JPS63139999A - Acyl acid nitrogen peracid precursor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Background of the invention]

(1) Field of the Invention The present invention provides novel peroxygen bleach activator compounds that, when combined with a source of hydrogen peroxide in an aqueous medium, help provide efficient peroxygen bleaching of fabrics over a wide temperature range. It is related to. These compounds have the following general structure. (1) R-X-(cHt)nC-0-N-R' (where R is a straight chain or branched chain Cl-1゜alkyno-alkoxyl, cycloalkyl, and mixtures thereof; R1 is a direct chain of N) containing at least one bonded carbon atom; n is l or an integer up to 6, and X is a methylene heteroatom.) or R1 (however,
n is the same as (1); R1 contains a carbon atom double bonded directly to N, and X is a heteroatom or R is c
a-+y alkyl, or both. (2) Brief Description of the Prior Art Peroxygen bleaches are well known to be effective in removing stains and/or soils from fabrics. They can be used on a wide variety of fabrics and colored garments. However, the effectiveness of peroxygen bleach can vary greatly with the temperature of the wash water. In washing water these are used,
These are also effective in normal amounts when the bleaching solution is above 130'F (55.6C). It has been found that below this temperature, peroxide bleaching effectiveness can be greatly increased by the simultaneous use of activators, otherwise known as peracid precursors. It is widely accepted that in aqueous media, the precursor and peroxygen combine to form a peracid species. However, the effectiveness of most precursors, such as tetraacetylethylene diamine (TAED), is also dependent on high wash water temperatures. However, at low temperatures (70~loO'F (21,i~37.8
There is a need for bleach activators or peracid precursor compounds that can react efficiently with peroxides to form peracids in good yields for adequate wash performance at temperatures below 10°C (°C)). Peracids themselves must be dangerous to manufacture and tend to decompose, especially on long-term storage. Therefore, it is advantageous to prepare more stable peracid precursor compounds that will react with peroxide anions in aqueous alkaline solution to form the desired peracid in situ. As can be seen from the extensive literature in this area, many such peroxygen activators (peracid precursors) have been proposed. However, perhydrolysis
) No literature appears to teach, disclose or suggest the benefits of nitrogen-containing leaving groups. Various compounds have been disclosed in the prior art that include nitrogen as part of the peracid precursor. Murray U.S. Patent No. 3,969,257; Gray U.S. Patent No. 3,655.51i7; Baebski U.S. Patent No. 3
, 061,550 and Murray U.S. Pat. No. 3,92.
No. 8.03 was published and discloses the use of an acyl group attached to a nitrogen atom as a leaving group for activators. In all of these examples, the acyl carbon atom is bonded directly to the nitrogen atom. Nitrogen may also be attached to other carbonyl carbons. Finlay et al. U.S. Patent No. 4. In IN, 395, a sulfonyl group is attached to the nitrogen atom of the leaving group. The activator structure is therefore a sulfonyl oxime. U.S. Pat. No. 3,975,153 to Douches et al. teaches the use of only in7olone oxime acetate as a bleach activator. It is claimed that this inf<1=r-'y derivative yields an active agent with low odor and low toxicity. U.S. Pat. No. 3, H6,319 to Salotto et al. teaches the use of diazylated glyoximes. Its usage is that the alkyl group is 1
Limited to diazylated dialkylglyoximes containing ~4 carbon atoms and the acyl group containing 2 to 4 atoms. Neither document discloses, teaches or suggests that if the peracid precursor contains an oxime as a leaving group, it is surprisingly necessary to bring the heteroatom alpha to the carbonyl of the acyl group. Furthermore, neither document discloses the unique advantages offered by surface-active peracid precursors containing about 4 to 14 carbons in the acyl group.

[Summary of the invention]

The present invention, in one embodiment, comprises the following bleaching composition. The bleaching composition comprises: (a) a peracid precursor having the general structure Cl-2゜alkyno-alkoxyl, cycloalkyl and mixtures thereof; R- contains at least one carbon atom directly single bonded to N; n is an integer from 1 to 6 and X is methylene or a heteroatom ): Or, (II) and (b) a bleaching effective amount of a hydrogen peroxide source.

[Description of preferred embodiments]

The complete precursor (ester) is: (1)R-X-(cHt)nC-0-N-R' (but
R is a straight chain or branched C1-2° alkyl, alkoxyl, cycloalkyl and mixtures thereof; R1 contains at least one carbon atom directly single bonded to N; n is an integer from 1 to 6; , X is methylene or a heteroatom. ); or (II) R-X-(cHt)nC-0-N-R"(
where n is the same as in (I); R1 contains a carbon atom double bonded directly to N, X is a heteroatom, or R is C4-IF alkyl, or both. ); is. Suitably R is C1-7°alkyl or alkoxylated alkyl. More preferably, R is C4-
17 and mixtures thereof. R can also be saturated or polyunsaturated. If alkoxylated, ethoxy(EO)-(-0CHtCH1) and propoxy(PO)(-0CIItCH!)
CH* ) groups are preferred, 1 per mole of ester
There may be up to 30 EO or PO groups, and mixtures thereof. R is preferably an alkyl chain of 4 to 17, especially 6 to 12 carbons. Such alkyl groups are surface active and may be desired when the precursor is used to form a surface active peracid for fouling of oxidized fats or oil components from substrates at relatively low temperatures. These alkyl groups are commonly introduced into esters via acid chloride synthesis, which is further described 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 allyl group, it is possible to use aromatic acid chlorides, such as phenoxyacetyl chloride.
However, at the same time a U.S. patent application was filed,
Commonly assigned to The Clorox Company,
It is the subject of a US patent application entitled "Phenoxyacetate Peracid Precursor and Retreat Water Splitting System Using the Same" by inventor Alfred G. Schielske et al. That application is incorporated by reference in its entirety. Furthermore, in the general structure for the precursor of the invention,
When n is 1, X is in the alpha position to the terminal carbonyl group. In the present invention, under certain circumstances, for example, when the nitrogen of an oxynitrogen bond double-bonds itself to a carbon atom (structure (n)), an oxime is formed, where X becomes 0 and oxygen. However, X may be other nonmetallic atoms, such as -5-(
R compound), -N-(acyl) or the same -N)Iny(
4,! ammonium). In the present invention, however, it is most preferred that X is 0 (oxygen) or methylene. As mentioned above, n = 1 to 6 carbylene substituents,
More preferably n=1-3, most preferably n does not exceed about 2. When n=1 or 2, the base carbonyl is an acetic acid or propionic acid derivative. Acetic acid derivatives have been found to be surprisingly effective and have been published in two concurrently filed U.S. patent applications commonly assigned to The Clorox Company: Inventor Ronald II. ``Glycolate Ester Peracid Precursor'' and ``Phenoxyacetate Peracid Precursor and Retreat Water Splitting System Using the Same'' by Alfred G. Schielske et al. Both applications are incorporated herein by reference. When the petero atom X is O (oxygen) and n is 1, the effect of the nonmetallic substituent alpha on the terminal carbonyl is:
Increase the reactivity of progressive precursors. The electronic effect of this modification on the base methylene group (when n-1) appears to render the carbonyl group more susceptible to nucleophilic attack by the perhydroxide anion. The resulting enhanced reactivity is reduced over a wider p i range (e.g., 70'F).
(H, I'0) ) to yield higher peracid yields and perform a retreating water splitting reaction, with a strict activator pair of 1120! Generates peracid with little effect on ratio. However, in other embodiments, when the leaving group of the precursor is of structure (1), -0NR', it is preferred that X is methylene. As a representative example, the octanoyl group, CrHuC-0-, does not contain any petero atoms within the alkyl chain. In the following description, certain definitions are used. Peracid precursors are equivalent to bleach activators. The two terms generally relate here to reactive esters that have a leaving group substituent and actually cleave off the acyl portion of the ester during perhydrolysis. Retraction water splitting is a reaction that occurs when a peracid precursor or activator is combined with an effective amount of a source of hydrogen peroxide in a reaction medium (aqueous medium). A leaving group is essentially a substituent that is attached to the acyl moiety of the ester via an oxygen bond and can be displaced by a perhydroxide anion (OOH-) during perhydrolysis. The reaction of the base is as follows. The present invention particularly provides -membrane structures (1)-ONR+ and (I+)-ON-R'
yielding novel acid nitrogen leaving groups with , which are coupled to the acyl 0 group to form the peracid -C- precursors of the present invention. These leaving groups have an oxygen atom attached to a nitrogen that can also be attached to a carbon atom in a variety of structural configurations. The leaving group oxygen is bonded directly to the carbonyl carbon, forming a perfect precursor. When considering the following dehydrogenation agent structures, there are at least two different types of structures for the R1 group and at least one type of structure for the R2 group. A first preferred structure for R1 is one in which the nitrogen atom is bonded to two carbonyl carbons. The leaving group would then be the oximide group below. However, R3 and R4 may be the same or different,
Preferably straight chain or branched C, -1° alkyl, allyl,
Acrylic allyl or a mixture thereof. If alkyl, Rs and R1 may be partially undersaturated. R3 and R4 are particularly preferably linear or branched Cl-1@alkyl and may be the same or different. R1 is preferably CI-2°alkyl, allyl or alkylaryl to complete the heterocycle. R5 includes the following preferred structures. ++ However, R6 is an aromatic ring integrated with a heterocycle, or C
,-, may be alkyl. Thus, these desynthesized group structures may include acyclic or cyclic oximide moieties. The precursor can be found in combination with carboxylic acid and hydroxyimide compounds. ＼C-R1・Carboxylic acid Hydroxyimide Esters of these double imides are Gre@ne+Protective
e Groups ia 0rIsaic S
y++1hssis. It can be prepared as described on page IN (incorporated by reference) and is generally the reaction product of an acid chloride and a hydroxyimide. Non-limiting examples of N-hydroxyimides that provide oximide leaving groups of the present invention include N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxyglutarimide, N-hydroxynaphthalimide, N-hydroxymaleimide, N-hydroxymaleimide, -Hydroxydiacetylimide and N-hydroxydiprobionylimide. Particularly suitable examples of oximide leaving groups are: When processing peroxide anions, peracids are formed,
The leaving group attaches to the nitrogen and leaves with the oxygen and the negative charge on the oxygen atom. The resulting pK* of the hydroxyimide (approximately 6
) are completely low, making them excellent leaving groups. A second preferred structure for R1 is one in which the nitrogen atom is bonded to at least two carbons. These are amine oxide leaving groups and consist of: In the first preferred structure for the amine oxide, Ra and Re may be the same or different, preferably C3
-1° Straight chain or branched chain alkyl, allyl, alkylaryl or mixtures thereof. If alkyl, the substituent may be partially subsaturated. Preferably, Ra and R'' are C11 alkyl;
They may be the same or different. R111 is preferred: lmi is C, -. Alkyl, allyl, alkylaryl and mixtures thereof. This R111
Substituents may also be partially subsaturated. R1 and R
” is a relatively short-chain alkyl group (c11, or CHz C
II s ) and RIO is preferably C3-2°alkyl, most preferably together forming a tertiary amine oxide. Furthermore, in a second preferred amine oxide structure, R11
may be Cl-2°alkyl, allyl or alkylaryl, completing the heterocycle. R11 preferably completes an aromatic heterocycle of 5 carbon atoms, CI-@
Can be alkyl or allyl substituted. R12 is preferably nothing, C, -. Alkyl, allyl, alkylaryl or mixtures thereof. RI2 is more preferably CI-!.alkyl if R'' completes an aliphatic heterocycle. If R11 completes an aromatic heterocycle, R■ is nothing. The structure is actually a carboxylic acid and an amine.
It is an oxide bond. Carboxylic acid amine/oxide Amine/oxide is available from March's Advanced Org*nic
Ch6a+1stry, 2d Ed12 1977
．． 1111, the contents of which are incorporated herein by reference. Non-limiting examples of amine oxides suitable for use as leaving groups herein can be obtained from: Pyridine/N-oxide, trimethylamine/N-oxide, 4-phenyl pyridine/N-oxide, decyldimethylamine/N-oxide, dodecyldimethylamine/N-oxide, tetradecyldimethylamine/N-oxide
oxide, hexadecyldimethylamine/N-oxide, octyldimethylamine/N-oxide, di(decyl)methylamine/N-oxide, di(dodecyl)methylamine/N-oxide, di(tetradecyl)methylamine, thylamine/ N-oxide, 3-picoline N-oxide and 2-picoline N-oxide. Particularly suitable amine oxide leaving groups include the following. Pyridinium N-oxide Phenylpyridinium
When the N-oxide precursor is attacked by the peroxide compound anion, peroxide is formed and the leaving group is removed from the amine.
As an oxide, I bonds to the nitrogen; it remains again with oxygen and the negative charge on the oxygen. When the acid nitrogen leaving group is of structure (II)-ON-R',
A suitable example thereof is an oxime. In these oxime leaving groups, the nitrogen atom is attached to a carbon atom via a double bond. I3 where R'' and R14 are each H%C,-, alkyl (which may be cycloalkyl, straight chain or branched), allyl or alkylaryl. Preferably R13 and R14 are the same or different and C8-1
and at least one of RI3 and R14 is I
Not I. The structure of oxime esters of carboxylic acids can be broken down into two parts. R-C-OHHO-N-C (R'h Carboxylic acid Oxime of carbonyl compound As mentioned above, R2 is a carbon double bonded directly to the nitrogen of the acid nitrogen bond, and (a) R group of acyl is preferably C4-12
and more preferably C117, alkyl (resulting in a surface-active ester), or (b) x, the heteroatom is oxygen, the carbylene number, n is l, or (c
) Both conditions occur, and either is true or not. An example of (a) is octanoyloxy dimethyl oxime ester. 113C(cJ)s-C-0-N■C(cH3)! (b
) is hexanoyl acetyl dimethyl oxime ester. HsC(cIlt)a-0-CIItC0-N-C(c
H*)t oximes are commonly obtained from the reaction of hydroxylamine with either an aldehyde or a ketone (Org!oic Chemistry of Allinger et al., 2dEd
12 562 (I976) (herein incorporated by reference)), both of which are within the scope of the present invention. Non-limiting examples of oxime leaving groups are: (a) Oximes of aldehydes (aldoximes), such as acetaldoxime, benzaldoxime, propionaldoxime, butyraldoxime, peptaldoxime, hexaaldoxime, phenylacetaldoxime, 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-pentanone oxime), 2-pentanone oxime, 2-hexanone oxime, 3-hexanone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime and cyclopetanone oxime. Particularly suitable oxime leaving groups are: Acetaldoxime Methyl Ethyl Ketoquine When attacked by the peracid anion, the oxime ester forms a peracid and the oxime becomes a leaving group. It is quite surprising that oximes are such good leaving groups. This is because their IIKI values (approximately 12) are quite high due to good leaving groups. Previous experience has shown that the pK for those conjugate acids is in the range of 8-10! It teaches that leaving groups with values make the best leaving groups. Prior art of oxime esters (U.S. Pat. No. 1,164)
, 395, U.S. Pat. No. 3,975,153), in fact, a petero atom alpha to the carbonyl group on the acyl moiety of the ester is necessary for good receding water splitting yields, or No mention is made of the fact that if the R group of is C1-1 alkyl, more preferably C6-1 □alkyl, a surface-active peracid precursor will result, giving rise to a surface-active peracid. . The precursors of the present invention can be prepared by dispersing the liquid or liquefied precursor in a substrate material such as an inert salt (e.g. NaCQ, N52SO4) or other solid substrates such as zeolites, sodium borate or molecular sieves. or by dissolving in a suitable solvent or surfactant, it can be incorporated into a liquid or solid matrix for use in liquid or solid cleaning bleaches. Examples of suitable solvents include acetone, non-nucleophilic alkoniethers or hydrocarbons. Other more water-dispersible or water-miscible solvents may be considered. As an example of an additive to a substrate material, the precursor of the present invention is described in European Patent Application EP9B+29
can be incorporated into non-particulate materials such as those disclosed in . The disclosure thereof is herein incorporated by reference. The advanced precursors with acid nitrogen leaving groups are clearly less soluble in aqueous media compared to phenyl sulfonate. Thus, a preferred embodiment of the invention is one in which the precursor is combined with a surfactant. These precursors,
It is particularly preferred to coat with a nonionic or anionic surfactant that is solid at room temperature and dissolves above about 40°C. The surfactant melt can be simply mixed with the peracid precursor, cooled, and granulated. Exemplary surfactants for such use are shown in Table I below. Table I Product Name Dan 1 Manufacturer Pluronic F-9g 55°C Nonionic BASF
Wyandotte Neodol 25-30 47℃ Nonionic shell φ Chemical Neodol 25-60 53℃
Non-ionic shell chemical tarsitroux S-3 [
141°C Nonionic Union Carbide Tarcitolu 5-4045°C Nonionic Union Carbide Pluronic lORg 16°C Nonionic BASF Wyandotte Bruronitsuta 1718 53°C Nonionic BASF Wyandotte Toronitsuta 90R847°
C Nonionic BASF Wyandotte Midox C5
The S5'O nonionic stepane precursor can be bleached, depending on the formulation, whether or not it is coated with a surfactant having a dissolution temperature of about 40° C. or higher. It can also be mixed with other surfactants to provide either additives or detergent compositions. Particularly effective surfactants are believed to be nonionic surfactants. Surfactants suitable for use include linear ethoxylated alcohols such as those sold under the trade name Neodol by Shell Chemical Company. Other suitable nonionic surfactants are:
May include: Other linear ethoxylated alcohols having about 2 to 20 moles of ethylene oxide per mole of alcohol and having an average length of 6 to 16 carbon atoms; an average of 0 to 10 moles of ethylene oxide per mole of alcohol. and linear and branched primary and secondary ethoxylated, propoxylated alcohols having about 1 to 10 moles of propylene oxide and having an average length of about 6 to 16 carbon atoms; having an average of 1.5-30 moles of ethylene oxide per mole and an average chain length of 8 to 16 carbon atoms,
Linear and branched alkylphenoxy (polyethoxy) alcohols, also known as ethoxylated alkylphenols: and mixtures thereof. Further suitable nonionic surfactants include polyoxyethylene carboxylic acid esters, fatty acid glycerol,
Esters, fatty acids and ethoxylated fatty acid alkanolamides, certain block copolymers of propylene oxide and ethylene oxide, and block copolymers of propylene oxide and ethylene oxide with propoxylated ethylene diamine may also be included. Also included are semipolar nonionic surfactants such as amine oxides, phosphine oxides, sulf7oxides, and ethoxylated derivatives thereof. Anionic surfactants may also be suitable. Examples of such nonionic surfactants are ammonium, substituted ammonium (e.g., hexanot, ci, and hydroethanolammonium), C, -C,. Alkali metal and alkaline earth metal salts of fatty acids and rosin acids, linear and branched alkyl-benzene sulfonates, alkyl sulfates, alkyl ether sulfates, alkane sulfonates, olefin sulfonates, hydroxyalkanes.
Sulfonates, fatty acid monoglycerides Φ sulfates, alkyl glyceryl ether sulfates, acyl-sarcosinates and acyl N-methyltaurides. Suitable cationic surfactants are those in which one of the groups attached to the nitrogen atom is typically C,! It may contain four ammonium compounds in which -C,S is an alkyl group and the other three groups are short chain alkyl groups with inert substituents such as phenyl groups. In addition, suitable amphoteric and zwitterionic surfactants containing anionic water-soluble groups, cationic groups and hydrophobic organic groups include amino carboxylic acids and their salts,
Can include amino dicarboxylic acids and their salts, alkyl betaines, alkyl sulfopetaines, alkyl imidoazolium derivatives, certain quaternary ammonium compounds, certain quaternary phosphonium compounds, and certain tertiary sulfonium compounds. . Other examples of potentially suitable zwitterionic surfactants are described by Jones at 11 of U.S. Pat. No. 4,005,029.
~15, the contents of which are hereby incorporated by reference. anionic, nonionic, suitable for use in the present invention;
Cationic and amphoteric surfactants are described in Kirk Othmer's Eacyclopedia olChcIIlicx.
l Techoolo (y. Third Edilio
n, Volume H, pages 347-30, and Mc
CaLcb*oa's Det-errents sa
d Emnlsiliers, Norlb A+*er
icsa Edition, 1913, herein incorporated by reference. As previously mentioned, other common detergent additives may be added if a bleach or detergent bleach product is desired. For example, if a dry bleach composition is desired, the following ranges (% by weight) are considered practical. 0,5 ~SO. O% Hydrogen peroxide source 02O5~2
5.0% Precursor 12O ~50.0% Surfactant 12O ~5
0.0% buffer S. O ~99.9% Fillers, stabilizers, dyes, fragrances, brighteners, etc. Sources of hydrogen peroxide include alkali metal salts of percarbonates, perborates, persilicates, and hydrogen peroxide adducts; It may be selected from hydrogen oxide. Most preferred are sodium percarbonate, mono- and tetrahydrates of sodium perborate, and hydrogen peroxide. Other sources of peroxygen may be possible, such as monopersulfate and monoperphosphate. Although liquid hydrogen peroxide is preferred in liquid applications, it may be necessary to separate the precursor from it prior to combination in aqueous solution to prevent premature decomposition. The range of peroxide to peracid precursor is preferably determined as the molar ratio of peroxide to ester groups contained in the precursor. Therefore, the range of peroxide to ester groups is approximately O:5
molar ratio of ~loll, more preferably about l=1-5
:1, optimally about l=1 to 2:1. The peracid precursor/peroxide composition preferably has a concentration of about 0.5 to 50 ppm A 2 O 12 + more preferably about 1 to 50 ppm A 2 O 12 in an aqueous medium.
It is preferred to provide 0 ppm A2O. A. 0. A description and explanation of the measurements can be found in "Peracids and Peroxide Oxidation" by Sheldon N. Lewis, Oxidario
o, 1969, H3-20 pages.
Incorporated herein by reference. For the measurement of peracid, use Org
anic PCracid, (by De Swernni), Vol. l, Sol page, el sB
. (ch., 7') (1970), incorporated herein by reference. An example of a practical implementation of a liquid delivery device is a method of applying separately measured amounts of liquid hydrogen peroxide and a precursor (in some non-reactive fluid medium) in a container, such as a - Described in US Pat. No. 4,585,150 to Beecham et al., commonly assigned to Clorox Company, and incorporated herein by reference. Buffers may be selected from sodium carbonate, sodium deuterate, sodium borate, sodium silicate, phosphates, and other alkali metal/alkaline earth metal salts well known to those skilled in the art. Organic buffers such as succinate, maleate and acetate may also be suitable for use. alkaline p
It is considered preferable to have sufficient buffering agent to obtain a pH of at least about 7 or higher, more preferably about pH 9.0 or higher, optimally about pH 10.0 or higher. The filler material, in detergent bleach applications, actually constitutes the majority component by weight of the detergent bleach, and is usually sodium sulfate. Sodium chloride is another potential filler. Dyes include anthraquinones and similar blue dyes. Pigments, such as ultramarine blue (UM
B) can also be used and can have a blue dyeing effect by being deposited on fabrics washed with a washing bleach containing UMB. Phthalocyanine colorants may also be included. Brightening agents, e.g. stilbene, stilnaphthalene brightening agents (fluorescent brighteners)
, may be included. Fragrances used for aesthetic purposes are commercially available from Norzo, International Flavors and Fragrantis and Gibaudon. Stabilizers include hydrated salts such as magnesium sulfate and boric acid. In one preferred embodiment where a compound such as (I) below is a precursor, a preferred bleaching composition has the following ingredients: 12°8% Sodium Tetrahydrate Perborate 8.3
% octanoyloxy dimethyl oxime ester 7.0% nonionic surfactant 15.0% sodium carbon In another preferred embodiment, the precursor is a compound such as (II): A suitable bleaching composition has the following ingredients. 12.1% Sodium Tetrahydrate Perborate 10.
0% octanoyloxy succinimide 7.0% nonionic surfactant 15.0% sodium carbonate Other sources of peroxygen are suitable, such as monohydrate sodium perborate or sodium percarbonate. If more detergent-type product is desired, increase the amount of filler;
Precursors can be reduced by half or even further.

【experiment】

Oxime esters can be prepared by treating oximes with the corresponding acid chlorides of carboxylic acids. Since we have a liquid reaction medium, a non-reactive solvent is added and then a base is added. Oximes can be prepared by treating carbonyl compounds with hydroxylamine or can be purchased commercially. Two oximes, acetone oxime and methyl ethyl ketone oxime, are readily available from commercial sources;
It is also inexpensive. [Example ■] (Preparation of acetone oxime ester of caprylic acid) A 500 mffi three-necked flask, equipped with a paddle stirrer, concentrator and drying tube, was submerged in an oil tank. To the flask, add T II F (100 ma), 7 setone oxime (15 g, 0.21 mol), then THF.
Ocranoyl chloride (351,0,0
mol) was added dropwise with rapid stirring. A white solid (pyridine hydrochloride) precipitated from the solution. The reaction is
It remained stirred for 3 hours at a temperature of 50°C in an oil bath. The reaction mixture was filtered and the solvent therein was removed via a rotary evaporator to yield an orange oil (318 g). Thin layer chromatography analysis of unpurified products (silica
gel,) IX-ETAC, 8O-20), Rf-0,
47 one major spot (12 visualizations), Rf-0
, a small spot at 90, a spot at the origin (maybe,
pyridine hydrochloride). The unpurified product was transferred to a silica gel column (125 g, 230-400 mesh, 4 cm diameter x 25 cm height).
and eluted using IIX-ETAC (8G-20). :,-"f' flux monitored by TLC, the appropriate ones were bound and the solvent was removed. In this way, 37.1 g of a colorless oil were obtained. Infrared of the oil The absorption spectrum showed a very strong carbonyl at 170 cm-' and no signs of hydroxyl groups, acid chlorides or carboxylic acids. 13c-NMR (cDC et al.
ppm downfield from TMS) showed only the expected absorption for the product. These designations are made using the following numbering system. Cy (168,3), Cm (160,9), Cs (2
9,9),C@(30,8),C,(27,2),C,
(23,0), Cm (20,7), Ct (19,6),
C+5 (12,0) and c, (14,5) acyloxyimides can be easily prepared by treating hydroxyimides with acid chlorides. While acid chlorides are readily available commercially, hydroxyimides are not so commercially available. [Example ■] (Preparation of octanoyloxy succinimide) 500
A three ml flask was equipped with a paddle stirrer, a concentrator and a drying tube and was submerged into an oil bath. To a flask, add THF (175 ml), N-hydroxysuccinimide (L5 g2O.013 mol), and pyridine (
6,7d2O. 0 Hmol) was added. Octanoyl chloride (14.2 ml! 20.083 mol) was dissolved in THF
(51 mM) medium t: Dissolved FL was added to the reaction vessel over a period of 15 minutes. The white precipitate (pyridine hydrochloride)
Been formed. The reaction mixture was heated to about 60 °C, filtered, and the solvent was removed via a rotary evaporator, yielding a light yellow oil (Is, ig), which was subsequently solidified. Thin layer chromatography analysis of unrefined oil (Silica Genotsu CH2C1x) revealed that the main spots of Rf -0.60 (
UV visualization) showed a small spot at Rf -0,95 and a spot (pyridine chloride) at the origin. The unpurified product was prepared using 5 μm of silica gel (150 g, 23 G-
400 mesh, 4 cm diameter x 30 cn+ height) and eluted with methylene chloride. The 7 lactations were monitored by TLC, the appropriate ones bound and the solvent removed. In this way, the melting point is 60.5 ~! 1.
A white solid (15.2 g, 76% yield) was obtained at 0°C. The infrared absorption spectrum of this solid is % +73Sc+a-
' shows a very strong and broad carbonyl, 179o and 1
It showed a sharp carbonyl at 822 cm-'. ”C-NMR (cD(, a3) is extremely J:cttt
It showed only the necessary absorption for the product. Therefore, it is 169.5 (pp from TMS
m downfield) and ester. carbonyl carbon,
imido carbonyl at 170.0, 14.0-31,
Analysis of the solid by Opom methylene and methyl Kishiyasu, f-saponification values showed 100% purity. Acyl oxy ammonium chloride type compounds can be prepared by treating amine oxides with chloric acid. Both amine oxides and chloride acids are commercially and readily available, thus providing a wide variety of practical precursors. However, the product is
It is believed that it is formed as a good solid only when certain high molecular weight amine oxides are used. Unless care is taken in selecting reaction conditions and reagents, the reaction will sometimes form an oil. Example ■ Preparation of octanoyloxy ester of 4-phenylpyridine oxide A SOOml three-loaf flask was equipped with a paddle stirrer, drying tube, and flushed with nitrogen for 7 mL. To the flask, T HF (150 ml) and 4-phenylpyridine N-oxide (5 g, cr, 9 moles of Ox)
was added. A light yellow colored solution resulted. To this was rapidly added octanoyl chloride (S, OmK, 0.029 mol) in THF (20 mffi). The mixture was stirred very rapidly for 172 minutes. A jelly-like precipitate formed quickly. When the viscous solution was diluted with ether (approximately 30011+D), a white solid layer separated. The mixture was filtered to yield a white solid that was washed with ether.
, 0.72% yield) is 100c in the infrared absorption spectrum.
It had carbonyl absorption at m-'. ”The C-NMR was very clean and showed only the absorption required for the product. 174.5 (ppm downfield from DMSO solvent, TMS) but due to the aromatic carbon. In addition to the absorption for the alkyl chains was observed. When treated with alkaline aqueous peroxide anion I;
When the precursor forms a peracid in solution. The table below shows the retreated water splitting yields of representative precursors. Table I i+ Structure Peracid Yield 1
CHs(cHt)s-C-0-N-C(cII3)t
46%*pH10.5.5 minutes, 70″″
F (21,1°C) 2:1 peroxide=activator molar ratio, Pluronic L63 surfactant (0,1% by weight) Comparison of No. 5 with all others shows that leaving group This shows the importance of the oxygen atom being directly bonded to the nitrogen atom. Although the foregoing examples and descriptions of the present invention represent detailed embodiments thereof, the application is not limited to such detailed embodiments, and this application is well known to those skilled in the art and departs from the teachings of the present invention. It should be understood that this includes all such changes, modifications and equivalents. The claims feature similarly non-limiting portions of the invention Patent Applicant: The Clorox Company

Claims (1)

[Claims] 1. A bleaching composition comprising: (a) a peracid precursor having the following general structure: (I)
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R is a straight chain or branched chain C_1-_2_0 alkyl, alkoxyl, cycloalkyl, and mixtures thereof; R
^1 contains at least one carbon atom directly single bonded to N; n is an integer from 1 to 6 and X is methylene or a heteroatom. ); or (II)▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, n is the same as in (I); R^2 contains a carbon atom directly double bonded to N, and X is a heteroatom or R is C_4-_1_7 alkyl, or both); and (b) a bleaching effective amount of a hydrogen peroxide source. 2. The bleaching composition according to claim 1, wherein the peracid precursor has the structure (I), and the leaving group -
O-N-R^1 is (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ (However, R, X and n are defined in claim 1; R^3 and R^4 are the same or different, and individually Branched chain C_1-_2
or (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R and n are defined in claim 1; R^8 and R^9 are are the same or different and are individually linear or branched C_1-_2_0 alkyl, allyl, alkylaryl or mixtures thereof; R^1^0 is C_1-_3_0 alkyl, allyl, alkylaryl and mixtures thereof; R^1^1 is a straight or branched chain C_1-_2_0 alkyl, allyl, alkylaryl that completes the heterocycle; R^1^2 is nothing or C_1-_2_0 alkyl, allyl, alkylaryl or a mixture thereof). 3. The bleaching composition according to claim 2, wherein R is C_6-_1_2 alkyl, a heteroatom,
is methylene and n is 1. Bleaching composition. 4. The bleaching composition according to claim 3, wherein the leaving group is (a) and the precursor is an oximide ester. 5. The bleaching composition described in claim 4, wherein the precursor has a leaving group ▲a mathematical formula, a chemical formula, a table, etc.▼ (provided that R^6 is methylene, the heterocycle is a fused aromatic ring, or C_1-_6 alkyl). 6. The bleaching composition according to claim 5, wherein the precursor is ▲a mathematical formula, a chemical formula, a table, etc.▼. 7. The bleaching composition according to claim 5, wherein the precursor is ▲a mathematical formula, a chemical formula, a table, etc.▼. 8. The bleaching composition according to claim 3, wherein the leaving group is (b) and the precursor is an amine oxide ester. 9. The bleaching composition described in claim 8, wherein the precursor has a leaving group ▲a mathematical formula, a chemical formula, a table, etc.▼ (provided that R^1^1 is an aromatic hetero Complete the ring, R^1
^2 is nothing). 10. The bleaching composition according to claim 9, wherein the precursor is ▲a mathematical formula, a chemical formula, a table, etc.▼. 11. The bleaching composition according to claim 9, wherein the precursor is ▲a mathematical formula, a chemical formula, a table, etc.▼. 12. The bleaching composition according to claim 2, wherein the heteroatom, X is oxygen, and n is 1. 13. The bleaching composition according to claim 1, wherein the peracid precursor has the structure (II), and the leaving group, -O-N-R^2, is represented by the formula ▲ , chemical formulas, tables, etc.▼ (However, R^1^3 and R^1^4 are H and C_ respectively.
1-_2_0 alkyl, allyl, or alkylaryl, or a mixture thereof, and at least one of R^1^3 and R^1^4 is not H; (a) the R group of said acyl is C_
4-_1_7 alkyl, (b) X, the heteroatom is oxygen, the carbylene number, n is 1, or (c
) A bleaching composition that is both ). 14. The bleaching composition described in claim 13, wherein R is C_8-_1_2 alkyl, and R^1^3 and R^1^4 are H, C_1-_6 alkyl, or A bleaching composition which is a mixture, R^1^3 and R^1^4 are the same or different, and at least one of R^1^3 and R^1^4 is not H. 15. A bleaching composition according to claim 13, wherein the precursor is an oxime ester according to (a) and has the structure ▲a mathematical formula, a chemical formula, a table, etc.▼ Bleaching composition. 16. The bleaching composition according to claim 14, wherein the precursor is an oxime ester according to (b) and has the structure ▲a mathematical formula, a chemical formula, a table, etc.▼ Bleaching composition. 17. A bleaching composition according to claim 1, wherein the hydrogen peroxide source (b) consists essentially of hydrogen peroxide, hydrogen peroxide adducts, alkali metal and alkaline earth perborides. A bleaching composition selected from the group consisting of: 18. The bleaching composition of claim 17, wherein the hydrogen peroxide source is an alkali metal perboride selected from mono- and tetrahydrate forms of sodium perborate. Bleaching composition. 19. The bleaching composition of claim 11, wherein the molar ratio of hydrogen peroxide source to precursor is from 0.5:1 to 10:1 based on moles of H_2O_2 to moles of ester. A bleaching composition. 20. A bleaching composition according to claim 1, further comprising (c) essentially surfactants, builders, fillers, enzymes, fluorescent brighteners, pigments, dyes, A bleaching composition comprising: additives selected from the group consisting of fragrances, stabilizers and buffers. 21. The bleaching composition of claim 1, wherein the precursor of (a) is coated with a surfactant having a melt completion temperature of about 40° C. or higher. .