US3758595A - Detergent - Google Patents
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- US3758595A US3758595A US00113079A US3758595DA US3758595A US 3758595 A US3758595 A US 3758595A US 00113079 A US00113079 A US 00113079A US 3758595D A US3758595D A US 3758595DA US 3758595 A US3758595 A US 3758595A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/005—Antimicrobial preparations
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/002—Surface-active compounds containing sulfur
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/755—Sulfoxides
Definitions
- ethoxy lates such as n-tetradecyl alcohol-7 moles ethylene oxide, dodecyl alcohol-l moles ethylene oxide and Sterox AJ (tridecyl alcohol-about 9.5 moles ethylene oxide).
- ethoxylates have detergent properties.
- thioether analogs of polyolethers and polyolpolyethers are surface active agents, e.'g.,- detergent actives, .dishwashing detergents, lime-soap dispersants and suds-boosters for other detergent .actives.
- the compounds of the invention also haveanti-microbial activity and are nontoxic, mild towardsskin andcompletely biodegradable.
- R is an aliphatic hydrocarbon group having six to 14 carbon atoms; Z is oxygen, sulfur or sulfoxide but at least one Z is sulfur or sulfoxide;.a is for 2, b is 0 or 1; m is 0 or 1; n is 0 or 1; 111+ n in all occurrences is l; and R is H, CH,OH or CH
- Subgeneric structures within the generic structure are as follows:
- R is an aliphatic saturated hydrocarbon group having five to 15 carbon atoms; Z is sulfur orsulfoxide; a is l or 2; m is 0 or 1; n is 0 or I; m+n in all occurrences is l; and R is H, CH,OH or CH,.
- R is an aliphatic saturatedhydrocarbon group having six to 14 carbon atoms; Z is oxygen, sulfur or sulfoxide but at least one Z is sulfur orsulfoxide; a is l or 2; m is 0 or 1; n is 0 or i; m +n in all occurrences is l; and R is H, CH,OH or CH,.
- these structures are intended to include isomeric compounds.
- any known method may be employed to prepare the aforementioned sulfur analogs of polyolethers and polyolpolyethers.
- One method is to react a long chain epoxide or long chain glycidyl ether with hydroxy alkyl mercaptans, such as, 2-mercapto-ethanol, 3-mercaptol,2-propanediol, l-mercapto-2-propanol, 3-mercaptol-propanol, 4-mercapto-l,2,butanediol and 4-mercapto-2-butanol, in the presence of a basic catalyst, e.g., NaOCl-l, The reaction can also be carried out without a catalyst, but in such cases, longer reaction times are required.
- the compounds of the invention are the reaction products of:
- R, a, and R are as defined heretofore and Z is oxygen or sulfur but at least one Z is sulfur.
- the thioether reaction product can be oxidized, for example with t-butyl hydroperoxide in methanol, to form the corresponding sulfoxide. It is also possible to react either a long-chain diol containing sulfur or a monoalkyl thioether of glycerol with one molar proportion of ethyleneoxide. By this process, however, a mixture of products is obtained containing large proportions of unreacted starting diolor thioether, with some monoethoxylated compound with which this invention is concerned, and with some poly-ethoxylated compounds such as those represented by the formula wherein x is greater than 1.
- a long-chain sulfur-containing epoxyalkane is a reactant, it may be obtained by any suitable method.
- long chain mercaptans can be reacted with epichlorohydrin to form 3-alkylthio-2-hydroxy-lchloropropanes which, in turn, are reacted with strong aqueous sodiumhydroxide to produce alkyl glycidyl thioethers.
- a long-chain sulfur-containing diol is a reactant, it may be obtained by any suitable method such as the reaction of hydrogen sulfide with long chain epoxides.
- Short-chain polyhydroxy reactant (Structure V) a R Z Name Structure I H O ethylene glycol HOCH,CH,OH l CH,OH 0 glycerol HOCH,CH(OH )CH.0H l CH, O i,2propanediol HOCH,CHOHCH, l H S Z-mercapto ethanol HSCH,CH,OH l CH,OH S 3-mercapto-l,2-
- sulfides having the following structures:
- Suitable specific compounds of this invention include sulfides such as Z-hydroxyundecyl 2- hydroxyethyl sulfide; 2hydroxydodecyl 2- hydroxyethyl sulfide; ZhydrOXy-C -C alkyl 2'- hydroxyethyl sulfide; 2-hydroxydodecyl 2',3'-dihydroxypropyl suflide; Z-hydroxydodecyl 2' hydroxypropyl sulfide; (2hydroxy-3-decyl)propyl 2'- hydroxyethyl sulfide; (2-hydroxy-3-dodecyl)propyl 2,3-dihydroxypropyl sulfide; (2-hydroxy-3- decyl)propyl 2-hydroxypropyl sulfide; (2-hydroxy-3- dodecylthio)propyl 2-hydroxyethyl ether; (Z-hydroxy- 3-tetradecylthi
- the compounds of the present invention may be used alone as detergents. However, the compounds of the invention may also be-used in combination with other detergents.
- detergent compounds with which the compounds of the invention may be admixed to form superior combinations are the well-known anionic types represented by the water-soluble and waterdispersible organic surface-active agents having in the molecule a hydrophobic group of about eight to about 22 carbon atoms and a hydrophilic sulfate, sulfonate or carboxylic group having a cation which does not insolubilize the compound.
- anionic detergents are suitable for use with the compounds of the present invention:
- Alkylbenzenesulfonates such as sodium and potassium salts having a branched or straight chain alkyl portion of about nine to about 15 carbon atoms.
- Alkyl sulfates such as the sodium and triethanolammonium salts of C -C, alkyl sulfuric acid, prepared by sulfating the alcohols derived from coconut oil or tallow, or prepared synthetically.
- alkali metal and ammonium salts of the sulfated ethoxylates of a long-chain alcohol and 3 to 5 molar proportions of ethylene oxide for example, the ammonium salt of an ethoxylate containing an average of 3.1 molar proportions of ethylene oxide and 1 mole of an alcohol mixture known commercially as Alfol 1412, composed of about s n-tetradecanol and about A: n-dodecanol.
- Alkanesulfonates such as ammonium dodecanesulfonate.
- Alkoxyhydroxypropanesulfonates such as the water-soluble salts of 3-dodecyloxy-2-hydroxy-l-propane-sulfonate.
- Soaps the surface-active substances formed usually by the reaction of caustic alkalies with natural glyceridic fats and oils, generally prepared in high purity, and having the generic molecular formula RCOONa, wherein R is a straight-chain hydrocarbon group having from about seven to about 21 atoms.
- the compounds of the invention are also sudsboosters for nonionic detergents.
- the following nonionic detergents, among others, are suitable for use with the compounds of the present invention.
- the Pluronics formed by condensing propylene oxide with propylene glycol to a molecular weight of about 600-2500 to form a base followed by condensing ethylene oxide to this base to the extent of about 10 to about percent, total molecule basis.
- U. S. Pat. Nos. 2,674,619 and 2,677,700 describe operable nonionic compounds.
- the compounds of this invention act as sudsboosters for ampholytic compounds such as hydroxyalkyl methyl taurates and zwitterionic surface-active substances, such as coco dimethyl sulfopropyl betaine.
- the compounds of this invention may interact synergistically with all suds-producing surface-active substances to provide mixtures having improved properties beyond those expected on the basis of the properties of the individual components of the mixture.
- the synergism may be evident in suds production or stability.
- soaps the synergism may be evident in the form of reduced lime-soap scum formation.
- new compounds have been formed.
- the compounds of the present invention have certain noteworthy features.
- the synergistic suds-producing properties of the compounds with other detergents and sudsing agents are surprising.
- the antimicrobial properties of the compounds are also surprising.
- the compounds of the invention are nonionic surfactants with foaming characteristics superior to both well-known anionic and nonionic detergents.
- the ability to formulate a detergent based on the nonionic materials of the invention having high foaming or dishwashing characteristics with built-in germicidal properties and which at the same time is biodegradable by sewage or natural water bacteria is certainly surprising and unexpected.
- Compound B 2hydroxy-C C alkyl 2'- hydroxyethyl sulfide, was prepared in the same manner except that 1,2 epoxy C C alkane was used as one of the reactants.
- Compound C a sulfoxide compound, 2- hydroxydodecyl 2'-hydroxyethyl sulfoxide, was formed by oxidizing Compound A, 2-hydroxydodecyl 2'- hydroxyethyl sulfide, with t-butyl hydroperoxide in methanol. More specifically, a solution of 8 g. of 2- hydroxydodecyl 2'-hydroxyethyl sulfide in 38 ml. of methanol was treated with 3 g. of t-butyl hydrogen peroxide and heated at 50C. for two days. The solvent was evaporated and the crystals washed with hexane.
- the dishwashing properties of the compounds prepared according to Examples A, B and C were determined by ascertaining the number of plates washed in duplicate tests with 1.8 g. of each of the above compounds in 6 quarts of 120 ppm water at 116F., both with or without 0.54 g. of coconut fatty acid monoethanolamide (CMEA). The results are shown in Table 1.
- the compounds listed in Table 2 are other compounds that are considered to be suitable detergents. They may be prepared by the same procedure described in Example I by varying the reactants to provide the required end product. i
- EXAMPLE Ill The germicidal activity of several compounds described in this invention was determined by the Streak Gradient Plate Method.
- the Streak Gradient Plate Method is a modification of the gradient plate method of Szybalski, Science 1 16: 46-48 (1952), for the determination of germicide MEC (Minimum Efiective Concentration) values. This method employs streaks of several organisms per plate.
- a detergent which is 2-hydroxy-C,,C, alkyl 2'- hydroxyethyl sulfide.
- a detergent which is Z-hydroxydodecyl 2'- hydroxyethyl sulfoxide.
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Abstract
This specification relates to a detergent. More particularly, it is concerned with a detergent which is a sulfur analog of a polyolether or polyolpolyether.
Description
United States Patent n 1 Lamberti et al.
[ 51 Sept. 11, 1973 DETERGENT Inventors: Vincent Lamberti, Upper Saddle River, N .J.; Henry Lamaire, Fairfield, Conn.
Lever Brothers Company, New York, NY.
Filed: Feb. 5, 1971 Appl. No.: 113,079
Related US. Application Data Continuation-impart of Ser. No. 764,362, Aug. 7, 1968, Pat. No. 3,562,337, which is a division of Ser. No. 502,299, Oct. 22, 1965, Pat. No. 3,427,248,
Assignee:
References Cited UNITED STATES PATENTS 2,565,986 8/l95l Olin 260/609 R 3,158,663 ll/l964 Von Brachel et al... 260/609 R 3,522,311 8/1970 Hickner 260/607 A 3,539,635 ll/l970 Priestley 260/607 A FOREIGN PATENTS OR APPLICATIONS 1,167,202 lO/l969 Great Britain 260/609 R Primary Examiner-Lewis Gotts Assistant ExaminerD. R. Phillips Attorney-Brumbaugh, Graves, Donohue & Raymond {57] ABSTRACT This specification relates to a detergent. More particu larly, it is concerned with a detergent which is a sulfur analog of a polyolether or polyolpolyether.
3 Claims, No Drawings DETERGENT This application is a continuation-in-part of applica- 'tion Ser. No. 764,362, filed Aug. 7, 1968, now issued as U.S. Pat. No. 3,562,337 which in turn is a divisional of application Ser. No. 502,299 filed Oct. 22, 1965, now issued as U.S. Pat. No. 3,427,248.
in the past a straight chain or branched chain alcohol has been reacted with ethylene oxide to form ethoxy lates, such as n-tetradecyl alcohol-7 moles ethylene oxide, dodecyl alcohol-l moles ethylene oxide and Sterox AJ (tridecyl alcohol-about 9.5 moles ethylene oxide). These ethoxylates have detergent properties.
It has now been discovered that certain thioether analogs of polyolethers and polyolpolyethers, known also as sulfides, are surface active agents, e.'g.,- detergent actives, .dishwashing detergents, lime-soap dispersants and suds-boosters for other detergent .actives. The compounds of the invention also haveanti-microbial activity and are nontoxic, mild towardsskin andcompletely biodegradable.
These new nonionic detergents have the following generic structure:
wherein R is an aliphatic hydrocarbon group having six to 14 carbon atoms; Z is oxygen, sulfur or sulfoxide but at least one Z is sulfur or sulfoxide;.a is for 2, b is 0 or 1; m is 0 or 1; n is 0 or 1; 111+ n in all occurrences is l; and R is H, CH,OH or CH Subgeneric structures within the generic structure are as follows:
wherein R is an aliphatic saturated hydrocarbon group having five to 15 carbon atoms; Z is sulfur orsulfoxide; a is l or 2; m is 0 or 1; n is 0 or I; m+n in all occurrences is l; and R is H, CH,OH or CH,.
wherein R is an aliphatic saturatedhydrocarbon group having six to 14 carbon atoms; Z is oxygen, sulfur or sulfoxide but at least one Z is sulfur orsulfoxide; a is l or 2; m is 0 or 1; n is 0 or i; m +n in all occurrences is l; and R is H, CH,OH or CH,. As used herein, these structures are intended to include isomeric compounds.
Any known method may be employed to prepare the aforementioned sulfur analogs of polyolethers and polyolpolyethers. One method is to react a long chain epoxide or long chain glycidyl ether with hydroxy alkyl mercaptans, such as, 2-mercapto-ethanol, 3-mercaptol,2-propanediol, l-mercapto-2-propanol, 3-mercaptol-propanol, 4-mercapto-l,2,butanediol and 4-mercapto-2-butanol, in the presence of a basic catalyst, e.g., NaOCl-l, The reaction can also be carried out without a catalyst, but in such cases, longer reaction times are required. In accordance with this method, the compounds of the invention are the reaction products of:
wherein R, a, and R are as defined heretofore and Z is oxygen or sulfur but at least one Z is sulfur. The thioether reaction product can be oxidized, for example with t-butyl hydroperoxide in methanol, to form the corresponding sulfoxide. It is also possible to react either a long-chain diol containing sulfur or a monoalkyl thioether of glycerol with one molar proportion of ethyleneoxide. By this process, however, a mixture of products is obtained containing large proportions of unreacted starting diolor thioether, with some monoethoxylated compound with which this invention is concerned, and with some poly-ethoxylated compounds such as those represented by the formula wherein x is greater than 1.
if a long-chain sulfur-containing epoxyalkane is a reactant, it may be obtained by any suitable method. For example, long chain mercaptans can be reacted with epichlorohydrin to form 3-alkylthio-2-hydroxy-lchloropropanes which, in turn, are reacted with strong aqueous sodiumhydroxide to produce alkyl glycidyl thioethers. Similarly, if a long-chain sulfur-containing diol is a reactant, it may be obtained by any suitable method such as the reaction of hydrogen sulfide with long chain epoxides.
The following short-chain polyhydroxy reactants among others are within thescope of, the above structure i:
Short-chain polyhydroxy reactant (Structure V) a R Z Name Structure I H O ethylene glycol HOCH,CH,OH l CH,OH 0 glycerol HOCH,CH(OH )CH.0H l CH, O i,2propanediol HOCH,CHOHCH, l H S Z-mercapto ethanol HSCH,CH,OH l CH,OH S 3-mercapto-l,2-
propanediol HSCH,CH(OH)CH,OH 1 CH, 8 l-merca to-2- propane HSCH,CHOHCH, 2 H O 1,3-propanediol HO-CH,-CH,CH,0H 2 CH,OH 0 l,2,4-butane- Preferred types of compounds in this invention, among others, include sulfides having the following structures:
HzC-S CHzCH-CH;
R l i H 0 H I OH HzC-O CHIC H:
HaC-OOHzCH-C HzOH H OH H: O CHzC H-CH:
(XII) (XIII) (XIV) (XVI) OH (XVII) wherein R in structures VI to XVII is an aliphatic saturated hydrocarbon group having five to 15 carbon atoms. The corresponding sulfoxides for structures VI to XVII are also suitable for the present invention.
Suitable specific compounds of this invention, among others, include sulfides such as Z-hydroxyundecyl 2- hydroxyethyl sulfide; 2hydroxydodecyl 2- hydroxyethyl sulfide; ZhydrOXy-C -C alkyl 2'- hydroxyethyl sulfide; 2-hydroxydodecyl 2',3'-dihydroxypropyl suflide; Z-hydroxydodecyl 2' hydroxypropyl sulfide; (2hydroxy-3-decyl)propyl 2'- hydroxyethyl sulfide; (2-hydroxy-3-dodecyl)propyl 2,3-dihydroxypropyl sulfide; (2-hydroxy-3- decyl)propyl 2-hydroxypropyl sulfide; (2-hydroxy-3- dodecylthio)propyl 2-hydroxyethyl ether; (Z-hydroxy- 3-tetradecylthio)propyl 2',3'-dihydroxypropyl ether; (2-hydroxy-3-dodecylthio)propyl 2'-hydroxypropyl ether; (2-hydroxy-3-dodecylthio)propyl 2'- hydroxyethyl sulfide; (2-hydroxy-3-tetradecylthio)propyl 2',3'-dihydroxypropyl sulfide; (2-hydroxy-3- dodecylthio)propyl 2'-hydroxypropyl sulfide; and corresponding sulfoxides thereof.
The compounds of the present invention may be used alone as detergents. However, the compounds of the invention may also be-used in combination with other detergents. Examples of detergent compounds with which the compounds of the invention may be admixed to form superior combinations are the well-known anionic types represented by the water-soluble and waterdispersible organic surface-active agents having in the molecule a hydrophobic group of about eight to about 22 carbon atoms and a hydrophilic sulfate, sulfonate or carboxylic group having a cation which does not insolubilize the compound. The following anionic detergents, among others, are suitable for use with the compounds of the present invention:
1. Alkylbenzenesulfonates, such as sodium and potassium salts having a branched or straight chain alkyl portion of about nine to about 15 carbon atoms.
2. Alkyl sulfates, such as the sodium and triethanolammonium salts of C -C, alkyl sulfuric acid, prepared by sulfating the alcohols derived from coconut oil or tallow, or prepared synthetically.
3. The alkali metal and ammonium salts of the sulfated ethoxylates of a long-chain alcohol and 3 to 5 molar proportions of ethylene oxide,'for example, the ammonium salt of an ethoxylate containing an average of 3.1 molar proportions of ethylene oxide and 1 mole of an alcohol mixture known commercially as Alfol 1412, composed of about s n-tetradecanol and about A: n-dodecanol.
4. The compounds known as Medialans", which are amido carboxylic acids formed by condensing fatty acids of C C, chain length with sarcosine,
CH NHCH COOH. Generally the alkali metal and basic nitrogen-radical salts are employed.
5. Alkanesulfonates, such as ammonium dodecanesulfonate.
6. Alkoxyhydroxypropanesulfonates, such as the water-soluble salts of 3-dodecyloxy-2-hydroxy-l-propane-sulfonate.
7. Soaps, the surface-active substances formed usually by the reaction of caustic alkalies with natural glyceridic fats and oils, generally prepared in high purity, and having the generic molecular formula RCOONa, wherein R is a straight-chain hydrocarbon group having from about seven to about 21 atoms.
8. Olefine sulfonates, such as dodecene sulfonate, and the compounds described in U.S. Pat. No. 3,332,880.
The compounds of the invention are also sudsboosters for nonionic detergents. The following nonionic detergents, among others, are suitable for use with the compounds of the present invention.
1. The Pluronics, formed by condensing propylene oxide with propylene glycol to a molecular weight of about 600-2500 to form a base followed by condensing ethylene oxide to this base to the extent of about 10 to about percent, total molecule basis. U. S. Pat. Nos. 2,674,619 and 2,677,700 describe operable nonionic compounds.
2. Compounds formed by the simultaneous polymer ization of propylene oxide and ethylene oxide, and containing randomly positioned oxypropylene and oxyethylene groups. These and related compounds are described in U.S. Pat. Nos. 2,979,528, 3,036,118, 3,022,335, 3,036,130 and 3,048,548.
3. Alkyl phenols having nine to 12 carbon atoms in the alkyl portion, (straight or branched) ethoxylated with 4-10 molar proportions of ethylene oxide.
4. Ethoxylates of fatty alcohols having eight to 18 carbon atoms per molecule and 5-30 molar proportions of oxyethylene groups.
In addition to being suds-boosters for the above detergent's, the compounds of this invention act as sudsboosters for ampholytic compounds such as hydroxyalkyl methyl taurates and zwitterionic surface-active substances, such as coco dimethyl sulfopropyl betaine.
The compounds of this invention may interact synergistically with all suds-producing surface-active substances to provide mixtures having improved properties beyond those expected on the basis of the properties of the individual components of the mixture. With nonsoaps, the synergism may be evident in suds production or stability. With soaps, the synergism may be evident in the form of reduced lime-soap scum formation.
Thus, in accordance with this invention, new compounds have been formed. The compounds of the present invention have certain noteworthy features. For example, the synergistic suds-producing properties of the compounds with other detergents and sudsing agents are surprising. The antimicrobial properties of the compounds are also surprising. Furthermore, the compounds of the invention are nonionic surfactants with foaming characteristics superior to both well-known anionic and nonionic detergents. The ability to formulate a detergent based on the nonionic materials of the invention having high foaming or dishwashing characteristics with built-in germicidal properties and which at the same time is biodegradable by sewage or natural water bacteria is certainly surprising and unexpected.
The following examples are submitted to illustrate but not to limit this invention. Unless otherwise indicated, all parts and percentages in the specification and claims are based upon weight.
EXAMPLE I in each case afforded the desired product, 2- hydroxydodecyl 2'-hydroxyethyl sulfide.
Compound B, 2hydroxy-C C alkyl 2'- hydroxyethyl sulfide, was prepared in the same manner except that 1,2 epoxy C C alkane was used as one of the reactants.
Compound C, a sulfoxide compound, 2- hydroxydodecyl 2'-hydroxyethyl sulfoxide, was formed by oxidizing Compound A, 2-hydroxydodecyl 2'- hydroxyethyl sulfide, with t-butyl hydroperoxide in methanol. More specifically, a solution of 8 g. of 2- hydroxydodecyl 2'-hydroxyethyl sulfide in 38 ml. of methanol was treated with 3 g. of t-butyl hydrogen peroxide and heated at 50C. for two days. The solvent was evaporated and the crystals washed with hexane.
The dishwashing properties of the compounds prepared according to Examples A, B and C were determined by ascertaining the number of plates washed in duplicate tests with 1.8 g. of each of the above compounds in 6 quarts of 120 ppm water at 116F., both with or without 0.54 g. of coconut fatty acid monoethanolamide (CMEA). The results are shown in Table 1.
TABLE I Boosted with No. of Dishes Comound CMEA Washed Compound No -24 B No 20 A Yes 38-42 B Yes 42 C Yes 42 This example shows that the sulfides and a corresponding sulfoxide within the purview of the present invention have excellent dishwashing properties.
EXAMPLE. II
The compounds listed in Table 2 are other compounds that are considered to be suitable detergents. They may be prepared by the same procedure described in Example I by varying the reactants to provide the required end product. i
TABLE 2 2-hydroxyundecyl 2-hydroxyethyl sulfide; 2-hydroxydodecyl 2',3'-dihydroxypropyl sulfide; 2-hydroxydodecyl 2'-hydroxypropyl sulfide;
(2-hydroxy-3-decyloxy)propyl 2'-hydroxyethyl sulfide;
(2-hydroxy-3-dodecyloxy )propyl propyl sulfide;
(2-hydroxy-3-decyloxy)propyl 2-hydroxypropyl sulfide;
(2-hydroxy-3-dodecylthio)propyl ether;
(2-hydroxy-3-tetradecylthio)propyl 2',3'-dihydroxypropyl ether;
(2-hydroxy-3-dodecylthio)propyl 2-hydroxypropyl ether;
(2-hydroxy-3-dodecylthio)propyl sulfide;
(2-hydroxy-3-tetradecylthio)propyl 2',3'-dihydroxypropyl sulfide;
(2-hydroxy-3-dodecylthio)propyl 2'-hydroxypropyl sulfide; and corresponding sulfoxides thereof.
EXAMPLE Ill The germicidal activity of several compounds described in this invention was determined by the Streak Gradient Plate Method.
The Streak Gradient Plate Method is a modification of the gradient plate method of Szybalski, Science 1 16: 46-48 (1952), for the determination of germicide MEC (Minimum Efiective Concentration) values. This method employs streaks of several organisms per plate.
As shown in Table 3, certain compounds of the invention have surprisingly high antimicrobial activity and they are superior to well-known germicides and soaps against a number of micro-organisms.
TABLE 3 Germicidal Activity by the Gradient Streak Plate Method 2'-hydroxyethyl 2 -hydroxyethyl Minimum Effective Concentration (MEC) in ppm Sa Mc Sf Ca An Compound Z-hydroxydodecyl Culture Codes: Sa S.aureu.r
Mc M.candidu.r Sf Srrepfaecalis Ca C.albicans An Am'ger Having set forth the general nature and specific embodiments of the present invention, the true scope is now particularly pointed out in the appended claims.
What is claimed is:
l. A detergent which is 2-hydroxydodecyl 2- hydroxyethyl sulfide.
2. A detergent which is 2-hydroxy-C,,C, alkyl 2'- hydroxyethyl sulfide.
3. A detergent which is Z-hydroxydodecyl 2'- hydroxyethyl sulfoxide.
e a a a a UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3, 758,595 Dated Sept. 11, 1973 Patent No.
Inventor) Vincent Lamberti and Henry Lamaire It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 7, line 44 (Table 1) "comound" should be "compound";
Column 7, Table 1, "compound" ,should be -A--.
Signed and sealed this 16th day' of July 1974.
(SEAL) Att-est:
c. MARSHALL DANN Mc-COY M. GIBSON; JR. Attesting Officer Commissioner of Patents
Claims (2)
- 2. A detergent which is 2-hydroxy-C11-C14 alkyl 2''-hydroxyethyl sulfide.
- 3. A detergent which is 2-hydroxydodecyl 2''-hydroxyethyl sulfoxide.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US50229965A | 1965-10-22 | 1965-10-22 | |
US76436268A | 1968-08-07 | 1968-08-07 | |
US11307971A | 1971-02-05 | 1971-02-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3758595A true US3758595A (en) | 1973-09-11 |
Family
ID=27381276
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US502299A Expired - Lifetime US3427248A (en) | 1965-10-22 | 1965-10-22 | Detergent |
US764362A Expired - Lifetime US3562337A (en) | 1965-10-22 | 1968-08-07 | Detergent |
US00113079A Expired - Lifetime US3758595A (en) | 1965-10-22 | 1971-02-05 | Detergent |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US502299A Expired - Lifetime US3427248A (en) | 1965-10-22 | 1965-10-22 | Detergent |
US764362A Expired - Lifetime US3562337A (en) | 1965-10-22 | 1968-08-07 | Detergent |
Country Status (11)
Country | Link |
---|---|
US (3) | US3427248A (en) |
BE (1) | BE688734A (en) |
CH (1) | CH495421A (en) |
DE (1) | DE1617213A1 (en) |
FI (1) | FI45339C (en) |
FR (1) | FR1500525A (en) |
GB (1) | GB1135640A (en) |
LU (1) | LU52225A1 (en) |
NL (2) | NL150355B (en) |
NO (1) | NO119603B (en) |
SE (1) | SE325089B (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3988377A (en) * | 1965-10-22 | 1976-10-26 | Lever Brothers Company | Hydroxy substituted sulfoxides and thiothers |
USRE29243E (en) * | 1968-10-08 | 1977-05-31 | Henkel & Cie G.M.B.H. | Polyalkyleneglycol ethers of hydroxyalkylmercaptans and process |
US4042632A (en) * | 1974-09-23 | 1977-08-16 | Sandoz Ltd. | Polyoxy sulfoxides and sulfones as antistatic agents |
US4310698A (en) * | 1978-10-20 | 1982-01-12 | Ciba-Geigy Corporation | Fluorochemical non-ionic surfactants |
US4460791A (en) * | 1978-09-22 | 1984-07-17 | Ciba-Geigy Corporation | Oil recovery by fluorochemical surfactant waterflooding |
US4608392A (en) * | 1983-08-30 | 1986-08-26 | Societe Anonyme Dite: L'oreal | Method for producing a non greasy protective and emollient film on the skin |
US4656030A (en) * | 1980-07-21 | 1987-04-07 | L'oreal | Surface-active oligmers, a process for their preparation and compositions containing them |
US4778675A (en) * | 1979-06-07 | 1988-10-18 | L'oreal | Perfluorinated surface-active oligomers, process for their preparation and compositions containing these oligomers |
US20110143885A1 (en) * | 2001-11-13 | 2011-06-16 | Cybex International, Inc. | Exercise device for cross training |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
LU51542A1 (en) * | 1966-07-12 | 1968-03-12 | ||
US3959460A (en) * | 1967-08-07 | 1976-05-25 | L'oreal | Cosmetic compositions containing anionic surface active agent containing mono- or polyhydroxylated mono- or poly ether chains and a terminal acid group |
US3998948A (en) * | 1968-11-05 | 1976-12-21 | Societe Anonyme Dite: L'oreal | Surface active agent containing hydroxylated alkylsulfinyl chains and composition containing surface active agent having hydroxylated alkylthio and/or hydroxylated alkylsulfinyl chains |
US3860625A (en) * | 1969-02-10 | 1975-01-14 | Chevron Res | Ethoxylated hydrocarbyl butanediols and their disulfate derivatives as phosphate-free compositions |
US3954884A (en) * | 1970-01-12 | 1976-05-04 | Monsanto Company | Method for producing beta hydroxy ethylene glycol ethers |
US3984480A (en) * | 1970-05-12 | 1976-10-05 | L'oreal | Polyhydroxyl monosulfoxide surfactant |
US3966398A (en) * | 1970-05-12 | 1976-06-29 | L'oreal | Hair dyeing composition containing a non-ionic surfactant |
JPS4920169B1 (en) * | 1970-12-15 | 1974-05-23 | ||
BE791534A (en) * | 1971-11-18 | 1973-05-17 | Oreal | |
US3856691A (en) * | 1972-12-15 | 1974-12-24 | Texaco Inc | Lubricating oil composition |
DE2331014C2 (en) * | 1973-06-18 | 1982-06-24 | Henkel KGaA, 4000 Düsseldorf | Ethoxylation products, a process for their production and their use in detergents and cleaning agents |
US3932532A (en) * | 1973-06-01 | 1976-01-13 | Ici United States Inc. | Ethers of polyglycerol |
US3988378A (en) * | 1974-01-10 | 1976-10-26 | Ciba-Geigy Corporation | Reaction product of mercaptans, alkylene oxides and glycidol |
DE2455287C3 (en) * | 1974-11-22 | 1987-12-03 | Basf Ag, 6700 Ludwigshafen | Use of water-in-oil emulsifiers |
US4086279A (en) * | 1975-02-07 | 1978-04-25 | Basf Wyandotte Corporation | Nonionic surfactants |
US4098713A (en) * | 1975-12-24 | 1978-07-04 | The Procter & Gamble Company | Detergent compositions |
US4206070A (en) * | 1975-12-24 | 1980-06-03 | The Procter & Gamble Company | Detergent compositions |
CA1081574A (en) * | 1975-12-24 | 1980-07-15 | Kenneth L. Jones | Detergent compositions |
US4411819A (en) * | 1979-10-22 | 1983-10-25 | Basf Wyandotte Corporation | Thickening aqueous compositions with polyethers modified with alpha-olefin oxides |
LU85952A1 (en) * | 1985-06-14 | 1987-01-13 | Oreal | NOVEL HEMIACETAL COMPOUNDS AND THEIR APPLICATIONS |
US4976953A (en) * | 1987-03-06 | 1990-12-11 | The Procter & Gamble Company | Skin conditioning/cleansing compositions containing propoxylated glycerol derivatives |
DE3815291A1 (en) * | 1988-05-05 | 1989-11-23 | Basf Ag | WAFER ACID CLEANSER FORMULATIONS |
KR19990067606A (en) * | 1995-11-16 | 1999-08-25 | 미첼 킴 에스. | Liquid Dish Washing Detergent |
US7138365B2 (en) * | 2001-07-19 | 2006-11-21 | Kawaken Fine Chemical Co., Ltd. | Thickener comprising hydroxyalkylated polyhydric alcohol ether compound and high-viscosity liquid detergent composition containing the same |
US7098181B2 (en) * | 2002-05-22 | 2006-08-29 | Kao Corporation | Liquid detergent composition |
TW200504201A (en) * | 2003-04-08 | 2005-02-01 | Kao Corp | Liquid detergent composition |
DE102004047553A1 (en) * | 2004-06-16 | 2006-01-05 | Cognis Ip Management Gmbh | Rinse aid containing polyol alkyl ethers |
DE102004048779A1 (en) * | 2004-10-07 | 2006-04-13 | Cognis Ip Management Gmbh | Cleaning agent containing Polyolhydroxyalkylether |
WO2011052113A1 (en) * | 2009-10-28 | 2011-05-05 | 三洋化成工業株式会社 | Anti-bacterial agent |
JP5086467B1 (en) * | 2011-08-30 | 2012-11-28 | 株式会社ピーアンドピーエフ | Cleaning composition |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2565986A (en) * | 1945-11-24 | 1951-08-28 | Sharples Chemicals Inc | Surface active agents |
US3158663A (en) * | 1959-07-28 | 1964-11-24 | Bayer Ag | Latex foam stabilized with an alkylated polyether-polythioether glycol |
GB1167202A (en) * | 1967-03-08 | 1969-10-15 | Arthur D Little Res Inst | Hydroxy-Substituted Thio-Ethers. |
US3522311A (en) * | 1968-04-15 | 1970-07-28 | Dow Chemical Co | Alkylsulfinylpropanediols |
US3539635A (en) * | 1967-06-26 | 1970-11-10 | Lever Brothers Ltd | 1-n-dodecylsulfinyl-2-hydroxy-3-methyl sulfinylpropane |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL83993C (en) * | 1951-05-15 | |||
US3240819A (en) * | 1960-02-17 | 1966-03-15 | Monsanto Co | Ethenoxy-substituted alkanols |
US3350460A (en) * | 1963-03-13 | 1967-10-31 | Lever Brothers Ltd | Method for the preparation of glycerol alpha ethers and thio ethers |
US3308068A (en) * | 1963-04-25 | 1967-03-07 | Pan American Petroleum Corp | Detergent composition |
-
1965
- 1965-10-22 US US502299A patent/US3427248A/en not_active Expired - Lifetime
-
1966
- 1966-08-18 NL NL666611611A patent/NL150355B/en not_active IP Right Cessation
- 1966-10-20 DE DE19661617213 patent/DE1617213A1/en active Pending
- 1966-10-20 GB GB46884/66A patent/GB1135640A/en not_active Expired
- 1966-10-20 CH CH1517666A patent/CH495421A/en not_active IP Right Cessation
- 1966-10-20 FI FI662759A patent/FI45339C/en active
- 1966-10-21 BE BE688734D patent/BE688734A/xx unknown
- 1966-10-21 LU LU52225D patent/LU52225A1/xx unknown
- 1966-10-21 FR FR81164A patent/FR1500525A/en not_active Expired
- 1966-10-21 NO NO165289A patent/NO119603B/no unknown
- 1966-10-21 SE SE14444/66A patent/SE325089B/xx unknown
- 1966-10-21 NL NL6614867A patent/NL6614867A/xx unknown
-
1968
- 1968-08-07 US US764362A patent/US3562337A/en not_active Expired - Lifetime
-
1971
- 1971-02-05 US US00113079A patent/US3758595A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2565986A (en) * | 1945-11-24 | 1951-08-28 | Sharples Chemicals Inc | Surface active agents |
US3158663A (en) * | 1959-07-28 | 1964-11-24 | Bayer Ag | Latex foam stabilized with an alkylated polyether-polythioether glycol |
GB1167202A (en) * | 1967-03-08 | 1969-10-15 | Arthur D Little Res Inst | Hydroxy-Substituted Thio-Ethers. |
US3539635A (en) * | 1967-06-26 | 1970-11-10 | Lever Brothers Ltd | 1-n-dodecylsulfinyl-2-hydroxy-3-methyl sulfinylpropane |
US3522311A (en) * | 1968-04-15 | 1970-07-28 | Dow Chemical Co | Alkylsulfinylpropanediols |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3988377A (en) * | 1965-10-22 | 1976-10-26 | Lever Brothers Company | Hydroxy substituted sulfoxides and thiothers |
USRE29243E (en) * | 1968-10-08 | 1977-05-31 | Henkel & Cie G.M.B.H. | Polyalkyleneglycol ethers of hydroxyalkylmercaptans and process |
US4042632A (en) * | 1974-09-23 | 1977-08-16 | Sandoz Ltd. | Polyoxy sulfoxides and sulfones as antistatic agents |
US4460791A (en) * | 1978-09-22 | 1984-07-17 | Ciba-Geigy Corporation | Oil recovery by fluorochemical surfactant waterflooding |
US4310698A (en) * | 1978-10-20 | 1982-01-12 | Ciba-Geigy Corporation | Fluorochemical non-ionic surfactants |
US4778675A (en) * | 1979-06-07 | 1988-10-18 | L'oreal | Perfluorinated surface-active oligomers, process for their preparation and compositions containing these oligomers |
US4656030A (en) * | 1980-07-21 | 1987-04-07 | L'oreal | Surface-active oligmers, a process for their preparation and compositions containing them |
US4608392A (en) * | 1983-08-30 | 1986-08-26 | Societe Anonyme Dite: L'oreal | Method for producing a non greasy protective and emollient film on the skin |
US20110143885A1 (en) * | 2001-11-13 | 2011-06-16 | Cybex International, Inc. | Exercise device for cross training |
Also Published As
Publication number | Publication date |
---|---|
NO119603B (en) | 1970-06-08 |
NL6611611A (en) | 1967-04-24 |
LU52225A1 (en) | 1967-04-21 |
FI45339B (en) | 1972-01-31 |
US3562337A (en) | 1971-02-09 |
NL6614867A (en) | 1967-04-24 |
US3427248A (en) | 1969-02-11 |
DE1617213A1 (en) | 1971-02-25 |
CH495421A (en) | 1970-08-31 |
SE325089B (en) | 1970-06-22 |
FI45339C (en) | 1972-05-10 |
GB1135640A (en) | 1968-12-04 |
NL150355B (en) | 1976-08-16 |
FR1500525A (en) | 1967-11-03 |
BE688734A (en) | 1967-04-21 |
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