CA2177693A1 - Bleach activator preparation - Google Patents
Bleach activator preparationInfo
- Publication number
- CA2177693A1 CA2177693A1 CA 2177693 CA2177693A CA2177693A1 CA 2177693 A1 CA2177693 A1 CA 2177693A1 CA 2177693 CA2177693 CA 2177693 CA 2177693 A CA2177693 A CA 2177693A CA 2177693 A1 CA2177693 A1 CA 2177693A1
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- CA
- Canada
- Prior art keywords
- anhydride
- process according
- water
- aryl
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for the manufacture of bleach activators is provided. The process comprises dissolving an acid halide or anhydride in a water miscible hydroxyl-free solvent prior to reaction with an aqueous dispersion of an aryl hydroxysulphonate. The aqueous dispersion additionally comprises an alkali, especially sodium hydroxyde. The preferred organic solvent is acetone. The process is particularly suited to the situation where the acid halide or anhydride is a solid or poorly soluble in water and in such situations can offer improvements in yield over the processes of the prior art.
Description
~ wo gs/15942 ~ 9 3 PCT/GB9-~102688 Bleach Activator Preparation This invention concerns a process for the preparation of bleach activators and particularly concerns an improved process for Ihe manufacture of bleach activators employing substantially water insoluble acid halides.
In recent years, there has been considerable interest in both the deter~qent and disinfection industries in organic peracids, particularly in the detergent industry, on account of their bleaching properties. A significant proportion of this interest has concentrated on the identification and development of compounds which, although not themselves peracids, are 20 hydrolysed on reaction with a peroxidic species (known as "perhydrolysis"~ to produce a peracid. Such compounds are commonly known as "bleach activators" or simply "activators".
Many different structures are described in the literature as being suitable for use as activators, but generally they comprise both a carrier moiety and a 25 leaving group, the peracid formed on perhydrolysis being derived from the carrier moiety. In many cases, the activators are prepared by reacting a compound that will form a suitable carrier moiety, commonly an acid chloride or anhydride, with a compound that will form a suitable leaving group, commonly but not exclusively a phenolsulphonate. The use of acid chlorides is 30 generally preferred because of their lower cost compared with anhydrides.
Several different processes for the production of activators have been described in the prior art. The reaction can be carried out in an organic solvent, such as those described in European Patent Application No. 0 120 591 and European Patent No. 0 220 826. An alternative process employing a 35 substantially aqueous route is described in European Patent No. 0 294 073. In International Patent Application W092/15556 a process is described for the production of benzoyloxybenzene sulphonates by the reaction between a phenolsulphonate and benzoyl chloride in the presence of a solvent comprising .. .... . .. . . . .. .
WOgS/159~2 2S~,77i~g3 PCT/GB9.~102688~
water and one or more organic solvents chosen from ethanol, isopropanol, dioxane and tetrahydrofuran. The benzoyl chloride is employed without any prior dissolution in a solvent. The aqueous process of European Patent 0 294 073 and the process of W092115556 are particularly suited to the case where 5 the acid chloride is either a liquid or has a relatively high solubility in water.
However, these processes are less suitable when the acid chloride is a solid and/or is poorly soluble in water, as is particularly the case when the peracid it is desired to produce by perhydrolysis is a relatively hydrophobic peracid, Hydrophokic peracids are particularly those meeting the criterion for the log 10 partition coefficient between water and n-octanol at 21 C outlined in European Patent Application No 0120 591. Particularly desirable hydrophobic peracids include pernonanoic acid and percarboxy trimellitimides.
The processes described above notwithstanding, it remains desirable to identify additional or alternative processes for the preparation of activators. It 15 is particularly desirable to identify a process for the preparation of activators from acid chlorides that 0ives improved performance with solid and/or poorly water soluble acid chlorides compared with the aqueous proc~sses of the prior art.
During the course of the studies leading to the present invention, it was 20 surprisingly found that an improved proces3 for the production of activators from solid or poorly water soluble acid chlorides could result if the acid chloride was dissolved in a ketone solvent prior to reaction with the carrier molecule.
It is an object of the present invention to provide an additional or 25 alternative process for the manufacture of peracid activators.
It is a second object of certain aspects of the present invention to provide a process for the preparation of activators from acid chlorides that gives improved yields with solid and/or poorly water soluble acid chlorides compared with the aqueous processes of the prior art.
According to the present invention, there is provided a process for the manufacture of a peracid activator by reacting an acid halide or anhydride with an aqueous dispersion of an aryl hydroxy sulphonate in the presence of an aikali in a reaction vessel, characterised in that the acid halide or anhydride is dissolved in a water-miscible hydroxyl-free solvent prior to introduction into the 35 reaction vessel.
The process of the present invention allows the advantages of add!tion in liquid form of solid acid halides or anhydrides to the reaction WO 95/159~2 ~ ~ 7 ~ ~ 9 3 PCT/GB9~/02688 vessel and can offer the additional advantage for such acid halides or anhydrides of imp~oved yields compared with addition in solid form.
The solvent employed to dissolve the acid halide or anhydride prior to introduction into the reaction vessel in the process according to the present 5 invention is a water-miscible hydroxyl-free solvent. Examples of such solvents include water miscible ketones, sulphoxides, amides, nitriles and cyclic ethers, preferably ketones. It will be recognised that mixtures of the solvents can be employed, depending for example, on the solubility of the acid halide or anhydride, but usually a single compound is employed as 10 solvent. Preferably, the solvent(s) employed is/are substantially free of water .
i<etones that can be employed as solvent in the process according to the present invention include acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone and N-methylpyrrolidinone. Preferably, the ketone is 1 5 acetone.
Sulphoxides that can be employed as solvent in the process according to the present invention include dimethylsulphoxide and sulpholane.
Amides that can be employed as solvent in the process according to 20 the present invention include dimethylformamide and dimethylacetarnide.
Nitriles that can be employed as solvent in the process according to the present invention include acetonitrile.
Cyclic ethers that can be employed as solvent in the process according to the present invention include tetrahydrofuran and dioxane.
Acid halides or anhydrides, preferably acid chlorides, that can be employed in the process according to the present invention can be either solid or liquid, and can be either relatively soluble in water or relatively poorly soluble. In certain preferred embodiments of the present invention, particularly advantageous results have been achieved employing solid acid 30 chlorides that are poorly water soluble. Examples of acid chlorides that can be employed include nonanoyl chloride, adipoyl chloride, nonanedioic acid chloride, dodecanedioic acid chloride, ethylene di-imidotrimellitic acid chloride, benzoyl chloride, 4,4'-sulphonyl bis-benzoyl chloride, sulphonimido benzoyl chloride, N-alkyl sulphonimidobenzoyl chlorides, including N-propyl 35 sulphonimidobenzoyl chlorides, iso- and sec- N-butyl sulphonimidobenzoyl chlorides, N-pentyl sulphonimidobenzoyl chlorides and N-heptyl sulphonimidobenzoyl chlorides, alkyimidotrimellitic acid chloride, aikylimidotrimellitic acid chlorides including isoamylimidotrimellitic acid 5/ 5 ~2 . PCT/GB9~/02688 WO9 19 ~1'776g3 4 chloride, N-propylimidotrimellitic acid chloride, iso- and sec- N-butylimidotrimellitic acid~chloride, N-pentylimidotrimellitic acid chloride and N-heptylimidotrimellitic acid chloride, and phthalimido alkanoyl chlorides, including particularly phthalimido caproyl chloride. Anhydrides that can be 5 employed include the anhydride equivalents of the acid chlorides listed hereinabove, but it will be recognised that in many cases, the choice of an anhydride will be less favoured on account of their generally higher cost.
Aryl hydroxy sulphonates that can be employed in the process according to the present invention can be either substituted or 10 unsubstituted on the aryl group. Where the aryl group is substituted, the substituent(s) can be at any position on the aryl group. Examples of substituents that can be present include short chain alkyl groups such as methyl or ethyl groups. In many embodiments, the aryl hydroxy sulphonate is not substituted. It will be recognised that the sulphonate group can be 15 either ortho-, meta- ot para- to the hydroxy group of the hydroxy sulphonate. Preferably, the sulphonate group is para- to the hydroxy group.
In most embodiments, the aryl group is selected from benzyl groups and naphthyl groups, and is preferably a benzyl group. ~he sulphonate can be introduced in the form of a free acid which is subsequently neutralised by 20 the alkali in the reaction vessel, or as an alkali metal or ammonium salt, and is preferably a sodium salt. The most preferred aryl hydroxy sulphonate is sodium p-phenolsulphonate.
The acid chloride or anhydride can be dissolved in the solvent shortly or immediately before introduction into the reaction vessel. However, it will 25 be reco~qnised that it is possible if desired for the dissolution to take place a significant time prior to introduction, for example several hours or more.
The dissolution can be effected by stirring the acid chloride or anhydride and the ketone in a suitable vessel. Depending on the natures of the acid chloride or anhydride and the solvent, the dissoiution can take place at 30 ambient temperature, such as from about 15 to about 30C, or can take place at elevated temperature such as up to about 50C to increase the rate of dissolution.
The concentration of acid halide or anhydride in the solution produced by dissolution in the solvent prior to introduction into the reaction 35 vessel can vary over a wide range up to the maximum solubility in the particular solvent and is chosen at the discretion of the user considering factors such as the desired space yield of the process, the solubility of the acid halide or anhydrioe and the nature of the solvent. In many . _ . . .
og~ 9~2 ?1 7 76 ~ 3 PcrlGBs~l02688 embodiments of the present invention, the concentration is in the range of from about 20% to about 75'3~0 w/w, particularly from about 25% to about 50% w/w.
The aqueous dispe~sion of aryl hydroxysulphonate can be produced 5 by stirring a mixture of water and the aryl hydroxysulphonate. The weight ratio of water to aryl hydroxysulphonate in the dispersion can vary over a 3 wide range, but in many embodiments is in the range of from about 0.5: 1 to about 1 5: 1 , and is preferably from about 1: 1 to about 5: 1 . The aqueous dispersion also comprises an alkali, commonly an alkali metal 10 hydroxide. Preferably, when an alkali metal hydroxide is present, the alkali metal corresponds to that of the aryl hydroxysulphonate. In many embodiments, the alkali metal hydroxide is sodium hydroxide. The mole ratio of alkali in excess of that required to neutralise any free sulphonic acid: aryl hydroxysulphonate is often from about 0.9: 1 to about 2: 1, 15 preferably from about 1: 1 to about 1.5: 1.
In the process according to the present invention, the mole ratio of acid halide or anhydride to aryl hydroxysulphonate is often at least about 0.75: 1, and is unlikely to be greater than about 2: 1. In many embodiments, the mole ratio is selected in the range of from about 0.8: 1 20 to about 1.4: 1.
It will be recognised that the weight ratio of solvent employed to dissolve the acid halide or anhydride to water in the aqueous dispersion of aryl hydroxysulphonate can very widely depending for example on the nature of the reagents. In many embodiments, the weight ratio of solvent 25 to water is chosen to be from about 5: 1 to about 1: 5, preferably from about 3: 1 to about 1: 3. In certain preferred embodiments, the weight ratio of solvent to water is chosen to be such that the activator produced is substantially insoluble in the reaction mixture, thereby causing it to precipitate. This can reduce or eliminate the need for extractive or 30 evaporative techniques to obtain the product on completion of the reaction period .
The temperature at which the reaction is carried out is commonly ambient temperature or less~ often from about 0C to about 25C and preferably from about 2C to about 10C. When a sub-ambient reaction 35 temperature is employed, a coolant at the appropriate temperature is usually employed. Examples of suitable coolants include water and glycol.
The introduction of the solution of acid halide or anhydride into the reaction vessel containing the aqueous dispersion of the aryl , . .... . , .. , .. , .. . , .. ,, _ _ _ _ ..
WOgS/159~2 ~1 77~3 PcTlGss~lo2688 hydroxysulphonate can be achieved in a number of ways. The introduction can be achieved in a single dose, but it will be recognised that on account of the exothermic nature of the reaction between the acid halide or anhydride with the aryl hydroxysulphonate, this can produce a slgnificant 5 rise in temperature and should therefore be avorded except in the case of very small scale preparations or those where extremely effective cooling is available to control the temperature rise. In many embodiments, the introductiQn takes place over an extended period, for example from about 30 minutes to several hours, particularly from about 45 minutes to 2 hours.
10 The introduction can take place continuously throughout this period or may take place in the form of a number of discrete additions throughout the introduction period. The rate of addition is usually controlled to maintain the reaction temperature at or around the desired reaction temperature, particularly in the case of reactions at sub-ambient temperatures, where the 15 exothermic nature of the reaction is balanced with the cooling employed.
On completion of the introduction of the solution of the acid halide or anhydride, the reaction is commonly maintained at the reaction temperature with stirring for a reaction period which may vary from about 30 minutes to several hours, for example 5 hours, depending on the reagents and 20 conditions employed. In many embodiments, the reaction period is from about 1 hour to about 3 hours.
The activators produced by the process accoroing to the present invention can be separated from the reaction mixture on completion of the desired reaction period by conventional means well known to those skilled 25 in the art. In many embodiments the activators are solids and therefore can relatively simply be separated from the reaction medium, for example by filtration. If desired, the activator so obtained can be washed to remove any contaminants, for example any unreacted reagents. Washing can be effected with water, preferably cooled to reduce the extent of dissolution of 30 the activator, or with a suitable volatile organic solvent. Preferably, the activator is washed with a solvent of the type used to dissolve the acid halide or anhydride.
The process can be operated as a batch process, but it will also be recognised that the process ca~ be operated continuously, for example 35 employing feeds of reagents to a reactor from which product a product stream is removed, the relative flow rates and reactor dimensions being arranged to give the desired reactionlresidence time.
~ Wo 9~159J2 ~ 1 7 7 ~ ~ 3 " ~ oo Solvent recovered in the product separation stage can be recycled, and re-employed to dissolve further acid halide or anhydride, or may be disposed of in a suitable manner.
According to a preferred aspect of the present invention, there is 5 provided a process for the manufacture of a bleach activator by reacting an acid halide or anhydride with an aqueous dispersion of sodium -' phenolsulphonate in a reaction vessel, characterised in that the acid halide or anhydride is dissolved in acetone prior to introduction into the reaction vessel, the aqueous dispersion additionally contains sodium hydroxide in a mole ratio 10 to sodium phenolsulphonate of from 1: 1 to 1.5: 1, the weight ratio of acetone to water is from 3: 1 to 1: 3 and the mole ratio of acid halide or anhydride to sodium phenolsulphonate is 0.3: 1 to 1.4: 1.
Having described the invention in general terms, specific embodiments thereof are described in greater detail by way of example 1 5 only.
ExamDle 1 3.59 sodium hydroxide and 13.59 sodium phenolsulphonate dihydrate were added to 309 demineralised water in a 250ml 3 necked flask and cooled to 20 5C with an ice bath. 12.59 nonanoyl chloride was dissolved in 15g acetone and also cooled to 5C with an ice bath. The solution of nonanoyl chloride in acetone was added with stirring to the 3-necked flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C throughout the addition by control of the addition rate. The reaction 25 was maintained at 5C for a further 2 hours after completion of the addition.The reaction mixture was filtered at 5C, and the product washed with water and then with 50mls acetone.
Analysis of the product showed it to be sodium 30 nonanoyloxyben~enesulphonate in a yield of 76% based on the weight of acid chloride employed, and having a purity of 79.7%.
ExamDle 2 - -7.449 sodium hydroxide and 24.49 sodium phenolsulphonate dehydrate were 35 added to 53.59 demineralised water in a 500ml 3 necked flask and cooled to 5C with an ice bath. 329 N-isoamylimidotrimellitic acid chloride was dissolved in 75ml acetone at 40 and allowed to cool to ambient temperature.
The solution of acid chloride in acetone was added with stirring to the 3-... . .. , _ , WO 951159-12 . PCT/GB9~102688 ~
217~93 8 necked flask dropwise via a dropping funnel over an addition period of 1 hour.
The temperature was maintained at < 1 0C throughout the addition by control of the addition rate. The reaction was maintained at ca. 5C for a further 1 hour after completion of the addition. The reaction mixture was filtered a 5 5C, and the product washed with water and then acetone.
Analysis of the product showed it to be sodium N-isoamylimidotrimellitoyloxybenzenesulphonate, having the chemical structure ~ N-(CH2)2CH~cH3)2 NaS03-Ph-OC C
O O
in a yield of 90.1% based on the weight of acid chloride employed, and having a purity of 100%.
F~amr~le 3 20 11.59 sodium hydroxide and 47.89 sodium phenolsulphonate dehydrate were added to 107.59 demineralised water in a 11 3 necked flask and cooled to 5C
with an ice bath. 609 N-isoamylimidotrimellitic acid chloride was dissolved in 150ml acetone at 40 and allowed tQ cool to ambient temperature. The solution of acid chloride in acetone was added with stirring to the 3-necked 25 flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C throughout the addition by control of the addition rate. A further 309 water was added to facilitate stirring and the reaction maintained at 5C for a further 1.5 hours after completion of the addition. The reaction mixture was filtered at 5C, and the product washed 30 with water and then with acetone.
Analysis of the product showed it to be sodium N-isoamylimidotrimellitoyloxybenzenesu~phonate in a yield of 86.7% based on the weight of acid chloride employed, and having a purity of 100C/o.
Exam~le 4 5.29 sodium hydroxide and 18.39 sodium phenolsulphonate dehydrate were added to 879 demineralised watet in a 11 3 necked flask and cooled to 5C
, . . . . , , . . .. . , . .. . . , . . . , _ . .. .. .. . . .... . . . . .
~ WO gS1159 ~2 ~ 1 ~ 7 ~ g 3 PCTIGB9.1102688 ., ~.
with an ice bath. 229 N-isoamylimidotrimellitic acid chloride was dissolved in 1 50ml tetrahydrofuran (THF~ at room temperature. The solution of acid chloride in THF was added with stirring to the 3-necked flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was 5 maintained at ca. 5C throughout the addition by control of the addition rate.The reactiorl temperature was allowed to reach room temperature over 1 hour after completion of the addition. The reaction mixture was filtered at room temperature, and the product washed with water and then 30mls THF, 10 Analysis of the product showed it to be sodium N-isoamylimidotrimellitoyloxybenzenesulphonate in a yield of 67.1% based on the weight of acid chloride employed, and having a purity of >90%.
ExamDle 5 .. . .
15 2.19 sodium hydroxide and 7.279 sodium phenolsulphonate dehydrate were added to 109 demineralised water in a 250ml 3 necked flask and cooled to 5C with an ice bath. 119 ethylene di-imidotrimellitic acid chloride was warmed in 200ml dimethylformamide ~DMF) until the acid chloride had dissolved. The solution of acid chloride in DMF was added with stirring to the 20 3-necked flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C throughout the addition by control of the addition rate. The reaction temperature was maintained at ca.
5C for a further 2 hours after completion of the addition and then allowed to reach room temperature over 1 hour. The reaction mixture was filtered at 25 room temperature and the product washed with water and then 30mls acetone.
Analysis of the product showed it to be disodium ethylene di-imidotrimellitoyloxybenzenesulphonate having the chemical structure O O
~I ti J~ N- ( CH2 1 2-N~
NaSO -Ph-OC C C C-O-Ph-SO3Na 3 l~
O O O O
in a yield of 71% based on the weight of acid chloride emp~oyed, and having a purity of ca. 100% by NMR.
...... . . .. .. . . . .. .. ....
In recent years, there has been considerable interest in both the deter~qent and disinfection industries in organic peracids, particularly in the detergent industry, on account of their bleaching properties. A significant proportion of this interest has concentrated on the identification and development of compounds which, although not themselves peracids, are 20 hydrolysed on reaction with a peroxidic species (known as "perhydrolysis"~ to produce a peracid. Such compounds are commonly known as "bleach activators" or simply "activators".
Many different structures are described in the literature as being suitable for use as activators, but generally they comprise both a carrier moiety and a 25 leaving group, the peracid formed on perhydrolysis being derived from the carrier moiety. In many cases, the activators are prepared by reacting a compound that will form a suitable carrier moiety, commonly an acid chloride or anhydride, with a compound that will form a suitable leaving group, commonly but not exclusively a phenolsulphonate. The use of acid chlorides is 30 generally preferred because of their lower cost compared with anhydrides.
Several different processes for the production of activators have been described in the prior art. The reaction can be carried out in an organic solvent, such as those described in European Patent Application No. 0 120 591 and European Patent No. 0 220 826. An alternative process employing a 35 substantially aqueous route is described in European Patent No. 0 294 073. In International Patent Application W092/15556 a process is described for the production of benzoyloxybenzene sulphonates by the reaction between a phenolsulphonate and benzoyl chloride in the presence of a solvent comprising .. .... . .. . . . .. .
WOgS/159~2 2S~,77i~g3 PCT/GB9.~102688~
water and one or more organic solvents chosen from ethanol, isopropanol, dioxane and tetrahydrofuran. The benzoyl chloride is employed without any prior dissolution in a solvent. The aqueous process of European Patent 0 294 073 and the process of W092115556 are particularly suited to the case where 5 the acid chloride is either a liquid or has a relatively high solubility in water.
However, these processes are less suitable when the acid chloride is a solid and/or is poorly soluble in water, as is particularly the case when the peracid it is desired to produce by perhydrolysis is a relatively hydrophobic peracid, Hydrophokic peracids are particularly those meeting the criterion for the log 10 partition coefficient between water and n-octanol at 21 C outlined in European Patent Application No 0120 591. Particularly desirable hydrophobic peracids include pernonanoic acid and percarboxy trimellitimides.
The processes described above notwithstanding, it remains desirable to identify additional or alternative processes for the preparation of activators. It 15 is particularly desirable to identify a process for the preparation of activators from acid chlorides that 0ives improved performance with solid and/or poorly water soluble acid chlorides compared with the aqueous proc~sses of the prior art.
During the course of the studies leading to the present invention, it was 20 surprisingly found that an improved proces3 for the production of activators from solid or poorly water soluble acid chlorides could result if the acid chloride was dissolved in a ketone solvent prior to reaction with the carrier molecule.
It is an object of the present invention to provide an additional or 25 alternative process for the manufacture of peracid activators.
It is a second object of certain aspects of the present invention to provide a process for the preparation of activators from acid chlorides that gives improved yields with solid and/or poorly water soluble acid chlorides compared with the aqueous processes of the prior art.
According to the present invention, there is provided a process for the manufacture of a peracid activator by reacting an acid halide or anhydride with an aqueous dispersion of an aryl hydroxy sulphonate in the presence of an aikali in a reaction vessel, characterised in that the acid halide or anhydride is dissolved in a water-miscible hydroxyl-free solvent prior to introduction into the 35 reaction vessel.
The process of the present invention allows the advantages of add!tion in liquid form of solid acid halides or anhydrides to the reaction WO 95/159~2 ~ ~ 7 ~ ~ 9 3 PCT/GB9~/02688 vessel and can offer the additional advantage for such acid halides or anhydrides of imp~oved yields compared with addition in solid form.
The solvent employed to dissolve the acid halide or anhydride prior to introduction into the reaction vessel in the process according to the present 5 invention is a water-miscible hydroxyl-free solvent. Examples of such solvents include water miscible ketones, sulphoxides, amides, nitriles and cyclic ethers, preferably ketones. It will be recognised that mixtures of the solvents can be employed, depending for example, on the solubility of the acid halide or anhydride, but usually a single compound is employed as 10 solvent. Preferably, the solvent(s) employed is/are substantially free of water .
i<etones that can be employed as solvent in the process according to the present invention include acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone and N-methylpyrrolidinone. Preferably, the ketone is 1 5 acetone.
Sulphoxides that can be employed as solvent in the process according to the present invention include dimethylsulphoxide and sulpholane.
Amides that can be employed as solvent in the process according to 20 the present invention include dimethylformamide and dimethylacetarnide.
Nitriles that can be employed as solvent in the process according to the present invention include acetonitrile.
Cyclic ethers that can be employed as solvent in the process according to the present invention include tetrahydrofuran and dioxane.
Acid halides or anhydrides, preferably acid chlorides, that can be employed in the process according to the present invention can be either solid or liquid, and can be either relatively soluble in water or relatively poorly soluble. In certain preferred embodiments of the present invention, particularly advantageous results have been achieved employing solid acid 30 chlorides that are poorly water soluble. Examples of acid chlorides that can be employed include nonanoyl chloride, adipoyl chloride, nonanedioic acid chloride, dodecanedioic acid chloride, ethylene di-imidotrimellitic acid chloride, benzoyl chloride, 4,4'-sulphonyl bis-benzoyl chloride, sulphonimido benzoyl chloride, N-alkyl sulphonimidobenzoyl chlorides, including N-propyl 35 sulphonimidobenzoyl chlorides, iso- and sec- N-butyl sulphonimidobenzoyl chlorides, N-pentyl sulphonimidobenzoyl chlorides and N-heptyl sulphonimidobenzoyl chlorides, alkyimidotrimellitic acid chloride, aikylimidotrimellitic acid chlorides including isoamylimidotrimellitic acid 5/ 5 ~2 . PCT/GB9~/02688 WO9 19 ~1'776g3 4 chloride, N-propylimidotrimellitic acid chloride, iso- and sec- N-butylimidotrimellitic acid~chloride, N-pentylimidotrimellitic acid chloride and N-heptylimidotrimellitic acid chloride, and phthalimido alkanoyl chlorides, including particularly phthalimido caproyl chloride. Anhydrides that can be 5 employed include the anhydride equivalents of the acid chlorides listed hereinabove, but it will be recognised that in many cases, the choice of an anhydride will be less favoured on account of their generally higher cost.
Aryl hydroxy sulphonates that can be employed in the process according to the present invention can be either substituted or 10 unsubstituted on the aryl group. Where the aryl group is substituted, the substituent(s) can be at any position on the aryl group. Examples of substituents that can be present include short chain alkyl groups such as methyl or ethyl groups. In many embodiments, the aryl hydroxy sulphonate is not substituted. It will be recognised that the sulphonate group can be 15 either ortho-, meta- ot para- to the hydroxy group of the hydroxy sulphonate. Preferably, the sulphonate group is para- to the hydroxy group.
In most embodiments, the aryl group is selected from benzyl groups and naphthyl groups, and is preferably a benzyl group. ~he sulphonate can be introduced in the form of a free acid which is subsequently neutralised by 20 the alkali in the reaction vessel, or as an alkali metal or ammonium salt, and is preferably a sodium salt. The most preferred aryl hydroxy sulphonate is sodium p-phenolsulphonate.
The acid chloride or anhydride can be dissolved in the solvent shortly or immediately before introduction into the reaction vessel. However, it will 25 be reco~qnised that it is possible if desired for the dissolution to take place a significant time prior to introduction, for example several hours or more.
The dissolution can be effected by stirring the acid chloride or anhydride and the ketone in a suitable vessel. Depending on the natures of the acid chloride or anhydride and the solvent, the dissoiution can take place at 30 ambient temperature, such as from about 15 to about 30C, or can take place at elevated temperature such as up to about 50C to increase the rate of dissolution.
The concentration of acid halide or anhydride in the solution produced by dissolution in the solvent prior to introduction into the reaction 35 vessel can vary over a wide range up to the maximum solubility in the particular solvent and is chosen at the discretion of the user considering factors such as the desired space yield of the process, the solubility of the acid halide or anhydrioe and the nature of the solvent. In many . _ . . .
og~ 9~2 ?1 7 76 ~ 3 PcrlGBs~l02688 embodiments of the present invention, the concentration is in the range of from about 20% to about 75'3~0 w/w, particularly from about 25% to about 50% w/w.
The aqueous dispe~sion of aryl hydroxysulphonate can be produced 5 by stirring a mixture of water and the aryl hydroxysulphonate. The weight ratio of water to aryl hydroxysulphonate in the dispersion can vary over a 3 wide range, but in many embodiments is in the range of from about 0.5: 1 to about 1 5: 1 , and is preferably from about 1: 1 to about 5: 1 . The aqueous dispersion also comprises an alkali, commonly an alkali metal 10 hydroxide. Preferably, when an alkali metal hydroxide is present, the alkali metal corresponds to that of the aryl hydroxysulphonate. In many embodiments, the alkali metal hydroxide is sodium hydroxide. The mole ratio of alkali in excess of that required to neutralise any free sulphonic acid: aryl hydroxysulphonate is often from about 0.9: 1 to about 2: 1, 15 preferably from about 1: 1 to about 1.5: 1.
In the process according to the present invention, the mole ratio of acid halide or anhydride to aryl hydroxysulphonate is often at least about 0.75: 1, and is unlikely to be greater than about 2: 1. In many embodiments, the mole ratio is selected in the range of from about 0.8: 1 20 to about 1.4: 1.
It will be recognised that the weight ratio of solvent employed to dissolve the acid halide or anhydride to water in the aqueous dispersion of aryl hydroxysulphonate can very widely depending for example on the nature of the reagents. In many embodiments, the weight ratio of solvent 25 to water is chosen to be from about 5: 1 to about 1: 5, preferably from about 3: 1 to about 1: 3. In certain preferred embodiments, the weight ratio of solvent to water is chosen to be such that the activator produced is substantially insoluble in the reaction mixture, thereby causing it to precipitate. This can reduce or eliminate the need for extractive or 30 evaporative techniques to obtain the product on completion of the reaction period .
The temperature at which the reaction is carried out is commonly ambient temperature or less~ often from about 0C to about 25C and preferably from about 2C to about 10C. When a sub-ambient reaction 35 temperature is employed, a coolant at the appropriate temperature is usually employed. Examples of suitable coolants include water and glycol.
The introduction of the solution of acid halide or anhydride into the reaction vessel containing the aqueous dispersion of the aryl , . .... . , .. , .. , .. . , .. ,, _ _ _ _ ..
WOgS/159~2 ~1 77~3 PcTlGss~lo2688 hydroxysulphonate can be achieved in a number of ways. The introduction can be achieved in a single dose, but it will be recognised that on account of the exothermic nature of the reaction between the acid halide or anhydride with the aryl hydroxysulphonate, this can produce a slgnificant 5 rise in temperature and should therefore be avorded except in the case of very small scale preparations or those where extremely effective cooling is available to control the temperature rise. In many embodiments, the introductiQn takes place over an extended period, for example from about 30 minutes to several hours, particularly from about 45 minutes to 2 hours.
10 The introduction can take place continuously throughout this period or may take place in the form of a number of discrete additions throughout the introduction period. The rate of addition is usually controlled to maintain the reaction temperature at or around the desired reaction temperature, particularly in the case of reactions at sub-ambient temperatures, where the 15 exothermic nature of the reaction is balanced with the cooling employed.
On completion of the introduction of the solution of the acid halide or anhydride, the reaction is commonly maintained at the reaction temperature with stirring for a reaction period which may vary from about 30 minutes to several hours, for example 5 hours, depending on the reagents and 20 conditions employed. In many embodiments, the reaction period is from about 1 hour to about 3 hours.
The activators produced by the process accoroing to the present invention can be separated from the reaction mixture on completion of the desired reaction period by conventional means well known to those skilled 25 in the art. In many embodiments the activators are solids and therefore can relatively simply be separated from the reaction medium, for example by filtration. If desired, the activator so obtained can be washed to remove any contaminants, for example any unreacted reagents. Washing can be effected with water, preferably cooled to reduce the extent of dissolution of 30 the activator, or with a suitable volatile organic solvent. Preferably, the activator is washed with a solvent of the type used to dissolve the acid halide or anhydride.
The process can be operated as a batch process, but it will also be recognised that the process ca~ be operated continuously, for example 35 employing feeds of reagents to a reactor from which product a product stream is removed, the relative flow rates and reactor dimensions being arranged to give the desired reactionlresidence time.
~ Wo 9~159J2 ~ 1 7 7 ~ ~ 3 " ~ oo Solvent recovered in the product separation stage can be recycled, and re-employed to dissolve further acid halide or anhydride, or may be disposed of in a suitable manner.
According to a preferred aspect of the present invention, there is 5 provided a process for the manufacture of a bleach activator by reacting an acid halide or anhydride with an aqueous dispersion of sodium -' phenolsulphonate in a reaction vessel, characterised in that the acid halide or anhydride is dissolved in acetone prior to introduction into the reaction vessel, the aqueous dispersion additionally contains sodium hydroxide in a mole ratio 10 to sodium phenolsulphonate of from 1: 1 to 1.5: 1, the weight ratio of acetone to water is from 3: 1 to 1: 3 and the mole ratio of acid halide or anhydride to sodium phenolsulphonate is 0.3: 1 to 1.4: 1.
Having described the invention in general terms, specific embodiments thereof are described in greater detail by way of example 1 5 only.
ExamDle 1 3.59 sodium hydroxide and 13.59 sodium phenolsulphonate dihydrate were added to 309 demineralised water in a 250ml 3 necked flask and cooled to 20 5C with an ice bath. 12.59 nonanoyl chloride was dissolved in 15g acetone and also cooled to 5C with an ice bath. The solution of nonanoyl chloride in acetone was added with stirring to the 3-necked flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C throughout the addition by control of the addition rate. The reaction 25 was maintained at 5C for a further 2 hours after completion of the addition.The reaction mixture was filtered at 5C, and the product washed with water and then with 50mls acetone.
Analysis of the product showed it to be sodium 30 nonanoyloxyben~enesulphonate in a yield of 76% based on the weight of acid chloride employed, and having a purity of 79.7%.
ExamDle 2 - -7.449 sodium hydroxide and 24.49 sodium phenolsulphonate dehydrate were 35 added to 53.59 demineralised water in a 500ml 3 necked flask and cooled to 5C with an ice bath. 329 N-isoamylimidotrimellitic acid chloride was dissolved in 75ml acetone at 40 and allowed to cool to ambient temperature.
The solution of acid chloride in acetone was added with stirring to the 3-... . .. , _ , WO 951159-12 . PCT/GB9~102688 ~
217~93 8 necked flask dropwise via a dropping funnel over an addition period of 1 hour.
The temperature was maintained at < 1 0C throughout the addition by control of the addition rate. The reaction was maintained at ca. 5C for a further 1 hour after completion of the addition. The reaction mixture was filtered a 5 5C, and the product washed with water and then acetone.
Analysis of the product showed it to be sodium N-isoamylimidotrimellitoyloxybenzenesulphonate, having the chemical structure ~ N-(CH2)2CH~cH3)2 NaS03-Ph-OC C
O O
in a yield of 90.1% based on the weight of acid chloride employed, and having a purity of 100%.
F~amr~le 3 20 11.59 sodium hydroxide and 47.89 sodium phenolsulphonate dehydrate were added to 107.59 demineralised water in a 11 3 necked flask and cooled to 5C
with an ice bath. 609 N-isoamylimidotrimellitic acid chloride was dissolved in 150ml acetone at 40 and allowed tQ cool to ambient temperature. The solution of acid chloride in acetone was added with stirring to the 3-necked 25 flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C throughout the addition by control of the addition rate. A further 309 water was added to facilitate stirring and the reaction maintained at 5C for a further 1.5 hours after completion of the addition. The reaction mixture was filtered at 5C, and the product washed 30 with water and then with acetone.
Analysis of the product showed it to be sodium N-isoamylimidotrimellitoyloxybenzenesu~phonate in a yield of 86.7% based on the weight of acid chloride employed, and having a purity of 100C/o.
Exam~le 4 5.29 sodium hydroxide and 18.39 sodium phenolsulphonate dehydrate were added to 879 demineralised watet in a 11 3 necked flask and cooled to 5C
, . . . . , , . . .. . , . .. . . , . . . , _ . .. .. .. . . .... . . . . .
~ WO gS1159 ~2 ~ 1 ~ 7 ~ g 3 PCTIGB9.1102688 ., ~.
with an ice bath. 229 N-isoamylimidotrimellitic acid chloride was dissolved in 1 50ml tetrahydrofuran (THF~ at room temperature. The solution of acid chloride in THF was added with stirring to the 3-necked flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was 5 maintained at ca. 5C throughout the addition by control of the addition rate.The reactiorl temperature was allowed to reach room temperature over 1 hour after completion of the addition. The reaction mixture was filtered at room temperature, and the product washed with water and then 30mls THF, 10 Analysis of the product showed it to be sodium N-isoamylimidotrimellitoyloxybenzenesulphonate in a yield of 67.1% based on the weight of acid chloride employed, and having a purity of >90%.
ExamDle 5 .. . .
15 2.19 sodium hydroxide and 7.279 sodium phenolsulphonate dehydrate were added to 109 demineralised water in a 250ml 3 necked flask and cooled to 5C with an ice bath. 119 ethylene di-imidotrimellitic acid chloride was warmed in 200ml dimethylformamide ~DMF) until the acid chloride had dissolved. The solution of acid chloride in DMF was added with stirring to the 20 3-necked flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C throughout the addition by control of the addition rate. The reaction temperature was maintained at ca.
5C for a further 2 hours after completion of the addition and then allowed to reach room temperature over 1 hour. The reaction mixture was filtered at 25 room temperature and the product washed with water and then 30mls acetone.
Analysis of the product showed it to be disodium ethylene di-imidotrimellitoyloxybenzenesulphonate having the chemical structure O O
~I ti J~ N- ( CH2 1 2-N~
NaSO -Ph-OC C C C-O-Ph-SO3Na 3 l~
O O O O
in a yield of 71% based on the weight of acid chloride emp~oyed, and having a purity of ca. 100% by NMR.
...... . . .. .. . . . .. .. ....
2 PCT/GB9~102688 2177693 lo Comr~arison 6 = =
1.69 sodium hydroxide, 8.49 sodium phenolsulphonate dehydrate were added to 59 ethanol and 13.39 demineralised water in a 100ml 3 necked flask and 5 cooled to 5C with an ice bath. 109 solid N-isoamylimidotrimellitic acid chloride was added with stirring to the 3-necked flask dropwise via a solids funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C throughout the addition by control of the addition rate. The reaction was maintained at 5C for a further 1 hours after completion of the addition, 10 and allowed to reach room temperature. The reaction mixture was filtered at room temperature, and the product washed with 30mls demineraiised water followed by 30mls acetone. ::
Analysis of the product showed it to be sodium N-15 isoamylimidotrimellitoyloxybenzenesulphonate in a yield of 83.5% based on the weight of acid chloride employed, and having a purity of 90.1~0.
Comr arison 7 ~ =
5.29 sodium hydroxide and 18.39 sodium phenolsulphonate dehydrate were 20 added to 879 demineralised water in a 113 necked flask and cooled to 5C
with an ice bath. 229 N-isoamylimidotrimellitic acid chloride was dissolved in 150ml ethanol at room temperature. The solution of acid chloride in ethanol was added with stirring to the 3-necked flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C
25 throughout the addition by control of the addition rate. The reaction temperature was ailowed to reach room temperature over 1 hour after completion of the addition. The reaction mixture was filtered at room temperature, and the product washed with water and then with 30mls ethanol.
30 Analysis of the product showed that no sodium N-isoamylimidotrimellitoyloxybenzenesulphonate had been produced.
The results of Examples 1 - 5 (according to the present inventionl show ~hat the process of the present invention can be employed to produce activators.
35 The results of Examples 1 - 3 show that acetone can be employed as solvent for the acid chloride, the result of Example 4 shows that THF can be employed and the result of Example 5 that DMF can be employed, particularly for acid chlorides that have only limited solubility in acetone. A comparison of the ..... . . . ., .. .. .. ... . .. . . ... . .. . .. _ . .. . .. . .. .
11 ~177i~3 results of Example 2 with the results of Comparison 6 (following the general teaching of International Application no. W092/15556) shows that the process of the present invention significantly increased the yield of activator with product purity at least as good as that from comparison 3. The results from 5 Comparison 7 show that the use of a hydroxyl-containing solvent, ethanol. to predissolve the acid chloride gave no yield of activator.
1.69 sodium hydroxide, 8.49 sodium phenolsulphonate dehydrate were added to 59 ethanol and 13.39 demineralised water in a 100ml 3 necked flask and 5 cooled to 5C with an ice bath. 109 solid N-isoamylimidotrimellitic acid chloride was added with stirring to the 3-necked flask dropwise via a solids funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C throughout the addition by control of the addition rate. The reaction was maintained at 5C for a further 1 hours after completion of the addition, 10 and allowed to reach room temperature. The reaction mixture was filtered at room temperature, and the product washed with 30mls demineraiised water followed by 30mls acetone. ::
Analysis of the product showed it to be sodium N-15 isoamylimidotrimellitoyloxybenzenesulphonate in a yield of 83.5% based on the weight of acid chloride employed, and having a purity of 90.1~0.
Comr arison 7 ~ =
5.29 sodium hydroxide and 18.39 sodium phenolsulphonate dehydrate were 20 added to 879 demineralised water in a 113 necked flask and cooled to 5C
with an ice bath. 229 N-isoamylimidotrimellitic acid chloride was dissolved in 150ml ethanol at room temperature. The solution of acid chloride in ethanol was added with stirring to the 3-necked flask dropwise via a dropping funnel over an addition period of 1 hour. The temperature was maintained at ca. 5C
25 throughout the addition by control of the addition rate. The reaction temperature was ailowed to reach room temperature over 1 hour after completion of the addition. The reaction mixture was filtered at room temperature, and the product washed with water and then with 30mls ethanol.
30 Analysis of the product showed that no sodium N-isoamylimidotrimellitoyloxybenzenesulphonate had been produced.
The results of Examples 1 - 5 (according to the present inventionl show ~hat the process of the present invention can be employed to produce activators.
35 The results of Examples 1 - 3 show that acetone can be employed as solvent for the acid chloride, the result of Example 4 shows that THF can be employed and the result of Example 5 that DMF can be employed, particularly for acid chlorides that have only limited solubility in acetone. A comparison of the ..... . . . ., .. .. .. ... . .. . . ... . .. . .. _ . .. . .. . .. .
11 ~177i~3 results of Example 2 with the results of Comparison 6 (following the general teaching of International Application no. W092/15556) shows that the process of the present invention significantly increased the yield of activator with product purity at least as good as that from comparison 3. The results from 5 Comparison 7 show that the use of a hydroxyl-containing solvent, ethanol. to predissolve the acid chloride gave no yield of activator.
Claims (17)
1. A process for the manufacture of a peracid activator by reacting an acid halide or anhydride with an aqueous dispersion of an aryl hydroxysulphonate in the presence of an alkali in a reaction vessel, characterised in that the acid halide or anhydride is dissolved in a water-miscible hydroxyl-free solvent prior to introduction into the reaction vessel.
2. A process according to claim 1, characterised in that the solvent for the acid halide or anhydride is acetone.
3. A process according to either preceding claim, characterised in that the acid halide is an acid chloride.
4. A process according to any preceding claim, characterised in that the mole ratio of acid halide or anhydride to aryl hydroxysulphonate is from 0.75 : 1 to 2 : 1.
5. A process according to claim 4, characterised in that the mole ratio of acid halide or anhydride to aryl hydroxysulphonate is from 0.8: 1 to 1.4: 1.
6. A process according to any preceding claim, characterised in that the weight ratio of solvent to water is from 5 : 1 to 1 : 5
7. A process according to claim 6, characterised in that the weight ratio of solvent to water is from 3: 1 to 1: 3.
8. A process according to any preceding claim, characterised in that the weight ratio of water to aryl hydroxysulphonate in the dispersion is in the range of from 0.5 : 1 to 15 : 1.
9. A process according to any preceding claim, characterised in that the weight ratio of water to aryl hydroxysulphonate in the dispersion is from about 1 : 1 to 5 : 1.
10. A process according to any preceding claim, characterised in that the mole ratio of alkali in excess of that required to neutralise any free sulphonic acid: aryl hydroxysulphonate is from 0.9: 1 to 2: 1.
11. A process according to claim 10, characterised in that the mole ratio of alkali to aryl hydroxysulphonate is from 1: 1 to 1.5: 1.
12 A process according to any preceding claim, characterised in that the alkali is sodium hydroxide.
13. A process according to any preceding claim, characterised in that the aryl hydroxysulphonate is sodium phenolsulphonate.
14. A process according to any preceding claim, characterised in that the acid halide or anhydride is nonanoyl chloride or isoamylimidotrimellitic acid chloride.
15. A process for the manufacture of a bleach activator by reacting an acid chloride or anhydride with an aqueous dispersion of sodium phenolsulphonate in a reaction vessel, characterised in that the acid chloride or anhydride is dissolved in acetone prior to introduction into the reaction vessel, the aqueous dispersion additionally contains sodium hydroxide in a mole ratio to sodium phenolsulphonate of from 1: 1 to 1.5: 1, the weight ratio of acetone to water is from 3: 1 to 1: 3 and the mole ratio of acid chloride or anhydride to sodium phenolsulphonate is 0.8: 1 to 1.4: 1.
16. A process for the manufacture of bleach activators substantially as described herein with reference to the Examples.
17. A process for the manufacture of bleach activators substantially as described herein with reference to any novel feature or combination of features .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9325303.7 | 1993-12-10 | ||
| GB939325303A GB9325303D0 (en) | 1993-12-10 | 1993-12-10 | Bleach activator preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2177693A1 true CA2177693A1 (en) | 1995-06-15 |
Family
ID=10746402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2177693 Abandoned CA2177693A1 (en) | 1993-12-10 | 1994-12-09 | Bleach activator preparation |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0733038A1 (en) |
| JP (1) | JPH09506396A (en) |
| CA (1) | CA2177693A1 (en) |
| GB (1) | GB9325303D0 (en) |
| WO (1) | WO1995015942A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9509287D0 (en) * | 1995-05-06 | 1995-06-28 | Solvay Interox Ltd | Detergent builder/activators |
| KR20040006083A (en) * | 2002-07-09 | 2004-01-24 | 주식회사 엘지생활건강 | Phthalimidocarboxylic Acid Composition for Activation of Bleaching and Bleaching Composition comprising the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8712909D0 (en) * | 1987-06-02 | 1987-07-08 | Interox Chemicals Ltd | Preparation of esters |
| DE4106843A1 (en) * | 1991-03-04 | 1992-09-10 | Henkel Kgaa | METHOD FOR PRODUCING BENZOYLOXYBENZENE SULFONATES |
-
1993
- 1993-12-10 GB GB939325303A patent/GB9325303D0/en active Pending
-
1994
- 1994-12-09 EP EP95903408A patent/EP0733038A1/en not_active Withdrawn
- 1994-12-09 JP JP7516047A patent/JPH09506396A/en active Pending
- 1994-12-09 WO PCT/GB1994/002688 patent/WO1995015942A1/en not_active Application Discontinuation
- 1994-12-09 CA CA 2177693 patent/CA2177693A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| GB9325303D0 (en) | 1994-02-16 |
| WO1995015942A1 (en) | 1995-06-15 |
| EP0733038A1 (en) | 1996-09-25 |
| JPH09506396A (en) | 1997-06-24 |
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