MXPA97007037A - Synthesis of activators of blanq - Google Patents

Abstract

The present invention relates to alkanoylamino phenolsulfonate esters is conducted in the presence of an aqueous base to provide bleach activating compounds, therefore, the acid chloride N-nonanoyl-6-aminocaproic is reacted with the sodium salt of p- Phenosulfonate in the presence of water at a pH in the range of about 9 to about 12 to produce the corresponding phenolsulfonate ester, the synthesis of the phenolsulfonate ester of the mono-acrylamide of adipic acid is also illustrated

Description

SYNTHESIS OF BLANK ACTIVATORS CflfIPO DE Lfl INVENTION The present invention relates to the chemical synthesis of organic compounds that are useful as activators in bleaching compositions of tolas and laundry compositions.

BACKGROUND OF THE INVENTION The formulation of modern cleansing compositions is a sophisticated and complex ema. The provider is faced with the need to use ingredients that are safe and L5 effective under a wide variety of conditions of use and with a wide variety of types of dirt and fabrics. For example, some consumers prefer to use detergents for laundry at temperatures as low as about 5 ° C, while those using such compositions at 0 temperatures that reaches the boiling point. The types of dirt vary from particulate silicates and clay soils, through dirt from carbohydrates, proteinaceous soils including body soils and food stains and other grease / oil stains. The Mixed spots, such as those produced by cosmetics and comprising more water soluble oily materials and highly colored particulate materials, are also often commonly encountered by the user. e has suggested a wide variety of ingredients f > for use in modern cleaning compositions, including various bleaching agents, surfactants, detergents, soil release agents and the like. Although a review of the literature would seem to suggest that such ingredients are widely available, many are special items that are not economical to use in the THE home In fact, one of the problems associated with many of the ingredients used in compositions for washing fabrics and bleaches is its high cost. Many of the sophisticated ingredients require multi-step reaction sequences that are costly by themselves. Further, Some of the proposed ingredients must be manufactured using organic solvent systems, which must be recovered and recirculated to minimize costs. In addition, reactions of organic solvents often require high reaction temperatures, resulting in '? 0 a poorly colored reaction product. In almost any conceivable circumstance, it is highly preferred to use ingredients that can be economically prepared using the least possible process steps. In particular, please use -t amen or [referred to use procedural steps that employ Water as the primary solvent L. A class of materials that has recently had commercial use in blenders and detergents for laundry with bleach comprise several so-called "activators" of bLanqueo. These organic activating molecules are designed to improve the performance of conventional inorganic bleaching agents such as percarbonate and μorborate. Unfortunately, many of the proposed bleach activating molecules are difficult and expensive to prepare, and therefore remain simple laboratory curiosities. By the present invention, certain amide bleach activators are prepared using inexpensive synthetic methods that employ water as one of the major reaction solvents. Additional benefits of the present invention include the ability to use short reaction times and low reaction temperatures, which helps to achieve reaction products that have excellent clear or useful anco light.

TECHNICAL BACKGROUND The action of alcohols and amines in aqueous solution using diluted lcali to combine with acid haiogenide formed is commonly known as the chotten-Baumann reaction. See Ohernistry of Organic Oompounds, 2a. ed., Nol ler, p. 549 (1957). L ibrary of Congress Catalog Card No. 57-7045 ,. Bleach activators of the type provided by the method herein are described in the Patents of .U.A. 4,634,551 and 4,852,909.

BRIEF DESCRIPTION OF THE INVENTION The present invention comprises a process for preparing hydrocarbon phenolsulfonate esters of the inaloids, comprising the steps of: a) reacting an amino acid of the formula OH 0 H II 0 II II 1 II II R- ~ 0-- N - (CH2) n COM or R-- N - C (CH2) n COM where n is from 1 to about 8, M is H or an alkali metal salt, and R is C? ", Alkenyl, aplo or arcaplo, preferably C7-C9 alkyl, is < Jec? R, an alkanoylamino acid, with an acid halide to prepare the corresponding amino acid halide; and b) reacting the amino acid halide of step a) with a phenol sulfate in the presence of water and base. Step a) of the present process can be conducted using an inorganic acid halide selected from the group consisting of CJOC12, PCI3, PCI5, POCI3 and their corresponding bromides, or oxalyl chloride (00C1) 2- e has discovered that SOCI2 it is not too hard to be used with reagents having a knotted group, it provides improved yields of the corresponding carboxylic acid chloride and is therefore preferred for use in step a). In a highly preferred mode, step b) is conducted in a reaction medium comprising a mixture of two phases of water and an organic solvent, most preferably using the reaction conditions that are digested below. The organic solvent is chosen from those which are compatible with (ie not reactive with) the amino acid halide formed in step a). Ether solvents, hydrocarbon solvents and the like are useful for this purpose. Alcohols, amines and other solvents that could react with the amino acid halide are avoided. All percents, ratios and proportions herein are by weight, unless otherwise specified. All the documents cited, in part important, are incorporated here by reference.

DETAILED DESCRIPTION OF THE INVENTION The process of the present invention is conducted using reagents and conditions as described more fully below. The overall reaction sequence is shown below for the synthesis of the "NACfi- OBS" activator. Step a): Acid chloride of n-nonanoyl-6-aminocaproic acid is prepared O H 0 H II I C l 2 || J H3 (CH2) 7 C - -N (CH2) 5 COOH CH3 (CH2) 7 O - - N (CH2) 5 COC 1 Ft20 Step b): Reacting acid chloride with Na phenolsulfonate under conditions of Sc or ten- Baumann Na Step a) of the reaction here is conducted as indicated below, typically at room temperature (15 ° C-25 ° C). Step b) of the reaction here is conducted at a temperature of about 5 ° C to about 20 ° C and the pH scale of about 9 to about 12.2, preferably about 10-11. It has now been discovered that the pH scale for the reaction medium is critical to allow the phenolsulfonate reagent to be present in its anionic form, but not so alkaline as to hydrolyze the desired reaction product. The reaction is almost instantaneous and can be monitored by the pH drop in the aqueous solvent phase. As the pH drops, the additional base is added to maintain the pH at the indicated scale.

EXAMPLE 1 Synthesis of N-nonanoyl-6-aminocaproic acid phenolsulfonate ester (NACA-OBS) - N-nonanovil-6-aminocaproic acid acid chloride. - A one-liter round bottom flask equipped for magnetic stirring is charged with 27.1 g (0.100 moles) of N-nonanoyl-6-aminocaproic acid and 150 ml of * - - diethyl ether. With stirring, 35.7 g (21.9 ml 0.300 moles) of thionyl chloride are added in portions over a period of 5 minutes. The addition of the first milliliters of thionyl chloride causes the majority of the amino acid to dissolve. The solution is stirred at room temperature for 10 minutes, and the ether and excess thionyl chloride are removed with a rotary evaporator. The removal of minimal amounts of thionyl chloride is achieved by adding twice 100 ml of isooctane and steaming in a rotary evaporator. After these procedures, 35.8 g of a pale yellow oil remain. This product is supposed to consist of 0.100 moles of acid chloride of N-nonanoyl-6-aminocaproic acid.

Phosolsulfonate ester of N-nonanoyl-6-a-innocaproic acid (Schotten-Baumann conditions) - A beaker of 600 ml equipped with a mechanical stirrer and equipped with a pH electrode is charged with 39.2 g (0.200 mole) of the sodium salt of p-phenolsulfonate and 200 ml of sodium hydroxide solution at 1.0 N. The resulting solution has a pH of 12.2. The solution is cooled in an ice bath and, with stirring, a solution of the acid chloride (prepared above) in 100 ml of diethyl ether is added dropwise over a period of 10 minutes. The pH of the solution drops rapidly as the acid chloride solution is added. When the pH falls below 9.0, a 50% solution of sodium hydroxide is added dropwise to maintain the pH above 9.0. With the addition of the acid chloride, the reaction mixture becomes thick with suspended solids. After the addition of the acid chloride is complete, the reaction mixture is stirred cold for 10 minutes. At this point the reaction mixture is thick with suspended solid and the pH has stabilized at 9.2. The ice bath is removed and the suspended solid is collected by filtration. This solid (still wet with reaction solution) is dried in air and then under vacuum to give 41.6 grams of a white solid having a light pink dye. Analysis by * H NMR (cfe-DMSO solvent) reveals a composition of 75% by weight of the phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS) and 25% of sodium phenolsulfonate. The yield of NACA-OBS is 31.3 grams (70% of theory).

Synthesis of N-nonanoyl-6-apinocaproic acid phenolsulfonate ester - Isolation by centrifugation - The acid chloride and the phenol sulfonate ester of N-nonaoyl-6-aminocaproic acid is prepared as described above. A weight of 74.0 grams (0.273 moles) of amino acid gives 0.273 moles of the acid chloride co or a light brown oil. This oil is dissolved in 100 ml of diethyl ether and reacted with 107.1 grams (0.546 moles) of sodium phenolsulfonate under Schotten-Bau ann conditions. At the end of the reaction period the pH of the solution is adjusted to 8.0 and the solid precipitate is collected by centrifugation (International Equipment Co., Boston, Wassachusetts, Model BE-50). The resulting solid is resuspended twice in water and collected by centrifugation. The resulting wet cake is freeze dried to give 60.1 grams (49%) of N-nonanoyl-6-aminocaproic acid phenolsulfonate ester (NACA-OBS) as a white solid. The NMR analysis indicated that the sample is 94.8 pure, containing 2.8% of sodium phenolsulfonate and 2.4% of the amino acid.

Per idolysis of N-nonanoyl-6-a? Ninocaproic acid phenolsul monate ester (NACA-OBS) - A 4-liter Erlen eyer flask is charged with 4 liters of distilled water at room temperature, 1.20 grams of sodium carbonate anhydrous, 0.040 grams of diethylenetriatapentaacetic acid (Aldrich), 0.36 grams of sodium perborate onhydrate, and 0.36 grams of the sodium salt of the p-phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (sieved through a sieve 35 mesh (Tyler equivalent) and dispersed in 10 ml of di-ethylformamide). At regular intervals, aliquots of the solution are removed and iodine is analyzed electrically for the presence of N-nonanoyl-6-aminoperoxycaproic acid. This analysis gives the peroxyacid concentration as ppm (parts per million) of available oxygen (AvO). The results obtained are tabulated below (time = 0 corresponds to the addition of the DMF solution of the phenolsulfonate ester to the aqueous solution of sodium carbonate, chelator and sodium perborate).

N-nonanoyl-6- to -nocaproic acid phenolsulfonate ester perhydrolysis (NACA-OBS) to produce N-nonanoyl-6-aminoperoxycaproic acid (NAPCA) Time (min) ppm of AvO found% theoretical AvO 2 2.3 73 6 2.0 63 10 2.8 88 30 2.4 76 EXAMPLE II Preparation of phenol sulphate ester of monononyl amide of adipic acid (NAAA-OB5) - The acid chloride of monononyla of adipic acid is prepared as described above for N-nonanoyl-6-aminocaproic acid. In this manner, 54.3 grams (0.200 mole) of the monononylamide of adipic acid is treated with 71.4 grams (0.600 mole) of thionyl chloride in 150 ml of diethyl ether to yield 0.200 mole of the acid chloride. The acid chloride is reacted with 78.5 grams (0.400) moles of sodium phenolsulfonate under aqueous alkaline conditions (Schotten-ann conditions). The resulting reaction mixture contained precipitated solid which was collected by filtration. After drying with air, this solid weighed 47.2 grams and is shown by H NMR analysis which "- contains 78.8% of the phenolsulfonate ester of monononylamide of adipic acid (NAAA-OBS), 13.6% of sodium phenolsulfonate and 7.8% of monononylamide of adipic acid. The yield of NAAA-OBS is 37.2 grams (41%). The above NACA-OBS and NAAA-OBS materials can be formulated in combination with known bleaching ingredients such as percarbonate, persulfate and other peroxy materials to provide cleaning compositions. Representative but not limiting examples of said compositions are the following.

EXAMPLE III A granular bleaching composition suitable for use in fabric washing and cleaning operations for general purposes is the following: Ingredient X (by weight) Sodium percarbonate 20.0 NAAA-OBS 7.0 Sulphate of sodium The rest EXAMPLE IV A laundry detergent composition with activated bleaching ingredients is as follows.

Ingredient% (by weight) C12-14 sodium alkylsulfate 7.0 Ethoxylated Cm-ishohydride (EO 1.0) 2.0 Zeolite A (0.1-10 microns) 28.0 Sodium carbonate 27.0 Sodium sulfate 12.0 Sodium percarbonate 6.0 NACA-OBS 3.0 Sodium silicate 3.0 Citric acid 2.0 sodium polyacrylate 3.5 Water and minor components * The rest «Includes optical brightener and enzymes protease, cellulase, lipase and amylase.

Claims (7)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for preparing phenolsulfonate esters of hydrocarbyl io acids comprising the steps of: a) reacting an amino acid of the formula 0 H "0 H 0 0 R - C II - N i--, (CH 2,) "JC! OM or R - N i - C II, (CH2,) n C IIOM wherein n is about 8, M is H or an alkali metal salt, and R is Ci-m alkyl, alkenyl, aryl or arkaryl, preferably C7-C9 alkyl, ie, an alkanoyl amino acid, with an acid halide to prepare the corresponding amino acid halide, and b) reacting the amino acid halide of step a) with a phenol sulfate in the presence of of water and base

2. A process according to claim 1, further characterized in that step A is conducted using an inorganic acid halide selected from the group consisting of SOCI2, PCI3, PCI5, POCI3 and their corresponding bromides; oxaloyl chloride

3. A process according to claim 1, characterized by else because R is C7-C9 alkyl and because the acid halide of step A is SOCI2.

4. A method according to claim 1, further characterized in that step b is conducted at a pH in the range of about 9 to about 12.2.

5. A process according to claim 4, further characterized in that the step b is conducted at a pH of about 10 to about 11, and at a temperature of about 5 ° C to about 20 ° C.

6. A process according to claim 1, further characterized in that step b is conducted in a two-phase reaction medium comprising water and an organic solvent that is compatible with the amino acid halide formed in step a.

7. A process according to claim 1, for the preparation of the phenolsulfonate ester of N-nonanoyl-6-amonocaproic acid. B. A process according to claim 1 for the preparation of the phenolsulfonate ester of the monononylamide of adipic acid.