JP2914484B2 - bleaching compound - Google Patents

Description

[Detailed description of the invention]

[0001]

FIELD OF THE INVENTION This invention relates to peroxygen bleaching compositions which provide effective bleaching of fabrics over a wide range of temperatures.

[0002]

Problem to be Solved by the Invention Conventional inorganic peroxygen bleaching compounds can effectively remove stains or soils from fabrics only in a relatively narrow temperature range, and effectively bleach fabrics over a wide range of temperatures. A compound obtained by

[0003]

DISCLOSURE OF THE INVENTION The present invention provides the following general formula:

[0004]

[Chemical 9] (wherein R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ² is an alkylene, arylene or alkarylene group having 4 to 8 carbon atoms, and R ⁵ is H or a Alkyl, aryl or alkaryl groups having 1 to 10) peroxyacid bleaching compounds.

A group of compounds which provide the above peroxyacids are represented by the following general formula:

[0006]

[Chemical 10] (wherein R ¹ , R ² and R ⁵ are as defined for peroxyacids, X is a compatible anion, n is 1 or 2, and Y is 0-6) is the magnesium salt of the peroxyacid of

Peroxyacids also include peroxygen bleaching compounds capable of producing hydrogen peroxide in aqueous solution and

[0008]

[Chemical 11] [wherein R ¹ , R ² and R ⁵ are as defined for the peroxyacid and L is a leavin
g) can be generated in situ from the bleach activator of the group ].

The invention also relates to bleaching compositions containing one of the above compounds. If the composition contains a bleach activator, another essential ingredient is a peroxygen bleaching compound capable of producing hydrogen peroxide in aqueous solution. In preferred embodiments, the bleaching composition is incorporated into a detergent composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides the following general formula

[0011]

[Chemical 12] (wherein R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, and R ² is a
and R5 is H or an alkyl, aryl, or alkaryl group having 1 to ¹⁰ carbon atoms)
of bleaching compounds that provide amide-substituted peroxyacids of R ¹ preferably has 6 to 12 carbon atoms. R.
¹ can be linear or branched alkyl, substituted aryl or alkylaryl containing branching, substitution or both. Similar structural diversity is permissible for ^R2 . Substitutions can include alkyl, aryl, halogen, nitrogen, sulfur, and other typical substituents of organic compounds. ^R5 is preferably H or methyl. R.
¹ and ^R5 should not have more than 18 total carbon atoms.

The bleaching compounds of the present invention provide effective and efficient surface bleaching of fabrics, thereby removing stains and/or soils from the fabrics. The compounds are particularly effective at removing dark stains from fabrics. Dark stains are those that build up on fabrics after multiple uses and washes and produce a gray or yellow tint on white fabrics. These soils are a blend of particulate and greasy materials.

The compounds of the present invention are stable over a wide range of temperatures (5°C to
85°C) (preferred range is 30°C to 60°C).

The presence of polar amide or substituted amide moieties yields peroxyacids with very low vapor pressures and thus low odor profiles as well as excellent bleaching performance.

Peroxyacids can be used directly as bleaching agents. The improved thermal stability of the peroxyacids of the present invention, particularly when incorporated in bleaching and detergent compositions described below, are well documented in the prior art, such as the alkyl peroxyacids of U.S. Pat. Surprising when compared to short chain peroxyacids.

While not wishing to be limited by theory,
The polarity of the amide group is believed to cause a decrease in peroxyacid vapor pressure and a corresponding increase in melting point.

Substituted amide-containing peroxyacids also have reduced vapor pressures and exhibit good odor profiles. These compounds are well suited for use in the bleach activator constructions described below.

Magnesium peroxycarboxylates have the general formula:

[0019]

[Chemical 13] wherein R ¹ , R ² and R ⁵ are as defined for peroxyacids, X is a compatible anion, n is 1 or 2, and Y is 0-6. The compounds are solids and have good storability under alkaline conditions, such as when mixed with detergent compositions. Active oxygen in magnesium peroxycarboxylate is readily available. This means that the solid magnesium peroxycarboxylate is readily soluble or dispersible and results in a solution containing the peroxyacid. If the solution is aqueous, it is indistinguishable from an aqueous solution prepared from the corresponding peroxyacid and an equivalent amount of magnesium when the solution is adjusted to the same pH.

The stability of the magnesium salts is believed to be due to the fact that the active oxygen atoms are more nucleophilic than electrophilic when in the corresponding peroxycarboxylic acid. Nucleophiles that will attack electrophilic oxygen are much more widely used than electrophiles in bleaching and detergent compositions.

Magnesium peroxycarboxylate can be produced by the method of US Pat. No. 4,483,781.

Bleach Activator The bleach activator of the present invention has the general formula:

[0023]

[Chemical 14] wherein R1, R2 and R5 are as defined for peroxyacids and L is as described below. A leaving group is a group displaced from a bleach activator as a result of nucleophilic attack onto the bleach activator by a perhydroxide anion. This, the perhydrolysis reaction, produces peroxycarboxylic acids. Generally, in order for a group to be a suitable leaving group, it must exhibit an electron-withdrawing effect. Also, the leaving group should form such that the reverse reaction rate is negligible. This facilitates nucleophilic attack by perhydroxide anions.

[0024] The L group is within the optimal time frame for reaction (eg
wash cycle). However, if L is too reactive, it will be difficult to stabilize the activator for use in bleaching compositions. These properties are generally paralleled by the pKa of the conjugate acid of the leaving group, although exceptions are known. Generally, leaving groups that exhibit such behavior are those whose conjugate acids have a pKa of 4-13, preferably 6-11, most preferably 8-11.

Preferred bleach activators are as defined where R ¹ , R ² and R ⁵ are peroxyacids and L is

[0026]

[Chemical 15] (Wherein, R3 is an alkyl chain or alkylene chain having 1 to 8 carbon atoms, Y is -SO3-M+ or -COO
-M+ and M is sodium or potassium).

Preferred bleach activators are those in which L is a leaving group as defined above, R1 is an alkyl group having 6 to 12 carbon atoms and R2 is an alkylene group having 4 to 8 carbon atoms. and R5 is H or methyl.

Particularly preferred bleach activators are those in which R ¹ is an alkyl group having 1 to 14 carbon atoms, R ² is an alkylene group having 4 to 8 carbon atoms, R ⁵ is H, and L is

[0029]

[Chemical 16] (wherein R3 is as defined above and Y is -
SO3-M+ or -COO-M+, and M is as defined above).

Particularly preferred bleach activators are those wherein R ¹ is a linear alkyl chain having 6 to 12 carbon atoms, R ² is a linear alkylene chain having 4 to 8 carbon atoms and R ⁵ is H. Yes, and L

[0031]

[Chemical 17] (wherein R3 is as defined above and Y is -
SO3-M+ or -COO-M+, and M is as defined above).

Bleaching Compositions The bleaching compositions of the present invention, when dissolved in an aqueous solution, have the formula

[0033]

[Chemical 18] wherein R ¹ , R ² and R ⁵ are as defined for peroxyacids.

Such compositions provide highly effective and efficient surface bleaching of fabrics, thereby removing stains and/or soils from the fabrics. The compositions are particularly effective in removing dark stains from fabrics. Darkened soils are soils that build up on fabrics after many cycles of use and washing, thus producing white fabrics with a gray or yellow tint. These soils tend to be a blend of particulate and greasy materials. This type of soil removal is sometimes referred to as "blackened fabric cleaning".

The bleaching composition provides such bleaching over a wide range of bleach liquor temperatures. Such bleaching is obtained in bleaching solutions having a liquor temperature of at least 5°C. Inorganic peroxygen bleaches will be ineffective and/or inoperable at temperatures below 60°C.

The present invention also provides a bleaching composition containing a peroxygen bleach capable of releasing hydrogen peroxide in aqueous solution and a specific bleach activator described below in a specific molar ratio of hydrogen peroxide to bleach activator. about things.

Bleaching mechanisms in general, and surface bleaching in particular, are not fully understood. However, it is generally believed that bleach activators undergo nucleophilic attack by perhydroxide anions generated from hydrogen peroxide generated by peroxygen bleaches to form peroxycarboxylic acids. This reaction is commonly referred to as perhydrolysis.

[0038] When an activator is used, the optimum surface bleaching performance is when the solution pH is between 8.5 and 10.5, preferably between 9.5 and 10.5 to facilitate the perhydrolysis reaction. Obtained using bleach. Such pH can be obtained using materials commonly known as buffering agents, which are optional components of the bleaching compositions of the present invention.

The bleach activator of the present invention also uses peroxygen bleach at bleach liquor temperatures above 60° C. where the bleach activator is not required to activate the bleach. It is believed that it can be made more efficient. Therefore, with the bleach compositions of the present invention, less peroxygen bleach is required to obtain the same level of surface bleaching performance as obtained using peroxygen bleach alone.

[0040] The bleaching composition in which the bleach activator is used is
As an essential ingredient it also has a peroxygen bleach capable of releasing hydrogen peroxide in aqueous solution.

Peroxygen Bleaching Compounds Peroxygen bleaching compounds useful in the present invention are those that produce hydrogen peroxide in aqueous solution. These compounds are well known in the art and include hydrogen peroxide and alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds such as alkali metal perborates, Including percarbonates, superphosphates and the like. Mixtures of two or more such bleaching compounds can also be used if desired.

Preferred peroxygen bleaching compounds are the monohydrate,
Including sodium perborate, sodium carbonate peroxide, sodium pyrophosphate peroxide, urea peroxide, and sodium peroxide, commercially available in trihydrate and tetrahydrate forms do. Particular preference is given to sodium perborate tetrahydrate and especially sodium perborate monohydrate. Sodium perborate monohydrate is particularly preferred as it is very stable on storage and still dissolves very quickly in the bleaching liquor. Such rapid dissolution is believed to produce large amounts of percarboxylic acid, thus enhancing surface bleaching performance.

The amount of bleach activator in the composition of the present invention is
0.1% to 60%, preferably 0.5% to 40%. When the bleaching composition of the present invention is also a detergent composition, the amount of bleach activator is preferably between 0.5% and 20%. Optional Ingredients As a preferred embodiment, the bleaching composition of the present invention can be a detergent composition. Thus, the bleaching composition
Typical detergent composition ingredients such as detergent surfactants and detergent builders may be included. In such preferred embodiments, bleaching compositions are particularly effective. The bleaching compositions of this invention can contain all of the usual ingredients of detergent compositions, such as those described in US Pat. No. 3,936,537. Such components are color speckles (colo
r speckles), suds boosters, suds suppressors, anti-corrosion agents and/or
or anticorrosive agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, bactericides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizers, perfumes, and the like.

[0044] Enzymes are highly preferred optional ingredients,
and 0.025% to 5%, preferably 0.05% to
Formulated in an amount of 1.5%. 0.01~ per 1 g of product
A proteolytic activity of 0.05 Anson units is desirable. Other enzymes, such as amylolytic enzymes, also
Desirably included in the composition.

Suitable proteolytic enzymes include many known to be suitable for use in detergent compositions. Commercial enzyme preparations, e.g. "Alcalase" sold by Novo Industries
and "Maxatase" sold by Gist Brokers of Delft, The Netherlands are suitable. Another preferred enzyme composition is manufactured and marketed by Novo Industries A/S of Copenhagen, Denmark under the trade name SP-72 ("Espera
se)" and manufactured and marketed by Gist Brokers of Delft, the Netherlands and available under the trade name "AZ-Protease".

Suitable amylases include "Rapidase" sold by Gist Brokers and "Termamyl" sold by Novo Industries.

A more complete disclosure of suitable enzymes can be found in US Pat. No. 4,101,457.

Detergent surfactants include anionic, nonionic,
There can be one or more surfactants selected from zwitterionic, amphoteric and cationic classes and compatible mixtures thereof. Detergent surfactants useful in the present invention are described in U.S. Pat. No. 3,664,961 and U.S. Pat.
19,678. Useful cationic surfactants also include those described in US Pat. Nos. 4,222,905 and 4,239,659. The following are representative examples of detergent surfactants useful in the present compositions.

Water-soluble salts of higher fatty acids, ie "soaps"
is an anionic surfactant useful in the present compositions. This includes alkali metal soaps such as sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids having from 8 to 24 carbon atoms, preferably from 12 to 18 carbon atoms. Soaps can be produced by direct saponification of fats or oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, namely sodium or potassium tallow soap and coconut soap.

Useful anionic surfactants are also water-soluble salts of organic sulfuric acid reaction products having an alkyl group of 10 to 20 carbon atoms and a sulfonate or sulfate group in their molecular structure, preferably includes alkali metal, ammonium and alkylolammonium salts (the term "alkyl" includes the alkyl portion of acyl groups). Examples of this group of synthetic surfactants are higher alcohols ₍ C8
and potassium alkylbenzene sulfonates in which the alkyl group has 9 to ₁₅ carbon atoms in a linear or branched configuration, e.g. 2,220,099 and 2,
It is of the type described in U.S. Pat. No. 477,383. Linear linear alkyl benzene sulfonates (abbreviated as _C11 - _C13 LA
S) is of particular value.

Other anionic surfactants are sodium alkylglyceryl ether sulfonates, especially ethers of higher alcohols derived from tallow and coconut oil: sodium cocoate monoglyceride sulfonate and sodium cocoate monoglyceride sulfate. a sodium or potassium salt of an alkylphenol ethylene oxide ether sulfate containing 1 to 10 units of ethylene oxide per molecule and having alkyl groups of 8 to 12 carbon atoms; and containing 1 to 10 units of ethylene oxide per molecule, and the alkyl group has 10 to 20 carbon atoms
is a sodium or potassium salt of an alkyl ethylene oxide ether sulfate having

Other anionic surfactants useful in the present invention are water-soluble α-sulfonated fatty acid esters having 6 to 20 carbon atoms in the fatty acid group and 1 to 10 carbon atoms in the ether group. Salt; 2-acyloxyalkane-1-sulfonic acid water-soluble salt having 2 to 9 carbon atoms in the acyl group and 9 to 23 carbon atoms in the alkane moiety;
water-soluble salts of olefin sulfonic acids and paraffin sulfonic acids having 20; and 1 to 1 carbon atoms in the alkyl group;
3 and having 8 to 20 carbon atoms in the alkane moiety.

Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionics include compounds produced by the condensation of alkylene oxide groups (hydrophilic) with organic hydrophobic compounds which can be fatty acids or alkylaromatics. The length of the polyoxyalkylene group condensed with a particular hydrophobic group can be easily adjusted to produce water-soluble compounds with the desired balance between hydrophilic and hydrophobic elements.

Suitable nonionic surfactants are polyethylene oxide condensates of alkylphenols, for example alkylphenols having alkyl radicals having from 6 to 15 carbon atoms in either linear or branched configuration, and 3 per mole of alkylphenol. Includes condensation products with ˜12 moles of ethylene oxide.

Preferred nonionic surfactants are water-soluble and water-dispersible fatty alcohols having from 8 to 22 carbon atoms in either a linear or branched configuration and from 3 to 12 moles of ethylene oxide per mole of alcohol. is a condensate of Particular preference is given to condensates of alcohols having alkyl groups of 9 to 15 carbon atoms with 4 to 8 mol of ethylene oxide per mol of alcohol.

Semipolar nonionic surfactants have 10 carbon atoms.
water-soluble amine oxides containing one alkyl moiety of -18 and two moieties selected from the group of alkyl and hydroxyalkyl moieties of 1-3 carbon atoms;
a water-soluble phosphine oxide containing one alkyl moiety of 18 carbon atoms and two moieties selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and hydroxylalkyl groups; and one alkyl moiety having 10 to 18 carbon atoms and It includes water-soluble sulfoxides containing one moiety selected from the group consisting of C1-C3 alkyl and hydroxyalkyl moieties.

Amphoteric surfactants are those in which the aliphatic moiety can be linear or branched and one of the aliphatic substituents has from 8 to 18 carbon atoms and at least one aliphatic substituent has Included are derivatives of aliphatic secondary and tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines that contain anionic water solubilizing groups.

Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which one of the aliphatic substituents has from 8 to 18 carbon atoms.

The amount of detergent surfactant that can be used is 0-50%, preferably 1-30%, most preferably 10-25% by weight of the total composition.

In addition to detergent surfactants, detergency builders can be used in bleaching compositions. Water-soluble inorganic or organic electrolytes are suitable builders. The builder can also be a water-insoluble calcium ion exchange material. Non-limiting examples of suitable water-soluble inorganic detergent builders include alkali metal carbonates, borates, phosphates, bicarbonates and silicates. Specific examples of such salts include sodium and potassium tetraborate, bicarbonate, carbonate, orthophosphate, pyrophosphate, tripolyphosphate and metaphosphate.

Examples of suitable organic alkaline detergency builders are (1) water-soluble aminocarboxylates and aminopolyacetates such as nitrilotriacetate, glycinate, ethylenediaminetetraacetate, N-
(2-hydroxyethyl)nitrilodiacetate and diethylenetriaminepentaacetate; (2) water-soluble salts of phytic acid such as sodium phytate and potassium phytate; (3) water-soluble polyphosphonates such as ethane-1-hydroxy-1, sodium, potassium and lithium salts of 1-diphosphonic acid; sodium, potassium and lithium salts of ethylenediphosphonic acid; (4) water-soluble polycarboxylates such as lactic acid, succinic acid, malonic acid, maleic acid; ,citric acid,
carboxymethyloxysuccinic acid, 2-oxa-1,
salts of 1,3-propanetricarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, mellitic acid and pyromellitic acid; and (5) water-soluble polyacetals (U.S. Pat. Nos. 4,144,266 and 4,246,49
5).

Another class of detergency builder materials useful in the present compositions are water-soluble materials capable of forming water-insoluble reaction products with water hardness cations, preferably as well as providing a growth point for said reaction products. It consists of crystalline species that can be formed. Such "seed builder" compositions are described in British Patent No. 1,424,4.
06 specification.

Yet another class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent No. 814,874. This patent describes the formula Naz _{( AlO2} ) _z ( _SiO2 ) _yXH2O , where z and _y are integers at least equal to 6 and the molar ratio of z to y is from 1.0:1 to 0. .5:1 and X is an integer from 15 to 264, which aluminosilicate has a calcium ion exchange capacity of at least 200 mg equivalent/g and a calcium ion exchange rate of at least 2 grains per gallon. /min/g) is disclosed and claimed. A preferred material is _Zeolite A of the _{formula Na12} ( _SiO2AlO2 ) _1227H2O .

The amount of detergency builder in the bleaching composition is 0%
~70%, preferably 10%-60%, most preferably 20%-60%.

[0065] The buffer is the desired alkaline pH of the bleaching solution.
can be used to maintain Buffers include, but are not limited to, many of the detergent builder compounds described above. Buffers suitable for use in the present invention are well known in the cleaning art.

Preferred optional ingredients include suds modifiers, especially those of the suds suppressing type exemplified by silicones and silica-silicone mixtures.

US Pat. No. 3,933,672;
and 4,136,045 disclose silicone suds controlling agents. Silicone materials can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and various hydrophobic silicas. The silicone material has the formula

[0068]

[Chemical 19] (wherein x is 20-2,000 and each R is an alkyl or aryl group, especially a methyl, ethyl, propyl, butyl and phenyl group). Molecular weight 200-2,000,00
All 0 and higher polydimethylsiloxanes (where both R are methyl) are useful as suds control agents. Additional suitable silicone materials in which the side groups R are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds control properties. Examples of similar components include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenylmethyl polysiloxanes, and the like.
Additional useful silicone antifoam agents may be represented by mixtures of alkylated siloxanes and solid silica as described above. Such mixtures are prepared by applying silicone to the surface of solid silica. Preferred silicone foam control agents are hydrophobic silanized (most preferably trimethylsilanized) silica having a particle size of 10 μm to 20 μm and a specific surface area greater than 50 m ² /g, and a molecular weight of 50
dimethylsilicone fluid having a 0 to 200,000 weight ratio of silicone to silanized silica of 19:1 to 1:2. The silicone suds suppressor is advantageously releasably formulated into a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier.

A particularly useful suds suppressor is US Pat. No. 4,07.
It is a self-emulsifying silicone suds suppressor as described in US Pat. No. 3,118. An example of such a compound is DB-544 (a siloxane/glycol copolymer) commercially available from Dow Corning. Foam modifiers such as those described above are used in amounts up to 2% by weight of the surfactant, preferably 0.1 to 11/2% by weight.

Melting point 35° C.-115° C. and saponification number 10
Microcrystalline waxes with less than 0 represent additional examples of preferred suds control components for use in the present compositions,
and is detailed in U.S. Pat. No. 4,056,481. Microcrystalline waxes are virtually water-insoluble, but are water-dispersible in the presence of organic surfactants. Preferred microcrystalline waxes have a melting point of 65°C to 100°C, a molecular weight of 400 to 1,000, and a penetration of at least 6 as measured by ASTM D1321 at 77°F (25.0°C). Suitable examples of said waxes include microcrystalline and oxidized microcrystalline petroleum waxes, Fischer-Tropsch wax and oxidized Fischer-Tropsch wax, ozokerite, ceracin, montan wax, beeswax, candelilla, and carnauba wax.

Alkyl phosphate esters represent preferred additional suds control agents for use in the present invention. These preferred phosphates are primarily monostearyl phosphates (which can additionally contain di- and tristearyl phosphates) and monooleyl phosphates (which can contain di- and monooleyl phosphates).

Other suds control agents useful in the practice of this invention are disclosed in US Pat. Nos. 2,954,347 and 2,95.
Soaps or mixtures of soaps and nonionic surfactants as disclosed in US Pat. No. 4,348.

[0073] In addition, the present invention can be applied to fabrics, when in an aqueous solution, by the following formula.

[0074]

[Chemical 20] (wherein R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, and R ² is a
and R ⁵ is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms).

[0075]

EXAMPLES The following examples are given to illustrate the parameters and compositions of this invention. All percentages, parts and ratios are by weight unless otherwise indicated.

Example I Preparation of N-lauroyl-6-aminoperoxycaproic acid
Method N-lauroyl-6-aminocaproic acid 1 l beaker, 250 ml of 1N sodium hydroxide solution
l (0.25 mol) and 6-aminocaproic acid 32.
8 g (0.25 mol) was charged. The resulting solution was cooled in an ice bath and, under stirring, a solution of lauroyl chloride (54.7 g, 0.25 mol) in 100 ml of ether was added to the pH of the stirred solution to that of 10% sodium hydroxide solution. Dropwise while maintaining 10-12 by addition. Addition of lauroyl chloride took 45 minutes. During this period the reaction mixture became solid and viscous and additional volumes of water and ether were added to keep the mixture stirrable. After the lauroyl chloride addition was complete, the ice bath was removed and the mixture was stirred at room temperature for 1.5 hours. The mixture was then quenched with concentrated hydrochloric acid.
Adjusted to H2 and the resulting precipitate was removed by filtration and washed with water. The resulting solid was dissolved in hexane (200
ml), filtered and washed with five 100 ml portions of hexane. This hexane slurrying/washing procedure was repeated again. The resulting solid was air dried to mp 87-9.
N-lauroyl-6-aminocaproic acid 70.7 at 0°C
g (90%) (E. Jungermann, J.
F. Gerrecht, and I.M. J. Clems, J. Amer. Che
M. Soc., 78, 172 ( 1956), mp85-
86° C.) N-Lauroyl-6-aminoperoxycaproic acid A 250 ml beaker was charged with 35.0 g (0.112 mol) of N-lauroyl-6-aminoperoxycaproic acid and 70 ml of 98% methanesulfonic acid. The resulting solution was cooled in an ice bath and stirred to 90%
21.2 g of hydrogen peroxide (19.0 g of hydrogen peroxide, 0.5
59 mol) was added dropwise at such a rate that the temperature of the reaction mixture did not rise above 20°C (took 15 minutes). The resulting solution was stirred at room temperature for 3 hours, cooled to -15°C and poured onto ice. Ethyl acetate (150 ml) was added, the mixture warmed to 60° C. in a water bath and the aqueous layer separated. An additional 100 ml of water was added and the solution was again brought to 60°C.
and the aqueous layer was separated and discarded. The ethyl acetate solution was cooled to -15°C and the resulting crystals were removed by filtration and treated with 2 x 50 ml of -15°C ethyl acetate.
washed in parts. Yield of N-lauroyl-6-aminoperoxycaproic acid was 33.1 g. Analysis for available oxygen (A _v O) showed 4.31% (theoretical yield = 36.9 g with 4.86% A _v O). mp
70-75°C.

Example II Preparation of N-decanoyl-6-aminoperoxycaproic acid
Method N-decanoyl-6-aminocaproic acid N-decanoyl-6-aminocaproic acid was prepared according to the method described in Example I by reaction of decanoyl chloride with 6-aminocaproic acid. Decanoyl chloride 95.4g
(0.500 mol) and 6-aminocaproic acid 65.
6 g (0.500 mol) gave 140 g (98%) of N-decanoyl-6-aminocaproic acid, mp 73-78°C.

N-decanoyl-6-aminoperoxyca
100% 98% methanesulfonic acid in a 400ml beaker of proacid
ml and N-decanoyl-6-aminocaproic acid 50
0 g (0.175 mol) was charged. The resulting solution is cooled in an ice bath and, under stirring, 90% hydrogen peroxide 3
3.1 g (29.8 g hydrogen peroxide, 0.877 mol)
was added dropwise at a rate such that the temperature of the reaction mixture did not rise above 20°C. The addition took a total of 10 minutes. The resulting mixture was stirred at room temperature for 3 hours, cooled to -15°C and
Poured into 500 ml of ice water. The precipitated solid was washed with 20 methylene chloride.
Extracted to 0 ml. The methylene chloride solution was separated, washed with 100 ml portions of water until the wash water was neutral (6 washes were required), dried over sodium sulfate and evaporated on a rotary evaporator. , peroxyacid A _v O4.
51.6 g of white solid with 93% yield was produced (theoretical yield = 52.7 g of A _v O 5.32%).

N-decanoyl-6-aminoperoxycaproic acid was recrystallized from 200 ml of ethyl acetate (60° C.
of ethyl acetate and then cooled to -15°C) to yield 47.2 g of product with peroxyacid A _v O 5.12% and mp 63-67°C.

Example III Preparation of N-nonanoyl-6-aminoperoxycaproic acid
Method N-nonanoyl-6-aminocaproic acid N-nonanoyl-6-aminocaproic acid was prepared according to the method described in Example I by reaction of nonanoyl chloride with 6-aminocaproic acid. Nonanoyl chloride 67.3g
(0.381 mol) and 6-aminocaproic acid 50.
From 0 g (0.381 mol), 103 g of N-nonanoyl-6-aminocaproic acid, mp 71-74°C, was obtained.

N-nonanoyl-6-aminoperoxyca
N-nonanoyl-6-aminoperoxycaproic acid proate is an example
It was prepared by reaction of N-nonanoyl-6-aminocaproic acid with hydrogen peroxide in 98% methanesulfonic acid according to the method described in II. N-nonanoyl-6-aminocaproic acid 103 g (0.381 mol), hydrogen peroxide 4
4 g (1.29 mol), and methanesulfonic acid 170
From ml, peroxyacid AvO 5.31% and mp60
74.2 g of N-nonanoyl-6-aminoperoxycaproic acid having a °C was obtained (theoretical yield = AvO 5.57%
of 109.5 g).

EXAMPLE IV Preparation of N-lauroylaminoperoxyacetic acid N-lauroylglycine N-lauroylglycine was prepared according to the method described in Example I by reaction of lauroyl chloride with glycine. from 109.4 g (0.500 mol) of lauroyl chloride and 37.6 g (0.500 mol) of glycine to mp 110
120.5 g of N-lauroylglycine at 118°C (94
%) was obtained. Literature mp 118-119°C [E. Jungerman, J. F. Gerrecht, and I.M. J. Clems, J. Amer. Chem. Soc. , 78 , 17
2 (1956)].

N-Lauroylaminoperoxyacetic Acid N-Lauroylaminoperoxyacetic acid was produced by reaction of N-lauroylglycine with hydrogen peroxide in metalsulfonic acid according to the method described in Example II. N-lauroylglycine 50.0 in 100 ml methanesulfonic acid
g (0.195 mol) and 33.1 g hydrogen peroxide
(0.973 mol) to N with AvO 3.03%
-Lauroylaminoperoxyacetic acid 38.0 g were obtained (theoretical yield = 53.2 g with AvO 5.86%).

EXAMPLE V Preparation of N-decanoylaminoperoxyacetic acid N-decanoylglycine N-decanoylglycine was prepared according to the method described in Example I by reaction of decanoyl chloride with glycine. From 47.7 g (0.25 mol) of decanoyl chloride and 18.8 g (0.25 mol) of glycine, mp 104-10
54.1 g (94%) of N-decanoylglycine at 8° C. were obtained.

N-Decanoylaminoperoxyacetic Acid N-decanoylaminoperoxyacetic acid was prepared by reaction of N-decanoylglycine with hydrogen peroxide in methanesulfonic acid according to the method described in Example II. 22.9 g of N-decanoylglycine in 50 ml of methanesulfonic acid
(0.100 mol) and 17.0 g of hydrogen peroxide (0.10 mol).
500 mol) gave 22.4 g of peroxyacid with an AvO of 0.06% (theoretical yield=24.5 g with an AvO of 6.53%). mp 75-80°C (gassing and melting).

Example VI Preparation of N-decanoyl-4-aminophenylperoxyacetic acid
Preparation N-decanoyl-4-4-aminophenylacetic acid N-decanoyl-4-aminophenylacetic acid was prepared according to the method described in Example I by reaction of decanoyl chloride with 4-aminophenylacetic acid. Decanoyl chloride 63.1
g (0.331 mol) and 4-aminophenylacetic acid 5
mp 156-159 from 0.0 g (0.331 mol)
°C of N-decanoyl-4-aminophenylacetic acid was obtained.

N-decanoyl-4-aminophenylper
Oxyacetic acid N-decanoyl-4-aminophenylperoxyacetic acid was prepared from N-decanoyl-4-aminophenylacetic acid and hydrogen peroxide in methanesulfonic acid according to the method described in Example II. N- in 150 ml of 98% methanesulfonic acid
Decanoyl-4-aminophenylacetic acid 70.0 g (0.
229 mol) and 39.0 g (1.15 mol) of hydrogen peroxide, N-decanoyl-
64.9 g of 4-aminophenylperoxyacetic acid were obtained (theoretical yield = 73.6 g giving AvO 4.99%).
mp 121°C.

Example VII of N-decylamino-6-oxoperoxycaproic acid
Preparation Method This ester/acid salt compound of 5-carbomethoxyvaleryl chloride was prepared according to Org. synthes
is Coll. Vol. 4 , 556 (1963).

Adipic acid monomethyl ester (50.0
g, 0.312 mol) and thionyl chloride (74.3
g, 0.624 mol) was added to a 125 mL Erlenmeyer flask. The flask was fitted with a drying tube and the mixture was allowed to stand overnight in a hood at room temperature. Heptane (10
0 ml) was added and excess thionyl chloride was removed on a rotary evaporator. An additional 50 mL of heptane was added and the resulting mixture was again evaporated on the rotary evaporator to yield 56.4 g of 5-carbomethoxyvaleryl chloride as a yellow oil.

6-decylamino-6-oxocaproic acid
Methyl Ester A 1 L beaker equipped with a mechanical stirrer, ice bath and pH electrode was charged with 49.1 g (0.312 mol) of decylamine in 350 ml water and 100 ml ether. To this stirred mixture was added dropwise the above solution of 5-carbomethoxyvaleryl chloride in 100 ml of ether with simultaneous dropwise addition of 20% sodium hydroxide solution such that the pH of the aqueous layer remained 10-12. Total addition time was 30 minutes. After addition of the acid chloride and base, the precipitated solid was removed by filtration and washed with 300 mL of hexane. The solids were then stirred with 200 mL of hexane, filtered and washed with 100 mL portions of hexane. After air drying, the weight of 6-decylamino-6-oxocaproic acid methyl ester was 56.8 g. mp 56-59°C.

Additional 19.1 g of 6-decylamino-6
-oxocaproic acid methyl ester was obtained from the filtrate by filtering and washing the collected solid with hexane.

6-decylamino-6-oxoperoxy
Caproic acid 6-decylamino-6-oxoperoxycaproic acid was prepared according to the method described in Example I for N-decanoyl-6-aminoperoxycaproic acid. Thus, methyl ester of 6-decylamino-6-oxocaproic acid (29.9 g, 0.10 mol), hydrogen peroxide (17.0 g, 0.50 mol), and 98% methanesulfonic acid (60 ml). was allowed to react for 2 hours at room temperature, the reaction mixture was poured onto ice and the peroxyacid was extracted into 125 ml of ethyl acetate at 60°C. The aqueous layer was discarded and the warm ethyl acetate solution was washed with two 100 mL portions of water. The ethyl acetate solution was added to a 250 ml Erlenmeyer flask (ethyl acetate 25
ml) and reheated to 60°C, then -1
Cooled to 5°C. Crystals of N-decylamino-6-oxoperoxycaproic acid were collected by filtration, washed twice with 50 ml of ice-cold ethyl acetate and air dried. Yield is
21.6 g with 4.49% AvO peroxyacid (theoretical yield = 30.1 g of 5.32% AvO). m
p77-85°C.

Example VIII of N-nonylamino-6-oxoperoxycaproic acid
Preparation 5-Carbomethoxyvaleryl Chloride 5-Carbomethoxyvaleryl chloride was prepared as described in Example VII. 100 g monomethyl ester of adipic acid
(0.624 mol) and 148.6 g of thionyl chloride
(1.248 mol) gave 111.5 g (0.624 mol) of the ester/acid chloride as a yellow oil.

6-nonylamino-6-oxocaproic acid
The previously obtained ester/acid chloride was reacted with nonylamine using the method described in Example VII for the preparation of the methyl ester 6-decylamino-6-oxocaproic acid methyl ester. 111.5 g of 5-carbomethoxyvaleryl chloride
(0.624 mol) and nonylamine 89.4 g
(0.624 mol) gave the methyl ester of 6-nonylamino-6-oxocaproic acid.

6-nonylamino-6-oxoperoxy
Caproic acid 6-nonylamino-6-oxoperoxycaproic acid was prepared according to the method described in Example VII for the decylamino derivative. 100 g (0.350 mol) of monomethyl ester of 6-nonylamino-6-oxocaproic acid,
59.6 g (1.75 mol) of hydrogen peroxide, and 98%
From 300 ml of methanesulfonic acid, AvO, mp 83-8
84.7 g of 6-nonylamino-6-oxoperoxycaproic acid at 7° C. were obtained (theory = 100.7 g, AvO
5.57%).

Example IX Phenol sulfone of 6-benzoylaminocaproic acid
6-benzoylaminope by perhydrolysis of the acid ester
Preparation of Ruoxycaproic Acid A three-necked flask containing 500 ml of 6-benzoylaminocaproic acid was equipped with a mechanical stirrer, a reflux condenser and a nitrogen inlet. The flask was flushed with nitrogen and 6-benzoylaminocaproic acid 35.3.
g (0.15 mol) [ Org. Synthesis C
oll. Vol. 2 , 76 (1943)] and 150 ml of toluene were charged. To the resulting stirred suspension was added 23.3 mL (34.7 mL) of trifluoroacetic anhydride (Fisher).
g, 0.165 mol) was added via syringe. Suspended solids dissolved quickly. To this solution was added 29.4 g (0.15 mol) of anhydrous sodium p-phenolsulfonate. The resulting suspension was heated under reflux for 2.5 hours, cooled in an ice bath and the precipitated solid filtered and washed well with ether. After air-drying, the solid was washed with 125 ml of ethanol.
, filtered and washed with ethanol. The resulting white paste was dried under vacuum to give 43.7 g of a hard white solid. Grind this solid and 2
Passed through a 4 mesh screen. NMR of this solid
Spectral analysis (methylsulfoxide _- d6 solvent)
showed that it contained 69% sodium salt of the phenolsulfonate ester of 6-benzoylaminocaproic acid and 31% sodium p-phenolsulfonate.

6-benzoylaminoperoxycaprone
Perhydrolysis of the phenolsulfonate ester to produce the acid 6-benzoylaminoperoxycaproic acid was accomplished according to the following procedure. 95°F (35.0°C)
5.00 g (12
50 ppm), 0.36 g sodium perborate monohydrate
(90 ppm) and 0.46 sodium salt of phenolsulfonic acid ester of 6-benzoylaminocaproic acid.
g (115 ppm) (0.67 g of the 69% mixture above) was added. After perhydrolysis of the ester to produce 6-benzoylamino-peroxycaproic acid, the solution was analyzed for available oxygen (AvO) using conventional iodometric titration. Complete softening of the ester to peroxyacid is
would yield an AvO of 4.5 ppm. The results obtained for AvO vs time are displayed below.

Time (min) AvO (ppm) % of theoretical AvO 2 3.0 67 7 3.2 71 12 3.3 73 20 3.0 67 Example X
Preparation method of gnesium salt
A suspension of 2.92 g (0.050 mol) of magnesium hydroxide was prepared by adding to a solution of 6.02 g (0.050 mol) of magnesium sulfate in 5 ml.
The resulting suspension was treated with 30.1 g of N-decanoyl-6-aminoperoxycaproic acid (0.1 g) in 150 ml of ethyl acetate.
10 molar) to a warm, stirred solution over 1 minute.
A heavy precipitate formed immediately. The mixture was stirred for 3 minutes, filtered, and the solid collected was washed with water and ethyl acetate. The weight of magnesium bis-(N-decanoyl-6-aminoperoxycaproate was 31.7 g. Available oxygen (AvO) 3.94%.

Example XI N-decanoyl-6-aminoperoxycaproic acid
The stability of qualitative N-decanoyl-6-aminoperoxycaproic acid (both alone and mixed with alkaline detergent granules) was measured at various temperatures and humidity. Samples were stored in glass jars with vented tops. Residual peroxyacid activity was determined by conventional iodometric titration for available oxygen. The sample, which was a mixture of peroxyacid and alkaline detergent granules, consisted of 7% peroxyacid and 93% detergent granules. The results for this sample are displayed below.

N-decanoyl-6-aminoperoxyca
Pronic acid stability [Table 1] % of original activity (stored alone) Storage time 80°F 100°F 120°F 80°F 80°F (26.7°C) (26.7°C) (weeks) (26.7°C) ) (37.8°C) (49°C) /RH15% /RH60% 1 99 98 93 95 98 2 100 101 98 100 101 4 100 99 89 100 96 8 99 93 59 94 101 14 97 86 7 76 99 °F 100°F 120 °F 80°F 80°F (26.7°C) (26.7°C) (weeks) (26.7°C) (37.8°C) (49°C) /RH15% /RH00% 1 96 98 90 96 93 2 89 84 86 89 85 4 96 89 87 90 85 8 101 88 66 86 81 14 96 72 61 59 80 Example XII N-decanoyl-6-aminoperoxycaproic acid bleaching
White Performance The bleaching performance of N-decanoyl-6-aminoperoxycaproic acid was determined in a series of experiments. These experiments compared the fabric whitening and stain removal of a treatment containing alkaline detergent granules and peroxyacid to a treatment containing detergent granules alone.

Thus, in each of the two top-loading automatic washers, 9 washer having 5 pounds (2.27 kg) of naturally soiled ballast fabric and a hardness of 6 grains per gallon.
68 liters of 5°F (35.0°C) tap water was added. To one washing machine was added 89 grams of alkaline detergent granules and sufficient N-decanoyl-6-aminoperoxycaproic acid to produce 3.5 ppm available oxygen (AvO) in the wash liquor. Alkaline detergent granules 89 in the second washing machine
only g was added.

Two sets of naturally soiled white fabrics and two sets of artificially soiled swatches were added to each of the above wash liquors. The washing machine was then completed through its normal wash and rinse cycle, and the ballast and test fabrics were dried in the dryer. This method was repeated three times using different sets of ballast fabrics, naturally soiled white fabrics and artificially soiled swatches for each iteration.

After completing the three iterations, the fabric and swatches were placed under suitable lighting to compare staining and removal. Three professional graders compared the degree of stain and stain removal using the following scale. 0 No difference between the two swatches 1 I believe there is a difference 2 Confident of a difference 3 Confident of a large difference 4 Confident of a very large difference The artificially soiled swatches were then compared for stain removal. The resulting grades were then averaged and normalized to yield the results shown below.

Treatment and average relative grade Detergent granules + N-decanoyl-6-detergent granules alone 3.5 ppm AvO from aminoperoxycaproic acid Naturally soiled fabric T-shirt 0 2.4s Dish towel 0 1.1s Pillow cover 0 2.2s Artificially soiled fabric clay 0 0.4 Spaghetti sauce 0 0.1 Barbecue sauce 0 -0.4 Tea 0 3.3s Grass 0 3.0s Menstrual blood 0 0.4 Blueberry 0 1.7s S = Statistically significant difference (90% confidence level) compared to treatment with detergent granules alone Example XIII Bis( N-decanoyl-6-aminoperoxycaprone
Acid) Bleaching Performance of Magnesium Using the method described in Example XII, N-dodecanoyl-6
The bleaching performance of magnesium salt of -aminoperoxycaproic acid was measured. magnesium salt in 50 ml of methanol
was added to the wash solution as a finely divided powder suspended in The amount of magnesium salt added is determined by the peroxyacid available oxygen (Av
O) The amount was to give an amount of 3.5 ppm.

The results obtained for this bleach performance test are shown below.

Treating agents and average relative grade AvO from Bis(N-decanoyl-6-amino detergent granules alone Magnesium peroxycaproate 3.5 ppm Naturally soiled fabric T-shirt 0 1.4s Dish towel 0 0.9s Pillow cover 0 1.1s Artificially soiled fabric clay 0 0.5s Spaghetti sauce 0 1.2s BBQ sauce 0 0.0 Tea 0 3 .4s Grass 0 3.1s Menstrual blood 0-0.1 Blueberry 0 1.4s s = Statistically significant difference (90% confidence level) compared to treatment with detergent granules alone

──────────────────────────────────────────────────── ──── continuation of the front page (73) Patent holder 592043805 ONE PROCTER & GANB LE PLAZA, CINCINNAT I, OHIO, UNITED STAT ES OF AMERICA (72) Inventors Frederick, Edward, Hardy England, Newcastle, Upon, Tyne, Gosforth, Melton, Par black, drive, 38 (72) Inventors Michael, Eugene, Barnes West, Ohio, USA Chester, Sunderland, Way, 9248 (56) References JP-A-50-146696 (JP, A) Japanese Patent Laid-Open No. 57-209260 (JP, A) Japanese Patent Laid-Open No. 58-213744 (JP, A) Japanese Patent Publication 44-3572 (JP, B1) J. O. C. Vol.33, No.12 (1968) p. 4524−4526

Claims (1)

(57) [Claims] 1. A compound having the general formula (wherein R1 is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, and R2 is a
and R5 is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms, and L is a leaving group, the conjugate acid of which is 4 to 13 and wherein L is selected from the group consisting of (wherein R3 is an alkyl or alkylene chain having 1 to 8 carbon atoms, Y is -SO3-M+ or -COO-M+, and M is sodium or potassium))2. 3. The compound of claim 1, wherein the conjugate acid of the L group has a pKa of 6-11. 3. L is the general formula 3. The compound of claim 1 having the formula wherein M is sodium or potassium.