US3873688A

US3873688A - Surface active compositions containing asparagine derivatives

Info

Publication number: US3873688A
Application number: US012477A
Authority: US
Inventors: Gregoire Kalopissis; Andre Viout; Guy Vanlerberghe
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1964-01-17
Filing date: 1970-02-12
Publication date: 1975-03-25
Anticipated expiration: 1992-03-25
Also published as: NL6500541A; BE658288A; CH433374A; CH437644A; US3891385A; FR1397231A; GB1058331A; DE1518075A1; US3534032A; GB1058332A; NL123441C

Abstract

Surface active compositions which contain a surface-active compound having the formula

IN WHICH R and R'' are an alkyl or alkenyl group which has 10-18 carbon atoms, R1 and R2 are lower alkyl or with the N atom a morpholino group and n is 2-5.

Description

United States Patent Kalopissis et al.

[ SURFACE ACTIVE COMPOSITIONS CONTAINING ASPARAGINE DERIVATIVES [75] Inventors: Gregoire Kalopissis; Andre Viout,

both of Paris; Guy Vanlerberghe, MOntjay-la-Tour, all of France [73] Assignee: LOreal, Paris, France [22] Filed: Feb. 12, 1970 [21] Appl. No.: 12,477

Related US. Application Data [63] Continuation-impart of Ser. No. 424,846, Jan. 11,

I965, Pat. NO. 3,534,032.

[30] Foreign Application Priority Data Jan. I7, 1964 France 64.60742 Mar. 25, 1975 [5 6] References Cited UNITED STATES PATENTS 2,821,521 l/l958 Price .I 260/534 X FOREIGN PATENTS OR APPLICATIONS 1,146,332 5/1957 France 424/70 l,344,2l2 lO/l963 France 2610/2472 Primary ExaminerStanley .I. Friedman Assistant Examiner-Vera C. Clarke Attorney, Agent, or FirmBrisebois & Kruger [57] ABSTRACT Surface active compositions which contain a surfaceactive compound having the formula R-NH-CH-COOH 2 in which R and R are an alkyl or alkenyl group which has 10-18 carbon atoms, R and R are lower alkyl Or with the N atom a morpholino group and n is 25.

9 Claims, N0 Drawings SURFACE ACTIVE COMPOSITIONS CONTAINING ASPARAGINE DERIVATIVES This application is a continuation-in-part of application Ser. No. 424,846, filed Jan. 11, 1965, now US. Pat. No. 3,534,032.

This invention relates to cosmetic compositions which contain new asparagine derivatives having surface-active properties, and to hair treating compsitions containing them.

US. Pat. Nos. 3,303,213 and 3,331,781 describe and claim asparagine derivatives having very interesting surfaceactive properties, which are of particular use in hair shampoos. We have now found that certain related asparagine derivatives not only show surface activity, but possess other properties which are of considerable interest in relation to the treatment of hair.

The asparagine derivatives used in the compositions of this invention are compounds having the formula:

where R and R are each an alkyl or alkenyl group which has -18 carbon atoms which can be the same or different; R, and R are each lower alkyl, which can be the same or different, or together with the nitrogen atom to which they are attached constitute a morpholino residue and n is an integer of 2-5 inclusive (especially 2 or 3 and sodium, potassium, ammonium and acid addition salts, such as lactate, phosphate, citrate and acetate salts, thereof. Preferred compounds are those in which R, and R are alkyl groups having l4 carbon atoms, for instance methyl or ethyl.

These compounds possess not only remarkable detergent properties, but also good softening and conditioning properties for the hair. Thus they can be used to advantage in hair shampoo or hair dyeing compositions.

Moreover, in acidic aqueous solutions these compounds show a very pronounced thickening and gelling effect. Since products currently employed as thickeners or gelling agents generally do not possess in themselves any detergent or hair treating property, it will be seen that compounds of the invention are particularly advantageous, and because of this combination of properties they have a very wide range of use, for example. in aqueous solutions which may contain other surface-active substances, especially those of cationic or non-ionic character, and in aqueous solutions of dyes.

The compounds of the invention can be prepared by a process which comprises condensing maleic anhydride with an alkylene diamine having the formula:

1 NH (CH N\ R NH where R has the meaning given above. Preferred alkylene diamines are. for example, N-dodecyl-N', N-diethylethylenediamine. N-cetyl-N, N'-diethylethylenediamine, N-dodecyl-N', N-diethyltrimethylenediamine, and ,B-(dodecylamino)ethylmorpholine.

Preferred primary fatty amines are, for example, decylamine and dodecylamine. It has been found that excellent results have been obtained using as primary amine a mixture of fatty amines derived from copra acid or tallow acid, which yield a mixture of coumpounds of formula l differing only in the value of the substituent R, the various R substituents being the various alkyl radicals present in tallow or copra acids respectively.

The invention is illustrated by the following Examples.

EXAMPLE 1 Preparation of the sodium salt of N -[alkyl(tallow)]-N-(dodecyl)-N-(N,N- diethylaminoethyl)asparagine.

l Preparation of N'N-diethyl-N-dodecylethylenediamine There are mixed with stirring 2 moles of dodecylbromide and 10 moles of N,N-diethylethylenediamine (96,6 the temperature being maintained below 50C. At the end of several hours, the reaction is complete. There are then added 4.3 moles of potassium hydroxide in pellet form, with vigorous stirring. The excess of potassium hydroxide and the potassium bromide formed are separated by filtration. The excess of N,N-diethylethylenediamine is thereafter evaporated under reduced pressure, and the crude product thus obtained is washed with water and dried in vacuo on the water bath.

N,N-diethyl-N-dodecyl-ethylenediamine is thus isolated in an almost quantitative yield and in a purity of 98 2 Preparation of N-dodecyl-N-( N ',N diethylaminoethyl) maleamic acid.

One mole of N',N'-diethyl-N-dodecylethylenediamine is dissolved in 300 ml of ethyl acetate.

To this solution is added with stirring, in an hour and a half, 1 mole of maleic anhydride in solution in 300 ml of ethyl acetate, the temperature being maintained between 35 and 40C. The solid which precipitates is separated, washed with ethyl acetate and dried in vacuo, and N-dodecyl-N',N-diethylaminoethyl)- maleamic acid is isolated as a white, water-soluble powder in a yield of 80 3 Addition of the primary amine derived from tallow fatty acids.

0.7 mole of N-dodecyl-N-(N,N'-diethylaminoethyl) maleamic acid is dissolved in 300 m1 of ethyl alcohol, and the solution is neutralized with a calculated quantity of concentrated aqueous sodium hydroxide solution.

There is then added 0.7 mole of a mixture of primary amines derived from tallow fatty acids, and the mixture is heated at C. for 11 hours. After evaporation of the alcohol. the product obtained takes the form of an oil dispersible in water, which contains 4 7! of unreacted primary amine.

EXAMPLE ll Preparation of the sodium salt of N -lalkyl(copra)]-N-(cetyl)-N-(N',N'-diethylaminoethyl)asparagine.

By proceeding in an analogous to Example I. N-cetyl- N-(N'.N'-diethylaminoethyl)maleamic acid is obtained from N',N'-diethyl-N-cetyl-ethylenediamine and maleic anhydride. The desired product is obtained by the addition to the sodium salt of the maleamic acid of a mixture of primary amines derived from copra fatty acids in an analogous way to Example I.

EXAMPLE lll Preparation of the sodium salt of N -[alltyl(tallow)l-N-(cetyl)-N-(N.' l'-diethylaminoethyl)asparagine By the process analogous to that described in Example I, this product is obtained by the addition of a mixture of primary amines derived from tallow fatty acids to sodium N-cetyLN-tN.N'-diethylaminoethyl)malea mate.

EXAMPLE lV Preparation of the sodium salt of N' -lalkyhcopra)LN-(dodecyll-N-(N'N diethylaminoethyl )asparagine This product is obtained by reacting the mixture of primary amines derived from copra fatty acids with sodium N-dodecyl-N-(N.N'-diethylaminoethyl)maleamate in a process analogous to that described in Example l.

EXAMPLE V Preparation of the sodium salt of N -lalkyhtallow)l-N-(dodecyl) N-(morpholinoethyl- )asparagine.

By a process analogous to that described in Example I. there is obtained from dodecyl bromide and aminoethylmorpholine. ,B-(dodecylamino)ethylmorpholine.

The condensation of this diamine with maleic anhydride gives the corresponding maleamic acid which. after neutralization with sodium hydroxide. is reacted with the mixture ofprimary amines derived from tallow fatty acids yielding the desired product in the form of an oil.

EXAMPLE Vl Preparation of the potassium salt of N'--[alkyl(tallow)]-N-(dodecyl)-N(N.N- diethylaminopropyl)asparagine.

N'.N'-diethyl-N-dodecyl-trimethylenediamine is first prepared by a process analogous to that described in Example I. Maleic anhydride is reacted with this diamine in solution in t-butyl alcohol. The maleamic acid thus formed is neutralized by an aqueous potassium hydroxide solution, and the potassium salt is reacted with the mixture of primary amines derived from the fatty acids of tallow. By evaporation of the solvent. the desired product is obtained in the form of a viscous oil.

EXAMPLE Vll Preparation of the sodium salt of N -[alkyl(copra)l-N-(cetyl) -N-(N'.N'-diethylaminopropyl)asparagine This product is obtained by a process analogous to that described in Example VI. It takes the form ofa viscous oil.

Examples Vlll to XVI below illustrate the use of compounds of the invention.

EXAMPLE VIII The following mixture is prepared:

sodium salt of N'-'-[alkyl(tallow)I-N-(dodccylla translucent gel is obtained.

EXAMPLE X There is prepared an aqueous solution containing:

the condensate obtained from 1 mole of tridec}! alcohol and [5 moles of ethylene oxide 7 diethanolamide of copra fatty acids 3 sodium salt of N"'-ltllk .l(tallow ll- N-t dodec l J-N-( N'.N'-diethylaniinoethyl )asparagine o g lactic acid. qs. for pH 5 water. q.s. l'or lUl) cc.

This solution is of oily consistency and when used as a shampoo imparts suppleness to the hair and makes it easy to comb. The viscosity of this shampoo is substantially higher than that obtained by replacing the compound of the invention with a cationic product in current use.

EXAMPLE XI There is prepared a solution containing:

the condensate obtained from 1 mole of copra fatty alcohol and I2 moles of ethylene oxide 8 g diethanolamide of copra fatty acids 4 g sodium salt of N -[alkyl(Copra]-N-(N'.N"

diethylaminopropylJasparagine 3 g sodium salt of N -lalkyluallow )I-N- (dodecyll-N lN.N-dicthylaminoethyl)asparagine 6 g lactic acid. q.s. for pH 5 water. q.s. for ltll) cc.

There is thus obtained a shampoo of viscous consistency which imparts suppleness to hair and makes it easy to comb. Moreover, the hair after having been washed with this shampoo does not exhibit any accumulation of electrostatic charge. The viscosity of this shampoo is clearly higher than that obtained in the absence of the compound according to the present application.

EXAMPLE XII the condensate of 1 mole of octylphenol and 5 t 1x mulcwf ethylene oxide 7g when applied to the hair, imparts a glistening effect dicihanummide r copra (any acids 4 g thereto, softens it and makes it easy to comb. cet \ltrimethylammonium bromide 3 g sodium salt of N -lalkylflullow)l-N-(cetyll-N- rN'.N'diethylaminoethyl)asparagine o g EXAMPLE XVI lactic acid. qvs. for pH 5 water as. for 100 cc.

I The following mixture is prepared: A thick solution obtained. This product constitutes a shampoo which renders the hair very soft and makes h d v v nitroparap enylene iamine l g It eds) to Comb 15 diethanolamine of copra fatty acids 4 g the condensate of 1 mole of lauryl alcohol and EXAMPLE XI" l0 moles of ethylene oxide 6 g sodium salt of N -[alkyl(copra)]-N-(cetyl) There are prepared: -N-(N.N'-dicthylaminoethyl)asparagine 3 g acetic acid. q.s. for pH 5.5 water q.s. for 100 cc .il a \(llUllUll containing: 7 sULlILIm bromate l5 g Mm so g There 18 thus obtained a viscous dyeing solution h 3" i l l h I which, when applied to the hair, besides dyeing it, im- L C(l'l LllSZlIC O moe O CCU, 11 CO 0 l I and 5 mm M ethylene Oxide 2 g parts to it a gloss and suppleness. sodium ml! of N*-[alk \l(tallo\\ )]-N-(dodccyl)-N- iN.N'-d|ethylaminoethylJasparagine 3 g phosphoric acid. qs. for pH (15 EXAMPLE XV Llltfl' l5 2 The following mixture is prepared: a) and b) are mixed at about 40C and make up to I00 cc with water. There is thus obtained a creamy fix- Y sodium salt of N [alkyl(copra)]-N-(N,N'-diethylatnei ot which 100cc diluted with 150 cc of hot water amino prowl) asparaginc h are used to neutralize a permanent Wave. sodium salt of N -[alkylflallow)]-N-(dodecyl)- -N-(morpholino ethyl)asparagine 3 g EXAMPLE XIV the condensate of 1 mole of lauric alcohol and 12 moles of ethylene oxide 7 g Th r is re ared b conventional rocedure a diclhflnolflmifle 0f P y Acids 3 B L t p y p lactic acid. q.s. for pH 3 CI'ClllTl C(llllllll'llllgi water, q.s. lor l(l() cc hum It Niymkmmnu WMCCQNN There is thus obtained shampoo of viscous consislNN'mllclh)lumlnucllqllllspilrngll'lc 5 g tency which makes the hair very soft and easy to comb. cctyl alcohol 3 g the condensate of l niolc olstearyl alcohol 40 and Ill moles ofethylcnc oxide 3 g EXAMPLE XVI" HllCl' 70 CC.

v i is 'ired: The mixture is allowed to cool to 40C and acidified The followmg on prep by the addition of citric acid until a pH of4 is reached, whereafter it is made up to 100 cc with water. Gem trimehyi ammonium bromide 3 g From 5 to 10 g of this cream are applied to hair sensisfldlum $1111 01 N=l y l y -N-(morpholino ethyl) asparagine 3 g used y ll decolorutloni Whlch massaged for Several the condensate of 1 mole oflauric alcohol minutes and then rinsed. The hair thus acquires soft 13 9 f ethylefle l0 s U I V dicthanolamide of copra fatty acids 3 g ness and a gloss and is easy to comb. lactic acid q's, [or pH 3 water qis, for 100 cc EXAMPLE XV There 18 thus obtained a VlSCOUS shampoo which The following mixture IS prepared: m k the hair supple and easy to comb.

The mixtures of primary amines used in Examples 1 d I f Ni H I u H N d d I) to VII have been used commercially. so rum sa t o a \'(t;\ ow o ecy N-i N' N'-diethxliiminoethyl)asparagine 5 g Other illustrative surface active asparagine com plClumlC ma 045 g pounds having the formula I include:

H gm at /GH CH 0O N 0H H e 1 2 2 2 UK .a 000E C H NH 3 fri s! nmco-N-(cH)- o CH m CODE 2) c 1: NE

pH (v.5 llll) cc lactic acid q.s. for water. q.s. for

There is thus obtained a thick dyeing solution which Illustrative other detergent or shampoo detergents that may be used in the detergent or shampoo compositions include sodium lauryl sulphate. sodium decyl benzene sulphonate, N-(sodium sulphoethyl) oleamide. sodium dioctyl sulphosuccinatet sodium lauryl sulphoacetater etc.

Illustrative hair dyes that may be used in the hair dye compositions include l,4 diethylolamino-3-nitro ben zene. l-(,8-ethylolaminol-Z-amino-4-nitrobenzene. lhydroxy-2-amino-5-nitrobenzene. and direct dyes such as those shown in US. Pat. Nos, 1983.65 l $040,064, 3.049393. 3100.73). etc

The compositions of this invention have preferably an acid pH.

What is claimed is:

l. A surface acti\e composition having an acid pH comprising an effective amount of a surface active compound having the formula:

I /1 H-CON-(CH)-N i2 2n R-NH- H-COOH R $12 24 /CH9 co N (c11 rt 0 11 an a COOH t- 9 fiz a tc n H2-CO-N-(CH2)2-N 4) c 3 -NH-CH-COOH 35 or its sodium, potassium. or ammonium salt, wherein R and R are selected from the group consisting of alkyl having 10-18 carbon atoms and alkenyl having 10 to 18 carbon atoms;

R and R are lower alkyl or together with the nitrogen atom on which they are attached constitute morpholino;

and n is an integer of 2 to 5 and an aqueous carrier.

2. The composition of claim 1 in the form of a gelv 3. The composition of claim 1, in which n is 2 or 3.

4. The composition of claim 1, in which R and R are alkyl having l4 carbon atoms.

5. The composition of claim 1, in which R and R and the N atom form morpholino.

6. The composition of claim 1, which also contains an effective amount of a detergent compound.

7. The composition of claim 1, which also contains an effective amount of a shampoo detergent 8. The process of softening and conditioning live human hair comprising applying to the hair an effective amount of the composition of claim I.

9. The process of shampooing and softening live human hair comprising applying to the hair an effective amount of the composition of claim 7.

Claims

1. A SURFACE ACTIVE COMPOSITION HAVING AN ACID PH COMPRISING AN EFFECTIVE AMOUNT OF A SURFACE ACTIVE COMPOUND HAVING THE FORMULA:

2. The composition of claim 1 in the form of a gel.

3. The composition of claim 1, in which n is 2 or 3.

4. The composition of claim 1, in which R1 and R2 are alkyl having 1-4 carbon atoms.

5. The composition of claim 1, in which R1 and R2 and the N atom form morpholino.

7. The composition of claim 1, which also contains an effective amount of a shampoo detergent.

8. The process of softening and conditioning live human hair comprising applying to the hair an effective amount of the composition of claim 1.