US3862221A

US3862221A - N,N{40 -di(hydroxymethylcarbamyl)cystamine

Info

Publication number: US3862221A
Application number: US284076A
Authority: US
Inventors: Gregoire Kalopissis; Jean-Louis Abegg; Guiliana Ghilardi; Beaulieu Henri Philippe De
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1967-08-02
Filing date: 1972-08-28
Publication date: 1975-01-21
Anticipated expiration: 1992-01-21

Abstract

Cosmetic composition comprising, in a suitable carrier, at least one active compound including both at least one disulfide function and at least one group responding to the formula:

IN WHICH: R is selected from the group consisting of hydrogen, a lower alkyl, a hydroxy-methyl or an alkoxy methyl radical; R'' is selected from the group consisting of hydrogen, and a lower alkyl radical; THE NITROGEN ATOM IN SAID GROUP BEING ATTACHED TO A REMAINDER WHICH IS SUFFICIENTLY ELECTROPHILE TO PREVENT THE IMMEDIATE RELEASE OF FORMOL.

Description

United States Patent [191 Kalopissis et a1.

[ Jan. 21, 1975 N,N'-DI(HYDROXYMETHYLCARBAMYL)- CYSTAMINE [75] Inventors: Gregoire Kalopissis, Paris;

Jean-Louis Abegg, Le Perreux; Guiliana Ghilardi; Henri Philippe de Beaulieu, both of Paris, all of France [73] Assignee: Societe Anonyme dite: LOreal, Paris, France 22 Filed: Aug. 28, 1972 211 App]. No.: 284,076

Related US. Application Data [62] Division of Ser. No. 749,278, Aug. 1, 1968, Pat. No.

2,977,386 3/1961 Kise 260/553 R 3,067,177 12/1962 Greco et a1. 260/553 R 3,534,135 10/1970 Wajaroff 424/71 FOREIGN PATENTS OR APPLICATIONS 951,273 10/1956 Germany 260/533 R OTHER PUBLICATIONS Behringer et al., Chem. Abs., Vol. 57, p. 3428d, (1962).

Primary Examiner-Bernard Helfin Assistant Examiner-Nicky Chan Attorney, Agent, or FirmCushman, Darby & Cushman [57] ABSTRACT Cosmetic composition comprising, in a suitable carrier, at least one active compound including both at least one disulfide function and at leastone group responding to the formula:

in which:

R is selected from the group consisting of hydrogen, a lower alkyl, a hydroxy-methyl or an alkoxy methyl radical;

R is selected from the group consisting of hydrogen, and a lower alkyl radical;

the nitrogen atom in said group being attached to a remainder which is sufficiently electrophile to prevent the immediate release of formol.

1 Claim, No Drawings 1 2 N,N'-DI(HYDROXYMETHYLCARBAMYL)CYSTA- R E I 'ICH,0R ThlS IS a dlVlSlOI'l, of application Ser. No. 749,278 filed Aug. 1, 1968, now U.S. Pat. No. 3,694,141. in which:

Keratinic fibers known to consist of chemical sub- 5 R represents hydrogen, a lower alkyl radical, a hystances having a high molecular weight and having a droxymethyl radical, or an alkoxy-methyl radical.

large number of transverse disulfide bonds. It is consid- R represents hydrogen or a lower alkyl radical. ered that these disulfide bonds impart a group of char- The nitrogen atom of said group is attached to a reacteristic physiochemical properties to the fibers. mainder sufficiently electrophile to insure the chemical It is also known that the disulfide bonds play an imstability of the group, that is to y to avoid the imme portant role in the chemical treatment undergone by diate release of a fOrInOl cu hair in order to impart permanent deformation thereto. In the present description the term lower alkyl radi- In order to produce such permanent deformation it cal is used to identify alkyl radicals having four or less is necessary to first open up the disulfide SS bonds of carbon atoms. the keratin, and then, after having imparted the desired In certain particular embodiments, the compositions deformation to the hair, to reconstitute the SS bonds, according to the invention may contain compounds reusually by means of oxidizing compounds. sponding to the general formula:

On the other hand the chemical rocesses for im arting a permanent deformation to the hair, which c ause HOH2C Q 0-120" S S (CI-12) Q opening of the SS bonds, substantially reduce the 2 CHZOH percentage of cystine, while other chemical treatments in which:

such as bleaches or combinations of bleaches and dyes, Q and O, which may be identical or different, reprewhich are carried out by using rather strong oxidizing sent nitrogenous groups capable of being methylolag also reduce the number of S- bOIldS in the ized, such as ureas, thioureas, amides and carbakeratine. mates,

Moreover, atmospheric g such as exposure to n and n, which may be identical or different, each the Sun of Sea Water, also degrade the hair, to a y represent a whole number less than or equal to 6. Substantial 6X16! in some CaSeS- In certain particular embodiments'of the invention,

Such a reduction in the q y of bonds in the the cosmetic compositions according to the invention hair produces an irreversible alteration in the keratinic may contain at least one of h foflowing compounds; tu hw amounts to a change In the Strength N N -dimethylol-dithiodiglycolamide having the forand cosmetic properties of the hair. mula;

It is for these various reasons that attempts have been made to improve by a cosmetic treatment the quality SCH2 NHCHEOH of hair which has been thus degraded.

It has already been proposed to strengthen the hair SCHQ-C-NHCIhOH by using polysulfhydryl polymers which make it possii ble to attach polymers of relatively high molecular weight to the natural keratlnrc fibers. These polymers 40 duhydroxymethylcarbamyl) cystamine having attach themselves solidly to the keratin because they the formula.

have a certain number of SH groups which can form mixed drsulfides with cystem. l s CH2 CH2 NH C NHCH20H It has also been suggested that degraded halr be 11 treated with cosmetic compositions containing such substances as formaldehyde or other compounds of this family which attach themselves to the keratin by reticulation, or polycondensation.

The present invention relates to new cosmetic comdt(hydroxymethyl acetamrdo) dimethyl cystamine positions based on active compounds which increase ammonium dichloride having the formula:

the percentage of disulfide bonds in the hair. di(hydroxymethyl-ethylurea) dimethyl cystamine It is an object of the present invention to provide as ammonium dichloride having the formula:

a new article of manufacture a cosmetic composition In a first embodiment of the invention, the cosmetic characterized by the fact that it contains at least one compositions are in the form of setting lotions which compound comprising at least one disulfide function may also contain an acid catalyst which facilitates the and at least one group responding to the formula: condensation of the methylol groups on the hair.

3 4 The new compositions have the advantage of increas-i the keratin. In effect, by utilizing the disulfides according the number of SS bonds in the keratinic fibers by, ing to the invention, all the disulfides, that is to say, means of compounds which penetrate into the kera both the disulfides according to the invention, and the tinic fiber and, because of the methylol groups in the mixed disulfides obtained from the disulfides and keraactive compounds according to the invention, become 5 tin are bonded to the keratin at each side of the SS chemically attached to the substance of the hair itself. bond through their methylol groups.

This addition to the number of SS bonds permits the The cosmetic compositions according to the invenformation of mixed disulfides between the compounds tion may take the form of a liquid containing the active according to the invention and cystine, which also compounds in a simple aqueous or hydroalcoholic solustrengthens the hair. tion Both the SS bonds added by the compositions ac- These compositions may also tak h f of a cording to the invention and the SS bonds of the cream or gel with the active compounds dispersed o mixed disulfides may be used in permanent waving P dissolved in one of the Phases of the composition. cesses' The compositions according to the invention may Fina y, the Compositions according to the invention also contain any other ingredients conventionally used have, independently of the additional SS bonds, he in cosmetology, such as dyes, perfumes, swelling advantage of strengthening the hair because of the pheagents, surface-active agents, etc. nomenon of condensation or reticulation which is due They may also be packaged as aerosols. to the presence of the methylol groups. The compositions according to the invention contain,

In another preferred embodiment of the composiin general, from 1 to 10 percent and preferably 2 to 4 tions according to the invention, the active compounds percent of the active compounds. are introduced into fixing lotions designed to carry out It is a further object of the invention to provide as a the second step of a permanent wave. In this case, parnew article of manufacture a chemical compound ticular reliance is placed on the oxidizing proportions which may be used in cosmetology characterized by the of the SS functions in the active compounds accordfact that it corresponds to the following formula: ing to the invention. In one particular method of using these composi- HOH2C Q (H2C)" E Y (Cl-I2) Q tions, they are employed as fixing lotions when perma- 2 nently setting the hair, which permits the hair, after in which: having been first reduced rolled up on setting rollers Q and O, which may be identical or different, repreand then impregnated with such a lotion to be dried disent either an aminoalcoylamide remainders which rectly. may be quaternized, or a remainders containing urea, In this case, the composition according to the inventhio-urea, or carbamate groups, which may also contion makes it possible to not only reconstitute the SS tain an eventually quaternized amine function, the bonds of the keratin, but also to strengthen the hair by Cl-l Ol-I groups being attached to the amide nitrogen reticulation or condensation of the methylol functions, of these remainders. while simultaneously increasing the quantity of sulfur n and n, which may be identical or different, each attached to the hair. represent a whole number less than or equal to 6.

In another embodiment, the compositions according The present invention has for its particular object the to the invention are compositions which make it possifollowing chemical compounds: ble to produce a long-lasting deformation of the hair in -N,N-di( ydr ym thy a a y cystamine ng a single step, with the reducing and oxidizing phases the formula: being carried out simultaneously.

It has already been suggested that permanent wavesbe produced by using compositions containing a mixture of thiols and disulfides, in which the molar concen- SC1IgClIr-NIIC--NIICIIzOII tration of the disulfides is greater than that of the thiols. H

In accordance with the present invention, it is advantageous to use in such compositions the new disulfide di(hydr xym thyl-a ta y y in compounds hereinbefore described. ammonium dichloride having the formula:

( a): Ila):

In this latter method of producing a self-neutralizing di(hydroxymethyl-ethylurea) dimethyl cystamine permanent, or long-lasting set, the compounds accordammonium dichloride N1I(ClIz)zI\+I( CHz)- -SS( o II2)2I3( 0112) Nrr-0 ONlI-CH:O 1r

NIICI[2O1[ ing to the invention have the advantage over known Afurther object of the present invention is to provide compounds of avoiding the formation of mixed disulseveral methods of preparing the chemical compounds fides, one part of which does not become attached to which have just been described.

-vention is obtained.

In an alternative method of preparing a compound according to the invention, the process starts with a halogen derivative having an amine function which is transformed into sodium S-amino-atceyl thiosulfate by reacting it with sodium thiosulfate. This salt may then be hydrolyzed to produce a disulfide which comprises, like the starting product, at least one amine function. This amine may be transformed into urea by reacting it with a cyanate, as has just been described, and methylolized by a solution of formaldehyde. The disulfide having a tertiary amine function may be quaternized with a compound which is itself methylolized or capable of becoming so, such as chloracetamide or N- methylol-chloracetamide. In both cases a chemical compound according to the invention results.

In order that the invention may be better understood, several examples of the preparation and use of the active compounds according to the invention will now be described purely by way of illustration.

EXAMPLE 1 Preparation of N,N-di(hydroxymethylcarbamyl) cystamine.

An aqueous solution of cystamine dihydrochloride is reacted with a stoichiometric quantity of potassium cyanate for 2 hours at 80C.

The reaction yields dithiodi(ethylurea) which is extracted and recrystallized in absolute ethanol. The melting point of the resulting product is between 152 and 153C and the yield is 77 percent.

A solution is then prepared which contains one mole of dithiodi(ethylurea) per liter of water, to which 187.5 g of formaldehyde in the form of a 40 percent aqueous solution is added. The pH value of the mixture is adjusted to 8 by adding an N/ 10 sodium hydroxide solution and heated while stirring to a temperature of 50C, while maintaining the pH at a value near 8. The reactants are completely dissolved at the end of about 30 minutes.

The reaction mixture is then cooled to 0C and a white crystalline product having a melting point of about 100C results.

The yield of the reaction is 70 percent and the product contains about percent combined formol.

EXAMPLE 11 Preparation of di(hydroxymethyl-acetamido), dimethyl cystamine ammonium dichloride.

The reaction is carried out at C for 30 minutes and a colorless paste is obtained which contains no tertiary amines. The yield of the reaction is 100 percent.

EXAMPLES OF APPLICATIONS EXAMPLE I A solution having the following composition is applied to hair which has first been washed and dried:

thioglycolic acid 2.5 g

di(hydroxymethyl acetamide) dimethyl cystamine ammonium dichloride 7 g monoethanolamine, q.s.p. pH 9.5

water, q.s.p. 100 cc The hair is then wound up on rollers and left under a hood for 15 minutes at a temperature of 35 to 40C. This hair is then rinsed in running water and impregmated with a solution comprising citric acid to bring its pH to about 2.5. The hair is then set in a conventional manner by drying the hair at a temperature of about 45 to 50C.

The hair exhibits excellent resilience and the wave lasts well.

EXAMPLE II The following composition is applied to hair which has previously been bleached:

N,N-di(hydroxymethylcarbamyl)cystamine 2 g polyvinylpyrrolidone/vinyl acetate copolymer 0.4 g

trimethyl cetyl ammonium bromide 0.l g

acetic acid q.s.p. pH 3 water, q.s.p. I00 cc The hair is set in a conventional manner and it is -found that the hair is harder and cleaner, and its tips are less dry than when bleached hair is set using a process other than one according to the invention. Moreover, the wave set exhibits excellent resilience.

EXAMPLE III A long lasting set is produced in a generally conventional manner, using the following composition:

thioglycerol 3 g ammonia, q.s.p. pH 9.5

water, q.s.p. 100 cc N,N"dimethylol dithiodiglycolamide 4 g phosphoric acid q.s.p. pH 2.5

water, q.s.p.

The hair is then placed under a hood and dried in a conventional manner. The resulting wave is of excellent quality and exhibits excellent stability in time.

, EXAMPLE IV The first step of a long lasting set is carried out as in Example III after which the following solution is applied to the hair:

N,N-dimethylol dithio dipropionamide 4 g phosphoric acid q.s.p. pH 2.5

I cc

water, q.s.pi

The hair is then placed under a hood and dried in a conventional manner. The resulting wave is of excellent quality and exhibits excellent stability in time:

EXAMPLE V The following composition is applied to hair which has first been washed and dried:

8 thioglycolic acid 2.5 g di(hydroxymethyl ethylurea) dimethyl cystamine ammonium dichloride 7 g monoethanolamine, q.s.p. pH 9.5

Claims

1. N,N''-DI(HYDROXYMETHYLCARBAMYL)CYSTAMINE.