US3755435A - N-(2-hydroxy-higher hydrocarbyl)-n-lower hydrocarbyl-aminocarboxylates - Google Patents

N-(2-hydroxy-higher hydrocarbyl)-n-lower hydrocarbyl-aminocarboxylates Download PDF

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US3755435A
US3755435A US00880991A US3755435DA US3755435A US 3755435 A US3755435 A US 3755435A US 00880991 A US00880991 A US 00880991A US 3755435D A US3755435D A US 3755435DA US 3755435 A US3755435 A US 3755435A
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hydrocarbyl
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B Sundby
E Kenney
H Wixon
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Colgate Palmolive Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

  • N-(Z-hydroxy-higher hydrocarbyl)-N-lower hydrocarbyl-aminocarboxylates or the corresponding aminocarboxylic acids are of the formula RICH(OH)CHQ-I!IR3COOX wherein R is an aliphatic hydrocarbon radical of to 20 carbon atoms, R is a hydrocarbon radical of 1 to 4 carbon atoms, R is a divalent aliphatic or aromatic hydrocarbon radical of 1 to 9 carbon atoms, and X is either hydrogen or a salt-forming element or radical.
  • R is an acyclic sat urated radical of 12 to 16 carbon atoms
  • R is methyl
  • R is of 1 to 2 carbon atoms
  • X is a monovalent metal or an alkanolamine, such as sodium or triethanolamine.
  • novel compounds are surface active and many exhibit excellent substantivities to fibrous materials, especially cotton. They are useful as detergents or as constituents of detergent preparations. Preferred compounds function very effectively as softening agents, which may be employed in the final rinsing of laundry or textiles, if used alone or in conjunction with other detergent composition materials, in the wash water.
  • the present N-(2- hydroxy-higher hydrocarbyD-N-lower hydrocarbyl-aminocarboxylates may also be converted to the corresponding N-oxides, which are also effective detergents, and many of which may be employed as excellent softening agents for laundry and textiles.
  • This invention relates to novel N-(2-hydroxy-higher hydrocarbyl)-N-lower hydrocarbyl-aminocarboxylates and the corresponding aminocarboxylic acids.
  • These compounds have been found to be useful surface active materials and many are substantive to a wide variety of fibrous substances, such as cotton, wool and synthetic textiles.
  • the invented compounds may be employed as emulsifiers, solubilizers for lipophilic compounds, as wetting agents, detergents and also, in many cases, as softeners for textiles. They are also useful as reagents from which the corresponding N-oxides are produced, such oxides also possessing surface active and textilesubstantive properties.
  • the present compounds were found to be useful surface active agents. They possess detergent activities in both hard and soft waters, at both elevated and lower temperatures, with little clogging foam being produced. In addition, they are excellent softeners of textiles, even when added in the washing step, rather than in the rinse, in a machine-laundering operation. Such activity shows a high degree of substantivity of the products, which is considered to be unpredictable and unexpected in a surface active material that functions to release absorbed and adsorbed substances from textiles and laundry being washed. The present compounds alsopossess anti-static properties, which increase their utility as treatments for clothes and fabrics.
  • novel compounds of the formula which are effective detergents and which also serve to soften fibrous materials, such as cotton, wool and synthetics, e.g., nylon, when applied to them, as in an aqueous wash solution.
  • R is an aliphatic hydrocarbon radical of 10 to 20 carbon atoms
  • R is a hydrocarbon radical of 1 to 4 carbon atoms
  • R is a divalent aliphatic or aromatic hydrocarbon radical of 1 to 9 carbon atoms
  • X is hydrogen or a salt-forming metal or ion.
  • X is an element, it is preferred that it should be an alkali metal, an alkaline earth metal or other suitable salt-forming metal, capable of making the present compounds water soluble.
  • alkylamine or alkanolamine either mono-, dior tri-alkylamine or mono-, dior tri-alkanolamine, in which the alkyl and alkanol groups of the salt-forming amines are of 1 to 4 carbon atoms, preferably of 2 to 3 carbon atoms.
  • the compounds are those Where R is an acyclic saturated radical of 12 to 16 carbon atoms, most preferably linear and terminally joined to the rest of the molecule, R is methyl, R is of 1 to 2 carbon atoms, most preferably of one carbon atom, and X is a monovalent metal or an alkanolamine, e.g., sodium potassium, diisopropanolamine or triethanolamine.
  • R is an acyclic saturated radical of 12 to 16 carbon atoms, most preferably linear and terminally joined to the rest of the molecule
  • R is methyl
  • R is of 1 to 2 carbon atoms, most preferably of one carbon atom
  • X is a monovalent metal or an alkanolamine, e.g., sodium potassium, diisopropanolamine or triethanolamine.
  • the preferred compounds mentioned above are found to be excellent as textile softeners, especially for cotton articles, which may be washed with them, even in the presence of builders, other detersive compounds and additives. They may also be used in normal washing procedures, including the rinsing operation.
  • most preferred compounds are the salts of N-(Z-hydroxy-higher alkyl)-N-lower alkyl-aminocarboxylic acids, wherein the higher alkyl is of 14 to 18 carbon atoms.
  • N-(Z-hydroxy-higher aIkyD-N-methyl glycines especially the alkali metal salts thereof, of which the sodium salts salts are most preferred.
  • such compounds are only slightly etfective or may be essentially ineffective as practical softeners, although they will often have the unexpected advantage of being very useful because of their other surface active properties, such as detergency, often in both hard and soft waters and at elevated and comparatively low washing temperatures.
  • substituents are amino, hydroxy, halogen, e.g., chlorine, bromine, fluorine, and hydroxy-lower alkyl wherein the alkyl is up to four carbon atoms.
  • the number of such substituents present will usually be small, often no more than four per molecule and usually, less than three. It is generally preferable that compounds be unsubstituted but many of the substituted compounds are often of utilities similar to those of the compounds literally within the formulas given and therefore, are also contemplated as relevant to this invention.
  • mixed salts maybe employed, as may be acid salts.
  • the hydrocarbyl groups, R include both saturated and relatively slightly unsaturated radicals.
  • one or two double bonds per R are acceptable and are within the present invention, although it is preferred to employ alkyl groups as R
  • alkyl groups straight chain alkyls, which are terminally joined to the carbon to which the hydroxy group is attached, are highly preferred, and are intended to be described herein, unless otherwise indicated, although those alkyl groups which are not terminally joined also possess utility, as do various alkyl groups of nonlinear structures.
  • keryl alkyl derived from kerosene
  • various polymeric radicals such as propylene tetramer and pentamer, a preferred form of which is often such a mixture thereof as to average 13 carbon atoms per group.
  • cycloalkyl groups employed, either alone or with linear alkyls, e.g., cyclohexyldecyl.
  • R it is important that the hydrocarbyl radical be short chain.
  • R may also include one or two aliphatic double bonds and may possess aromatic unsaturation.
  • aromatic groups such as phenyl, are useful and within the invention, as are cycloaliphatic groups, e.g., cyclohexyl, cyclobutyl, it is preferred to employ linear alkylene, terminally joined to the amino nitrogen and the carboxyl group.
  • X may be hydrogen, it is preferred that it be a salt-forming ion and of the salt-forming ions those which are monovalent are usually best.
  • salts made tend to be more stable and freer flowing than the acids and because of this and because the product is most frequently employed in alkaline solutions, the salts are preferable. However, even if water solubility is low, salts of such solubility can be employed in other polar media and may even be useful in aqueous media, especially if solvents or solubilizers are present.
  • novel compounds of the present invention can be prepared by reacting a hydrocarbon-1,2-epoxide with an N-substituted aminocarboxylic acid. Such reactions are in accordance with the equation.
  • the reaction normally goes in aqueous solution wherein the aminoacetic acid, as a salt dissolved in the aqueous medium, is mixed with an approximately stoichiometric proportion of the hydrocarbon-1,2-epoxide.
  • An additional solvent such as alcohol, may be employed.
  • the reaction mixture is heated, often to about the boiling point, to speed the reaction. After cooling, water may be removed therefrom by any convenient means, e.g., freeze drying, and if desired, the product may be recrystallized, as from alcohol.
  • N-substituted aminoacids and their salts are known compounds, as are the hydrocarbon epoxides. Methods for making such compounds from readily available starting materials are known to those of skill in the art and accordingly, they need not be described herein. In the reaction of although stoichiometric proportions are preferred, it is within the present invention to use an excess of either reagent, depending upon the circumstances, with the usual excess not exceeding 50% and only in rare cases being in excess of 20%. Sometimes an excess of a reagent, such as the epoxide, results in an impure product, in which cases use thereof is avoided.
  • the excess employed will be no more than
  • the reactions may be effected at various temperatures, depending upon the particular reagents, it is normally preferred that during at least part of the reaction, the reaction mixture should be at a temperature within the range of 60 C. to 170 0, preferably 70 C. to 130 C.
  • the reagents will usually be admixed at a lower temperature, often approximating room temperature. Such lower temperature will usually be within the range of C. to 40 C.
  • the times of contact of the reagents with each other at the temperatures mentioned will normally be 15 seconds to one hour at the lower temperature and subsequently, from five minutes to 24 hours at the higher temperature.
  • the time of contact at the lower temperature will be from one minute to ten minutes and at the higher temperature it will be from minutes to four hours.
  • the reaction medium will usually be aqueous and one or both of the reagents may be admixed with the other as an aqueous solution or suspension.
  • the aminoacid salt be employed, in aqueous solution.
  • the proportion of water in the reaction mixture may be variable, it will usually be within the range of from 20 to 90% of the reaction mixture.
  • the reaction mixture After holding at the higher temperature, preferably the boiling or reflux temperature, for sufiicient time for completion of the reaction, which is often evidenced by thickening of the product, the reaction mixture is cooled and the water present is removed by a suitable technique, such as by freeze drying, evaporation, distillation, or selective extraction, depending upon the particular materials being employed.
  • the product resulting usually present as a residue, may be deoiled with lower ketone, preferably boiling acetone, which removes n'onsalts, such as epoxide, olefins and byproducts e.g., diols.
  • the residue left is a white solid in most cases, the desired product.
  • a suitable solvent such as a lower alcohol, e.g., absolute ethanol.
  • a suitable solvent such as a lower alcohol, e.g., absolute ethanol.
  • the lower ketone is of 3 to 6 carbon atoms, and the alcohols are usually of 1-6 carbon atoms.
  • the products produced are usually white and are sufficiently free-flowing to be successfully employable as detergent compositions or textile softeners, either by themselves or with other materials.
  • solvents include acetone, lower alcohols of l to 4 carbon atoms, glycols and other known suitable solvents for reactions such as this.
  • novel compounds made according to the present invention are usually employed in aqueous solution, either alone or with other materials, to produce improved detersive compositions or emulsions and to act as wetting agents. They are also used in such compositions to soften fabrics, especially cotton textiles, although they also act to improve the feel of other fabrics, including wool and synthetics.
  • the invented compounds usefully wash and soften textiles in a single operation. Such activities, wherein the softening agents are eifective despite being added to the wash water, rather than to the rinse water and wherein they themselves act to remove other substances from the fibers or laundry being washed, in the cleaning process, are considered to be unusual and unpredicatable.
  • EXAMPLE 1 400 parts of n-dodecane-l,2-epoxide and 700 parts of a 32% aqueous solution of sodium N-methyl glycinate are admixed with vigorous stirring at room temperature (25 C.) over a period of two minutes. Then, the reaction mixture is heated to a boil at C. and heating is continued with reflux for one hour, until the mixture becomes too viscous to boil. The reaction mixture is then cooled to room temperature, after which it is frozen and moisture vapor is removed by sublimation (freeze drying). The residue remaining is treated several times with a total of 1000 parts of boiling acetone. The deoiled residue is dissolved in 800 parts of absolute ethanol at a temperature of 7 0 C.
  • the chemical identity of the product is ascertained by titration with hydrochloric acid of know normality, indicating that the molecular weight of the product is about 300. Titration with perchloric acid in acetic acid indicates an equivalent weight of about 150. The theoretical molecular and equivalent weights are 295 and 148, respectively.
  • an infrared spectrum of the compound shows a band at 3.1 microns, indicating the presence of hydroxyl, and gtgtg bands at 6.2 and 7.1 microns, indentifying the
  • the glycine salt employed is an ammonium salt, a diammonium salt, a triethanolamine salt, a mixture of sodium and potassium salts, or a diisopropylamine salt, and the same general method for manufacture described above is employed, the corresponding N-(Z-hydroxyalkyl)-N-methyl glycinates are obtained. In such reactions stoichiometrically equivalent amounts of such glycinate reagents will be employed.
  • Example 1 The procedure of Example 1 is also carried out, utilizmg different aminoacetic acid salts, such as N-methyl aminopropionic acid, sodium salt; N-ethyl aminobutyric acid, potassium salt; N-isopropyl amino-n-pentanoic acid,
  • EXAMPLE 2 342 parts of a 32.4% solution of sodium N-methyl glycinate are admixed with 212 parts of n-tetradecane- 1,2-epoxide, with vigorous stirring, at room temperature, over a period of three minutes. The reaction mixture is then heated under reflux, utilizing a foam trap, for a period of 45 minutes, until the mixture becomes too viscous for further heating and foaming becomes excessive. At this point heating is stopped and the reaction mixture is allowed to cool, after which it is frozen and the water is removed therefrom by freeze-drying. Unreacted epoxide is extracted by heating the dried product two or three times, each time with approximately 200 parts of boiling acetone. The residue is taken up in 500 parts of absolute ethanol and the alcohol-insolubles, which include unreacted sodium N-methyl glycine, are removed by centrifuging the solution at 60 C. The solution is then allowed to cool and the desired product,
  • N-(2-hydroxy-n-tetradecyl)-methyl glycine, sodium salt crystallizes and is separated by filtration.
  • the product resulting, recrystallized from absolute ethanol, is a completely water soluble white powder which possesses strong foaming action. Its melting point is 119-123 C.
  • the product obtained is a white powder of a melting point of ll41l7 C., which is found to be substantially insoluble in water at room temperature but which makes a viscous solution when heated. This product does not foam well.
  • EXAMPLE 3 The method of Example 1 is followed, using equimolar proportions of the reagents, sodium sarcosine and mixed normal C1548 olefin oxide. The oxygen is present across a terminal bond of the olefin, making an epoxide corresponding to those previously recited, except for being based on mixed olefin, rather than being a substantially pure material. After completion of the reaction, water is removed by freeze drying. The product resulting is not purified further.
  • a mixed C1144 alkyl alpha-epoxide having as an average a molecular weight of 210, is reacted with sodium sarcosinate, utilizing about a 10% excess of the sareosinate.
  • 315 parts of the mixed epoxides and 600 parts of 30% aqueous solution of sodium sarcosinate are stirred together and heated to boiling, 105-110" C. After 30 minutes, the reaction mixture becomes viscous and 200 parts of cold water are added to quench the boiling mixture. The mixture is stirred at 100 C. for two more hours to insure complete reaction.
  • the product resulting is comprised 60% of the desired active ingredient, the N-(2-hydroxy-C alkyl)-sarcosine, sodium salt.
  • Such material may be subsequently oxidized by gradual addition, with stirring, of 180 parts of a 30% aqueous hydrogen peroxide solution.
  • the product obtained comprises 65% of the corresponding N-oxide.
  • EXAMPLE 4 The compounds described in Examples 1 and 2 are tested for their utilities as textile softeners and as detergents. Although various of these compounds have excellent detersive and softening effects, the best effects appear to be obtained from N-(2-hydroxy-higher alkyl)- N-methyl glycine, sodium salt, wherein the higher alkyl is of 14 to 18 carbon atoms, is straight chain and is terminally joined to the nitrogen atom.
  • N-(Z-hydroxyoctadecyl)-N-methyl glycine, sodium salt When tested as fabric softeners, N-(Z-hydroxyoctadecyl)-N-methyl glycine, sodium salt, N-(Z-hydroxyhexadecyl)- I-methyl glycine, sodium salt, N-(Z-hydroxytetradecyl)-N-methyl glycine, sodium salt, and N-(Z-hydroxydodecyl)-N-methyl glycine, sodium salt obtain ratings of 10+, 10, 8 and 3, respectively, indicating their softening effects on cotton. They also impart anti-static properties to the cotton. The test by which they are evaluated for softening action is one in which one-half of a terrycloth towel is washed in 3 gallons of 10 p.p.m.
  • the swatches are rinsed and are tested for whiteness, using a color difference meter.
  • the comparison of readings, using the R scale, between the materials before and after washing, is made and the delta R is calculated.
  • the greater the delta R the more efficient is the soil removal and the better is the detergency obtained.
  • Linear tridecyl benzene sulfonate, as the sodium salt, is usually employed as a standard of comparison for detergency in this test.
  • the pressure vessel, a Blew-Knox autoclave is sealed after mixing of the reactants and the temperature is raised to about 330 F. by passing steam at a pressure of 90 lbs/sq. in. through the autoclave jacket.
  • R is an aliphatic hydrocarbon radical of 10 to 20 carbon atoms, containing at most, 2 aliphatic double bonds
  • R is a hydrocarbon radical of 1 to 4 carbon atoms, containing at most, a single aliphatic double bond
  • R is a divalent aliphatic hydrocarbon radical, containing at most, 2 aliphatic double bonds or aromatic hydrocarbon radical of 1 to 9 carbon atoms
  • X is selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, ammonium, monoalkylamine, dialkylamine, trialkylamine, monoalkanolamine, dialkanolamine, and trialkanolamine, in which the alkyl and alkanol groups are 1 to 4 carbon atoms.
  • R is alkyl, terminally joined to the rest of the molecule, R is alkyl of 1 to 2 carbon atoms, R is alkylene of 1 to 4 carbon atoms and X is monovalent.
  • R is of 12 to 16 carbon atoms
  • R is methyl
  • R is alkylene of 1 to 2 carbon atoms
  • X is alkali metal or triethanolamine.

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  • Life Sciences & Earth Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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US00880991A 1969-11-28 1969-11-28 N-(2-hydroxy-higher hydrocarbyl)-n-lower hydrocarbyl-aminocarboxylates Expired - Lifetime US3755435A (en)

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Application Number Priority Date Filing Date Title
US88090969A 1969-11-28 1969-11-28
US88098269A 1969-11-28 1969-11-28
US88099269A 1969-11-28 1969-11-28
US88091569A 1969-11-28 1969-11-28
US88097769A 1969-11-28 1969-11-28
US88099169A 1969-11-28 1969-11-28
US324314A US3864389A (en) 1969-11-28 1973-01-17 N-(2-Hydroxyhydrocarbyl) Iminodicarboxylates

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US00880991A Expired - Lifetime US3755435A (en) 1969-11-28 1969-11-28 N-(2-hydroxy-higher hydrocarbyl)-n-lower hydrocarbyl-aminocarboxylates
US00880915A Expired - Lifetime US3726797A (en) 1969-11-28 1969-11-28 Detergent compositions and processes incorporating n-(2-hydroxy hydrocarbyl)iminodicarboxylates
US00880992A Expired - Lifetime US3725473A (en) 1969-11-28 1969-11-28 N-(2-hydroxyhydrocarbonyl) iminodicarboxylates
US880977A Expired - Lifetime US3700607A (en) 1969-11-28 1969-11-28 Detergent compositions containing n-oxide-aminocarboxylates
US00880909A Expired - Lifetime US3728385A (en) 1969-11-28 1969-11-28 N-oxide-iminodicarboxylates
US324314A Expired - Lifetime US3864389A (en) 1969-11-28 1973-01-17 N-(2-Hydroxyhydrocarbyl) Iminodicarboxylates

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US00880992A Expired - Lifetime US3725473A (en) 1969-11-28 1969-11-28 N-(2-hydroxyhydrocarbonyl) iminodicarboxylates
US880977A Expired - Lifetime US3700607A (en) 1969-11-28 1969-11-28 Detergent compositions containing n-oxide-aminocarboxylates
US00880909A Expired - Lifetime US3728385A (en) 1969-11-28 1969-11-28 N-oxide-iminodicarboxylates
US324314A Expired - Lifetime US3864389A (en) 1969-11-28 1973-01-17 N-(2-Hydroxyhydrocarbyl) Iminodicarboxylates

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DE (1) DE2057355A1 (en:Method)
FR (1) FR2099030A5 (en:Method)
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Cited By (9)

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US4039460A (en) * 1973-11-10 1977-08-02 Henkel & Cie G.M.B.H. Hydroxyalkyl-aminobutyric acid lubricants for the cold-working of aluminum
US4055596A (en) * 1974-09-13 1977-10-25 Merck & Co., Inc. 11,12-Seco-prostaglandins
US4090845A (en) * 1975-12-15 1978-05-23 Henkel Kommanditgesellschaft Auf Aktien Process for the dyeing of polyacrylonitrile fibrous material
US4259249A (en) * 1979-06-13 1981-03-31 The Procter & Gamble Company Preparation of hydroxyl zwitterionic compounds
US4358368A (en) * 1979-03-02 1982-11-09 Berol Kemi Ab Process for the froth flotation of calcium phosphate-containing minerals and flotation agents therefor
US4511733A (en) * 1981-12-25 1985-04-16 Daikin Kogyo Co., Ltd. Fluorine-containing aminocarboxylic acid compounds
US4914232A (en) * 1982-04-12 1990-04-03 The B. F. Goodrich Company Polysubstituted 2-morpholones, related compounds, processes for their preparation, and U-V light stabilized compositions
US5089614A (en) * 1982-04-12 1992-02-18 The B. F. Goodrich Company Polysubstituted 2-morpholones
US5243072A (en) * 1988-06-13 1993-09-07 Th. Goldschmidt Ag Betaine group-containing polysaccharides with recurring anhydroglucose units, their synthesis and their use in cosmetic preparations

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888797A (en) * 1970-08-04 1975-06-10 Carapus Company Limited Detergent composition
US3888798A (en) * 1970-11-16 1975-06-10 Colgate Palmolive Co Liquid detergent composition
DE2111950A1 (de) * 1971-03-12 1972-11-23 Degussa Verwendung von Salzen bestimmter Hydroxyalkylaminosaeuren als waschaktive Substanzen
FR2327310A1 (fr) * 1972-11-30 1977-05-06 Modokemi Ab Composition detergente liquide
US3953379A (en) * 1973-10-26 1976-04-27 Colgate-Palmolive Company Manufacture of improved aqueous alkali metal silicate-alkali metal hydroxyalkyl iminodiacetate compositions
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US4129527A (en) * 1974-11-07 1978-12-12 The Clorox Company Liquid abrasive detergent composition and method for preparing same
SE386083B (sv) * 1975-01-15 1976-08-02 Berol Kemi Ab Forfarande for flotation av bly-, uran- och sellsynta jordartsmineral ur malmer
DE2616800A1 (de) * 1976-04-15 1977-11-03 Henkel & Cie Gmbh Kosmetische reinigungsmittel
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US4359413A (en) * 1981-03-17 1982-11-16 The Procter & Gamble Company Solid detergent compositions containing alpha-amine oxide surfactants
US4375422A (en) * 1981-11-12 1983-03-01 Lever Brothers Company Homogeneous detergent containing nonionic and surface active iminodipropionate
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DE3544045A1 (de) * 1984-12-24 1986-06-26 Asta-Werke Ag Chemische Fabrik, 4800 Bielefeld Neue n-(2-hydroxyalkyl)-aminosaeuren und ihre derivate, verfahren zu ihrer herstellung und diese enthaltende pharmazeutische praeparate
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DE3712330A1 (de) * 1987-04-11 1988-10-20 Basf Ag 2-hydroxy-3-amino-propionsaeure-n,n-diessigsaeure und ihre derivate, ihre herstellung und verwendung insbesondere als komplexbildner und diese enthaltende wasch- und reinigungsmittel
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FR2707289B1 (fr) * 1993-07-06 1995-08-11 Chemoxal Sa Procédé de préparation d'un composé hydroxylé d'amine secondaire ou tertiaire.
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US5843029A (en) * 1995-10-16 1998-12-01 Gerber/Baby Care Manual breast pump
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US4039460A (en) * 1973-11-10 1977-08-02 Henkel & Cie G.M.B.H. Hydroxyalkyl-aminobutyric acid lubricants for the cold-working of aluminum
US4055596A (en) * 1974-09-13 1977-10-25 Merck & Co., Inc. 11,12-Seco-prostaglandins
US4090845A (en) * 1975-12-15 1978-05-23 Henkel Kommanditgesellschaft Auf Aktien Process for the dyeing of polyacrylonitrile fibrous material
US4358368A (en) * 1979-03-02 1982-11-09 Berol Kemi Ab Process for the froth flotation of calcium phosphate-containing minerals and flotation agents therefor
US4259249A (en) * 1979-06-13 1981-03-31 The Procter & Gamble Company Preparation of hydroxyl zwitterionic compounds
US4511733A (en) * 1981-12-25 1985-04-16 Daikin Kogyo Co., Ltd. Fluorine-containing aminocarboxylic acid compounds
US4914232A (en) * 1982-04-12 1990-04-03 The B. F. Goodrich Company Polysubstituted 2-morpholones, related compounds, processes for their preparation, and U-V light stabilized compositions
US5089614A (en) * 1982-04-12 1992-02-18 The B. F. Goodrich Company Polysubstituted 2-morpholones
US5243072A (en) * 1988-06-13 1993-09-07 Th. Goldschmidt Ag Betaine group-containing polysaccharides with recurring anhydroglucose units, their synthesis and their use in cosmetic preparations

Also Published As

Publication number Publication date
CH569695A5 (en:Method) 1975-11-28
US3725473A (en) 1973-04-03
FR2099030A5 (en:Method) 1972-03-10
DE2057355A1 (de) 1971-07-22
US3700607A (en) 1972-10-24
GB1319130A (en) 1973-06-06
BE759533A (fr) 1971-04-30
US3728385A (en) 1973-04-17
CH558332A (de) 1975-01-31
US3726797A (en) 1973-04-10
CA941557A (en) 1974-02-12
CA942458A (en) 1974-02-26
NL7017496A (en:Method) 1971-06-02
US3864389A (en) 1975-02-04
CA941556A (en) 1974-02-12

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