DE1492067C3 - Mixtures of asparagine derivatives, their production and cosmetic compositions containing them - Google Patents

Description

CH ₂ -CO-NH- (CH ₂ ) _n -N
R —N — CH — COOM R ²

CO -CH, -CH-COOM

"I.

R '-NH

in which R ¹ and R ² , which can be identical or different, Ci-C ₄ -alkyl radicals or R ¹ + R ²

- (CH ₂ J ₂ -O - (CH ₂ J ₂ -

are, η is an integer from 2 to 5, R and R ', which can be identical or different, are aliphatic hydrocarbon radicals having 10 to 18 carbon atoms and M is a hydrogen atom, sodium, potassium or ammonium; optionally in a mixture with other anionic, cationic or non-ionic surface-active substances. Preferably η is 2 or 3.

These agents can be used in the form of aqueous solutions whose pH is acidic, neutral or can be alkaline. They then act as either cationic or anionic agents.

As mentioned above, aqueous solutions, which mixtures of asparagine derivatives according to Claim 1 contain, harmless to the mucous membrane of the eye. This harmlessness was proven through experiments confirmed, which are summarized in the table below. The ones mentioned in the table Mixtures of compounds Ia to Ig according to the invention are characterized in the preparation example below.

table

Action of aqueous solutions of the products according to the invention on the eye of rabbits. The evaluation took place 24 hours (column X) and 7 days (column Y) after application of the test solution

Apply
tes invent
dungge
moderate Ge
mix;
0.05 mole in
more watery
solution pH 3
Rabbit no.
1 2 Y X Y 3 Y 4th Y pH 7
Rabbit no.
Γ 2 Y X Y 3 Y 4th Y ph 8
Rabbit no.
1 2 Y X Y 3 Y 4th Y Yes X 0 *) 1 0 *) X 0 *) X 0 *) X 0 0 0 X 0 X 0 X 0 0 0 X 0 X 0 Ib 1 0 0 0 1 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 [C 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Id 0 0 1 0 ») 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 e 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 If 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ig 0 0 *) 1 0 *) 0 - 0 0 *) 0 0 1 0 *) 0 0 *) 0 0 0 1 0 *) 0 0 *) 0 *) = cured, 1 2 +) - 1 0 1 0 0 0 2+) = 2 weak.

The test and evaluation method used is in the "Journal Officiel de la Republique Francaise" from April 21st. 71, pages 3862-3864. The evaluation numbers used in the table above have the following meaning:

0 = no irritation,

1 = irritation of the conjunctiva of the eyeball or the

Eyelids,

2 = irritation of the conjunctiva of the eyeballs and the

Eyelids,

3 = 2 as well as tears of the eye - (healing),

4 = 3 plus additional non-purulent discharge -

(Cure),

5 = 4 as well as additional purulent secretion - closing

Enhancement of the eyelids, dull cornea, if necessary with insensitivity - (healing slowly but possible),

6 = 5 as well as additional attack of the eyelid margins and even

of the skin

The phenomena marked with the numbers 1 to 6 can vary depending on the severity of the impact be accompanied by apparitions 1 to 5.

Since the damage to the cornea can be of two types, the most severe can lead to the phenomena Corresponding to the effect, the following damage is also added:

a) loss of gloss (dull cornea),

b) more or less complete destruction of the corneal epithelium with more or less extensive Ulceration and loss of corneal sensitivity.

The cornea can be attacked after 5 and 6, either by the one being used Product itself or through the pathological conjunctival discharge caused by this product would. The loss of corneal sensitivity facilitates ulcer formation.

From the experiments summarized in the table above it is clear that the inventive Agents do not attack the cornea, as is often the case with the known anionic, cationic or nonionic agents. Have comparative tests show that the application of solutions of the same concentration and the same pH value of trimethylcetylammonium bromide on the rabbit eye caused damage that, according to the above scale, is between 3 and 6 lie.

The agents according to the invention can be used in various fields, in particular in cosmetics. As already mentioned, they can also be used advantageously for thickening hair washing compositions will.

The new chemical used as active ingredients for the surface active agents according to the invention Compounds of the general formula (I) are prepared according to the invention in such a way that one Asparagine derivative of the general formula II:

CH ₂ - CONH- (CH ₂ ) ,, - N

R-NH-CH-COOM

R ¹

R ²

(Π)

in which R ¹ and R ² , which can be identical or different, are dC ₄ -alkyl radicals or R ¹ + R ²

- (CH ² ) ₂ -O- (CH ₂ ) ₂ -

mean, π is an integer from 2 to 5, R is an aliphatic hydrocarbon radical having 10 to 18 carbon atoms and M is hydrogen, sodium, potassium or

Ammonium means that it is reacted in a manner known per se with maleic anhydride and attached to the double bond of the product thus obtained, in a manner known per se, a fatty amine of the general formula III:

R'-NH ₇

(III)

where R 'denotes a hydrocarbon radical having 10 to 18 carbon atoms, is added on.

Fatty amines are particularly suitable
Consideration:

Decylamine, dodecylamine and the amines derived from copra and tallow fatty acids.

The asparagine derivatives of the general formula (II) listed above can be obtained according to the DT-AS 12 23 994 by mixing maleic anhydride with an alkylenediamine of the general formula

H ₂ N- (CH ₂ ) "- N

R ¹

R ²

in which π, R ¹ and R ^{2 have} the above meanings, and the amide of the general formula, optionally converted into a salt (M = Na, K or NH4)

R ¹

CH-CO-NH- (CH ₂ ), -N
CH-COOM R ²

in which n, R ¹ , R ² and M have the meanings mentioned above, with a primary amine of the general formula

R-NH ₂

wherein R has the abovementioned meaning

Preferably η is 2 or 3.

In the following examples both the preparation of the new mixtures from asparagine derivatives as well as the production of the cosmetic agents containing them

Production of the new mixtures from asparagine derivatives.

a) Preparation of the disodium salt of the formula:

.C ₂ H ₅

CH ₂ -CO-NH- (CH ₂ ) ₃ -N

R-N-CH-COONa

CO-CH ₂ -CH-COONa R'-NH

C ₂ H ₅

in which R and R 'represent aliphatic hydrocarbon radicals derived from copra fatty acids.

To a solution of 444 g (1 mol) of the sodium salt of the N ¹ - [y- (N ', N'-diethylamino) propyl] -N ² - (alkyl) -asparagine of the formula

CH ₂ - CONH- (CH ₂ ) ₃ - N

RNH-CH- COONa

QH ₅

C ₂ H ₅

in which R is an alkyl radical derived from Koprafettsäuren in 300 cm ³ of tert-butyl alcohol means are added at a temperature of 50 ⁰ C and with stirring, 99 g (1 mol) of maleic anhydride added. The whole thing is kept at 50 ^° C. for about an hour and then allowed to cool to room temperature. It is then neutralized with an aqueous 40% NaOH solution (approx. 112 g). Then 1 mole of fatty amine derived from copra fatty acids is added. added and heated for 12 hours with stirring at 65 ° C The solution was dried in vacuo at about 0.1 to 1 mm Hg pressure and a temperature between about 90 and 180 ⁰ C, depending on which starting amine was used evaporated until practically nothing more distilled over. The process product obtained in this way is practically colorless and can be ground into flakes. Basic number: calculated: 53, found 5.3. It contains 2-4% unreacted primary amine.

The following starting asparagine derivatives are made in an analogous manner of the general formula II converted to the corresponding products Ib, c, d, e, f and g:

R ¹

/ CH ₂ - CO — NH- (CH ₂ ), - N (II)

R-NH-CH-COOM R ²

at
game Parent asparagine derivative
R ¹ and R ² R. η M. Amount (g)
Starting
asparagine
derivative II
each I mole tert.-
Butanol
(cm ³ ) NaOH
40%
(G) Malein
acid
anhydride
1 mole
(G) Amine mixture
R'-NH ₂
(1 mole) b -C ₂ H ₅ Tallow alkyl 3 N / A 520 350 117 99 Tallow alkyl C. -C ₂ H ₅ Tallow alkyl 3 N / A 520 350 117 99 Copra-
alkyl d -CH ₃ Copra-
alkyl 3 N / A 416 500 108 99 Copra-
alkyl e (_ti ₃ Tallow alkyl 3 N / A 416 500 108 99 Tallow alkyl f C ₂ H ₅ Copra-
alkyl 2 N / A 430 500 108 99 Copra-
alkyl

continuation

Example home asparagine crival game

R 'and R ² R

CH-?

CH ₂ -CH ₂ (R ₁ + R ₂ )

Copraalkyl

2 K

Amount (g) of starting asparagine derivative 11 in each case 1 mol

460

tert-butanol

(cm x ¹ )

650

NaOH maleic 40% acid

anhydride 1 mole (g) (g)

50% KOH

Amine mixture R'-NH ₂

(1 mole)

Copraalkyl

The amine mixtures used for the preparation of the products according to the invention, which differ from copra or tallow fatty acids have the following composition:

Composition of the length of the C chain of the amines Composition of the of

Copra fatty acids derived from tallow fatty acids

Amine mixture, amine mixture,

2.0

5.1

68.5

18.5

4.3

1.1 0.5

Cs sense Cio 0.2 Cl2 1.4 Ch 28.4 Cl6 31.2 Ci 8 (unsaturated) 38.8 Cl8

The products I a-g obtained are characterized by the following structure and basicity number.

/ CH ₂ - CO - NH - (CH ₂ ) ,, - N

R-N-CH-COOM R ²

CO-CH ₂ -CH-COOM ^(I) '

R'-NH

product R ¹ and R ² R. R ' η M. Basicity number
(mAqu./g) ber. Not implemented
primary amines found 5.28 Yes -C ₂ H ₅ Copraalkyl 3 N / A 5.3 4.39 Ib -C ₂ H ₅ Tallow alkyl 3 N / A 4.67 4.79 Ic -C ₂ H ₅ Tallow alkyl copra
alkyl 3 N / A 5.31 5.47 Id -CH ₃ Copraalkyl 3 N / A 5.68 4.53 3.2% Ie -CH ₃ Tallow alkyl 3 N / A 4.63 5.37 2% If -C ₂ H ₅ Copraalkyl 2 N / A 5.42 3.6% CH ₂ -CH ₂ 5.35 Ig / \
O
\ / Copraalkyl 2 K 5.4 3.4% \ /
CH ₂ CH ₂ I’m sure. (R ¹ + R ² ) The basicity number was With HClOa in E.

709 516/456

Production of the cosmetic agents Example 1

Prepare an aqueous solution of the following composition:

Mixture Ia 7 g

N ^I - [y- (N ', N'-diethylamino) -

propyl] -N ² - (copra-alkyl) -

asparagine 6 g

Lactic acid until achieved

a pH of 6

Make up to 100 cm ^{3 with water}

This solution results in a shampoo with a viscous consistency that lathers well and is easy to detangle of the hair.

Mixture Id

Lactic acid until achieved

a pH of

Fill up with water

5g

100 cm ³

Example 2

One mixes

Fatty alcohol with 12 to

14 carbon atoms, condensed with

12 moles of ethylene oxide

Mixture Ia

Lactic acid until achieved

a pH of

Fill up with water

12g 6g

100 cm ³

Example 3

One mixes

Octylphenol condenses with 8g 15 moles of ethylene oxide 2g Copra fatty acid diethanolamide 6g Mixture Ic Lactic acid until achieved 7th a pH of 100 cm ³ Fill up with water

An oily shampoo is obtained which makes the hair soft and silky. In addition, the hair shows does not develop any electrostatic charge during treatment.

Example 4

One mixes

Branched chain tridecyl 7g alcohol condensed with 6g 15 moles of ethylene oxide Mixture Id 6th Lactic acid until achieved 100 cm ³ a pH of Fill up with water

This oily shampoo makes it easy to comb your hair and make it easier soft and silky.

Example 5

One mixes

Lauric alcohol, condensed
with 15 moles of ethylene oxide
Copra fatty acid diethanolamide

8g 2g

This shampoo with an oily consistency makes hair silky soft and prevents build-up electrostatic charge after drying.

Example 6

One mixes

Sulfuric acid monoester of

Alcohols with 12 to

14 carbon atoms (80% alcohols

with 12 carbon atoms + 20%

Alcohols with 14 carbon atoms)

as ammonium salt (calculated as

Ammonium sulfonate to 100%)

Mixture Ia

Lactic acid until achieved

a pH of

Fill up with water

9g
Ig

6.8
100 cm ³

A shampoo with an oily consistency is obtained, which makes the hair supple and combs through facilitated. In addition, the hair does not show any electrostatic charge after the treatment.

This shampoo gives the hair softness and prevents static electricity.

Comparative experiments

The compounds corresponding to Examples Ia to Ig are investigated.

The selected comparison compound is a betaine with the following formula

CH ₃
R ³ -CO-NH- (CH ₂ ) ₃ -N-CH ₃

CH, -COO®

in which R ^{3 has} an average chain length of 14 carbon atoms and which was used as a commercial product with 30% active material.
The tests were carried out with 6% strength aqueous solutions, and it has been shown that gelled and denser solutions can be obtained with the products according to the invention at the same concentration than with the above betaine.
The thickening of the solutions according to the invention occurs with each product at a precisely defined pH value and is maintained within a range of 4 pH units or, in contrast to the comparison product, it only varies over a much smaller range.

In contrast, the solution of the comparison product remains fluid at any pH.

The compounds are added to water and stirred with a magnetic stirrer at ambient temperature solved

no you will be using lactic acid as in the table indicated, adjusted to different pH values and the measurements of the viscosity of these solutions are made carried out at 25 ° C using viscometers with coaxial cylinders.

C ₅ Since the solutions of the products according to the invention do not show any Newtonian behavior, the viscosity occurring at a given gradient is given in the table.

Solution of pH of the solution viscosity
at 25 ° C = 200cP Yes 8th 45s- = 21OcP Ib 3.5 45s- = 220 cP Ic 4th 45s- = 750cP Id 8th 45s- = 36 cP Ie 3 50s- = 420 cP If 8th 45s- = 18OcP Ig 4th 45s- = 1.1 cP Comparative betaine 4th

Claims (3)

Patent claims: 1. Mixtures of asparagine derivatives of the general formula: R ¹ CH ₂ - CO - NH - (CH ₂ ) 1 - N
R-N-CH-COOM CO-CH ₂ -CH-COOM
R'-NH R ² (D in which R ¹ and R ² , which can be identical or different, Q- to C ₄ -alkyl radicals or R ¹ + R ² - (CH ₂ J ₂ -O- (CH ₂ J ₂ - are, π is an integer from 2 to 5, R and R ', which can be the same or different, aliphatic hydrocarbon radicals having 10 to 18 carbon atoms and M is a hydrogen atom, sodium, potassium or ammonium. 2. Process for the preparation of the substance mixtures according to claim 1, characterized in that one asparagine derivatives of the general formula II: R ¹ CH ₂ - CONH— (CH ₂ ) ,, - N (II) R -NH-CH-COOM R ² 35 in which R, R ¹ , R ² , η and M have the meanings given in claim 1, in each case in a manner known per se one after the other with maleic anhydride and a fatty amine of the general formula III: R'-NH ₂ (III) in which R 'has the meanings given in claim 1. 3. Cosmetic agent, characterized by a content of one or more mixtures of substances according to claim 1, optionally in a mixture with other anionic, cationic or nonionic surfactants. The invention relates to the subject matter characterized in the patent claims. In DT-AS 12 23 994 shampoos are described, characterized by a content of Derivatives of asparagine of the general formula R ¹ CH, -CONH- (CH,) ,, - N ^ S, R-NII - CII -COOM R ² in which R ¹ and R ^{2 are} identical or different lower alkyl radicals with up to 4 carbon atoms, which taken together can also be parts of a heterocycle, η is an integer from 2 to 5, preferably 2 or 3, R is an aliphatic hydrocarbon radical with 10 to 18 carbon atoms and M denotes hydrogen, sodium, potassium or ammonium. It has now been found that cosmetically valuable products are obtained if the number of by long-chain aliphatic hydrocarbon radicals substituted amino groups and the number of Increased carboxyl groups in the above molecule. Cosmetic agents produced on the basis of the mixtures according to the invention from asparagine derivatives have the following advantages in particular: 1) They have good surface-active properties, making them suitable for washing hair, and in a very wide pH range, which can range from 3 to 10. In this case they have In addition to their good washing effect, shampoos also have the advantage of electrostatic charging to prevent the hair, to soften the hair and to allow easy combing. 2) They are very well tolerated by the mucous membrane of the eye. 3) They have a very good thickening effect and can therefore be used as an additive for aqueous Solutions of other surface-active substances with cationic, anionic or non-ionic Structure to be used. The latter advantage should not be underestimated in practice, since the thickening effect with the help of Substances can be obtained that can be used for yourself to wash your hair, as opposed to to the known agents that are not thickening and detergent at the same time. The cosmetic agents according to the invention, which are used for washing and cleaning purposes, as surface-active Agents that can be used, in particular, as shampoos, are characterized in that they are a mixture of asparagine derivatives of the general formula I: R ¹