US2159967A

US2159967A - Oxides of amino acids

Info

Publication number: US2159967A
Application number: US202358A
Authority: US
Inventors: Engelmann Max
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1938-04-15
Filing date: 1938-04-15
Publication date: 1939-05-30
Anticipated expiration: 1956-05-30

Description

wherein dialkylamino 5 hydrocarbon radical having a Patented May 30, 1939 UNITED STATES PATENT OFFICE OXIDES OF AMINO ACIDS Max Engelmann,

E. I. .du Pont de Nemours & Company, a corporation of Delaware Application April 15, 1938, erial No. 202,358

mlngton, DeL,

No Drawlnms 13 Claims. (01. Zeb- 404) This invention relates to new and useful surface active materials. More particularly it relates to new pentavalent nitrogen compounds containing acidic groups which are superior to soap and 5 soap substitutes. Still more particularly it relates to di-alkyl-oxamino long chain fatty acids and the salts thereof and processes for preparing the same. r

It is an object of this invention to produce new and useful surface active materials which may be substituted for or'used in admixture with various soaps and soap substitutes. A still further object is to produce new products which overcome many of the disadvantages of soap and soap substitutes.

The above and other objects are accomplished in accordance with the herein described invention boxylic acids are reacted with oxidizing agents tov produce dialkyloxamino' aliphatic acids. The acids prepared may be represented by the following general formula;

N*-Rl m t wherein R1 and R2 represent aliphatic or cyclo- 40 aliphatic hydrocarbon radicals, and R3 is an allphatic hydrocarbon radical containing an acidic group, e. g., a carboxylic or sulfonic acid group, least one of the radicals represented by R1, R2 and R3 must have a chain length .of at least 8 45 carbon atoms.

In a more limited sense the invention pertains to penta'valent'nitrogen compounds containing-a carboxylic acid group having. the following general formula:

N-ilr-CO OM- RC 1 I wherein one of the Rs represents an aliphatic chain length of carboxyl group of preceding paragraph may be replaced by a suiand detergent agents.

long chain aliphatic carcarbon an at least '1 atoms, R1 represents phatic or cycloaliphatic hydrocarbon radical conthan 6 carbon atoms, and Ra taining not more containing from 1 to 4 carbon is alkylene radical atoms, and M represents hydrogen or a water soluble salt forming component.

In another valuable form of this invention the the formula of the immediately ionic acid group and the R attached to Rs is a hydrogen atom.

In its preferred embodiment this invention pertains to dialkyl-ox o carboxylic acids and the salts thereof having the general formula:

wherein onefR is an alkyl radical containing at least '1 and preferably 11 to 17 carbon atoms, and the other R is hydrogen and M represents hydrogen or a water soluble salt forming component, e.-- g., alkali or alkaline earth metals and organic amines, such as diethylamin'e, triethanolamine,

etc.

The invention not intended to will be further illustrated but is be limited by the following examples in which the quantities stated are in parts by weight:

. Example I Thirty-one parts of alpha-dimethyl-aminostearicacid which may be prepared-by reacting alpha-brom-stearic acid and dimethyl-amine, 12 parts of hydrogen-pe'roxide-urea compound (Beilstein Vol. III,'p. 54) and 150 parts of methyl alcohol are heated under reflux for 10 hours. The clear solution is then neutralized with 6 parts of a 20% aqueous solution of sodium hydroxide and evaporated on a steam bath to dryness. The crystalline product is a mix ure of the sodium salt and the free dimethyl-oxamino-stearic acid.

It is easily soluble in warm water, forming a very L viscous solution. It is also soluble in methyl alcohol. Calcium or mangesium salt solutions or acids or alkalies do not form insoluble precipitates in aqueous solutions. It is a very effective scouring agent.-

' Example II Fifty parts of alpha-dimethyl-amino-palmitic acid, 200 parts of ethyl alcohol, and 50 parts of hydrogen peroxide (27% aqueous solution), are boiled under reflux for l0.hours. After cooling, a small part of unreacted amino-acid is filtered oil, the filtrate neutralized with sodium hydroside solution and the alcohol evaporated on a steam bath. The residue, containing dimethyl-' ox-amino palmitic acid, shows very similar properties as the corresponding stearic acid derivative.

Example III Sixty parts'of ammonium persulfate are dissolved in 125 parts of a 20% aqueous sulfuric acid solution and mixed with 50 parts of alpha dimethyl-amino-stearic acid. The mixture, ,kept at room temperature, is slowly converted into a paste-like mass. After standing for 48 hours, it is neutralized with 170 parts of 20% sodium hydroxide solution. The resulting product is a gelatinous paste, containing as active ingredient dimetirvl-oxamino-stearic acid.

In place of the specific oxidizing agents of the preceding examples any of the usual types of oxidizing agents which are capable of liberating free oxygen may be used. Other agents which may be substituted are per mono-sulfuric acid (Coros acid) organic peroxides, e. g., benzoylperoxide, sodium hypochlorite, etc.

In place of the dialkyl-amino fatty acids of the preceding ,examples, any acid which complies withthe instructions set forth in the above formulae may be substituted. As further examples of such acids may be mentioned diethyla-amino myristic acid, dimethyl e-amino palmitic acid, methyl-hydroxyethyl a-amino lauric acid, dibutyl a-amino capric acid. Mixtures of alkyl or hydroxyalkyl fatty acids obtained from natural oils or fats such; as coconut oil, palm oil, lard, etc. The class of compounds may be prepared by alkylating a-amino long chain fatty acids, e. g., a-aminolauric acid, a-aminostearic acid a-methylamino palmitic acid, etc. with an alkylating agent in the usual manner, e. g., with methyl or ethyl chloride, dimethyl sulfate, sodium butyl sulfate, ethylene oxide, propylene oxide, cyclohexyl chloride, etc.

Another series of dialkyl-amino long chain fatty acids which may be used are those which may be prepared, for example, by reacting a long chain secondary amine with a halogenated aliphatic acid, preferably a carboxylic acid. Amino acids of this type are methyl-stearyl-aminoacetic acid, propyl-lauryl-aminobutyric acid, octylhydroxyethyl amino-Valerie acid, methyl-decylaminoethane-sulfonic acid, ethyl heptadecylamino propane sulfonic acid, etc.

The long chain radicals present in the oxamino acids can be derived from animal and vegetable oils or fats or from crude mineral oils (naphthenic acids) or from carboxylated or aminated natural or' synthetic long-chain hydrocarbons.

The uses of the compounds embraced within the scope of this application are legion and since i of a few uses will follow.

they are of chief value because of their surface active properties, no detailed description here is deemed essential. However, in order to exemplify the value of the products in the arts, a mention For example, they may be used alone or in combination with other suitable detergents for cleansing and scouring vegetable and animal fibers when removing fatty or oily materials. They may be used as penetrants in acid solutions which are used for carbonizing vegetable matter in wool. When added to flax rotting baths, they function as wetting and penetrating agents. They may be employed as assistants in fulling and felting processes. They may be used in sizing preparations in combination with the usual materials such as starchesor gelaof stripping dyes from dyed ments or pigments or azo,

tine or their. equivalents, clays, talcs or their equivalents, weighting salts such as magnesium sulfate or calcium chloride, oils and oils processed by oxidation, polymerization, sulfonation, etc. The penetrating power of these new compositions is utilized with advantage when they are added liquors used for mercerizing cotton goods. They improve the absorption capability of fibrous materials when such materials are subjected to treatments for finishing, softening, stiffening, coloring, preshrinking, impregnating, waterproof ing, and mildew-proofing. They may be used alone or in combination with other materials for lustering or delustering fabrics. They may be employed to oil or lubricate textile materials and as assistants in processes of weighting or loading fabrics. They may be used as assistants in silk degumming liquors and silk soaking solutions. They can also be used to assist in twist setting in yarn and in processes of stripping colors. These compounds may be used as assistants in processes textile materials.

Another, important class of ,uses of these new compositions is as assistants in the preparation and application of dyestufis. They may be used in the preparation of dyestuffs in readily dispersible form and for the production of inorganic pigbasic, acid, vat, and sulfur dyes in a finely divided condition. 'As penetrants and wetting agents they assist in producing level dyeings in neutral, acid or alkaline dyeing baths. They facilitatedyeing with developed dyes,

yeing of cellulose acetate fibers with insoluble dyes, dyeing and printing with aniline black, and the dyeing of leather. In printing pastes they assist in the dispersion of the dye or dye component and facilitate its penetration into the natural or synthetic fiber. Solutions of these compounds are useful for increasing the fastness of dyeings on textile materials. Solutions of these compounds may be used for increasing the amnityof textile fibers of vegetable origin for acid-chrome dyestuifs. These compounds may be used as assistants'in resist printing processes.

In the leather industry these compositions function as useful wetting agents in soaking, deliming, hating, tanning, and dyeing baths. They are useful in softening and treating baths for hides and skins, particularly in baths used for fat-liquoring leather and'in processes of waterproofing leathen. Solutions of these compounds are useful for pretreating leather prior to dyeing.

The dispersing and emulsifying powers of these new compositions give rise to many interesting uses. They may beutilized for converting liquid or solid substances normally insoluble in water, such as hydrocarbons, higher alcohols, pitches and pitchy substances into clear solutions or stable emulsions or dispersions. They are useful in preparing emulsions of wax and wax-like compositions which are used as leather dressings or floor polishes. They may be used to prepare artificial dispersions of crude, ized or reclaimed water in such organic solvents as are usedin the dry cleaning industry. They are also of value in the breaking of petroleum emulsions, such as those naturally occurring in nature or produced during the refining of petroleum.

These compositions bactericides and contact insecticides and for on hancing the spreading and penetrating power of other parasiticides. They may be employed in agricultural sprays in combination with the ordinary insecticides and fungicides. They are useful for promoting the penetrating power of wood preservatives.

In the paper industry these products may be used as penetrants in the liquors used for cocking rags and pulp, and as assistants in paper softening, filling, and processes to increase absorbency.

These compositions may be employed as detergents in several different relations. They may be used in the washing of fruits and vegetables for spray residue removal. They may be used in combination with metal cleaning compounds in neutral, acid, or alkaline liquors. They may be used for paints, varnish, and lacquer cleaners.

. They may advantageously be employed as cleans.-

7 primary interest compounds may where a fatty or a.

ing agents in hard water and oily film resists the. .ordinary cleansing medi They may be added to soap in acid or hard water baths, since these compositions do not form precipitates so readily in hard and acid stabilizing agents, especially for use in air-foam fire extinguishing compositions. They may be used to stabilize rubber later. They may also be .used as frothing and collecting agents in ore fictation processes, and in other processes such as the recovery of fixed oil from the oil sands. The uses mentioned will suggest many similar ones.

By means of the present invention a large class of new and commercially feasible surface active materials has been rendered available for use. These compounds possess satisfactory colloidal properties and are of particular value for use in place of or in combination with soap and soap substitutes. This invention is of considerable it are for the most part readily available at a relatively low cost. The large variety of reactions which may be relied upon t considerable latitude in the selection of reactants and the conditions of reaction. Lihewisethe large number of compounds embraced within this category permit the selection of individual members therein? for a wide variety of purposes. In other words, where high wetting and dispersing properties are the molecular, weight of these compounds may be lowered. ,On the other hand, where detergent properties are of the molecular weight or the be increased.

As many apparently widely diflerent embodimerits of this invention may be made without demay also be used alone as wherein R1 be employed as foam V 3 parting from the spirit and scope thereof, it is to be understood that the invention is not limited to the-specific embodiments thereof except asdefined in the appended claims.

I claim: l. The new products /N-Ra' R: and R: represent a radical selected from the group consisting of aliphatic and cycloaliphatic radicals, and R: is an aliphatic hydrocarbon radical containing an acidic group and at least one of the radicals represented by R1, R2 and R: has a chain length of at least 8 carbon of the formula:

atoms.

2. The new products of the formula:-

N-Bs a i wherein R1 and R: represent a radical selected from the group consistingoi aliphatic and cycloaliphatic radicals and R: is an aliphatic hydro-- carbon radical containing a monobasic acidic group and at least one of the radicals represented by R1, R2 and R: has a chain length of at least 8,

carbon atoms;

3. The new products of the formula:

N-Rr-X I B--C wherein R is an 7 carbon atoms, R1 is a hydrocarbon radical selected from the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals containing not more than 6 carbon atoms, R: is an alkylene radical containing from 1 to d carbon atoms, and X is an acid group selected from the class consis' of sulionic d bowlic acid groups.

a. The new products all the formula -COOM a -om t i wherein one R is nit? radical containing at least '2 carbon atoms and the other It is hydrogen, R1 is a hydrocarbon radical selected from the group consist of aliphatic and cycloaliphatic hydrbcif contng not more than 6 carbon-atoms, he is a lone radical containing from 1 to 4. carbon etc, and M represents a of the group on ting of hydrogen and a water soluble t to group. 5. The new products of the formula a N-ts coon wherein one R is an 1 real containing at least '1 carbon atdms and the other R is hydrogen, R1 is a hydrocarbon radiwl selected from the group canals of phatic and cycloaiiphatic hydrocarbon radicals contng not more than 6 carbon atoms, and M reprnts a member of the group consisting oi hydrogen and a water salt forming group.

6. The new acts oi a n-ori oooin iormula alml radical containingat least soluble Y wherein one R is an alkyl radical containing at least 7 carbon atoms and the other R is hydrogen, R1 is an aliphatic hydrocarbon radical. containing not more than 6 carbon atoms, and M represents wherein R1 and R2 represent a radical selected from the group consisting of aliphatic and cycloa member of the group aliphatic radicals, R: is an aliphatic hydrocarbon radical containing an acidic group and at least one of the radicals represented by R1, R2 and Ba has a chain of at least 8 carbon atoms with an oxidizing agent.

8. The process. which comprises reacting an amino acid 01' the formula wherein R1 and R2 represent a radical selected from the group consisting of aliphatic and cycloaliphatic radicals, R3 is an aliphatic hydrocarbon radical containing an acidic group and at least one of the radicals represents by R1, R2 and R: at least 8 carbon atoms with an oindizing agent containing free oxygen.

9. The process which comprises reacting an amino acid of the formula R, wherein R1 and R2 represent a radical selected from the group consisting of aliphatic and cycloaliphatic radicals, R: is an aliphatic hydrocarbon radical containing an acidic group and at least has a chain of at least 8 soluble salt forming one oi the radicals represented by R1, R2 and Ba carbon atoms with a peroxide. w

10. The process which comprises reacting an amino acid of the formula wherein one B is an alkyl radical containing at least 7 carbon atoms and the other R is hydrogen, R1 is a hydrocarbon radical selected from the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals containing not more than 6 carbon atoms, and R2 is an alkylene radical containing from 1 to 4 carbon atoms with an oxidizing agent containing i'ree oxygen.

' 11. The new products of the formula CHI I R 1- rcn--cooM R-CH1 wherein one R is an alkyl radical containing at least '7 carbon atoms and the other R is hydrogen,

and M represents a member of the group consisting of hydrogen and a water soluble salt forming group.

i 12. The new products of the formula wherein R is an alkyl-radica1 containing from 11 to 17 carbon atoms and M represents a member of the group consisting of hydrogen and a water group.

13. Alpha-dimethyl-oxamino stearic acid which has the formula MAX ENGEIMANN.