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Publication numberUS3803138 A
Publication typeGrant
Publication dateApr 9, 1974
Filing dateMar 27, 1972
Priority dateFeb 20, 1968
Publication numberUS 3803138 A, US 3803138A, US-A-3803138, US3803138 A, US3803138A
InventorsBore P
Original AssigneeOreal
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Cosmetic compounds
US 3803138 A
Abstract  available in
Images(6)
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 5 Int. Cl. C07d 87/42 US. Cl. 260-242 2 Claims ABSTRACT OF THE DISCLOSURE Compositions for setting hair containing bivalent metal dithiolate derivative having at least one N-methylol group and the process of treating human hair with these compositions.

SUMMARY OF THE INVENTION This is a division of application Ser. No. 800,721, filed Feb. 19, 1969, parent application Ser. No. 800,721 is now U.S. Pat. 3,674,038.

This invention relates to compounds having properties which make them valuable in cosmetic treatment of human hair.

It is an object of the present invention to provide a product which consists of a bivalent metal thiolate having at least one N-methylol group which may be esterified or converted by the Mannich reaction (Organic Chemistry by Szmant, p. 459, Prentice Hall, 1957) With a secondary amine.

It is a particular object of the present invention to provide compounds corresponding to the formula:

in which Me represents a vibalent metal.

X and X which may or may not be identical and may be omitted, have the following significances:

(a) carbon-carbon bond,

(b) substituted or unsubstituted, straight or branched chain aliphatic hydrocarbons having 1 to 6 carbon atoms, such as alkyl,

(c) aryl chains, such as benzene,

(d) Z--NR- chains, in which Z represents a substituted or unsubstituted, straight or branched chain hydrocarbon having 1 to 6 carbon atoms, such as alkyl, alkenyl, etc., R represents a hydrogen atom or hydrocarbon group, which may be substituted. (These substitutions may be of very different types, such as carboxyl, amine, etc.).

Y and Y which may or may not be identical, represent a hydrogen atom or a hydroxyl group (in the case of free methylols), which may, in certain cases, be etherified, or converted by the Mannich reaction with a secondary amine, but only one of Y and Y may represent a hydrogen atom.

One may have, for example:

Y1=HY2=OH (monomethylols) Yi=Yz=OH (dimethylols) Yi=HYz=OR Y1=Y2=OR Y1=0HY2=ORI (in which R represents an alkyl radical having up to 6 carbon atoms.)

Patented Apr. 9, 1974 In accordance with the invention the bivalent metal may be selected from the group consisting of tin II, chromium II, nickel, manganese II, cadmium, zinc, antimony II, barium, strontium, calcium, magnesium, cobalt II, iron II, etc.

Among the compounds according to the invention which respondto the above formula are:

Cadmium bis [N-hydroxymethyl carbamoyl methyl thiolate] having the formula:

Zinc bis [N-hydroxymethyl carbamoyl methyl thiolate] having the formula:

Cadmium bis [N-morpholinomethylureido methylthiolate] having the formula Cadmium bis [2-(N-hydroxymethylureido)-ethyltbiolate] having the formula:

s-om-cm-rvn-oo-rzn-omon s-om-cm-nn-c ONHCH:OH

Cadmium bis [2-(N'-morpholinomethylureido)-ethylthiolate] having the formula:

Cadmium bis [2-methoxycarbonyl-2-(N'-morpholinomethylureido)-ethylthiolate] having the formula:

It is also an object of the present invention to provide a method of preparing the above-described new compounds, which method is characterized by the fact that a thiol having a function which can be converted to N- methylol is transformed by reacting it with a salt of a bivalent metal, and the resulting thiolate is transformed by reaction with formol into a methylol thiolate.

In a preferred embodiment of the invention the thiolate of the thiol which can be transformed into N-methylol is precipitated by adding said thiol little by little to a solution of a bivalent metallic salt such as Zn, Cu, Cd, Ba, Sr, Ca salts.

In a particular embodiment of the invention the N- methylol group of said thiolate is esterified or subjected to a Mannich reaction.

The new compounds which have just been described have a bifunctional structure which imparts thereto properties which are particularly valuable in the cosmetic field.

These compositions have both a thiolate group and at least one methylol group, each of these groups having a reactivity with keratinic fiber which imparts particularly advantageous properties to the composition.

In fact, the reactivity and analytic behaviour of the thiolates approach those of thiols, but they are not as readily oxidized as thiols. On the other hand, these compounds are more reactive than disulfides and have the particular advantage of being able to form mixed disulfides by reacting with the keratocystine of the hair.

Moreover, thanks to the presence of at least one monomethylol function, and in particular a monomethylolamide function, the compounds according to the invention have in addition to their substantial reactivity with the amino-acids of keratin, the peculiarity that they poly condense with themselves, while first forming oxyrnethylene bonds and then methylene bonds.

As a consequence of these particular properties, the new compounds which have just been described may be used for a wide variety of purposes in the cosmetic field.

On the one hand by reason of their double reactivity with keratocystine and the amine groups of basic aminoacids or of thyrosine, they have an extremely valuable reticulating effect on keratinic fiber.

On the other hand they are capable of supplying very bright transparent insoluble polymers when heated under different conditions in a medium having a pH greater than the pH at which the MeS bond ruptures. This characteristic is particularly valuable in making setting lotions.

The invention relates to various methods of treating the hair characterized by the fact that the hair is impregnated with compositions containing compounds according to Formula I in proportions varying between 0.1 and 20% by weight.

In a preferred method of carrying out the invention the neutralization step of a permanent wave or a twostep permanent set is carried out by impregnating the hair, while it is rolled up on curlers, with a composition comprising at least one compound according to Formula I at a concentration between 0.05 mol and 0.4 mol per liter, the pH of the composition being preferably alkaline and between 8 and 10.

The process according to the invention is particularly useful in fixing permanent sets.

In this process the hair is wound up on setting rollers of average diameter, after having been impregnated with a reducing solution such as a solution of thiol utilized in permanent waving. The method of fixing the permanent set according to the invention is particularly advantageous in the present case because in order to fix the set it suffices to apply a solution of the compound of Formula I to hair which has first been reduced and rinsed, and to dry the hair under a dryer without rinsing it. This results in excellent chemical fixation and an addition of polymers which results from the polymerization of the compounds according to Formula I.

In accordance with the invention, a permanent hair set may be produced by following a new technique made possible by using thiolates according to the invention. This consists in treating the hair with a reducing solution without putting it up on curlers, rinsing it, impregnating it with a thiolate solution according to the invention, then winding the hair up on setting rollers, and finally drying the hair.

This produces excellent permanent sets, the quality of which results from the fact that the reconstitution of the disulfide bonds of the keratin takes place simultaneously with the formation of a resinous sheath on the hair.

In accordance with the invention, the compounds of Formula I also make it possible to recondition hair which has been degraded as the result of bleaching, for example.

It is particularly well known that the thioglycolic acid used in permanent waving has an adverse effect on strongly bleached hair.

In accordance with the invention the first step of a permanent waving process consists in applying to a head of hair which has been strongly bleached an aqueous solution which is prepared at the moment of use and contains a mixture of at least one compound according to Formula I and ethylene diamine tetracetic acid, the pH of the solution being brought to between 8 and 10. The second step of this permanent waving process may be carried out in a conventional manner.

This process has, moreover, a particular advantage in that it makes it possible to prepare a permanent waving powder in a simple manner, since the thiolates according to the invention keep much better when exposed to the air than conventional thiols do.

In the same field of protecting and restoring bleached hair, such hair may be protected from the adverse eflFects of permanent waving liquids by applying thereto a solution containing at least one compound according to Formula I, and then drying the hair before permanently waving it in a conventional manner.

In accordance with the invention bleached hair may be permanently set by impregnating it with a composition comprising at least one compound of Formula I, and having a pH value which is preferably between 8 and 10. It is then dried while wound up on setting rollers at a temperature between 40 and 60 C.

In accordance with the invention a shampoo followed by a set may be carried out by washing the hair with a composition comprising at least one compound responding to Formula I and a detergent, the pH of the composition being between 3 and 10, after which the hair is rinsed and set in a conventional manner.

It is a further object of the present invention to provide a cosmetic composition adapted to be used in carrying out the above described processes, which composition is characterzied by the fact that it comprises at least one compound according to Formula I in a concentration between 0.1 and 20% and has a pH value between 7 and 10 and preferably between 8 and 10.

The compositions according to the invention may take the form of an aqueous solution, a cream, a gel or an aerosol, depending on which method of application is most appropriate to the end desired. They may also take the form of a powder which is dissolved at the moment of use.

The compositions according to the invention may also contain various active ingredients conventionally included in cosmetics such as swelling agents, surfaceactive agents, dyes, and perfumes. These various agents may be selected to suit the particular treatment which is to be carried out by means of the composition.

A further object of the present invention is to provide a method of coating metals characterized by the fact that a film of a solution containing at least one thiolate according to Formula I is applied to a metallic surface which has first been washed and degreased. The metallic surface is then left at the ambient temperature for a moment, after which it is put in an oven for from 1 to 48 hours until it sets to form a varnish type coating.

Among the metals and alloys which may be most advantageously coated in accordance with the invention are copper brass and steel.

In order that the invention may be better understood, several examples showing the preparation of compounds according to the invention, and several examples showing how such compounds may be used will now be described, purley by way of illustration, without in any way suggesting that the scope of the invention is limited to the specific subject matter disclosed in said examples.

EXAMPLES OF THE PREPARATION OF COM- POUNDS ACCORDING TO THE INVENTION Example 1 Preparation of cadmium bis [N-hydroxymethylcarbamoly methylthiolate] corresponding to the formula:

The starting reactant used in this preparation is thioacetamide, which may be obtained by aminolysis of ethyl thioglycolate.

The reaction producing the thiolate is the following:

Cd ZCHaCO OH S-CHzCONH:

150 ml. of an 81% solution of cadmium acetate, which represents a stoichiometeric excess of 20% is poured little by little into a 35% solution of thio-acetamide containing 200 g. of thio-acetamide. The mixture is vigorously agitated all the time this addition is being made. The result is a white precipitate which is easily decanted and can be filtered on fritted No. 2 glass. This precipitate is washed with 1 liter of water per 100 ml. and dried after washing.

Finally, the precipitate is washed three times with 100 ml. of acetone. The precipitate is then dried for 30 minutes at 80" C. The yield of the reaction is 88%.

The resulting thiolate is then methylolized utilizing the following reaction:

S-CHzC ONH:

S-CHsCONH-CHzOH.

Cd (EH in excess S-CHzCONH-CHzOH 150 g. of cadmium thiolate and 340 ml. of 36% formol is mixed in a 500 ml. Erlen. flask. The mixture is heated to 80 C. under constant agitation. At the end of 2 hours at 80 C. the cadmium thiolate is completely dissolved.

The resulting solution is a little cloudy, and is filtered on No. 4 fritted glass.

It is then precipitated in 4.5 l. of acetone at 0 C., which is continuously agitated while the methylol thiolate solution is introduced drop by drop. The precipitate is left to drain at room temperature for an hour, and the cloudy supernatant liquid is eliminated. The precipitate is filtered on fritted No. 4 glass.

The resulting product is washed with 3 liters of acetone in small fractions, the precipitate is malaxated and dried after each washing.

The resulting product is dried by spreading it out in thin layers and being left to stand for 3 to 4 days while exposed to the air.

The yield of the reaction is 95%.

A quantitative analysis of the various constituents of the resulting product was made, with the following results:

Theoretical (percent): N, 7.95; C, 20.45; H, 3.40; SH, 18.75; S, 18.18; Cd, 31.93; free formol, 0; total formol, 17.04. Found (percent): N, 7.56-7.80; C, 20.90- 4 6 Example 11 Preparation of cadmiumbis[2-(N'-hydroxymethylureido)ethylthiolate] having the formula:

In a first step, cysteamine cadmium thiolate is prepared by carrying out the following reaction:

by mixing 20 g. (0.18 mol) of cysteamine hydrochloride and 23.4 g. (0.09 mol) of cadmium acetate in a 50% solution, and adding water to make up a total volume of 100 ml.

The resulting solution contains 29.7% by weight of cysteamine cadmium thiolate.

In a second step, the corresponding ureide is prepared by the following process:

S-CHr-CHz-NHz. H01

Cd CNOK 14.30 g. of potassium isocyanate dissolved in 10 m1. of water is added to the preceding solution and left standing for 2 hours. The solution is then precipitated by adding a 2 N solution of sodium hydroxide and the result is a sticky nacreous mass which is washed with water. It is then purified by redissolving it in hot water and reprecipitated at 0 C. The precipitate is malaxated in acetone to produce a powder. A 65% yield of the ureide is obtained.

Elementary analysis of the resulting compound yields the following results: SH=17.90%; N=13.52%; Cd=33.3%. Theoretical: SH=18.83%; N=15.98%; Cd=32.0%.

The resulting ureide is methylolized according to the following process:

10 g. (0.03 mol) of the ureide obtained as indicated above is mixed with 17.2 g. (0.23 mol) of formol in 40% aqueoussolution and 10 ml. of water. The reaction mixture is brought to a temperature of C. and agitated for an hour. J

The methylolur'eideiremains insoluble in the mixture. It is filtered outand washed with water and acetone.

The yield of the reaction is 83%;

7 Example 111 Preparation of cadmium bis[N'-morpholinomethylcarbamoyl methylthiolate] having the formula:

This composition is prepared by the following process:

S-CHr-CONH:

+ 2110011 2HN e The cadmium bis[carbamoylmethylthiolate] is prepared as described in Example I.

29.2 g. (0.1 mol) of cadmium thiolate is mixed with 30 g. (0.8 mol) of a commercial 40% forrnol solution and 34.8 g. (0.8 mol) of morpholine.

The resulting mixture is heated while being agitated for 2 hours at 80/ C. The cadmium thiolate dissolves. The mixture is left to cool at room temperature and then poured drop by drop into a liter of acetone at C. The resulting precipitate is left to stand for about 2 hours at room temperature.

This precipitate is then filtered on fritted No. 2 glass and washed copiously with acetone, using 100 ml. of acetone at a time. The product is then vacuum dried until the traces of acetone disappear.

The result is a 54% yield in the form of a white powder.

Analysis of the product obtained yields the following results:

Theoretical (percent): C, 34.25; H, 5.25; N, 11.42; SH, 13.48; Cd, 22.93; CH O, 12.24. Found (percent): C, 31.68; H, 5.87; N, 11.15; SH, 13.0; Cd, 28.l; CH=O, 11.5.

Example IV Preparation of cadmium bis[2-(N'-morpholinomethyluredio)-ethyl thiolate] This compound is prepared by the following process:

Cysteamine cadmium thiolate and its ureide are prepared as described in Example H.

35 g. of ureide is suspended in 100 ml. of water. 15 g. of 40% formol and 17.4 g. of morpholine are added while agitating vigorously. This is heated at 60 C. until it dissolves. The water of the solution, which is quite viscous, is evaporated under vacuum, in the presence of P 0 A solid white product is obtained after two days of vacuum drying. The yield is 93%.

Analysis of the resulting product yields the following results:

Theoretical (percent): SH, 12.03; N, 15.31; Cd, 20.49. Found (percent): SH, 11.8; N, 14.15; Cd, 25.9.

EXAMPLES OF APPLICATIONS OF THE COM- POUNDS ACCORDING TO THE-INVENTION Example 1 A 25% aqueous solution of cadmu'im bis [N-hydroxymethyl carbamoyl methyl thiolate] is prepared at the moment of use.

This composition is brushed onto metallic surfaces of copper, brass, or steel, which have first been washed and degreased with acetone.

The specimens coated in this manner were left to stand for an hour at room temperature, and then placed in an oven at 120 C. for 24 hours.

The metallic surfaces were then found to be coated with a hard, adherent varnish.

This varnish may be very easily removed by means of dilute acid or a solution of ethylene diarnine tetracetic acid.

Example 2 A female head of live human hair was shampooed, dried, rolled up on setting rollers of normal diameter while each lock is successively impregnated with a conventional permanent waving solution.

After the winding process is completed, the hair is again saturated and left for 10 to 20 minutes under a hood.

The hair is then rinsed again, and a 5% solution of a compound having the following formula, which is prepared at the moment of use, is applied to the hair, after being brought to pH 9.5 by the addition of ammonia.

A mixture of cadmium bis [N-hydroxymethyl carbamoyl methylthiolate] and E.D.T.A. is dissolved in an ammonia solution at the moment of use. After mixing, the composition contains:

Percent The above thiolate 18.7 -E.D.T.A. 14.6

Ammonia, q.s.p. pH=9.5. Water, q.s.p. cc.

This solution is applied to strongly bleached hair as if it were a conventional permanent waving solution. The head is covered by a hood. After 30 to 40- minutes the hair is rinsed, and fixed in a conventional manner with hydrogen peroxide. It is again rinsed and a permanent of good quality results. It has an attractive curl, body, and is in good condition.

Example 4 mercial liquid having the following composition:

Percent Thioglycolic acid 5 Ammonium sesquicarbonate 4 Ammonia, q.s.p. pH=7.3. Water, q.s.p. 100 cc.

Strongly bleached hair was treated with a setting lotion comprising 2% of cadmium bis [N-hydroxymethyl carbamoyl methylthiolate] having a pH of 8.3 which may also comprise 3% of polyvinyl pyrrolidone, a conventional ingredient. The hair is wound up on setting rollers and dried. The rollers are then removed. The resulting wave has excellent holding power and the hair is in good condition.

Example 6 A shampoo is prepared at the moment of use by mixing g. of cadmium bis [N-hydroxymethyl carbamoyl methylthiolate] with a solution containing:

G. Technical (30%) laurylether-sodium sulfate 25 Laurie monoethanolamide 2 Triethanolamine, q.s.p. pH=8.5. Water, q.s.p. 100 cc.

Hair is shampooed twice with this mixture, and left to stand, preferably under a plastic cap, for ten minutes. It is then rinsed and set.

The set lasts well, and is clearly superior to one preceded by the same shampoo, without the thiolate, as can be demonstrated by comparative tests on opposite sides of the same head of hair.

Example 7 After a head of hair has been shampooed and dried, it is reduced by a permanent waving liquid having an alkaline or neutral pH. Such a liquid may, for example, be a commercial permanent waving solution. After being left for a short time, preferably under a hood, the hair is rinsed and an aqueous solution prepared at the moment of use is applied. This contains 5 or 10% of cadmium bis[N-hydroxymethyl carbamoyl methylthiolate] and has a pH of 9.5. The hair is wound up on setting rollers, dried, and combed.

This process results in a long-lasting set, without any of the technical complications resulting from a conventional permanent setting process. The wave has better holding power, even though the moist hair shows practically no permanent waves.

When the composition according to the invention is a shampoo, the detergents can be alkyl sulfates, alkyl ether sulfates, alkyl pol'yether sulfates, alkyl sulfonates, in which the alkyl groups have 8 to 18 carbon atoms, sulfated monoglyceridcs, sulfonated monoglyceridcs, sulfated alkanolamides, sulfonated alkanolamides, soaps of fatty acids, monosulfosuccinates of fatty alcohols, the products of the condensation of fatty acids with methyltaurine, the products of the condensation of fatty acids with sarcosine, the products of the condensation of fatty acids with a protein hydrolysate; cationic detergents such as long chain quaternary ammonium, esters of fatty acids and of amine alcohols, polyether amines; non-ionic detergents such as: the esters of polyols and sugars, the products of the condensation of ethylene oxide with fatty acids, fatty alcohols, long chain alkyl phenyls, long chain 7 mercaptans, and long chain amides, the polyethers of polyhydroxylated fatty alcohols; or amphoteric detergents such as asparagine derivatives, the products of the condensation of monochloroacetic acid and imadazolines, and alkyl aminopropionates.

Cosmetic carriers which can be utilized can be wateralcohol, gel, cream and aerosol.

The difference between a permanent wave and a permanent set consists in the fact:

In a permanent wave:

(a) the hairs are rolled on curlers of little diameter, (b) the hairs are rinsed with water after neutralization, (c) the hairs do not need to be dried on curlers after neutralization. In a permanent set:

(a) the hairs are rolled on rollers of middle diameter, (b) the hairs are not rinsed after neutralization, (c) the hairs are dried on the rollers.

What is claimed is: 1. A compound of the formula s-cH;-xlc 0NHCH:Y|

B-C H3X:C 0-NH-C Hg-Y:

wherein Me is a bivalent metal selected from the group consisting of zinc and cadmium, X and X, each independently are selected from the group consisting of carbon-carbon bond,

and Y and Y, are each independently selected from the group consisting of 2. The compound of claim 1 which is selected from the group consisting of cadmium-bis-[N-hydroxymethylcarbamoyl-methylthiolate], zinc-bis-[N-hydroxymethylcarbamoyl-methylthiolate],

OTHER REFERENCES Hellmann: Newer Meth. of Prep. Org. Chem., vol. II, pp. 278-79, 288 (1963).

HARRY I. MOATZ, Primary Examiner US. Cl. X.R.

0 260-429 R, 429.7, 429.9, 438.5 R, 439 R UNITED STATES PATENT OFFICE CER'ITIFICATE ()F- C()RRE(I'[I1()N Patent No. 3,803,138 7 Dated April 9, 1974 Inventor(s) Pierre Bore It is. certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Colmnn 1, line 40, should read --bivalent--.

Column 2, the structural formula between lines 48 and 57 should read COOCH S -CH CH ILH CO-NH CH N 0 v Cd I \ TOOCH S-CH NHCO-NH-CH -N 0 Column 6, line 31, should read --+2 CNOK--;

line 60 should read -+HCOH-.'

Signed and sealed this 24th day of. September 1974.

(SEAL) Attest:

MCCOY M; GIBSON JR. C. MARSHALL DANN Arresting Officer Commissioner of Patents USCOMM-DC 60376-969 ORM PO-IOSO (10-69! I u sv covuuuun nmmuo omu nu o-no-au

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4618625 *Jul 31, 1984Oct 21, 1986Laboratorios Vinas, S.A.Zinc carbocysteinate
US4670545 *Jul 30, 1986Jun 2, 1987University Patents, Inc.Chelating agents for technetium-99M
Classifications
U.S. Classification544/64, 556/130
International ClassificationC07C323/00, C07C323/44
Cooperative ClassificationC07C323/44
European ClassificationC07C323/44