CA2269082A1 - Process for preparation of unsymmetrical acyclic imide bleach activators - Google Patents
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- C07—ORGANIC CHEMISTRY
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- C07C233/00—Carboxylic acid amides
- C07C233/90—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated
- C07C233/91—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated with carbon atoms of the carboxamide groups bound to acyclic carbon atoms
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Abstract
A process for preparation of unsymmetrical acyclic imide bleach activators is provided. The compounds prepared by this process have formula (I) wherein R1 is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a C1-C8 linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group.
The process comprises the steps of reacting an amide having formula (II) with a reactive acyl compound to form said imide; wherein Y is selected from the group consisting of R1 and R3, and wherein said reactive acyl compound contains said R3 group when Y is R1 and contains said R1 group when Y is R3, wherein said reactive acyl group is preferably selected from the group of compounds consisting of carboxylic acid halides, carboxylic acid esters, and carboxylic acid anhydrides; and separating said imide from the reaction mixture.
The process comprises the steps of reacting an amide having formula (II) with a reactive acyl compound to form said imide; wherein Y is selected from the group consisting of R1 and R3, and wherein said reactive acyl compound contains said R3 group when Y is R1 and contains said R1 group when Y is R3, wherein said reactive acyl group is preferably selected from the group of compounds consisting of carboxylic acid halides, carboxylic acid esters, and carboxylic acid anhydrides; and separating said imide from the reaction mixture.
Description
PROCESS FOR PREPARATION OF
UNSYMMETRICAL ACYCLIC IMIDE BLEACH ACTIVATORS
TECHNICAL FIELD
This case relates to the preparation of unsymmetrical acyclic imide bleach activators. In particular, this case relates to the preparation of unsymmetrical acyclic bleach activators employed in bleach additives and bleaching compositions in both liquid and granular form. The activators prepared herein are particularly useful in laundry, automatic dishwashing and hard surface cleaning compositions.
BACKGROUND OF THE INVENTION
Oxygen bleaching agents, such as hydrogen peroxide, have become increasingly popular in recent years in household and personal care products to facilitate stain and soil removal. Bleaches are particularly desirable for their stain-removing, dingy fabric cleanup, whitening and sanitization properties. Oxygen bleaching agents have found particular acceptance in laundry products such as detergents, in automatic dishwashing products and in hard surface cleaners. Oxygen bleaching agents, however, are somewhat limited in their effectiveness. Some frequently encountered disadvantages include color damage on fabrics and surfaces. In addition, oxygen bleaching agents tend to be extremely temperature rate dependent. Thus, the colder the solution in which they are employed, the less effective the bleaching action. Temperatures in excess of 60oC are typically required for effectiveness of an oxygen bleaching agent in solution.
To solve the aforementioned temperature rate dependency, a class of compounds known as "bleach activators" has been developed. Bleach activators, typically perhydrolyzable acyl compounds having a leaving group such as oxybenzenesulfonate, react with the active oxygen group, typically hydrogen peroxide or its anion, to form a more effective peroxyacid oxidant. It is the peroxyacid compound which then oxidizes the stained or soiled substrate material. However, bleach activators are also somewhat temperature dependent. Bleach activators are more effective at warm water temperatures of from about 40oC to about 60oC. In water temperatures of less than about 40oC, the peroxyacid compound loses some its bleaching effectiveness.
Numerous substances have been disclosed in the art as effective bleach activators.
One widely-used bleach activator is tetraacetyl ethylene diamine (TAED). TAED
provides effective hydrophilic cleaning especially on beverage stains, but has limited performance on hydrophobic stains, e.g. dingy, yellow stains such as those resulting from body oils. Another type of activator, such as nonanoyloxybenzenesulfonate (HOBS) and other activators which generally comprise long chain alkyl moieties, is hydrophobic in nature and provides excellent performance on dingy stains.
However, many of the hydrophobic activators developed demonstrate limited performance on hydrophilic stains.
The search, therefore, continues for more effective activator materials, especially for those which provide satisfactory performance on both hydrophilic and hydrophobic soils and stains. Improved activator materials should be safe, effective, and will preferably be designed to interact with troublesome soils and stains. Various activators have been described in the literature. Many are esoteric and expensive.
It has now been determined that certain selected bleach activators are unexpectedly effective in removing both hydrophilic and hydrophobic soils and stains from fabrics, hard surfaces and dishes.
The present invention discloses a process for the preparation of unsymmetrical acyclic imide bleach activators for use in both solid and liquid additive, bleaching and detergent compositions. The unsymmetrical imide bleach activators of the present invention display the unique ability to form both hydrophilic and hydrophobic bleaching agents in aqueous liquors such as bleaching solutions. Thus, fabrics, hard surfaces or dishes having hydrophobic stains such as dingy and/or hydrophilic stains such as beverages can be effectively cleaned or bleached using the imide bleach activators of the present invention. T'he imide bleach activators prepared by the present invention provide a unique and superior capability and benefit over the activators of the prior art.
Accordingly, there is need for an efficient, high volume means of producing the above described imide bleach activator in high purity.
BACKGROUND ART
Bleach activators of various types are described in U.S. Patents 3,730,902;
4,179,390; 4,207,199; 4,221,675; 4,772,413; 5,106,528; European Patent 063,017;
European Patent 106,584; European Patent 163,331; Japanese Patent 08/27487 and PCT
Publication W.O. 94/18298. Imide Compounds of various types are disclosed in U.S.
Patents 4,745,103 and 4,851,138. A process for preparing diimides is described in U.S.
UNSYMMETRICAL ACYCLIC IMIDE BLEACH ACTIVATORS
TECHNICAL FIELD
This case relates to the preparation of unsymmetrical acyclic imide bleach activators. In particular, this case relates to the preparation of unsymmetrical acyclic bleach activators employed in bleach additives and bleaching compositions in both liquid and granular form. The activators prepared herein are particularly useful in laundry, automatic dishwashing and hard surface cleaning compositions.
BACKGROUND OF THE INVENTION
Oxygen bleaching agents, such as hydrogen peroxide, have become increasingly popular in recent years in household and personal care products to facilitate stain and soil removal. Bleaches are particularly desirable for their stain-removing, dingy fabric cleanup, whitening and sanitization properties. Oxygen bleaching agents have found particular acceptance in laundry products such as detergents, in automatic dishwashing products and in hard surface cleaners. Oxygen bleaching agents, however, are somewhat limited in their effectiveness. Some frequently encountered disadvantages include color damage on fabrics and surfaces. In addition, oxygen bleaching agents tend to be extremely temperature rate dependent. Thus, the colder the solution in which they are employed, the less effective the bleaching action. Temperatures in excess of 60oC are typically required for effectiveness of an oxygen bleaching agent in solution.
To solve the aforementioned temperature rate dependency, a class of compounds known as "bleach activators" has been developed. Bleach activators, typically perhydrolyzable acyl compounds having a leaving group such as oxybenzenesulfonate, react with the active oxygen group, typically hydrogen peroxide or its anion, to form a more effective peroxyacid oxidant. It is the peroxyacid compound which then oxidizes the stained or soiled substrate material. However, bleach activators are also somewhat temperature dependent. Bleach activators are more effective at warm water temperatures of from about 40oC to about 60oC. In water temperatures of less than about 40oC, the peroxyacid compound loses some its bleaching effectiveness.
Numerous substances have been disclosed in the art as effective bleach activators.
One widely-used bleach activator is tetraacetyl ethylene diamine (TAED). TAED
provides effective hydrophilic cleaning especially on beverage stains, but has limited performance on hydrophobic stains, e.g. dingy, yellow stains such as those resulting from body oils. Another type of activator, such as nonanoyloxybenzenesulfonate (HOBS) and other activators which generally comprise long chain alkyl moieties, is hydrophobic in nature and provides excellent performance on dingy stains.
However, many of the hydrophobic activators developed demonstrate limited performance on hydrophilic stains.
The search, therefore, continues for more effective activator materials, especially for those which provide satisfactory performance on both hydrophilic and hydrophobic soils and stains. Improved activator materials should be safe, effective, and will preferably be designed to interact with troublesome soils and stains. Various activators have been described in the literature. Many are esoteric and expensive.
It has now been determined that certain selected bleach activators are unexpectedly effective in removing both hydrophilic and hydrophobic soils and stains from fabrics, hard surfaces and dishes.
The present invention discloses a process for the preparation of unsymmetrical acyclic imide bleach activators for use in both solid and liquid additive, bleaching and detergent compositions. The unsymmetrical imide bleach activators of the present invention display the unique ability to form both hydrophilic and hydrophobic bleaching agents in aqueous liquors such as bleaching solutions. Thus, fabrics, hard surfaces or dishes having hydrophobic stains such as dingy and/or hydrophilic stains such as beverages can be effectively cleaned or bleached using the imide bleach activators of the present invention. T'he imide bleach activators prepared by the present invention provide a unique and superior capability and benefit over the activators of the prior art.
Accordingly, there is need for an efficient, high volume means of producing the above described imide bleach activator in high purity.
BACKGROUND ART
Bleach activators of various types are described in U.S. Patents 3,730,902;
4,179,390; 4,207,199; 4,221,675; 4,772,413; 5,106,528; European Patent 063,017;
European Patent 106,584; European Patent 163,331; Japanese Patent 08/27487 and PCT
Publication W.O. 94/18298. Imide Compounds of various types are disclosed in U.S.
Patents 4,745,103 and 4,851,138. A process for preparing diimides is described in U.S.
3,899,509..
SUMMARY OF THE INVENTION
The bleach activator of the present invention is an unsymmetrical acyclic imide having the formula:
(I) O O
R~N~ 3 R
wherein R1 is a C~-C13 linear or branched chain saturated or unsaturated alkyl group, preferably a C~-C 11 linear or branched saturated alkyl group, R2 is a C 1-Cg~
linear or branched chain saturated or unsaturated alkyl group, preferably a CI-C4 linear saturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group. More preferably, R1 is a C~-C11 saturated alkyl group and most preferably, R1 is a linear Cg or Cg saturated alkyl group and R2 and R3 are CH3. In preferred situations, the sum of the number of carbon atoms in R1, R2 and R3 is less than 19, more preferably Iess than 15.
It has been discovered that unsymlnetrical acyclic imide having the formula:
(I) O O
R~N~R3 wherein R1 ~ R2 and R3 are as described hereinbefore can be prepared by a process which comprises the steps of:
(a) reacting an amide having the formula:
(II) O
YJ\N/ H
with a reactive acyl compound to form said imide; wherein Y is selected from the group consisting of R1 and R3, and wherein said reactive acyl compound contains said R3 group when Y is R 1 and contains said R 1 group when Y is R3, wherein said reactive acyl group is preferably selected from the group of compounds consisting of carboxylic acid halides, carboxylic acid esters, and' carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acid chlorides, carboxylic acid methyl esters, and carboxylic acid anhydrides; most preferably Y is R1 and said reactive acyl compound is carboxylic acid anhydride; and (b) separating said imide from the reaction mixture.
The scope of the present invention further encompasses a process which includes a step wherein the amide having the formula (II) above is prepared by the reaction of an acyl compound containing said Rl or R3 group, preferably R1 , with an amine compound containing said R2 group; wherein said acyl compound is preferably selected from the group consisting of amides, carboxylic acids, carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acids, carboxylic acid chlorides and carboxylic acid methyl esters, most preferably selected from carboxylic acids.
Accordingly it is an object of the present invention to provide a process to prepare unsymmetrical acyclic imide bleach activator which can provide both hydrophobic and hydrophilic bleaching agents. These, and other, objects, features and advantages will be clear from the following detailed description and the appended claims.
All percentages, ratios and proportions herein are on a weight basis unless otherwise indicated. All documents cited herein are hereby incorporated by reference.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The unsymmetrical acyclic imide bleach activators prepared by the present invention provide superior bleaching ability and performance over the bleach activators of the prior art. While not wishing to be bound by theory, it i$ believed that the unsymmetrical acyclic imide bleach activators prepared by the present invention provide both hydrophobic and hydrophilic bleaching agents in aqueous solutions. This is believed to be due to the fact that perhydrolysis can occur at either of the carbonyl groups in the activator. Thus, any molecule of the activators of formula (I) would undergo perhydrolysis in an aqueous solution to form either a bleaching agent (R1C(O)bOH) having hydrophobic properties and a bleaching agent (R3C(O)OOH) having hydrophilic properties when Rl and R3 are defined as above. The bleaching agent may of course be protonated or deprotonated depending upon the in-use pH. A
bleaching solution will then include both the hydrophilic bleaching agent and the hydrophobic bleaching agent. Thus, the bleaching capabilities of a mixed activator system (hydrophobic and hydrophilic) and even increased performance can be achieved through the use of a single bleach activator. Elimination of mixed activator systems may provide enormous potential benefits by eliminating the significant expense of an additional bleach activator.
Furthermore, while not wishing to be bound by theory, it is believed that the bleach activators of formula (I) prepared by the present invention are either liquids or wax-like, non-crystalline solids with melting points at or moderately above room temperature. Thus, they are easily handled and processed into liquid formulations. In addition, the activators prepared by the present invention may be easily formulated into stable liquid compositions.
The present invention relates to preparation of unsymmetrical acyclic bleach activators. The unsymmetrical acyclic imide activators of the present invention have the formula:
(I) R~N
R
wherein R 1 is a C~-C 13 linear or branched chain saturated or unsaturated alkyl group, R2 is a CI-Cg~ linear or branched chain saturated or unsaturated alkyl group and R3 is a C 1-C4 linear or branched chain saturated or unsaturated alkyl group.
Preferred activators are those in which the Rl is a C~-C11 linear or branched saturated alkyl group, more preferably, R1 is a C~-C 11 saturated alkyl group, R2 is a C 1-C4 linear or branched saturated alkyl group and R3 is a C 1-C4 linear or branched chain saturated or unsaturated alkyl group. More preferably, R2 and R3 are C 1-C4 linear saturated alkyl groups and even more preferably are the same.
. Further preferred activators prepared according to the present invention are .the N-alkanoyl-N-methyl acetamides. The activators have the formula (I) wherein both R2 and R3 are methyl groups. Thus, N-aikanoyl-N-methyl acetamides have the formula:
(III) O O
R~~N~Me Me where RI is C~-Cl 1 linear saturated alkyl group. Particularly preferred are N-octanoyl-N-methyl acetamide (when RI is C~), N-nonanoyl-N-methyl acetamide (when Rl is Cg), N-decanoyl-N-methyl acetamide (when RI is Cg) and N-dodecanoyl-N-methyl acetamide (when R 1 is C I l ).
While not wishing to be bound by theory, it is believed that as the number of carbons in the activators of formula (I) increases, the solubility of the compound decreases. Thus, as the activators prepared by the present invention are ideally soluble for optimum performance of the activators, it is preferred that the number of carbon atoms in the activator compound be such that the activator compound displays satisfactory solubility profiles. In the present invention, the sum of the carbons in Rl, R2 and R3 is preferably less than 19 and more preferably less than 15.
It has been discovered that unsymmetrical acycIic imide having the formula:
(I) O O
R~N~ R3 l wherein R1 ~ R2 and R3 are as described hereinbefore can be prepared by a process which comprises the steps of {a) reacting an amide having the formulae:
(II) O
YJ\N/H
with a reactive acyl compound to form said imide; wherein Y is selected from the group consisting of R1 and R3, and wherein said reactive acyl compound contains said R3 group when Y is R1 and contains said RI group when Y is R3, wherein said reactive acyl group is preferably selected from the group of compounds consisting of carboxylic acid halides, carboxylic acid esters, and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acid chlorides, carboxylic acid methyl esters, and carboxylic acid anhydrides; most preferably Y is R1 and said reactive acyl compound is carboxylic acid anhydride; and (b) separating said imide from the reaction mixture.
The scope of the present invention further encompasses a process which includes a step wherein the amide having the formula (II) above is prepared by the reaction of an acyl compound containing said R1 or R3 group, preferably said Rl group, with an amine compound containing said R2 group; wherein said acyl compound is preferably selected from the group consisting of amides, carboxylic acids, carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acids, carboxylic acid chlorides and carboxylic acid methyl esters, most preferably selected from carboxylic acids.
A key aspect of the present invention is to afford an efficient process for the preparation of the above described unsymmetrical acyclic imide in high purity with low levels of malodorous side-products and color forming bodies.
The comprehensive process for preparation of compounds of formula (I) comprises the following general steps:
i) formation of the amide of formula (II):
O O
H
Y + NH2 R2 --.~ Y N/
L
1~
wherein YCOL is an acyl compound preferably selected from the group consisting of amides, carboxylic acids, carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acids, carboxylic acid chlorides and carboxylic acid methyl esters, most preferably selected from carboxylic acids; wherein Y and are as described hereinbefore;
ii) separatiorY of said amide from the reaction mixture;
iii) formation of the unsymmetrical acyclic imide of formula (I):
O O O O
H ~
R / + R -'' R~N~R3 or O O O O
H '~ ~
R~ / + Rt~ ~ R" 'N' \ R3 N Ll wherein R3COL1 and R1COL1 are reactive acyl compounds, preferably selected' . from the consisting of carboxylic acid halides, carboxylic acid esters, and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acid chlorides, carboxylic acid methyl esters, and carboxylic acid anhydrides, most preferably said reactive acyl compound is carboxylic acid anhydride; and iv) separation of said unsymmetrical acyclic imide from the reaction mixture.
(i) Amide Formation The amide of step (i) is prepared by acylation of a primary amine. Acylation of amines to form amides is well known in the art. The amide of formula (II) can be prepared via numerous routes. Amides, carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides, containing R1 or R3 can all be used to form the amide precursor when reacted with a primary amine containing R2. General acylation chemistry is described in March, Advanced Organic Chemistry, Third Edition, pp. 370-371 (acylation of amines by acyl halides), pp. 371 (acylation of amines by anhydrides), pp.371-371 (acylation of amines by acids), pp. 375-376 (acylation of amines by esters), pp. 376-377 (acylation of amines by amides). The preparation of amides is described in U.S. Patents 2,864,683; 3,870,756; 3,914,302; 4,331,815; and 4,841,086 which are hereby incorporated by reference.
In a preferred embodiment, the amide precursor is prepared via the reaction of an amine with a carboxylic acid under superatmospheric pressure conditions. This embodiment is particularly preferred in cases where the desired product requires the use of an amine which is gaseous at room temperature and pressure. The reaction is generally carried out with a molar excess of the amine, preferably a ratio of amine to carboxylic acid of about 1.25:1 to about 5.0:1, more preferably from about 1.75:1 to about 2.25:1 is used. The excess of amine shifts the equilibrium of the reaction to favor the formation of the amide and acts to lessen the formation of the di-Y-imide impurity.
In a preferred embodiment, the amine containing the desired R2 group is charged to a vessel under superatmospheric pressure and agitated. The carboxylic acid containing the desired Y group is then gradually added via a pump. After addition, the reactor is then heated to reaction temperature, preferably from about 250 °F to about 400 °F, more preferably from about 275°F to about 350°F, and most preferably from about 325°F to about 330°F. The pressure of the reactor is held above atmospheric pressure, preferably from about 200 PSIG to about 400 PSIG, more preferably from about 300 PSIG to about 350 PSIG. The reaction can be monitored and samples analyzed by gas chromatography.
Typically the reaction proceeds to greater than 95% conversion, based on the carboxylic acid consumed, in from about 2 to about 10 hours, preferably from about 4 to about 8 hours.
ail Separation of the Amide The amide formed in step (i) can be separated from the reaction mixture in order to improve the odor, appearance, or purity of the final imide or in order to avoid sidereactions during the imidation reaction in step (iii). The amide may be separated from the reaction mixture by one or more methods including: recrystallization with organic solvent such as diethyl ether; extraction with aqueous washes using organic and inorganic reagents to neutralize free acids and amines or hydrolyze anhydrides and acid chlorides; and distillation of any volatile excess reagent and/or side-product.
One feature of the preferred embodiment which reacts an amine with a carboxylic acid, is that the excess amine used and the water formed during the reaction is very volatile relative to the desired amide and can be removed by distillation prior to the imidation step.
liii) Imide Formation The imide (I) is formed by acylation of the amide formed in step (ii) above.
This acylation is similar to the acylation in step (i) except that the amide of formula (II) is less reactive than the primary amine R2NH2 . The imide can be formed by reaction of the amide of formula (II) with a reactive acyl compound having the R3 or Rl group as described hereinbefore. Preferably this reactive acyl compound is selected from the group of compounds consisting of carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides; more preferably from the group consisting of carboxylic acid chlorides, carboxylic acid methyl esters, and carboxylic acid anhydrides; most preferably from carboxylic acid anhydrides having said R3 group. a In a preferred embodiment, the imide is formed from the reaction of the R I
amide with carboxylic acid anhydride having the R3 group. This reaction is generally carned out with a molar excess of anhydride, preferably a ratio of anhydride to amide of from greater than about 1:1 to about 20:1, more preferably from. about 2:1 to about 10:1, most preferably from about 4:1 to about 6:1. After the amide product of step (ii) has had the excess amine and water removed by distillation, the carboxylic acid anhydride is charged to the vessel. The vessel is then heated to a reaction temperature of from about 120°F to about 375°F, preferably from about 175°F to about 300°F, more preferably from about 250°F to about 275°F. The reaction can be monitored and samples analyzed by gas chromatography. Typically the reaction proceeds to greater than 95%
conversion, based on the amide consumed, in from about 0.5 to about 48 hours, preferably from about 3 to ' about 10 hours, more preferably from about 4 to 6 hours.
!iv) Separation of the Imide The imide formed in step (iii) can be separated from the reaction mixture in order to improve the odor, appearance, or purity of the final imide. In particular, the crude WO 98!16496 PCT/US97J17910 imide reaction mixture can contain levels of free carboxylic acid which present a serious malodor problem when used in consumer products. The crude imide can also contain levels of carboxylic acid anhydrides would be unacceptable in a finished consumer product. The imide may be separated from the reaction mixture by one or more methods including: liquid/liquid organic solvent extraction; extraction with aqueous washes using organic and inorganic reagents to neutralize free acids and amines or hydrolyze anhydrides and acid chlorides; and distillation of any volatile excess reagent, side-product, and or final imide product.
In the preferred embodiment using carboxylic anhydrides to form the imide, the final imide product is preferably isolated by first distilling excess R3 anhydride and low molecular weight (C,~) carboxylic acids, extracting with aqueous washes, and finishing by fractional distillation of the pure imide. It has been discovered that aqueous washes are particularly useful in enabling the separation of the final imide product.
Aqueous washes optionally comprising methanol and inorganic carbonate salts, such as sodium carbonate and/or sodium bicarbonate, have been shown to effectively reduce the level of R1 methyl ester and mixed R1-R3 anhydride impurities. The reduction in the level of these ester and anhydride impurities is critical to reduce the risk of unwanted side-products during the fractional distillation of the final imide product.
In the specification and examples herein, ali percentages, ratios and parts are by weight unless otherwise specified and all numerical limits are normal approximations.
The following examples illustrate the esters and compositions of this invention, but are not intended to be limiting thereof.
EXAMPLE I
a. Preparation of n-Methyl Nonanoyl Amide A 50 L, 3-necked round-bottomed flask equipped with a 2 L pressure equalizing addition funnel, mechanical stirrer, argon inlet, thermometer, and reflux condenser is charged with methylamine (40 wt% in water, 8 L, 93 mol, 2.5 eq) and cooled in an ice/methanol bath to 10 °C. Nonanoyl chloride/diethyl ether (approximately 1:1 volume ratio) is mixed in the addition funnel and added to the aqueous methylamine at a rate slow enough to maintain reaction temperature below 30 °C. The reaction is stirred slowly enough to allow the organic and aqueous layers to remain separate. Upon complete addition of the initial nonanoyl chloride/diethyl ether, 2 L of diethyl ether is added directly to the reaction. Nonanoyl chloride/diethyl ether is then added in higher ratio until 6.59 kg (37.3 mol) of nonanoyl chloride and 14 L of diethyl ether has been added. The stirred reaction is allowed to slowly warm to room temperature overnight.
Distilled water (2 L) is added and the reaction is stirred vigorously. The aqueous layer is removed and discarded. The organic layer is then washed with saturated sodium bicarbonate solution and dried over magnesium sulfate. Solvent is removed under reduced pressure to give a white solid.
b. Preparation of N nonanoyl-N methylacetamide (NMA) A 100 mL three-necked, round bottomed flask equipped with a short path distillation apparatus with vacuum adapter, Vigreaux column, and pressure equalizing addition funnel is charged with acetic anhydride (14.9 g, 146 mmol) and N
methylnonanamide (2.5 g, 14.6 mmol). The reaction mixture is heated (65° C) and three drops (ca. 0.07 g, .7 mmol) of H2S04 (conc) is added. Aspirator vacuum is applied to remove acetic acid formed from the reaction mixture. Additional acetic anhydride (ca.
18 g) is added to replace that which has been reacted and removed. Upon completion of the reaction the remaining acetic anhydride/acetic acid is removed under reduced pressure. The residue is purified by Kugelrohr distillation (100° C, 0.35 mm Hg) to give a water white oil.
EXAMPLE II
a.Preparation of n-MethyI Nonanoyl Amide Under nitrogen pressure, 20.39 lbs. of liquid monomethyI amine (MMA) is pushed into a 25 gallon agitated pressure vessel. The pressure vessel is held at a pressure of about 25-40 PSIG after MMA addition. The vessel's agitator is started.
51.95 Ibs. of pelargonic acid is added to the vessel over a 0.5 to 1 hour period through a diaphragm pump. The reactor temperature rises to about 60-100 F and 50-100 PSIG during acid addition. When all of the acid is in the reactor, heating is started while agitation continues. The reactor is raised to 325-330 °F . The pressure rises to about 350 PSIG
during this heatup process. The reactor is held at this temperature for 7 hours. Samples are taken hourly during this period and analyzed by gas chromatography. Final n-methyl nonanoyl amide content is above about 97%. Free pelargonic acid is less than about 3 %. At the end of 7 hours the reactor, while at 325-330 °F, is vented slowly to a sulfuric acid scrubber tank where the excess MMA is neutralized. The reactor is cooled to 122 °F
and the resulting amide pressured out of the tank through a line to a 100 gallon glass lined reactor.
b. Preparation of n-Methyl n- Nonyl Acetamide (NMA) The remaining MMA and water that resulted from the amidation reaction are removed in the glass lined reactor at 122 °F and less than about 10 mm Hg vacuum. The reactor pressure is set at 100 mm Hg and 335.1 lbs. acetic anhydride is pulled in from a drum on a weigh scale via a Teflon lined stainless steel hose. The reactor is returned to atmospheric pressure by breaking vacuum with nitrogen. Heating and agitation are continued. The reactor is heated to 248 °F and sampled hourly and the samples analyzed by gas chromatography (GC). After approximately 10 hours conversion to crude NMA
is 87.2%.
Crude composition GC Area Di CZ Imide 1.929 C2/C9 Mixed Anhydride 6.377 n-Methyl n-Nonanoyl 1.669 Amide iso C9 NMA 0.900 Linear C9 NMA 86.301 Di C9 Anhydride 0.105 Di C9 Imide 0.617 Other 2.102 c. NMA Isolation Excess acetic anhydride is removed in the 100 gallon reactor at 122 °F
and less than about 10 mm Hg vacuum. After the acetic anhydride is removed vacuum is broken with nitrogen.
A wash mixture made up of 95 lbs. of water 10 lbs. of sodium bicarbonate, and 35 lbs. of methanol is prepared. This mixture is added to the reactor, stirred for 1 hour and settled for I hour. The bottom layer is drained off. A second wash mixture consisting of 95 lbs. water, 6 lbs. sodium bicarbonate, 4 Ibs. sodium carbonate and 35 lbs. of methanol is prepared. This mixture is added to the reactor, stirred for 1 hour and settled fox 1 hour. The bottom layer is drained off. The product is washed a third time with 140 lbs. of pure water. The bottom layer is drained off. The product is then fractionally distilled in the reactor at pressure less than 10 mm Hg.
Final purity of the NMA is > 95% combined iso and linear NMA. The yield as compared to theoretical based on pelargonic acid is greater than about 75%.
SUMMARY OF THE INVENTION
The bleach activator of the present invention is an unsymmetrical acyclic imide having the formula:
(I) O O
R~N~ 3 R
wherein R1 is a C~-C13 linear or branched chain saturated or unsaturated alkyl group, preferably a C~-C 11 linear or branched saturated alkyl group, R2 is a C 1-Cg~
linear or branched chain saturated or unsaturated alkyl group, preferably a CI-C4 linear saturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group. More preferably, R1 is a C~-C11 saturated alkyl group and most preferably, R1 is a linear Cg or Cg saturated alkyl group and R2 and R3 are CH3. In preferred situations, the sum of the number of carbon atoms in R1, R2 and R3 is less than 19, more preferably Iess than 15.
It has been discovered that unsymlnetrical acyclic imide having the formula:
(I) O O
R~N~R3 wherein R1 ~ R2 and R3 are as described hereinbefore can be prepared by a process which comprises the steps of:
(a) reacting an amide having the formula:
(II) O
YJ\N/ H
with a reactive acyl compound to form said imide; wherein Y is selected from the group consisting of R1 and R3, and wherein said reactive acyl compound contains said R3 group when Y is R 1 and contains said R 1 group when Y is R3, wherein said reactive acyl group is preferably selected from the group of compounds consisting of carboxylic acid halides, carboxylic acid esters, and' carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acid chlorides, carboxylic acid methyl esters, and carboxylic acid anhydrides; most preferably Y is R1 and said reactive acyl compound is carboxylic acid anhydride; and (b) separating said imide from the reaction mixture.
The scope of the present invention further encompasses a process which includes a step wherein the amide having the formula (II) above is prepared by the reaction of an acyl compound containing said Rl or R3 group, preferably R1 , with an amine compound containing said R2 group; wherein said acyl compound is preferably selected from the group consisting of amides, carboxylic acids, carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acids, carboxylic acid chlorides and carboxylic acid methyl esters, most preferably selected from carboxylic acids.
Accordingly it is an object of the present invention to provide a process to prepare unsymmetrical acyclic imide bleach activator which can provide both hydrophobic and hydrophilic bleaching agents. These, and other, objects, features and advantages will be clear from the following detailed description and the appended claims.
All percentages, ratios and proportions herein are on a weight basis unless otherwise indicated. All documents cited herein are hereby incorporated by reference.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The unsymmetrical acyclic imide bleach activators prepared by the present invention provide superior bleaching ability and performance over the bleach activators of the prior art. While not wishing to be bound by theory, it i$ believed that the unsymmetrical acyclic imide bleach activators prepared by the present invention provide both hydrophobic and hydrophilic bleaching agents in aqueous solutions. This is believed to be due to the fact that perhydrolysis can occur at either of the carbonyl groups in the activator. Thus, any molecule of the activators of formula (I) would undergo perhydrolysis in an aqueous solution to form either a bleaching agent (R1C(O)bOH) having hydrophobic properties and a bleaching agent (R3C(O)OOH) having hydrophilic properties when Rl and R3 are defined as above. The bleaching agent may of course be protonated or deprotonated depending upon the in-use pH. A
bleaching solution will then include both the hydrophilic bleaching agent and the hydrophobic bleaching agent. Thus, the bleaching capabilities of a mixed activator system (hydrophobic and hydrophilic) and even increased performance can be achieved through the use of a single bleach activator. Elimination of mixed activator systems may provide enormous potential benefits by eliminating the significant expense of an additional bleach activator.
Furthermore, while not wishing to be bound by theory, it is believed that the bleach activators of formula (I) prepared by the present invention are either liquids or wax-like, non-crystalline solids with melting points at or moderately above room temperature. Thus, they are easily handled and processed into liquid formulations. In addition, the activators prepared by the present invention may be easily formulated into stable liquid compositions.
The present invention relates to preparation of unsymmetrical acyclic bleach activators. The unsymmetrical acyclic imide activators of the present invention have the formula:
(I) R~N
R
wherein R 1 is a C~-C 13 linear or branched chain saturated or unsaturated alkyl group, R2 is a CI-Cg~ linear or branched chain saturated or unsaturated alkyl group and R3 is a C 1-C4 linear or branched chain saturated or unsaturated alkyl group.
Preferred activators are those in which the Rl is a C~-C11 linear or branched saturated alkyl group, more preferably, R1 is a C~-C 11 saturated alkyl group, R2 is a C 1-C4 linear or branched saturated alkyl group and R3 is a C 1-C4 linear or branched chain saturated or unsaturated alkyl group. More preferably, R2 and R3 are C 1-C4 linear saturated alkyl groups and even more preferably are the same.
. Further preferred activators prepared according to the present invention are .the N-alkanoyl-N-methyl acetamides. The activators have the formula (I) wherein both R2 and R3 are methyl groups. Thus, N-aikanoyl-N-methyl acetamides have the formula:
(III) O O
R~~N~Me Me where RI is C~-Cl 1 linear saturated alkyl group. Particularly preferred are N-octanoyl-N-methyl acetamide (when RI is C~), N-nonanoyl-N-methyl acetamide (when Rl is Cg), N-decanoyl-N-methyl acetamide (when RI is Cg) and N-dodecanoyl-N-methyl acetamide (when R 1 is C I l ).
While not wishing to be bound by theory, it is believed that as the number of carbons in the activators of formula (I) increases, the solubility of the compound decreases. Thus, as the activators prepared by the present invention are ideally soluble for optimum performance of the activators, it is preferred that the number of carbon atoms in the activator compound be such that the activator compound displays satisfactory solubility profiles. In the present invention, the sum of the carbons in Rl, R2 and R3 is preferably less than 19 and more preferably less than 15.
It has been discovered that unsymmetrical acycIic imide having the formula:
(I) O O
R~N~ R3 l wherein R1 ~ R2 and R3 are as described hereinbefore can be prepared by a process which comprises the steps of {a) reacting an amide having the formulae:
(II) O
YJ\N/H
with a reactive acyl compound to form said imide; wherein Y is selected from the group consisting of R1 and R3, and wherein said reactive acyl compound contains said R3 group when Y is R1 and contains said RI group when Y is R3, wherein said reactive acyl group is preferably selected from the group of compounds consisting of carboxylic acid halides, carboxylic acid esters, and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acid chlorides, carboxylic acid methyl esters, and carboxylic acid anhydrides; most preferably Y is R1 and said reactive acyl compound is carboxylic acid anhydride; and (b) separating said imide from the reaction mixture.
The scope of the present invention further encompasses a process which includes a step wherein the amide having the formula (II) above is prepared by the reaction of an acyl compound containing said R1 or R3 group, preferably said Rl group, with an amine compound containing said R2 group; wherein said acyl compound is preferably selected from the group consisting of amides, carboxylic acids, carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acids, carboxylic acid chlorides and carboxylic acid methyl esters, most preferably selected from carboxylic acids.
A key aspect of the present invention is to afford an efficient process for the preparation of the above described unsymmetrical acyclic imide in high purity with low levels of malodorous side-products and color forming bodies.
The comprehensive process for preparation of compounds of formula (I) comprises the following general steps:
i) formation of the amide of formula (II):
O O
H
Y + NH2 R2 --.~ Y N/
L
1~
wherein YCOL is an acyl compound preferably selected from the group consisting of amides, carboxylic acids, carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acids, carboxylic acid chlorides and carboxylic acid methyl esters, most preferably selected from carboxylic acids; wherein Y and are as described hereinbefore;
ii) separatiorY of said amide from the reaction mixture;
iii) formation of the unsymmetrical acyclic imide of formula (I):
O O O O
H ~
R / + R -'' R~N~R3 or O O O O
H '~ ~
R~ / + Rt~ ~ R" 'N' \ R3 N Ll wherein R3COL1 and R1COL1 are reactive acyl compounds, preferably selected' . from the consisting of carboxylic acid halides, carboxylic acid esters, and carboxylic acid anhydrides, more preferably selected from the group consisting of carboxylic acid chlorides, carboxylic acid methyl esters, and carboxylic acid anhydrides, most preferably said reactive acyl compound is carboxylic acid anhydride; and iv) separation of said unsymmetrical acyclic imide from the reaction mixture.
(i) Amide Formation The amide of step (i) is prepared by acylation of a primary amine. Acylation of amines to form amides is well known in the art. The amide of formula (II) can be prepared via numerous routes. Amides, carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides, containing R1 or R3 can all be used to form the amide precursor when reacted with a primary amine containing R2. General acylation chemistry is described in March, Advanced Organic Chemistry, Third Edition, pp. 370-371 (acylation of amines by acyl halides), pp. 371 (acylation of amines by anhydrides), pp.371-371 (acylation of amines by acids), pp. 375-376 (acylation of amines by esters), pp. 376-377 (acylation of amines by amides). The preparation of amides is described in U.S. Patents 2,864,683; 3,870,756; 3,914,302; 4,331,815; and 4,841,086 which are hereby incorporated by reference.
In a preferred embodiment, the amide precursor is prepared via the reaction of an amine with a carboxylic acid under superatmospheric pressure conditions. This embodiment is particularly preferred in cases where the desired product requires the use of an amine which is gaseous at room temperature and pressure. The reaction is generally carried out with a molar excess of the amine, preferably a ratio of amine to carboxylic acid of about 1.25:1 to about 5.0:1, more preferably from about 1.75:1 to about 2.25:1 is used. The excess of amine shifts the equilibrium of the reaction to favor the formation of the amide and acts to lessen the formation of the di-Y-imide impurity.
In a preferred embodiment, the amine containing the desired R2 group is charged to a vessel under superatmospheric pressure and agitated. The carboxylic acid containing the desired Y group is then gradually added via a pump. After addition, the reactor is then heated to reaction temperature, preferably from about 250 °F to about 400 °F, more preferably from about 275°F to about 350°F, and most preferably from about 325°F to about 330°F. The pressure of the reactor is held above atmospheric pressure, preferably from about 200 PSIG to about 400 PSIG, more preferably from about 300 PSIG to about 350 PSIG. The reaction can be monitored and samples analyzed by gas chromatography.
Typically the reaction proceeds to greater than 95% conversion, based on the carboxylic acid consumed, in from about 2 to about 10 hours, preferably from about 4 to about 8 hours.
ail Separation of the Amide The amide formed in step (i) can be separated from the reaction mixture in order to improve the odor, appearance, or purity of the final imide or in order to avoid sidereactions during the imidation reaction in step (iii). The amide may be separated from the reaction mixture by one or more methods including: recrystallization with organic solvent such as diethyl ether; extraction with aqueous washes using organic and inorganic reagents to neutralize free acids and amines or hydrolyze anhydrides and acid chlorides; and distillation of any volatile excess reagent and/or side-product.
One feature of the preferred embodiment which reacts an amine with a carboxylic acid, is that the excess amine used and the water formed during the reaction is very volatile relative to the desired amide and can be removed by distillation prior to the imidation step.
liii) Imide Formation The imide (I) is formed by acylation of the amide formed in step (ii) above.
This acylation is similar to the acylation in step (i) except that the amide of formula (II) is less reactive than the primary amine R2NH2 . The imide can be formed by reaction of the amide of formula (II) with a reactive acyl compound having the R3 or Rl group as described hereinbefore. Preferably this reactive acyl compound is selected from the group of compounds consisting of carboxylic acid halides, carboxylic acid esters and carboxylic acid anhydrides; more preferably from the group consisting of carboxylic acid chlorides, carboxylic acid methyl esters, and carboxylic acid anhydrides; most preferably from carboxylic acid anhydrides having said R3 group. a In a preferred embodiment, the imide is formed from the reaction of the R I
amide with carboxylic acid anhydride having the R3 group. This reaction is generally carned out with a molar excess of anhydride, preferably a ratio of anhydride to amide of from greater than about 1:1 to about 20:1, more preferably from. about 2:1 to about 10:1, most preferably from about 4:1 to about 6:1. After the amide product of step (ii) has had the excess amine and water removed by distillation, the carboxylic acid anhydride is charged to the vessel. The vessel is then heated to a reaction temperature of from about 120°F to about 375°F, preferably from about 175°F to about 300°F, more preferably from about 250°F to about 275°F. The reaction can be monitored and samples analyzed by gas chromatography. Typically the reaction proceeds to greater than 95%
conversion, based on the amide consumed, in from about 0.5 to about 48 hours, preferably from about 3 to ' about 10 hours, more preferably from about 4 to 6 hours.
!iv) Separation of the Imide The imide formed in step (iii) can be separated from the reaction mixture in order to improve the odor, appearance, or purity of the final imide. In particular, the crude WO 98!16496 PCT/US97J17910 imide reaction mixture can contain levels of free carboxylic acid which present a serious malodor problem when used in consumer products. The crude imide can also contain levels of carboxylic acid anhydrides would be unacceptable in a finished consumer product. The imide may be separated from the reaction mixture by one or more methods including: liquid/liquid organic solvent extraction; extraction with aqueous washes using organic and inorganic reagents to neutralize free acids and amines or hydrolyze anhydrides and acid chlorides; and distillation of any volatile excess reagent, side-product, and or final imide product.
In the preferred embodiment using carboxylic anhydrides to form the imide, the final imide product is preferably isolated by first distilling excess R3 anhydride and low molecular weight (C,~) carboxylic acids, extracting with aqueous washes, and finishing by fractional distillation of the pure imide. It has been discovered that aqueous washes are particularly useful in enabling the separation of the final imide product.
Aqueous washes optionally comprising methanol and inorganic carbonate salts, such as sodium carbonate and/or sodium bicarbonate, have been shown to effectively reduce the level of R1 methyl ester and mixed R1-R3 anhydride impurities. The reduction in the level of these ester and anhydride impurities is critical to reduce the risk of unwanted side-products during the fractional distillation of the final imide product.
In the specification and examples herein, ali percentages, ratios and parts are by weight unless otherwise specified and all numerical limits are normal approximations.
The following examples illustrate the esters and compositions of this invention, but are not intended to be limiting thereof.
EXAMPLE I
a. Preparation of n-Methyl Nonanoyl Amide A 50 L, 3-necked round-bottomed flask equipped with a 2 L pressure equalizing addition funnel, mechanical stirrer, argon inlet, thermometer, and reflux condenser is charged with methylamine (40 wt% in water, 8 L, 93 mol, 2.5 eq) and cooled in an ice/methanol bath to 10 °C. Nonanoyl chloride/diethyl ether (approximately 1:1 volume ratio) is mixed in the addition funnel and added to the aqueous methylamine at a rate slow enough to maintain reaction temperature below 30 °C. The reaction is stirred slowly enough to allow the organic and aqueous layers to remain separate. Upon complete addition of the initial nonanoyl chloride/diethyl ether, 2 L of diethyl ether is added directly to the reaction. Nonanoyl chloride/diethyl ether is then added in higher ratio until 6.59 kg (37.3 mol) of nonanoyl chloride and 14 L of diethyl ether has been added. The stirred reaction is allowed to slowly warm to room temperature overnight.
Distilled water (2 L) is added and the reaction is stirred vigorously. The aqueous layer is removed and discarded. The organic layer is then washed with saturated sodium bicarbonate solution and dried over magnesium sulfate. Solvent is removed under reduced pressure to give a white solid.
b. Preparation of N nonanoyl-N methylacetamide (NMA) A 100 mL three-necked, round bottomed flask equipped with a short path distillation apparatus with vacuum adapter, Vigreaux column, and pressure equalizing addition funnel is charged with acetic anhydride (14.9 g, 146 mmol) and N
methylnonanamide (2.5 g, 14.6 mmol). The reaction mixture is heated (65° C) and three drops (ca. 0.07 g, .7 mmol) of H2S04 (conc) is added. Aspirator vacuum is applied to remove acetic acid formed from the reaction mixture. Additional acetic anhydride (ca.
18 g) is added to replace that which has been reacted and removed. Upon completion of the reaction the remaining acetic anhydride/acetic acid is removed under reduced pressure. The residue is purified by Kugelrohr distillation (100° C, 0.35 mm Hg) to give a water white oil.
EXAMPLE II
a.Preparation of n-MethyI Nonanoyl Amide Under nitrogen pressure, 20.39 lbs. of liquid monomethyI amine (MMA) is pushed into a 25 gallon agitated pressure vessel. The pressure vessel is held at a pressure of about 25-40 PSIG after MMA addition. The vessel's agitator is started.
51.95 Ibs. of pelargonic acid is added to the vessel over a 0.5 to 1 hour period through a diaphragm pump. The reactor temperature rises to about 60-100 F and 50-100 PSIG during acid addition. When all of the acid is in the reactor, heating is started while agitation continues. The reactor is raised to 325-330 °F . The pressure rises to about 350 PSIG
during this heatup process. The reactor is held at this temperature for 7 hours. Samples are taken hourly during this period and analyzed by gas chromatography. Final n-methyl nonanoyl amide content is above about 97%. Free pelargonic acid is less than about 3 %. At the end of 7 hours the reactor, while at 325-330 °F, is vented slowly to a sulfuric acid scrubber tank where the excess MMA is neutralized. The reactor is cooled to 122 °F
and the resulting amide pressured out of the tank through a line to a 100 gallon glass lined reactor.
b. Preparation of n-Methyl n- Nonyl Acetamide (NMA) The remaining MMA and water that resulted from the amidation reaction are removed in the glass lined reactor at 122 °F and less than about 10 mm Hg vacuum. The reactor pressure is set at 100 mm Hg and 335.1 lbs. acetic anhydride is pulled in from a drum on a weigh scale via a Teflon lined stainless steel hose. The reactor is returned to atmospheric pressure by breaking vacuum with nitrogen. Heating and agitation are continued. The reactor is heated to 248 °F and sampled hourly and the samples analyzed by gas chromatography (GC). After approximately 10 hours conversion to crude NMA
is 87.2%.
Crude composition GC Area Di CZ Imide 1.929 C2/C9 Mixed Anhydride 6.377 n-Methyl n-Nonanoyl 1.669 Amide iso C9 NMA 0.900 Linear C9 NMA 86.301 Di C9 Anhydride 0.105 Di C9 Imide 0.617 Other 2.102 c. NMA Isolation Excess acetic anhydride is removed in the 100 gallon reactor at 122 °F
and less than about 10 mm Hg vacuum. After the acetic anhydride is removed vacuum is broken with nitrogen.
A wash mixture made up of 95 lbs. of water 10 lbs. of sodium bicarbonate, and 35 lbs. of methanol is prepared. This mixture is added to the reactor, stirred for 1 hour and settled for I hour. The bottom layer is drained off. A second wash mixture consisting of 95 lbs. water, 6 lbs. sodium bicarbonate, 4 Ibs. sodium carbonate and 35 lbs. of methanol is prepared. This mixture is added to the reactor, stirred for 1 hour and settled fox 1 hour. The bottom layer is drained off. The product is washed a third time with 140 lbs. of pure water. The bottom layer is drained off. The product is then fractionally distilled in the reactor at pressure less than 10 mm Hg.
Final purity of the NMA is > 95% combined iso and linear NMA. The yield as compared to theoretical based on pelargonic acid is greater than about 75%.
Claims (12)
1. A process for the preparation of unsymmetrical acyclic imide having the formula:
wherein R1 is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a C1-C8 linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group which comprises the steps of:
(a) reacting an amide having the formula:
with a reactive acyl compound to form said imide; wherein Y is selected from the group consisting of R1 and R3, and wherein said reactive acyl compound contains said R3 group when Y equals R1 and contains said R1 group when Y
equals R3; and (b) separating said imide from the reaction mixture.
wherein R1 is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a C1-C8 linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group which comprises the steps of:
(a) reacting an amide having the formula:
with a reactive acyl compound to form said imide; wherein Y is selected from the group consisting of R1 and R3, and wherein said reactive acyl compound contains said R3 group when Y equals R1 and contains said R1 group when Y
equals R3; and (b) separating said imide from the reaction mixture.
2. A process for the preparation of unsymmetrical acyclic imide having the formula:
wherein R1 is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a C1-C8 linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4, linear or branched chain saturated or unsaturated alkyl group which comprises the steps of:
(a) reacting a carboxylic acid having the formula:
with an excess of amine having the formula NH2-R2 under pressure of from about 200 PSIG to about 400 PSIG and a temperature of from about 250 °F
to about 400 °F to form an amide having the formula:
(b) removing said excess of amine from said amide;
(c) reacting said amide with an excess of carboxylic acid anhydride containing said R3 group to form said imide; and (d) separating said imide from the reaction mixture.
wherein R1 is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a C1-C8 linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4, linear or branched chain saturated or unsaturated alkyl group which comprises the steps of:
(a) reacting a carboxylic acid having the formula:
with an excess of amine having the formula NH2-R2 under pressure of from about 200 PSIG to about 400 PSIG and a temperature of from about 250 °F
to about 400 °F to form an amide having the formula:
(b) removing said excess of amine from said amide;
(c) reacting said amide with an excess of carboxylic acid anhydride containing said R3 group to form said imide; and (d) separating said imide from the reaction mixture.
3. The process as claimed in any of claims 1-2 wherein R2 is a C1 to C4 linear saturated alkyl group.
4. The process as claimed in any of claims 1-3 wherein R1 is a C7-C11 linear or branched saturated alkyl group.
5. The process as claimed in any of claims 1-4 wherein R1 is a C7, C8, C9, C10, or C11, preferably C8 or C9 saturated alkyl group and R2 and R3 are CH3.
6. The process as claimed in any of claims 1-5 wherein the sum of the carbon atoms in R1, R2 and R3 of said unsymmetrical acyclic imide is less than 19.
7. The process as claimed in any of claims 1-6 wherein said reactive acyl compound is selected from the group consisting of carboxylic acid halides, carboxylic acid esters, and carboxylic acid anhydrides, and preferably is a carboxylic acid anhydride.
8. The process as claimed in any of claims 1-7 wherein said amide and said reactive acyl compound are reacted in a molar ratio of reactive acyl compound to amide of greater than about 1:1 to about 20:1.
9. The process as claimed in any of claims 1-8 wherein step (a) is carried out at a reaction temperature of from about 120 °F to about 375 °F.
10. The process as claimed in any of claims 1-9 wherein step (b) comprises at least one operation selected from the group consisting of liquid/liquid solvent extraction;
fractional distillation; and treatment with an aqueous wash.
fractional distillation; and treatment with an aqueous wash.
11. The process as claimed in any of claims 1-10 wherein said amide used in step (a) is prepared by the reaction of an acyl compound containing said Y group with an amine compound containing said R2 group; wherein said acyl compound is selected from the group consisting of amides, carboxylic acids, carboxylic acid halides, carboxylic acid esters, and carboxylic acid anhydrides, preferably said acyl compound containing said Y
group is a carboxylic acid, said amine compound is NH2R2..
group is a carboxylic acid, said amine compound is NH2R2..
12. The process any of claims 1-11 wherein said reaction forming said amide is performed under superatmospheric pressure.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2859996P | 1996-10-16 | 1996-10-16 | |
| US60/028,599 | 1996-10-16 | ||
| PCT/US1997/017910 WO1998016496A1 (en) | 1996-10-16 | 1997-10-09 | Process for preparation of unsymmetrical acyclic imide bleach activators |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2269082A1 true CA2269082A1 (en) | 1998-04-23 |
Family
ID=21844344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002269082A Abandoned CA2269082A1 (en) | 1996-10-16 | 1997-10-09 | Process for preparation of unsymmetrical acyclic imide bleach activators |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0934251A1 (en) |
| AU (1) | AU4745397A (en) |
| CA (1) | CA2269082A1 (en) |
| WO (1) | WO1998016496A1 (en) |
| ZA (1) | ZA979200B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT201600070454A1 (en) * | 2016-07-06 | 2016-10-06 | 3V Sigma Spa | PEROSSIGENATED COMPOUND ACTIVATORS |
| CN113548977A (en) * | 2021-07-12 | 2021-10-26 | 广州乐信生物科技有限公司 | Process for producing N-methyl-beta-alanine derivative |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2672470A (en) * | 1948-02-24 | 1954-03-16 | Armour & Co | Preparation of the higher monoacylamides from monoamides and acid halides |
| DE2509481C3 (en) * | 1975-03-05 | 1978-03-02 | Bayer Ag, 5090 Leverkusen | Process for the preparation of N-acetylsalicylamide |
| US4158560A (en) * | 1977-11-17 | 1979-06-19 | Gaf Corporation | Broad spectrum herbicidal diacylimide compositions |
-
1997
- 1997-10-09 CA CA002269082A patent/CA2269082A1/en not_active Abandoned
- 1997-10-09 WO PCT/US1997/017910 patent/WO1998016496A1/en not_active Application Discontinuation
- 1997-10-09 AU AU47453/97A patent/AU4745397A/en not_active Abandoned
- 1997-10-09 EP EP97909967A patent/EP0934251A1/en not_active Ceased
- 1997-10-14 ZA ZA979200A patent/ZA979200B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998016496A1 (en) | 1998-04-23 |
| AU4745397A (en) | 1998-05-11 |
| EP0934251A1 (en) | 1999-08-11 |
| ZA979200B (en) | 1998-07-20 |
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