salts. 
DETAILED DESCRIPTION 
It has been found that sulfanimines operate even more effectively than 
sulfonimines as catalysts for activating peroxygen compounds to transfer 
active oxygen to stains. Consumer and industrial articles can effectively 
be bleached to remove stains present on such articles. Sulfanimines 
covered by the present invention are those whose structure is: 
EQU R.sup.1 R.sup.2 C.dbd.NSO.sub. --XR.sup.3 
wherein: 
X is a radical selected from the group consisting of oxygen, nitrogen and 
NR.sup.1 radicals; 
R.sup.1 may be hydrogen or a C.sub.1 -C.sub.40 substituted or unsubstituted 
radical selected from the group the group consisting of phenyl, aryl, 
acyl, heterocyclic ring, alkyl and cycloalkyl radicals; 
R.sup.2 may be hydrogen or a C.sub.1 -C.sub.40 substituted or unsubstituted 
radical selected from the group consisting of phenyl, aryl, heterocyclic 
ring, alkyl, cycloalkyl, R.sup.1 C.dbd.NSO.sub.2 --XR.sup.3, nitro, halo, 
cyano, alkoxy, keto, carboxylic and carboalkoxy radicals; 
R.sup.3 may be a C.sub.1 -C.sub.40 substituted or unsubstituted radical 
selected from the group consisting of phenyl, aryl, heterocyclic ring, 
alkyl, cycloalkyl, nitro, halo and cyano radicals; and 
R.sup.1 with R.sup.2 and R.sup.2 with R.sup.3 may respectively together 
independently form a cycloalkyl, heterocyclic or aromatic ring system. 
Often advantageous are sulfanimines having at least one of R.sup.1, 
R.sup.2, R.sup.3 substituted with a water-solubilizing functional group. 
These functional groups may be selected from carboxylates, phosphates, 
phosphonates, sulfates, sulfonates in acid and salt form and quaternary 
ammonium salts. Suitable salts include those whose counterions are 
selected from alkali metal, ammonium, and C.sub.2 -C.sub.6 alkanolammonium 
cations. 
Amine functional groups may also be incorporated into R.sup.1, R.sup.2 or 
R.sup.3 to provide water-solubilization of the sulfanimines. An example 
combining the amine and heterocyclic structure is that of pyridine. 
A water-solubilizing functional group is one which renders the sulfanimines 
soluble to the extent of at least 2 mg/l, preferably at least 25 mg/l, 
optimally at least 250 mg/l by weight in water at 25.degree. C. 
Heterocyclic rings according to this invention include cycloaliphatic and 
cycloaromatic type radicals incorporating an oxygen, sulfur and/or 
nitrogen atom within the ring system. Representative nitrogen heterocycles 
include pyridine, morpholine, pyrrole, imidazole, triazole, tetrazole, 
pyrrolidine, piperidine and piperazine. Suitable oxygen heterocycles 
include furan, tetrahydrofuran and dioxane. Sulfur heterocycles may 
include thiophene and tetrahydrothiophene. Among the various heterocycles, 
it has been found that those incorporating nitrogen are the most active. 
The term "substituted" is defined in relation to R.sup.1, R.sup.2, R.sup.3 
as a substituent which is a nitro, halo, cyano, C.sub.1 -C.sub.20 alkyl, 
acyl, amino, aminoalkyl, thioalkyl, sulfoxyalkyl, carboxyester, hydroxy, 
C.sub.1 -C.sub.20 alkoxy, polyalkoxy and C.sub.1 -C.sub.40 quaternary di- 
or trialkylammonium function. 
Novel sulfanimine compounds are described below wherein R.sup.1 is 
hydrogen, R.sup.2 is phenyl with a Z substitutent, and R.sup.3 is phenyl 
with a Y substituent. Very often Z and Y groups are water-solubilizing 
groups, most commonly being carboxylic acid or salts thereof. 
Representative structures are as follows: 
______________________________________ 
##STR1## 
Z Y 
______________________________________ 
O-SULF 1 4-CO.sub.2 H 
4-Cl 
O-SULF 2 4-CO.sub.2 H 
4-CO.sub.2 H 
O-SULF 3 4-Cl 4-CO.sub.2 H 
O-SULF 4 H 4-CO.sub.2 H 
O-SULF 5 4-CH.sub.2 H 
4-CH.sub.2 H 
O-SULF 6 4-CO.sub.2 H 
3-NO.sub.2 
O-SULF 7 4-CN 4-CO.sub.2 H 
O-SULF 8 4-OMe 4-CO.sub.2 H 
O-SULF 9 3-OH 4-Cl 
O-SULF 10 
##STR2## 
______________________________________ 
Illustrative of cycloaromatic and of heterocyclic nitrogen ring 
sulfanimines are the respective O-SULF 11 and O-SULF 12 whose structures 
are outlined below. 
##STR3## 
The following further compounds are illustrative of sulfanimes of the 
present invention. 
N-Benzylidenebenzenesulfamate 
N-(3-Pyridinylmethylene)benzenesulfamate 
N-(4-Pyridinylmethylene)benzenesulfamate 
N-(2-Pyridinylmethylene)benzenesulfamate 
N-(N-Methyl-3-pyridinylmethylene)benzenesulfamate chloride salt 
N-(2-Furfurylidene)benzenesulfamate 
N-(2-Furfurylidene)-4-carboxybenzenesulfamate sodium salt 
N-(2,6-Dicarboxy-4-pyridinylmethylene)benzenesulfamate disodium salt 
N-(4-Cholyloxycarbonylbenzylidene)benzenesulfamate chloride salt 
N-Benzylidene-4-cholyloxycarbonylbenzenesulfamate chloride salt 
N-Cyclohexylidenebenzenesulfamate 
N-(4-Trifluoromethylbenzylidene)benzenesulfamate 
N-(4-Methylsulfonylbenzylidene)benzene sulfamate 
N-(4-Trimethylammoniobenzylidene)benzenesulfamate chloride salt 
N-Benzylidene-4-trimethylammoniobenzenesulfamate chloride salt 
4-Trimethylammoniomethyl-1,2,3-benzoxathiazine-2,2-dioxide chloride salt 
4-Carboxymethyl-1,2,3-benzoxathiazine-2,2-dioxide sodium salt 
4-Trifluoromethyl-1,2,3-benzoxathiazine-2,2-dioxide 
5-Hydroxy-4-phenyl-1,2,3-benzoxathiazine-2,2-dioxide 
6,7-Dimethoxy-4-methyl-1,2,3-benzoxathiazine-2,2-dioxide 
N',N'-Dimethyl-N-(4-Trimethylammoniobenzylidene)sulfamide chloride salt 
N',N'-Dimethyl-N-(4-Carboxybenzylidene)sulfamide sodium salt 
N',N'-Dimethyl-N-(4-Trifluoromethylbenzylidene)sulfamide 
N',N'-Dimethyl-N-(4-Cholyloxycarbonylbenzylidene)sulfamide chloride salt 
1-Phenyl-4-trimethylammoniomethyl-2,1,3-benzthiadiazine-2,2-dioxide 
chloride salt 
4-Methyl-1-Trifluoromethyl-2,1,3-benzthiadiazine-2,2-dioxide 
1-Acetyl-4-methyl-2,1,3-benzthiadiazine-2,2-dioxide 
The foregoing oxygen transfer agents may be incorporated into detergent 
bleach compositions along with a further essential component which is a 
peroxygen compound capable of yielding peroxide anion or peroxyacid in an 
aqueous solution. 
Amounts of oxygen transfer agent suitable for the present invention may 
range from 0.01 to 10%, preferably from 0.1 to 5%, optimally between 0.5 
and 1.5% by weight of the composition. 
The peroxygen compound may be present from 1% to 65%, preferably from 1.5 
to 5%, optimally between about 2 and 10% by weight. 
The molar ratio of peroxygen compound to oxygen transfer agent will range 
from about 250:1 to 1:2, preferably 100:1 to 1:1, optimally between about 
25:1 to 2:1. 
Peroxyacid and peroxide anion sources are well known in the art. They 
include the alkali metal peroxides, organic peroxides such as urea 
peroxide, and inorganic persalts, such as the alkali metal perborates, 
percarbonates, perphosphates, persilicates and persulfates (e.g. 
Oxone.RTM.). Mixtures of two or more such compounds may also be suitable. 
Particularly preferred are sodium percarbonate, Oxone.RTM. and sodium 
perborate monohydrate. 
Alkylhydroperoxides are another suitable class of peroxygen compounds. 
Examples of these materials include cumene hydroperoxide and t-butyl 
hydroperoxide. 
Organic peroxy acids may also be suitable as the peroxygen compound. Such 
materials have a general formula: 
##STR4## 
wherein X is oxygen or nitrogen, n=0 or 1, R is an alkylene or substituted 
alkylene group containing from 1 to about 22 carbon atoms or a phenylene 
or substituted phenylene group, and Y' is hydrogen, halogen, alkyl, aryl 
or 
##STR5## 
The organic peroxy acids usable in the present invention can contain either 
one or two peroxy groups and can be either aliphatic or aromatic. When the 
organic peroxy acid is aliphatic, the unsubstituted acid has the general 
formula: 
##STR6## 
where Y' can be, for example, H, CH.sub.3, CH.sub.2 Cl, COOH, NHCOOOH or 
COOOH; and n is an integer from 0 to 20. 
When the organic peroxy acid is aromatic, the unsubstituted acid has the 
general formula: 
##STR7## 
wherein Y' is hydrogen, alkyl, alkylhalogen, halogen, COOH, NHCOOOH or 
COOOH. 
Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl 
peroxy acids such as: 
(i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. 
peroxy-.alpha.-naphthoic acid; 
(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g. 
peroxylauric acid, peroxystearic acid, and N,N-phthaloylaminoperoxycaproic 
acid (PAP). 
Typical diperoxy acids useful herein include alkyl diperoxy acids and 
aryldiperoxy acids, such as: 
(iii) 1,12-diperoxydodecanedioic acid; 
(iv) 1,9-diperoxyazelaic acid; 
(v) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic 
acid; 
(vi) 2-decyldiperoxybutane-1,4-dioic acid; 
(vii) 4,4'-sulfonylbisperoxybenzoic acid; 
(viii) N,N'-terephthaloyl-di(6-aminoperoxycaproic acid). 
Particularly preferred organic acids are N,N-phthaloylaminoperoxycaproic 
acid, peracetic acid, monoperoxyphthalic acid (magnesium salt 
hexahydrate), and diperoxydodecanedioic acid. Under certain circumstances, 
hydrogen peroxide itself may directly be employed as the peroxygen 
compound. 
Optionally, compositions of the present invention may further include a 
pre-bleach precursor that reacts with peroxide anion or peroxyacid and 
forms therewith a peracid, percarbonic acid or perimidic acid. 
The preferred precursors are N,N,N',N'-tetraacetylethylene diamine (TAED), 
tetraacetyl-glycoluril (TAGU), glucose pentaacetate, xylose tetraacetate, 
sodium acetyloxybenzene sulfonate (SABS) and sodium nonanoyloxybenzene 
sulfonate (SNOBS). Levels of precursor may range from 0.1 to 40%, 
preferably from 1 to 10%, optimally from 2 to 8% by weight. 
Bleach systems of the present invention may be employed for a wide variety 
of purposes, but are especially useful in the cleaning of laundry. When 
intended for such purpose, the peroxygen compound and oxygen transfer 
agent of the present invention will usually also be combined with 
surface-active materials, detergency builders and other known ingredients 
of laundry detergent formulations. 
The surface-active material may be naturally derived, or synthetic material 
selected from anionic, nonionic, amphoteric, zwitterionic, cationic 
actives and mixtures thereof. Many suitable actives are commercially 
available and are fully described in the literature, for example in 
"Surface Active Agents and Detergents", Volumes I and II, by Schwartz, 
Perry and Berch. The total level of the surface-active material may range 
up to 50% by weight, preferably being from 0.5 to 40% by weight of the 
composition, most preferably 4 to 25%. 
Synthetic anionic surface-actives are usually water-soluble alkali metal 
salts of organic sulphates and sulphonates having alkyl radicals 
containing from about 8 to about 22 carbon atoms. 
Examples of suitable synthetic anionic detergent compounds are sodium and 
ammonium alkyl sulphates, especially those obtained by sulphating higher 
(C.sub.8 -C.sub.18) alcohols produced for example from tallow or coconut 
oil; sodium and ammonium alkyl (C.sub.9 -C.sub.20) benzene sulphonates, 
sodium alkyl glyceryl ether sulphates, especially those ethers of the 
higher alcohols derived from tallow or coconut oil and synthetic alcohols 
derived from petroleum; sodium coconut oil fatty acid monoglyceride 
sulphates and sulphonates; sodium and ammonium salts of sulphuric acid 
esters of higher (C.sub.9 -C.sub.18) fatty alcohol-alkylene oxide, 
particularly ethylene oxide, reaction products; the reaction products of 
fatty acids such as coconut fatty acids esterified with isethionic acid 
and neutralized with sodium hydroxide; sodium and ammonium salts of fatty 
acid amides of methyl taurine; alkane monosulphonates such as those 
derived by reacting alpha-olefins (C.sub.8 -C.sub.20) with sodium 
bisulphite and those derived by reacting paraffins with SO.sub.2 and 
Cl.sub.2 and then hydrolyzing with a base to produce a random sulphonate; 
sodium and ammonium C.sub.7 -C.sub.12 dialkyl sulfosuccinates; and olefin 
sulphonates, which term is used to describe the material made by reacting 
olefins, particularly C.sub.10 -C.sub.20 alpha-olefins, with SO.sub.3 and 
then neutralizing and hydrolyzing the reaction product. The preferred 
anionic detergent compounds are sodium (C.sub.11 -C.sub.15) alkylbenzene 
sulphonates, sodium (C.sub.16 -C.sub.18) alkyl sulphates and sodium 
(C.sub.16 -C.sub.18) alkyl ether sulphates. 
Examples of suitable nonionic surface-active compounds which may be used, 
preferably together with the anionic surface-active compounds, include in 
particular the reaction products of alkylene oxides, usually ethylene 
oxide, with alkyl (C.sub.6 -C.sub.22) phenols, generally 5-25 EO, i.e. 
5-25 units of ethylene oxide per molecule; the condensation products of 
aliphatic (C.sub.8 -C.sub.18) primary or secondary linear or branched 
alcohols with ethylene oxide, generally 2-30 EO, and products made by 
condensation of ethylene oxide with the reaction products of propylene 
oxide and ethylene diamine. Other so-called nonionic surface-actives 
include alkyl polyglucosides, long chain tertiary amine oxides, and fatty 
amido polyols such as methyl glucamines. 
Amphoteric or zwitterionic surface-active compounds such as 
alkylamidopropyl betaines can also be used in the compositions of the 
invention. If any amphoteric or zwitterionic detergent compounds are used, 
it is generally in small amounts in compositions based on the much more 
commonly used synthetic anionic and nonionic actives. 
Soaps may also be incorporated into the compositions of the invention, 
preferably at a level of less than 30% by weight. They are particularly 
useful at low levels in binary (soap/anionic) or ternary mixtures together 
with nonionic or mixed synthetic anionic and nonionic compounds. Soaps 
which are used are preferably the sodium, or less desirably potassium, 
salts of saturated or unsaturated C.sub.10 -C.sub.24 fatty acids or 
mixtures thereof. The amount of such soaps can be varied between 0.5 and 
25% by weight, with lower amounts of 0.5 to 5% being generally sufficient 
for lather control. Amounts of soap between 2 and 20%, especially between 
5 and 15, are used to give a beneficial effect on detergency. This is 
particularly valuable in compositions used in hard water where the soap 
acts as a supplementary builder. 
The detergent compositions of the invention will normally also contain a 
detergency builder. Builder materials may be selected from (1) calcium 
sequestrant materials, (2) precipitating materials, (3) calcium 
ion-exchange materials and (4) mixtures thereof. 
In particular, the compositions of the invention may contain any one of the 
organic or inorganic builder materials, such as sodium or potassium 
tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium 
orthophosphate, sodium carbonate, the sodium salt of nitrilotriacetic 
acid, sodium citrate, carboxymethylmalonate, carboxymethyloxysuccinate, 
tartrate mono- and di- succinate, oxydisuccinate, crystalline or amorphous 
aluminosilicates and mixtures thereof. 
Polycarboxylic homo- and co-polymers may also be included as builders and 
to function as powder structurants or processing aids. Particularly 
preferred are polyacrylic acid (available under the trademark Acrysol from 
the Rohm and Haas Company) and acrylic-maleic acid copolymers (available 
under the trademark Sokalan from the BASF Corporation) and alkali metal or 
other salts thereof. 
These builder materials may be present at a level of, for example, from 1 
to 80% by weight, preferably from 10 to 60% by weight. 
Upon dispersal in a wash water, the initial amount of peroxygen compound 
should range anywhere from 0.05 to 250 ppm active oxygen per liter of 
water, preferably from 1 to 50 ppm. Within the wash media the amount of 
oxygen transfer agent initially present should be from 0.01 to 300 ppm, 
preferably from 5 to 100 ppm. Surfactant should be present in the wash 
water from 0.05 to 1.0 grams per liter, preferably from 0.15 to 0.20 grams 
per liter. When present, the builder amount will range from 0.1 to 3.0 
grams per liter. 
Apart from the components already mentioned, the detergent compositions of 
the invention can contain any of the conventional additives in the amounts 
in which such materials are normally employed in detergent compositions. 
Examples of these additives include dye transfer inhibition agents (e.g. 
polymers based on N-vinylpyrrolidone and N-vinylimidazole), lather 
boosters such as alkanolamides, particularly the monoethanolamides derived 
from palmkernel fatty acids and coconut fatty acids, lather-depressants 
such as alkyl phosphates and silicones, anti-redeposition agents such as 
sodium carboxymethylcellulose and alkyl or substituted alkylcellulose 
ethers, stabilizers such as ethylene diamine tetraacetic acid and 
phosphonic acid derivatives (Dequest.RTM.), fabric softening agents, 
inorganic salts such as sodium sulphate, and, usually present in very 
small amounts, fluorescent agents, perfumes, enzymes such as proteases, 
cellulases, lipases and amylases, germicides and colorants. 
The oxygen transfer agents in combination with a peroxygen compound may be 
useful for removing stains both in consumer type products and for 
industrial applications. Among consumer products incorporating this 
invention are laundry detergents, laundry bleaches, hard surface cleaners, 
toilet bowl cleaners, automatic dishwashing compositions and even denture 
cleaners. Stained consumer products benefiting from treatment with 
compositions of this invention may include clothes and other fabrics; 
household fixtures and applicants such as sinks, toilet bowls and oven 
ranges; tableware such as drinking glasses, dishes, cookware and utensils; 
and even dentures. Hair colorants may also be formulated with the bleach 
composition of this invention. The bleaching system of this invention may 
also be applied to industrial uses such as for the bleaching of wood pulp. 
The system of the present invention may be delivered in a variety of 
product forms including powders, on sheets or other substrates, in 
pouches, in tablets, in aqueous liquids, or in nonaqueous liquids such as 
liquid nonionic detergents.

The following examples will more fully illustrate the embodiments of this 
invention. All parts, percentages and proportions referred to herein and 
in the appended claims are by weight unless otherwise illustrated. 
EXAMPLES 
The oxygen transfer agents described below were synthesized according to 
the procedure of Kamal, A. and Sattur, P. B., Synthesis, 1981, pages 
272-273. 
Synthesis Procedure for Et-O-Sulf 
To a stirred solution of the 2-hydroxy propiophenone (46 mmol) in 40 mL of 
toluene (or xylene) at 108.degree. C. (or 135.degree. C.) was added 
chlorosulfonyl isocyanate (46 mmol) 5 mL in toluene (or xylene) over a 20 
minute period. After stirring for 3 hours at the reaction temperature, the 
solvent was removed in vacuum and the residue was added to 50 mL of cold 
water followed by extraction with hexane. The remaining mass was then 
recrystallized from ethanol to yield the desired material Et-O-Sulf in 
about 25% yield. 
Bleaching Data for the 1,2,3-Benzoxathiazine 2,2-dioxide Class of Molecules 
Bleaching studies were conducted by comparing the performance of 
representative bleaches with and without the presence of sulfanimines. In 
this regard, the stain removal observed without the intervention of 
sulfanimines served as an experimental blank and the amount of stain 
removal by the sulfanimine containing system constituted activation of a 
given bleach. 
Stain bleaching experiments were conducted in a Terg-O-Tometer in 1000 mL 
of milli-Q water. These experiments were run employing 0.01M NaHCO.sub.3 
buffer with the pH adjusted to the reported value with 1N NaOH solution. 
Four tea stained (BC-1) half cloths were added to each Terg pot. All the 
runs were performed at 40.degree. C. unless otherwise stated. The peracid 
drivers were either PAP or Oxone.RTM. and these were dosed at 7.5 ppm a.o. 
level. A given peracid was added to the system followed by an appropriate 
amount of sulfanimine. 
Stain bleaching was measured reflectometrically using a Colorgard System/05 
Reflectometer. Bleaching was indicated by an increase in reflectance less 
the effect of oxidant alone, reported as .DELTA..DELTA.R. 
The following molecules were tested in the different experiments described 
in the tables. Data for SulfD is provided for comparison. 
TABLE I 
______________________________________ 
Bleaching data for the Different Catalysts at a 
Concentration of 3 .times. 10.sup.-4 M and 40.degree. C. 
##STR8## 
##STR9## 
##STR10## 
##STR11## 
SulfD O-Sulf O-SulfD 
pH Oxone* PAP** Oxone PAP Oxone PAP 
______________________________________ 
8 4.9 0.33 11.8 2 12.2 2 
9 7.9 5.3 -- -- 12.2 7.6 
10 10 9.6 7.7 -1.4 13.9 4.6 
______________________________________ 
*2KHSO.sub.5 /KHSO.sub.4 /K.sub.2 SO.sub.4 trisalt, ex. DuPont. 
**N,Nphthaloylaminoperoxycaproic acid. 
TABLE II 
______________________________________ 
Bleaching Data for the Different Catalysts 
at a Concentration of 6 .times. 10.sup.-5 M at 40.degree. C. with PAP 
pH SulfD O-SulfD Et-O-Sulf 
______________________________________ 
8 0.8 2.6 3.7 
9 4.6 8.6 6.7 
10 6.4 6.2 7.8 
______________________________________ 
TABLE III 
______________________________________ 
Bleaching Data for the Different Catalysts 
at a Concentration of 6 .times. 10.sup.-5 M at 20.degree. C. with PAP 
pH SulfD O-SulfD Et-O-Sulf 
______________________________________ 
8 -- -- 3.4 
9 2 5.1 3.9 
10 3.4 5.5 6.1 
______________________________________ 
Also tested was the Ph-O-Sulf catalyst which showed a small benefit with 
Oxone and none with PAP as reported in Table IV. 
TABLE IV 
______________________________________ 
Bleaching with PhO-Sulf at 40.degree. C. at a 
Catalyst Concentration of 6 .times. 10.sup.-5 M 
##STR12## 
PhO-Sulf 
pH PAP Oxone 
______________________________________ 
8 -2.4 0.6 
9 -0.6 1.0 
10 -0.3 1.1 
______________________________________ 
The foregoing description and Examples illustrate selected embodiments of 
the present invention. In light thereof, various modifications will be 
suggested to one skilled in the art all of which are within the spirit and 
purview of this invention.