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Publication numberUS3303213 A
Publication typeGrant
Publication dateFeb 7, 1967
Filing dateSep 13, 1965
Priority dateFeb 15, 1962
Also published asDE1223994B, DE1543806A1, DE1543806B2, DE1617689A1
Publication numberUS 3303213 A, US 3303213A, US-A-3303213, US3303213 A, US3303213A
InventorsViout Andre, Kalopissis Gregoire
Original AssigneeOreal
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Nu-tertiary aminoalkyl-nu'-hydrocarbon asparagine amides
US 3303213 A
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Description  (OCR text may contain errors)

United States Patent 6 Claims. (21. 260-534) This invention relates to a new product comprising new amphoteric chemical compositions and a process for preparing these compositions.

This application is a continuation-in-part of applicants copending application Serial No. 256,142, filed February 4, 1963, now abandoned.

It has been found that the new compositions according to the invention comprise very valuable surface-active agents which may be used either alone or mixed with other cationic, anionic or non-ionic surface active agents, in many different fields, and particularly for shampooing the hair and in the preparation of hair dyeing solutions.

Their use in shampooing is the more attractive because they offer the valuable advantage of being very well tolerated by the mucous membrane of the eye.

The new surface active compositions according to the invention may be considered as derivatives of asparagine and are characterized by the following general formula:

R1 HzN(CH2)nN in which n, R and R havethe significances indicated in the above Formula I; then, after salification, treating the maleamic acid derivative thus obtained, which has the formula:

in which 11, R and R also have the significances previously assigned, with a primary fatty amine having the following formula:

in which R has the above-mentioned significance, thus obtaining the composition of Formula I.

As an example of particularly suitable alkylene diamines the following may be mentioned:

N,N-dimethylor N,Ndiethylethylenediamines,

N,N-dimethylor N,N-diethylor N,N-dipropylpropylenediamines,

N- (fl-amino-ethyl) -morpholine,

N- (.fl-aminopropylpiperidine) The following may, of course, also be used:

N,N-dimethylor N,N-diethylbutylenediamines, N,N-dimethylor N,N-diethylpentamethylenediamines.

As examples of particularly suitable fatty amines the following may be cited: decylamine, dodecylamine, the amines derived from the fatty acids of copra-0r tallow, etc.

The new amphoteric chemical compositions according to the invention may be used in aqueous solutions at acid, neutral or alkaline pH values. In the first case they act as cationic surface active agents; in the last case, as anionic surface active agents. I

The invention thus also envisages, as a new article of manufacture, a surface active composition characterized by the fact that it contains a composition having the general Formula I as given above.

Thenew composition according to the invention may naturally comprise other known cationic, anionic, or nonionic surface active agents. It is particularly valuable for use in sha-mpooing the hair.

I have moreover found, and this was entirely unforseeable, that aqueous solutions of the compositions of Formula I are remarkably innocuous to the mucous membrane of the eye.

This harmlessness has been established by many tests made 'by applicants and these tests are summarized in the following tables:

at a concentration of 0.1 M (molecular weight, 452) Observation 24 h. after application Observation 7 days after application pH Rabbits pH 3 Recovered.

TABLE II Application of a solution of can, 0112 0 o-nrncnnm RNH-(EHO o ONa Cans at a concentration of 0.1 M (molecular Weight, 449) R= copra Observation Rabbits 24 h. after application Observation 7 days after application pH 3. Recovered.

3 4 TABLE III The cornea may be attacked in cases 5 and 6 either by the product itself or by the pathological conjunctival Apphcatmn ofasolutlon of secretion caused by the product.

The loss of corneal sensitivity facilitates ulceration. The tests summarized in the foregoing tables clearly lJHgCONHwHmN show that products according to the invention donot at- RNHCH COON3 tack the cornea, as is frequently the case with cationic, at a concentration of 0.1 M (molecular weight, 505) amomc or Products R=tanow The new compositions according to the invention which have valuable surface active properties may be used in Observation Observation 10 various fields and especially in the cosmetic field. pH Rabbits 24 h after 7days after They are particularly valuable for the preparation of apphcaflm apphcatw shampoos having excellent foaming and detergent properties. Their application to hair renders it supple and easy p113 gg to comb. Moreover hair which has been shampooed D0. with them does not have an accumulated electrostatic DH 7 g8: charge after drying.

Do. The preparation of the maleamic acids by condensation of alkylene diamine with maleic anhydride is taught pH8 130. by US. Patent No. 2,821,521, wherein the preparation of 3: N-(N',N'-diethylaminopropyl) maleamic was first described. The present invention describes an improvement over the process described in said patent, which improve- By way of contrast, the following table shows the effect mehts may be classed two eategohes: 'of the introduction of a conventional surface-active agent Those Y h P h the very easy lsolahoh of the into the eyes of rabbits: Pure maleamlc held;

TABLE IV Those which permit the recovery of the maleamic acid in a solution, which can be directly employed for the Application of a solution of cetyltrinietliylanimoniuin bromide in a lti at d tio a ti with .a fatt amine, d concemmmn ofol M scribed later in the present application.

p The following examples illustrate methods of preparing the maleamic acids in each of the above categories: Rabbits Observation 24 h. Observation 7 days after after application application A. PROCESS OF PREPARING MALEAMIC ACID WHICH PERMITS THE RECOVERY AND ISOLA- a H l 5 TION OF THAT ACID Hcziled-cornea less shiny. b lfilli g Ethyl acetate or tertiary butyl alcohol is used as a sol- Partially Opaque eomeavent. The reaction conditions are specified in the table below:

R1 Amine nitrogen in Acid index in meqs. Temp. Concentration Percent meqs. per gram per gram CI-I-C ON H(CH2) ,.N Solvent in C. of Reaetants Yield (in grams/100 g.)

CHC O OH R2 Cale. Found Cale. Found R1=Rz=C2H5 Ethyl acetate e5 38.8 100 4.38 4.39 4.33 4.41 R1=R2=CH3 t-Butyl alcohol 50 33.4 98 5.00 4.87 5.00 5.13 R1 =R2= CH5 .do 50 89 4. 67 4. 59 4.67 4.

The symbols employed in these tables have the follow- The reaction is carried out in a homogeneous medium ing significances: and the products begin to precipitate only at the end of the maleic anhydride addition.

=f h l of the bulbar or palpebral eohluhelflve A solid white product is obtained directly, easy to dry 2=irritation of the bulbar and palpebral con unctiva and usable Without f th purification. 3:2 P Waterlhg 0f the e (curable) By way of example, two particular preparations cor- P hon-purulent seel'etloh h responding to this general process can be described: 5:4 plus Purifier. secrellon closmg eyehds 60 Example A1.Preparati0n 0 N,N-diethylaminopropyl cornea roughened with possible loss of sensitivity. (Remaleamic acid covery slow, but possible.)

6:5 plus damage to the palpebral edges and even the oles) of N,N-diethylaminopropylamine Skin 4 d ssolved in 600 ml. of ethyl acetate, 297 g. of maleic anhydride dissolved in 600 ml. of ethyl acetate is added The numerals 1-6 may be followed by from 1 to 5 with agitation, through a p g fllhhel- The p crosses according to h acuteness f the ff t ture is maintained between 0 and 5 C. during the addi: The corneal lesions being of two types, the numbers tion of the anhydride The length of h operfitioh is 2 corresponding to the most serious damage may also be hours 30 s, and the N,N-diethyl aminopropyl f ll wed b maleamic acid begins to precipitate several minutes before the end of this addition. (a) Which corresponds to a loss of brilliance (cornea The reaction mixture is allowed to stand, at ambient roughened), temperature, for a few hours. The maleamic acid which (b) Which corresponds to the more or less complete has formed is then separated by filtration. After washdestruction of the corneal epithelium withmore or less g with ethyl acetate, the Product is dried and re ov r d extensive ulceration and loss of corneal sensitivity.

in the form of a white powder.

The yield is 100%.

Example A-2 204 g. (2 moles) of N,N-dimethylaminopropylamine is dissolved in 800 g. of t-butyl alcohol, and the temperature of the solution thus obtained is brought to 50 C. 198 g. of powdered maleic anhydride is added with agitation. This operation is completed over one hour at a temperature of 50 C.

The reaction mixture is allowed to stand for several hours. The dimethylaminopropyl maleamic acid forms a precipitate. It is separated by filtration. After washing with acetone, draining, and drying, the product is recovered in the form of a white powder.

The yield is 98%.

B. PROCESS OF SYNTHESIS OF MALEAMIC ACID PERMITTING THE RECOVERY OF THE ACID IN A SOLUTION WHICH IS DIRECTLY USABLE FOR A FINAL CONDENSATION WITH A FATTY AMINE The solvents which are usable are lower alcohols, such as methanol and ethanol, as well as water.

The choice of temperature is important: it should be less than 30 C. in order to avoid esterification, when an alcohol is the solvent, and hydrolysis, when water is the solvent.

The yield of the amide is always greater than 90%.

Example B-1.--Preparatin of N-(morplzolinobutyD- maleamic acid CHz-OH:

OH-COOH OER-CH2 To 31.6 g. (0.2 mole) of morpholinobutylamine dissolved in 160 g. of methanol, 19. 8 g. of powdered maleic anhydride is added, with agitation. The temperature is maintained between 5 and C. After the end of the maleic anhydride addition, the reaction mixture is maintained at 10 C. for one hour, then at 25 C. for 2 hours.

N-(m0rph0linobutyl3-maleamic acid in methanol is obtained.

Example B-2.Preparation 0 N-(N,N'- diethylaminopentyl)-maleamic acid CH-CONH-(CHm-N I one-coon 02m 7 The same procedure employed in Example B'1 is used, and N-(N',N'-diethylaminopentyl)-maleamic acid is ob- ,tained in a methanol solution starting with diethylamino- S-pentylamine and maleic anhydride.

Example B-3 In the same manner as Example B-1, N-(piperidinopropyl)-maleamic acid in an ethanol solution is prepared, starting from piperidinopnopylarnine and maleic anhydride.

Example B-4.-Preparati0n of N,N-(diethylamin0- pr0pyl)-maleamic acid in water solution Milliequivalents/gram Acidity 4.54 Amino nitrogen 4.36

Example B-5.Preparati0n of N,N-(dimethylamin0- pr0pyl)-maleamic acid in water solution Milliequivalents/ gram Acidity 5.39 Amine nitrogen 5 The following examples illustrate Ways of preparing the new chemical compositions according to the invention.

EXAMPLES OF THE PREPARATION OF NEW COMPOSITIONS Example 1 Preparation of the sodium salt of N-(N',N'-diethyl- 'aminopropyl)-N -dodecy1-asparagine having the following formula:

N-(N',N'-diethylaminopropyl)-maleamic acid is first prepared in the manner described in US. Patent No. 2,821,521, issued January 28, 1958.

To a solution of 0.2 mol plus a 5% excess of this substituted maleamic acid in 100 cc. of ethanol there is added a stoichiometric quantity of soda dissolved in a minimum of water.

The solution of the sodium salt of N-(N',N'-diethylaminopropyl) maleamic acid thus obtained is added drop by drop, while stirring, to 0.2 mol of dodecylamine.

The mixture is then caused to reflux for six hours. After evaporation of the alcohol a pasty product is obtained which is soluble in water at any pH, and the purity of which, after dosing with amine functions, rises to 93%. A 10% aqueous solution has a pH of 11.2.

Example 2 Preparation of the sodium salt of N-(N',N-diethylaminopropyl)-N -alkyl (fatty) asparagine having the following formula:

CaFIr OHz-OONH(CH2):N

R=alkyl residue derived from the fatty acids of copra.

The procedure is the same as in Example 1, but the primary amines deriving from the fatty acids of copra are used instead of dodecylamine. A product having the following formula and a purity of 95% is thus obtained, in the form of a viscous clear yellow mass, soluble in water at any pH. A 10% aqueous solution has a pH of 11.9.

Example 3 Preparation of the sodium salt of N-(N,N'-diethylaminoethyl)-N -alkyl (fatty) asparagine having the following formula:

CHrCONH(CH2)2N R=alkyl residue derived from the fatty acids of copra.

N-(N',N-diethylaminoethyl)-maleamic acid is first prepared in the same way as in Example 1 by reacting N,N-

diethylaminoethylamine with maleic anhydride. Then the 7 primary amine of thefatty acids of copra is reacted with the sodium salt of this acid. This yields a viscous mass which is soluble in water at any pH, with a purity of 94%. A 10% aqueous solution has a pH of 11.5.

Example 4 Preparation of the sodium salt of N-(N',N'-dimethylaminopropyl)-N -alkyl (fatty) asparagine having the following formula:

CH: C 113-0 NH (0 H1) :r-N

RNH--CHC O ONa CH3 Preparation of the sodium salt of N-(N,N'-diethyla1ninopropyl)-N -decyl asparagine having the formula:

CgH5

CI-IzC ONH(CHz)aN C mHnNH-CH-C 0 ONE 01115 This product is obtained in the same manner as in Example 1, except for using decyl-amine in place of dodecylamine.

This asparagine derivative is obtained in a purity of 96%, in the form of a viscous clear yellow mass, soluble in water at all pH values. A aqueous solution has a pH of 11.1.

Example 6 Preparation of the sodium salt of N-(N',N'-diethylaminoethyl)-N -alkyl (fatty) asparagine having the formula:

RNH- HCOON8 02H;

in which R is an alkyl residue derived from the fatty acids of tallow.

This product is obtained by following the procedure hereinbefore described, using N,N-diethyl-ethylene diamine and the fatty amines derived from the fatty acids of tallow. Its purity is 94%. A 10% aqueous solution has a pH of 11.7.

Example 7 Preparation of the sodium salt of N-(N',N-dimethylaminopropy1)-N -alkyl (fatty) asparagine, having the formula:

CH: omooNHwHmH RNH-CH-OOONa CHa R being an alkyl residue derived from the fatty acids of copra.

Proceeding as in Example 1, but replacing dodecylamine with the primary amine derived from the fatty acids of copra, the above-mentioned asparagine derivative is obtained in a purity of 98%. A 10% aqueous solution has a pH of 11.5.

8 Example 8 Preparation of the potassium salt of N-(morpholinoethyl)-N -alkyl (fatty) asparagine, having the formula:

R being an alkyl residue derived from the fatty acids of copra.

N-(morpholinoethyl)maleamic acid is first prepared in the same way as in Example 1, by reacting N-(fi-amino ethyl) morpholine with maleic anhydride.

The product is in the form of a white solid having its melting point at 161-162 C.

The primary amines derived from the fatty acids of copra are then reacted with the potassium salt of that acid. The desired product is obtained in a purity of in the form of a yellow-orange viscous mass, soluble in water at all pH values.

A 10% aqueous solution has a pH of 11.6.

Example 9 (a) Preparation of N-(piperidinopropyl)-maleamic acid, having the formula:

To 14.2 g. (0.1 mole) of N-(B-aminopropyl)-piperidine dissolved in g. of ethyl alcohol, 10 g. of pulverized maleic anhydride is added over a period of 30 minutes with agitation, maintaining the temperature between 6 and -8 C.

After agitation of the mixture for 2 hours at 25 C., the amino nitrogen and the acid are quantitatively determined.

The corresponding results were obtained from the dry products:

Milliequivalents gram Acidity 3.87 Amino nitrogen 4.2

(b) Preparation of the sodium salt of N-piperidinopropyl-N -dodecyl asparagine, having the formula:

The N-(piperidinopropyl)-malearnic acid obtained in alcoholic solution is neutralized with 11.1 g. of 33. 8% sodium hydroxide solution after which 17.5 g. of dodecylamine are added. The mixture is then heated at 65 C. for 5 hours, and concentrated by the evaporation from the solution of 60 g. of alcohol, the temperature being maintained at 65 C. for another 3 hours. The alcohol and the water are removed under vacuum; a pasty product is obtained, which is soluble in water.

Example 10.Preparati0n of the sodium salt of N-(morph0lin0butyl)-N -alkyl (fatty) asparagine (a) Preparation of N-(morpholinobutyl)-ma1eamic acid, having the formula:

To 31.6 g. (0.2 mole) of morpholinobutylamine dissolved in 1 60 g. of methanol, 19.8 g. of powdered maleic anhydride is added, with agitation. The temperature is maintained between 5 and 10 C. After the end of the maleic anhydric addition, the reaction mixture is maintained for 1 hour at 10 C., and then for 2 hours at 25 C.

9 N-(morpholinobutyl)-malearnic acid in methanol is obtained.

(b) Preparation of the sodium salt of N-(morpholinobutyl)-N -alkyl (fatty) asparagine, having the formula:

wherein R is an alkyl residue derived from the fatty acids of copra.

The N-(morpholinobutyl)-maleamic acid (0.2 mole) obtained in methanol solution above, is neutralized 'by a stoichiometric amount of a 33% aqueous solution of sodium hydroxide. 0.2 mole of primary amines derived from the fatty acids of copra is added, and themixture is heated to 65 C. for 12 hours. On evaporation to dryness, a white paste containing 90% of the product of the above formula is obtained. 1

Example 11.Preparation of the 'soa'iam salt of N-(N', N-diethylaminpentyl)-N2-alkyl (fatty) asparagine (a) Preparation of N-(N',N'-diethylaminopentyl)- maleamic acid, of the formula: t

The same procedureemployed in Example 10(a) is used, and N-(N,N'-diethy1aminopentyl)-maleamic acid is obtained in a methanol solution starting from diethylamino--pentylamine and maleic anhydride.

(b) Preparation of the sodium salt of N-(N,N-diethylaminopentyl)-N -alkyl (fatty) asparagine, of the formula:

wherein R is an alkyl residue derived from the fatty acids of copra.

The N-(N,N'rdiethylaminopentyl)-maleamic acid obtained in part (a) above in methanol solution is neutralized by a stoichiometric amount of sodium hydroxide. The mixture is heated at 65 C. for8 hours, with the primary amine derivatives of the [fatty acids of copra.

On evaporation to dryness, a pasty product is obtained, which is water-soluble.

Example 12.Preparation o f the sodium salt of N-(N', N'-diethylaminopr0pyl)-N alkyl (fatty) asparagine (a) Preparation of 'N,N -(diethylaminopropyl)-male:

amic acid, of the formula:

4 a s i To 1955 g. of N,N-diethylaminopropyl amine dissolved in 3475 g. of distilled water, 1495 g. of powdered maleic anhydride are added while agitating, the temperature being maintained between 0 and 5 C. The time of addition is about 1% hours. The mixture is then allowed to return to ambient temperature under agitation.

The maleamic acid derivative is thereby obtained.

(b) Preparation of the sodium salt of N-(N',N"-diethylaminopropyl) N alkyl (fatty) asparagine, of the formula:

wherein R is an alkyl radical derived from the fatty acids of copra.

. The maleamic acid derived according to the above procedure is neutralized with 1362 g. of 46.3% aqueous sodium hydroxide solution, the temperature being main- Example 13 Preparation of a sodium salt of a derivative of asparagine in which the fatty radical is derived from the fatty acids of copra and tallow:

By using the same method of operation as used in Example 12, diluting the reaction medium by introduction during the course of the reaction of 1575 g. of water at 70 C. into the mixture, and by using a mixture of 11.55 moles of fatty amines derived from the fatty acids of copra and 3.45 moles of the fatty amines derived from the fatty acids of tallow, a product represented by the following formula is obtained:

EXAMPLES OF THE APPLICATION OF THE NEW COMPOSITIONS IN SHAMPOOING HAIR Example 1A A solution is prepared which contains:

Sodium salt of N (N QN' diethylaminopropyl)-N -do decyl asparagine, 10 g.

Lactic acid in a quantity sufi'icient to bring the pH value Water, q.s.p., cc.

This solution gives a foamy shampoo and permits the ha tq'b easily ombe W' P .4 The following solution is.prepared:

. G. Sodium salt of N-(N',N-diethylaminopropyl)-N dodecyl asparagine 5 Sodium salt of N-(N,N'diethylaminoethyl)-N alkyl (tallow) asparagine 2 5 Sufficient lactic acid to bring the solution to pH 6. Water, q.s.p. 100 cc. 1 1

This yields an excellent foaming shampoo which renders the hair soft and easy to comb. Moreover, hair which has been shampooed with it does not have an accumulated electrostatic charge after-drying.

Example 3A A solution is prepared which contains:

Sodium salt of N-(N,N',-diethylaminopropyl)-N -dodec yl asparagine, 10 g.

Sufficient lactic acid to bring to a pH of 7.5. Sufiicient water to bring to a total of 100 cc.

This yields. an excellent foaming shampoo which renders the hair soft and easy to comb.

1 1 Example 4A The shampoo thus obtained foams well and imparts great softness to the washed hair.

Example 5A An aqueous solution is prepared which contains the following:

G. Sodium salt of N-(N,N-diethylaminopropyl)-N -dodecyl asparagine 4 Sodium salt of N-(N,N'-dimethylaminopropyl)-N alkyl (tallow) asparagine 2 Nonyl phenol at 12 mols of ethylene oxide per mol of nonyl phenol 8 Sulficient lactic acid to bring to pH 6. Sufiicient water to bring to 100 cc.

This shampoo foams well and imparts great softness to the washed hair.

Example 6A An aqueous solution is prepared which contains the following:

Sodium salt of N-(N,N-diethylaminopropyl)-N dodecyl asparagine 1.1

100% technical ammonium lauryl sulfate 9 Lauryl hydroxy ethylamide 0.8 Sufficient lactic acid to bring to pH 7.

Sufficient water to bring to 100 cc.

This solution constitutes shampoo which is an effective detergent, foams well, and imparts great softness to the washed hair.

Example 7A An aqueous solution is prepared which contains:

Sodium salt of N-(N',N'-dimethylaminopropyl)-N alkyl (tallow asparagine 0.5 100% technical ammonium lauryl sulfate 1 Oleic acid 0.2

Lauryl dihydroxy ethyl amide 2 Sufiicient lactic acid to bring to a pH of 6.5.

Sufiicient water to bring to 100 cc.

This viscous shampoo is a good detergent and foams well. It imparts great softness to the hair which is washed with it.

Example 8A An aqueous solution is prepared which contains:

Potassium salt of N-(morpholino-ethyl)-N -a1kyl (fatty) asparagine, 7 g.

Sufficient lactic acid to bring to a pH of 7.5.

Sufficient water to make 100 cc.

This solution constitutes an excellent shampoo which is an effective detergent, foams well and imparts great softness to the washed hair.

Example 9A An aqueous solution is prepared which contains:

Ammonium salt of N-(N,N-diethylaminopropyl)-N alkyl (fatty) aspara'gine wherein the fatty residues are constituted by /5 of the fatty chain deriving from the fatty acids of copra and by /3 of the fatty chain deriving from the fatty acids of tallow, 10 g.

Sutficient water to make cc. Sufiicient lactic acid to bring to a pH of 8.6.

This solution constitutes a shampoo having good foaming and detergent properties. It makes the hair supple and easy to comb.

Example 10A An aqueous solution is prepared which contains:

Sodium salt of N (N',N' diethylaminopropyl) N alkyl (fatty) asparagine wherein the fatty residues are constituted by /3 of the fatty chain deriving from the fatty acids of copra and by /3 of the fatty chain deriving from fatty acids of tallow, 10 g.

Sufficient lactic acid to bring to a pH of 8.5.

Sufficient water to make 100 cc.

This yields an excellent foaming shampoo which renders the hair soft and easy to comb.

Example 11A An aqueous solution is prepared which contains:

The sodium salt of N-piperidinopropyl-N-dodecyl asparagine, 7 g.

Lactic acid, q.s.p., pH 7.5.

Water, q.s.p. 100 cc.

This solution constitutes an excellent shampoo, which has good deter-gent and foaming properties, and gives the hair a brilliant sheen.

While in the above examples the shampooing compositions have been adjusted to have a pH of 4 to approximately 8.6 by the addition of lactic acid, other acids may be used, and a higher pH may also be used.

Example 12A A solution is prepared which contains:

Sodium salt of N-(N',N'-diethylaminopropyl)-N -dodecyl asparagine, 10 g.

Hydrochloric acid in a quantity sufficient to bring the pH value to 4.

Water, q.s.p. 100 cc.

This solution gives a foamy shampoo and permits the hair to be easily combed.

Example 13A A solution is prepared which contains:

Sodium salt of N-(N,N-diethylaminopropyl)-N -dodecyl asparagine, 9 g. Acetic acid in a quantity sufficient to bring the pH value to 5. Water, q.s.p., 100 cc.

This solution gives a foamy shampoo and permits the hair to be easily combed.

Example 14A The following solution is prepared:

G. Sodium salt of N-(N',N-diethylaminopropyl)-N dodecyl asparagine, 7.5

Sodium salt of N-(N,N-diethylaminoethyl)-N alkyl (tallow) asparagine 2.5 Sufficient phosphoric acid to bring the solution to pH 6. Water, q.s.p., 100 cc.

This solution constitutes a shampoo having foaming and detergent properties and making the hair supple and easy to comb.

Moreover, hair which has been shampooed with it does not have an accumulated electrostatic charge after drymg.

13 7 Example 15A The following solution is prepared;

I G- Sodium salt of N-(N,N-diethylaminopropyl)-N -dodecyl asparagine 8 Sodium salt of N-(N',N-diethylaminoethyl) N -alkyl (tallow) asparagine L 2 Sufficient formic acid to bringthe solution to .pH 6. Water, q.s.p., 100 cc.

This solution constitutes a shampoo having foaming and detergent properties and making the hair supple and easy to comb. I

Moreover, hair which has been shampooed with it does not have an accumulated electrostatic charge after drying. 7

Example 16A A solution is prepared which contains:

Sodium salt of N-(N,N'-diethylaminopropyl)-N -dodecyl asparagine, 10 g. I

Sufficient tartic acid .to bring the solutionto a pH 7.51

Water, q.s.p., 100 cc. 1

This yields an excellent foaming shampoo which rendersthe hair soft and easyto comb.

Example 17A A solution is prepared which contains:

Sodium salt of N-(N,N'-diethylaminopropyl)-N -dodecyl asparagine, 10 g.

Sufficient citric acid to bring the solution to a pH 7.5.

Sufficient water to bring to 100 cc.

This yields an excellent foaming shampoo which renders the hair soft and easy to comb.

Example 18A An aqueous solution is prepared which contains the following:

i Sodium salt of N-(N,N-diethylaminopropyl)-N -dodecyl asparagine Laurie alcohol condensed with 10 mols of ethylene oxide per mol of alcohol 8 Suflicient acetic acid to bring the solution to a pH 5. Sufiicient water to bring to 100 cc.

The shampoo thus obtained foams well and imparts great softness to the washed hair. I

Example 19A I An aqueous solution is prepared which contains the following:

- G. Sodium salt of N-(N,N'-diethylaminopropyl)-N dodecyl asparagine 4 Sodium salt of N-(N',N'-dimethylaminopropyl)-N alkyl (tallow) asparagine 2 Nonyl phenol at 12 mols of'ethylene oxide per'mol of nonyl phenol L' 8 Suflicient citric acid to bring the solution to a pH '6. Sufficient water to bring to 100 cc.

This shampoo foams well and imparts great softness to the washed hair.

Example 20A An aqueous solution is prepared which contains the following:

Sodium salt of N-(N,N'-diethylaminopropyl)-N dodecyl asparagine 1.1 100% technical ammonium lauryl sulfate 9 Lauryl hydroxy ethylamide 0.8

Suflicient hydrochloric acid to bring the solution to a pH 7. Water, q.s.p., 100 cc.

14 This solution constitutes .shampoo which is an effective detergent, foams well and imparts great softness to the washed hair.

i 5 Example 21A An aqueous solution is prepared which contains: Potassium salt of N (morpholino-ethyl)-N alkyl (fatty) asparagine, 7 'g. Sufiicient citric acid to bring to a pH of 7.5. Sufiicient water to make cc.

This solution constitutes an excellent shampoo which is an effective detergent, foams well and imparts great softness to the washed hair.

EXAMPLES OF THE APPLICATION OF THE NEW COMPOSITIONS IN DYEING HAIR Example 13 A hair dyeing composition is prepared, which contains the following: 7

Sodium salt of N-(N',N'-diethylaminopropyl)-N dodecyl asparagine g 4 Nonyl phenol+4 mols ethylene oxide g 20 Nonyl phenol+8.75 mols ethylene oxide g 20 Diethylene glycol g 17 Ethyl alcohol s g 3 Ammonia at 22 B. ml 12 Paratoluylene diamine g 0.6 Metadiaminoanisol sulfate g 0.5 Resorcine g 0.5 Paraaminophenol g 0.4 Metaaminophenol g 0.1

Water, q.s.p., 100 cc.

This solution is diluted weight by weight with hydrogen peroxide to 20 volumes. The final pH is 9.9.

The shade of dyeing which is obtained is chestnut.

Example 2B A hair dyeing solution is prepared which contains: Sodium salt of N-(N',N'-diethylaminopropyl)-N dodecyl asparagine g 3 Sodium salt of N-(N,N-diethylaminoethyl)-N alkyl (tallow) asparagine g 1 Nonyl phenol+4 mols ethylene'oxide g 20 Nonyl phenol+8.75 mols ethylene oxide g 20 Diethylene glycol g 17 Ethyl alcohol g 3 Ammonia at 22 B. ml 12 Paratoluylene diamine g 0.2 Metadiaminoanisol sulfate g 0.01 Resorcine g 0.1 p- Aminophenol g 0.3 m-Aminophenol g 0.05

Water, q.s.p., 100 cc.

This solution is diluted weight for weight with hydrogen peroxide to 20 volumes. The final pH is 9.7. I The shade of dyeing obtained is blonde.

Example 3B A hair dyeing solution is prepared which contains the Water, q.s.p., 100 cc.

. I 15f. {This solutionis dilutedweight for weight with hydrogen peroxide to'20 volumes. The final pH is 10. i

The shade of dyeing obtained is golden chestnut.

V Example 4B 7 A hair dyeing solutionis prepared which contains: Ammonium salt of N-(N,N-diethylaminopropyl)- N -alkyl (fatty.).aspa ragine, in .which .the fatty residues are composed of of the fattychain portion of thefatty acidsof copra and /3 of the fatty chain portion of the fatty acids .of tal- .low g 4 Nonyl phenol+4 mols ethylene oxide g 20 Nonyl phenol+8.75 mols ethylene oxide g 20 Diethylene glycol g 17 Ethyl alcohol g 3 Ammonia at 22 B. ml 12 Paratoluylene diamine g 0.6 Metadiaminoanisol sulfate g 0.15 Resorcine g.. 0.5 p-Aminophenol g 0.4 m -Aminophenol g 0.1

Water, q.s.p., 100 cc.

This solution is diluted weight for weight with hydrogen peroxide to 20 volumes. The final pH is 9.5. -The shade of dyeing obtained is chestnut brown.

Example 5B Water, q.s.p., 1000 g.

This solution is mixed with an equal volume of hydrogen peroxide and applied inthe usual manner to the hair.

The shade imparted to the hair is chestnut brown.

Example 6B The following solution is prepared:

G. RNHCHC O ONa CiHt HzCONH(CHz)a-N 2 wherein R is 80% copra residue and 20% tallow residue. Oxyethylene lauryl alcohol, with 15 to 20 mols of ethylene oxide 3 Diethanolamide of coca 2 p-Nitrophenylenediamine 0.5

Citric acid (40%) solution to bring to a pH of 8. Water, q.s.p., 100 g.

Example 7B 7 The following composition is prepared:

- I G. RNHCHC o oNa C2H5 CHrCONH(GHz)a-N 2 CgH5 wherein R is copra residue and 20% tallow residue. Oxyethylene lauryl alcohol, with 15 to 20 mols of ethylene oxide 3 Diethanolamide of coca 2 p-Nitrophenylenediamine 0.5 Methyl violet 0.1 Citric acid (40% solution) to bring pH to 5.

Water, q.s.p., g.

This solution is applied to the hair in the usual manner, and gives the hair a violine color.

While the foregoing examples disclose a pH range of 5 to 10 in the dyeing compositions, and while the preferred'range for the pH of these solutions when utilized as hair dyes is between 9 and 10, any pH between about 4 and about 11.9 may be used.

What is claimed is: r 1. A compound of the formula:

CH2-CONH(CHz)n-N\ wherein R and R are alkyl of up to four carbon atoms or together with the nitrogen atom to which they are attached form morpholino or piperidino, n is an integer having a value between 2 and 5 inclusive, R is a saturated aliphatic hydrocarbon having from 10 to 18 carbon atoms inclusive, and M is selected from the group consisting of sodium, hydrogen, potassium and ammonium.

2. A compound as claimed in claim 1 in which M is sodium.

3. A compound as claimed in claim 1 in which M is potassium.

4. A compound as claimed in claim 1 in which R --NR is dimethylamino.

5. A compound as claimed in claim 1 in which R NR is diethylamino.

6. The compound of claim 1, wherein said R is selected from the group consisting of copra or tallow.

References Cited by the Examiner UNITED STATES PATENTS 2,246,264 6/ 1941 Pinkernelle 260475 2,761,874 9/1956 Bersworth 260534 2,821,521 1 /1958 Price 26078 3,158,635 11/1964 Kezerian et a1. 260534 ALEX MAZEL, Primary Examiner.

HENRY R. JILES, Examiner.

JOSE TOVAR, Assistant Examiner.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3891385 *Sep 6, 1972Jun 24, 1975OrealHair softening dye compositions containing surface-active asparagine derivatives
US3957863 *Nov 12, 1974May 18, 1976Hoechst AktiengesellschaftAnti-microbially active surface-active agents
US4020155 *Apr 15, 1971Apr 26, 1977Societe Anonyme Dite: L'orealAmphoteric cosmetic
US4652585 *Mar 15, 1985Mar 24, 1987Henkel Kommanditgesellschaft Auf AktienN-substituted diaminopropane/glutamic acid reaction products
US4837012 *Jun 19, 1987Jun 6, 1989S. C. Johnson & Son, Inc.Dry shampoo; degreasing; conditioners; texture
US6043218 *Oct 22, 1996Mar 28, 2000Medical University Of South CarolinaPositively charged non-natural amino acids, methods of making thereof, and use thereof in peptides
US6358922Dec 1, 1999Mar 19, 2002Medical University Of South CarolinaPositively charged non-natural amino acids, methods of making thereof, and use thereof in peptides
US6547833Feb 23, 2001Apr 15, 2003Clairol IncorporatedA two-part high aqueous-content system for oxidative coloration of hair utilizing a developer formulation of water, a peroxide oxidizer and an anionic acrylate/beheneth-25 methacrylate copolymer
US6566330Sep 11, 2000May 20, 2003Medical University Of South Carolina Foundation Research DevelopmentPositively charged non-natural amino acids, methods of making and using thereof in peptides
US6764523Jun 3, 2002Jul 20, 2004The Procter & Gamble CompanyTwo-part aqueous composition for oxidative coloration of hair
US6783946Jan 10, 2002Aug 31, 2004Medical University Of South CarolinaPositively charged non-natural amino acids, methods of making thereof, and use thereof in peptides
US6858396Mar 6, 2002Feb 22, 2005Medical University Of South CarolinaAmino acids where primary amine group is replaced by azide; use in peptides screening for bioactivity, crossing blood-brain barrier, increasing selectivity; treating brain disorders
Classifications
U.S. Classification562/561, 510/126, 510/490, 424/70.19, 546/247, 544/168, 424/70.21
International ClassificationC11D1/88, C07C233/46, B01F17/00, C07C237/00, C07D295/13
Cooperative ClassificationC11D1/88, C07D295/13, A61Q5/10, A61K8/44
European ClassificationC11D1/88, A61Q5/10, A61K8/44, C07D295/13