GB1596599A - Organo-aluminium compounds - Google Patents

Description

(54) ORGANO-ALUMINIUM COMPOUNDS (71) We, F. HOFFMANN-LA ROCHE & CO., AKTIENGESELLSCHAFT, a Swiss Company of 124-184 Grenzacherstrasse, Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to antiperspirant compositions containing organo-aluminium compounds some of which are novel, to such novel organoaluminium compounds and to a process for the manufacture thereof.

The antiperspirant compositions provided by the present invention contain as an essential active ingredient or essential active-ingredients one or more organoaluminium compounds of the general formula

wherein X represents a chlorine or bromine atom, R1 represents an alkyl group and R2 represents an alkyl, cycloalkyl, alkenyl cycloalkenyl, aryl, alkanoyl, alkenoyl or aroyl group, whereby the alkyl, alkenyl, alkanoyl and alkenoyl groups denoted by R2 can each be substituted by optionally alkyl-substituted cycloalkyl, optionally alkyl-substituted cycloalkenyl, optionally alkyl- and/or alkoxysubstituted aryl, alkoxy, cycloalkoxy, cycloalkenyloxy and/or aryloxy and the cycloalkyl, cycloalkenyl, aryl and aroyl groups denoted by R2 can each be substituted by alkyl, alkoxy and/or aryl and whereby two adjacent alkyl and/or alkoxy groups present on a phenyl group denoted by R2 can also be joined with one another to form a 5-membered or 6-membered saturated ring, in association with a compatible cosmetic carrier.

The organo-aluminium compounds of formula I have the advantage that they possess not only a very high initial, but also a long-lasting, antitranspiration activity.

The organo-aluminium compounds provided by the present invention have the general formula

wherein X represents a chlorine or bromine atom, R1 represents an alkyl group and R2, represents a cycloalkenyl, alkanoyl, alkenoyl or aroyl group, whereby the alkanoyl and alkenoyl groups denoted by R2, can each be substituted by optionally alkyl-substituted cycloalkyl, optionally alkyl-substituted cycloalkenyl, optionally alkyl- and/or alkoxy-substituted aryl, alkoxy, cycloalkoxy, cycloalkenoyloxy and/or aryloxy and the cycloalkenyl and aroyl groups denoted by R2, can each be substituted by alkyl, alkoxy and/or aryl.

The alkyl, alkoxy, alkenyl, alkanoyl and alkenoyl groups denoted by R2 in formula I and alkyl, alkoxy, alkanoyl and alkanoyl groups in the definition of R2' in formula (I') can be straight-chain or branched-chain and preferably contain up to 30 carbon atoms, especially from 2 to 20 carbon atoms. The alkyl groups denoted by R have an analogous significance to the alkyl groups denoted by R2, but preferably contain from 2 to 8 carbon atoms since the remaining compounds, especially the methyl compound, are less readily accessible. Examples of alkyl groups denoted by R, or R2 are methyl, ethyl, n-propyl, isopropyl, n-butyl. isobutyl.

sec.butyl, tert.butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-decyl, nundecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl and ntriacontyl. The alkoxy groups have an analgous significance. Examples of alkenyl groups denoted by R2 are allyl, but-2-enyl, penta-2,4-dienyl,

Geranyl nerolyl phytylCH2 3,7-dimethyl-octa-2,6-dien-l-yl. The alkanoyl groups denoted by R2 and R2 contain at least 2 carbon atoms. Examples of such alkanoyl groups are acetyl, propionyl, nbutyryl, isobutyryl, pivaloyl, n-pentanoyl, n-hexanoyl, n-octanoyl, n-decanoyl, nundecanoyl, n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl, n-octadecanoyl, neicosanoyl and n-triacontanoyl. Examples of alkenoyl groups denoted by R2 are acryloyl, but-2-enoyl (crotonyl), penta-2,4-dienoyl, hexa-2,4-dienoyl (sorbyl), undec- 1 0-enoyl, geranoyl

octadec-9-enoyl (oleyl), octadeca-9, 1 2-dienoyl (linalyl), octadeca - 9,12,15 trienoyl (linolenyl) and eicos - 5 - enoyl.

Cycloalkyl and cycloalkenyl groups denoted by R2 and cycloalkenyl groups denoted by R2, preferably contain 5 or 6 carbon atoms (e.g. cyclopentyl.

cyclohexyl, cyclopentenyl and cyclohexenyl).

The term "aryl" denotes an aromatic, mononuclear or polynuclear hydrocarbon group such as, for example, phenyl, naphthyl or phenanthryl. The term "aryloxy" or "aroyl" means an aryl-O- or aryl-CO- group, respectively, in which "aryl" has the significance given earlier. Examples of aryloxy groups are phenoxy, naphthyloxy and phenanthryloxy, and examples of aroyl groups are benzoyl, naphthoyl and phenanthroyl. Preferred aryl, aryloxy and aroyl groups are those having 1 or 2 aromatic nuclei.

The aforementioned R2 and R2, groups can optionally carry further substituents. Examples of such substituted groups R2, and, where appropriate, R2, are the following: cycloalkyl-alkyl, e.g. cyclohexylmethyl and cyclopentyl-ethyl; cycloalkyl-alkenyl, e.g. cyclohexylallyl cycloalkyl-alkanoyl, e.g. cyclopropylacetyl and cyclo-hexylacetyl; cycloalkyl-alkenoyl, e.g. cyclohexylhexa-2,4-dienoyl: alkenyl substituted by alkyl-substituted cycloalkenyl, e.g. retinyl (such as alltrans-retinyl:

alkenoyl substituted by alkyl-substituted cycloalkenyl, e.g. retinoyl (such as all-trans-retinoyl:

alkyl substituted by optionally alkyl- and/or alkoxy-substituted aryl, e.g.

benzyl, phenethyl, naphthylmethyl, p-tolylmethyl, p-methoxyphenylethyl and p methoxy - o - methyl - phenylmethyl alkenyl substituted by optionally alkyl- and/or alkoxy-substituted aryl, e.g.

styryl, cinnamyl, p-methylstyryl and o - methoxy - p - methylcinnamyl; alkanoyl substituted by optionally alkyl- and/or alkoxy-substituted aryl, e.g.

phenacetyl, tolylacetyl and - p - methoxy - phenylacetyl; alkenoyl substituted by optionally alkyl- and/or alkoxy-substituted aryl, e.g.

cinnamoyl, p-methoxy-cinnamoyl and 9 - (4 - methoxy - 2,3,6 trimethylphenyl) - 3,7 - dimethyl - nona - 2,4,6,8 - tetraenoyl (e.g. the all-trans form:

alkoxy-alkyl, e.g. 2-methoxyethyl, ethoxymethyl and 7 - methoxy - 3,7 dimethyl - octyl; alkoxy-alkenyl, e.g. I-methoxyallyl and 7 - methoxy - 3,7 - dimethyl - octa 2 - enyl; alkoxy-alkanoyl, e.g. ethoxyacetyl and 3-methoxypropionyl; alkoxy-alkenoyl, e.g. 3 - methoxy - acryloyl and 6 - methoxy - hexa - 2,4 dienoyl (6-methoxysorbyl); cycloalkoxy-alkyl, e.g. 2-cyclohexoxy-ethyl; aryloxy-alkyl, e.g. 2-phenoxyethyl and 6 - phenoxy - n - hexyl; aryloxy-alkanoyl, e.g. phenoxyacetyl; alkyl-cycloalkyl, e.g. 4 - methyl - cyclohexyl and menthyl:

alkyl-aryl, e.g. o-, m- and p-tolyl- alkyl-aroyl, e.g. o-, m- and p-toluoyl; alkoxy-aryi, e.g. o-, m- and p-methoxyphenyl (anisyl; alkoxy-aroyl, e.g. o-, m- and p-methoxybenzoyl (anisoyl); aryl-aryl, e.g. 4-phenyl-phenyl; aryl-aroyl, e.g. 4-phenyl-benzoyl.

As mentioned earlier, in formula I two adjacent alkyl and/or alkoxy groups present on a phenyl group denoted by R2 can also be joined with one another to form a 5-membered or 6-membered saturated ring. This provides organoaluminium compounds of formula I in which R2 represents an indanyl, benzofuranyl, 1,3-benzodioxolyl, tetrahydronaphthyl, chromanyl or 1,4benzodioxanyl group (linked with the oxygen atom via the benzene nucleus) which can be optionally substituted in the benzene nucleus by alkyl and/or alkoxy and/or in the saturated nucleus by alkyl. An example of such a group is the -tocopheryl group

A preferred group of organo-aluminium compounds of formula I, which can be used as antitranspirants, comprises those in which R1 represents an alkyl group containing from 2 to 8 carbon atoms and R2 represents an alkyl or alkanoyl group containing from 8 to 18 carbon atoms or a cycloalkyl or cyclo-alkenyl group substituted by alkyl.

According to the process provided by the present invention, the organoaluminium compouds of formula I' hereinbefore are manufactured by (a) treating a compound of the general formula (Ri)mAlXn (Il) wherein m and n each stand for I or 2 with the proviso that the sum of m and n is 3, and R1 and X have the significance given earlier, with a compound yielding the group -OR21 in which R2, has the significance given earlier; or (b) reacting a compound of the general formula (R1)2-Al-OR2, (III) with a compound of the general formula R1-AlOR2,)2 (IV) and a compound of the general formula AIX3 (V) wherein R1, R2, andX have the significance given earlier; or (c) reacting a compound of the general formula (R1)3AI (VI) with a compound of the general formula Al(OR2,)3 (all) and a compound of the general formula AIX3 (V) wherein R1, R2' and X have the significance given earlier; or (d) treating a compound of the general formula (R1)2A1-OR2, (Ill) with hydrogen chloride or hydrogen bromide.

The treatment of a compound of formula II with a compound yielding the group -OR2, such as R2'OH, R2,O-alkali metal" (R2,O)2-alkaline earth metal or (R2,O)3 Al in accordance with embodiment (a) of the process and the treatment of a compound of formula III with hydrogen chloride or hydrogen bromide in accordance with embodiment (d) of the process are preferably carried out in an inert organic solvent. As the solvent there can be used, in particular, a lower aliphatic or aromatic, optionally halogenated hydrocarbon such as n-hexane, nheptane, methylene chloride, benzene, toluene or chlorobenzene, or an ether such as diethyl ether, tetrahydrofuran or dioxan.

Although embodiments (b) and (c) of the process can be carried out in the presence of an aforementioned inert organic solvent, these embodiments are preferably carried out in the absence of a solvent.

In all process embodiments (a) to (d) the temperature is not critical; it preferably lies, however, in a range between room temperature and 90"C.

Because of the known sensitivity of organo-aluminium compounds (e.g. to hydrolysis or oxidation all embodiments (a) to (d) of the process are preferably carried out in a dry apparatus under an inert gas atmosphere (e.g. nitrogen or argon).

It is not necessary to maintain the stoichiometric quantitative ratios of the starting components exactly in order to obtain a product falling within formula I'.

On the contrary, the quantitative ratios can be varied over a wide range.

Advantageously, however, stoichiometric amounts of purest starting materials are used, since in so doing the desired products are obtained in analytically pure form and further expensive purification procedures become unnecessary.

The organo-aluminium compounds of formula I are strongly hygroscopic, liquid or solid substances and, in general, have no defined melting point. They are often viscous substances similar to the organo-aluminium compounds found in nature. Most of them have a good solubility in inert organic solvents such as aliphatic and aromatic hydrocarbons (e.g. n-hexane, n-heptane, benzene and toluene), ethers (e.g. diethyl ether, tetrahydrofuran, dioxan and 6 - acetoxy - 2,4 dimethyl - 1,3 - dioxan and esters (e.g. ethyl acetate and isopropyl myristate).

In order to demonstrate the antiperspiration activity of the organo-aluminium compounds of formula I, representative compounds were tested on human volunteers.

For this purpose there was used a combined moisture-temperature measuring apparatus (ROTRONIC HYGROSKOP T DT-2), which permits the measurement of the transpiration at the skin surface with the aid of a special skin probe whose ohmic resistance varies with increasing moisture. During the measurement, the probe is placed on the skin surface so that during the 4 minutes measurement procedure no foreign air can penetrate into the measurement cell. The humidity feeling cell works with an accuracy of +2%. The measurement values are given qualitatively and quantitatively in percentages as the moisture increase or decrease. The linked linear-writer registers the measurement value in the form of a transpiration curve for each measurement point in time. The testings are carried out in climatised rooms without air circulation at a room temperature of 36"C and a humidity of 50%.

Test material: The active substances are tested in a concentration of 4% (wt.%). They are first dissolved in a suitable anhydrous aprotic solvent and then filled into conventional spray containers. A dosage valve on the spray container permits the precise dosing of 40 mg of substance per application on each 4 cm2 of skin surface. As the comparison preparation there is used the marketed product "REXONA "(Trade Mark) (aluminium hydroxychloride).

Test subjects: 15 healthy volunteers (women and men), aged from 20 to 50 years, who were especially suitable for this experiment (pre-selected).

Method: In order to determine the activity of local antitranspirants there is used the skin on the inner side of both fore-arms. Four to five 4 cm2 sized skin zones are first marked with a stamp and the sweat secretion of these skin zones is measured during a time interval of 4 minutes with a ROTRONIC hygrometer and registered in the form of a hydgometric curve. Shortly thereafter, the first test zone is treated with one of the active substance concentrations or test preparations and, after a period of 5-10 minutes, the second measurement of the transpiration (measurement time 4 minutes) is made in order to obtain the immediate activity of the antitranspirants or preparations. In order to determine the duration of activity yet a further measurement time point is determined, namely 2 hours after application of the active substances or the test preparations. Three further test zones are successively treated with 3 further preparations in the same manner and the transpiration of the skin is determined. One test zone is untreated and serves as the negative control. The sequence in which the preparations are applied within the volunteer group must rotate in that the regional and individual differences in the sweat secretion of the inner sides of the fore-arm'have no effect on the test results.

Evaluation: The percentage inhibition of the transpiration compared with that of the untreated control zones is ascertained at each measurement time point. The individual measurement values for the novel active substances or the standard preparation ("REXONA"), expressed in absolute numbers as the measured humidity (in %), are compiled hereinafter and evaluated not only in relation to the strength but also to the duration of the sweat-inhibiting activity of the various preparations.

Results: I) Organo-aluminium compounds which bring about an initial sweat inhibition of 75--100Od and an inhibition after 2 hours of 1525%: Chloro(hexadecanolato)isobutylaluminium, chloro(octadecanolato)isobutylaluminium, chloro(hexadecanoato)isobutylaluminium, chloro(tetradecanoato)isobutylaluminium, chloro(mentholato)isobutylaluminium, chloro(mentholato)octylaluminium, chloro(2-ethylhexanolato)isobutylaluminium, and chloro(isophytolato)isobutylaluminium.

II) Organo-aluminium compounds which bring about an initial sweat inhibition of 5075% and an inhibition after 2 hours of 10--15 :,: chloro(ethanolato)isobutylaluminium, chloro(2-phenoxyethanolato)isobutylaluminium, chloro(2-phenoxyethanolato)ethylaluminium, bromo(2-phenoxyethanolato)isobutylaluminium, bromo(2-phenoxyethanolato)ethylaluminium, bromo(ethanolato)ethylaluminium, chloro(ethanolato)ethylaluminium, and bromo(ethanolato)isobutylaluminium.

III) Organo-aluminium compounds which bring about an initial sweat inhibition of 3050% and an inhibition after 2 hours of 5-l0,: chloro(l0-undecenoato)isobutylaluminium, chloro(phenoxy)isobutylaluminium, chloro(benzoato)isobutylaluminium, bromo( l0-undecenoato)ethylaluminium, bromo( 1 0-undecenoato)isobutylaluminium, chloro(tert.butoxy)isobutylaluminium, bromo(tert.butoxy)isobutylaluminium, chloro(sorbato)isobutylaluminium, chloro( 10-undecenoato)hexylaluminium, chloro(ethanolato)hexylaluminium, and chloro( l0-undecenoato)ethylaluminium.

IV) Standard preparation: With the comparison preparation ("REXONA"-Sport) there was observed an initial activity of 9% and an activity after 2 hours of 8.5%.

Examples of carriers present in the antiperspirant compositions provided by the present invention include the customary carriers used for antiperspirants in cosmetics (e.g. in powders, sticks, creams, solutions and aerosols). As solvents there may be used the aforementioned anhydrous solvents which can be admixed with the customary cosmetic additives; for example, additives for increasing the skin metabolism or the skin elasticity such as panthenol or one of its lower alkyl ethers (e.g. the ethyl ether), bactericidal agents (e.g. quaternary ammonium salts) and/or perfume. The present antiperspirant compositions are preferably used in the form of aerosols containing the commonly used propellants such as low-boiling, liquified, optionally halo-substituted, especially chlorinated and fluorinated, alkanes (e.g. n-propane, n-butane, isobutane, n-hexane, dichlorodifluoromethane and dichlorotetrafluorothane) as well as mixtures thereof. A very expedient propellant mixture consists of about equal portions of dichlorodifluoromethane and dichlorotetrafluoroethane. The antiperspirant compositions provided by the present invention preferably contain between 1 and 30 weight percent, especially between 2 and 5 weight percent, of essential active ingredient. Apart from the additives mentioned earlier, the present compositions can also contain other cosmetically valuable substances such as, for example, other sweat-inhibiting or deodorising compounds.

The following Examples illustrate the preparation of the organo-aluminium compounds provided by the present invention or used in antiperspirant compositions of the present invention. In these Examples, the products have been characterised by microanalyses (determination of the carbon, hydrogen and aluminium content; limit of error 1--2b).

Example 1 10.1 g of cetyl alcohol (1 -hexadecanol) in 70 ml of absolute n-heptane are placed in a 250 ml four-necked flask under an argon atmosphere at room temperature. A solution of 7.35 g of diisobutylaluminium chloride in 30 ml of absolute n-heptane is added dropwise from a dropping funnel over a period of 0.5 hour while stirring. During this addition the temperature in the flask rises to 400 C.

The mixture is then stirred at 80"C for 2 hours. Subsequently, the solvent is removed at 800C in a water-jet vacuum. The condensate which collects in the cooling trap contains 2.35 g of isobutane (98.6% of the calculated amount). The chloro(hexadecyloxy) - isobutylaluminium which remains in the flask is freed from the last residues of solvent over a period of 2 hours at 800C on an oil pump at 10-2 Torr. The analytically pure product is a colourless oily liquid. Yield: 15.0 g (99.8 of theory).

The following organo-aluminium compounds are prepared in an analogous manner: a) Chloro(octadecyloxy)isobutylaluminium, a colourless viscous oil. Yield: 97.5% of theroy.

b) Chloro(mentholato)isobutylaluminium, a colourless oil. Yield: 96.3%.

c) Chloro(2 - ethyl - 1 - hexyloxy)isobutylaluminium, a colourless oil. Yield 97of.

d) Chloro(3,7,11,15 - tetramethyl - I - hexadecen - 3 - yloxy) - isobutylaluminium, a yellowish coloured moderately viscous oil. Yield: 94.6%.

Example 2 9.1 g of diisobutylaluminium chloride in 100 ml of n-heptane at 700C are placed in a 500 ml four-necked flask under nitrogen gasification. From a dropping funnel there is added dropwise into the flask during ca 20 minutes a solution, held at 70"C, of 13.2 g of palmitic acid in 80 mi of n-heptane. The mixture is then stirred at 90"C for 3 hours and the solvent is removed in vacuo (18 Torr). The condensate which collects in the cooling trap contains 2.9 g of isobutane (96.9% of the calculated amount). The chloro(hexadecanoato)isobutylaluminium which remains in the flask is freed from the solvent residues over a period of 2 hours at 800C on an oil pump at 10-2 Torr. The thus-obtained product is analytically pure and is a colourless, very slightly turbid oil. Yield; 18.8 g (97.3%).

The following organo-aluminium compounds are manufactured in an analogous manner: a) Chloro(tetradecanoato)isobutylaluminium, a colourless liquid. Yield: 92.8%.

b) Chloro(l0-undecenoato)isobutylalumini.um, a viscous, almost colourless oil.

Yield: 94.6%.

c) Chloro(benzoato)isobutylaluminium, a colourless, viscous, slightly turbid oil. Yield 93.7%.

d) Chloro(sorbato)isobutylaluminium, a slightly yellowish coloured oil. Yield: 92.3%.

Example 3 1.54 g of anhydrous aluminium chloride and 50 ml of n-heptane are added to a 250 ml four-necked flask under nitrogen gasification. There is added dropwise to the flask while stirring a solution of 8.47 g of tri-n-octylaluminium dissolved in 25 ml of n-heptane and the mixture is warmed to 500C for 1 hour. The initially undissolved aluminium chloride thereby dissolves. There is now added dropwise to the flask during ca 15 minutes a solution of 5.4 g of menthol in 50 ml of n-heptane and the mixture is then warmed to 80"C for 3 hours. The volatile is subsequently removed at 800C on the water-jet pump. The condensate which collects in the cooling trap contains 3.7 g of n-octane (corresponding to 93.4% of theory). The analytically pure chloro(mentholato)octylaluminium which remains in the flask is freed from solvent residues over a period of 3 hours on an oil pump at 10-2 Torr.

The product is a gum-like, slightly turbid oil. Yield: 94.1%.

The following compounds are manufactured in an analogous manner by varying the three starting materials (aluminium alkyl, aluminium halide or alcohol): a) Chloro(ethanolato)isobutylaluminium, a colourless liquid. Yield 92.1%.

b) Chloro(2-phenoxyethanolato)isobutylaluminium, white crystals of melting point 1010-1020C. Yield 93.2%.

c) Chloro(2-phenoxyethanolato)ethylaluminium, white crystals. Yield: 89.5%.

d) Bromo(2-phenoxyethanolato)isobutylaluminium, white crystals. Yield 93.2%.

e) Bromo(2-phenoxyethanolato)ethylaluminium, white crystals. Yield: 94.3%.

f) Bromo(ethanolato)ethylaluminium, a colourless clear liquid (after freeing from solvent residues at 300C and 10-2 Torr). Yield: 91.6 .

g) Chloro(ethanolato)ethylaluminium, a clear colourless liquid (after freeing from solvent residues at 300C and 10-2 Torr). Yield: 90.4%.

h) Bromo(ethanolato)isobutylaluminium, a colourless liquid. Yield; 92%.

i) Chloro(phenoxy)isobutylaluminium, a clear colourless oil. Yield: 97.1%.

k) Chloro(tert.butoxy)isobutylaluminium, a clear colourless oily liquid. Yield: 96?b.

1) Bromo(tert.butoxy)isobutylaluminium, a very slightly yellowish oily liquid.

Yield: 94.3%.

m) Chloro(ethanolato)hexylaluminium, white crystals. Yield: 92.3%.

Example 4 1.67 g of anhydrous aluminium bromide and 100 ml of absolute n-hexane are added to a 500 ml four-necked flask under argon gasification. There are added dropwise to the flask within 10 minutes while stirring at room temperature 1.43 g of triethylaluminium dissolved in 100 ml of absolute n-hexane. During the reaction which sets in the aluminium bromide dissolves. The mixture is stirred at 50"C for 2 hours and then cooled to room temperature.

3.46 g of undecylenic acid in 100 ml of absolute n-hexane are placed in a second four-necked flask, also under an argon atmosphere. The solution of diethylaluminium bromide prepared in the first flask (as described in the preceding paragraph) is transferred with the exclusion of air and moisture into the dropping funnel of this second flask. This solution is now allowed to drop into the dissolved undecylenic acid over a period of 0.5 hour at room temperature. After completion of the addition, the mixture is stirred at 500C for 2 hours. The ethane resulting during the reaction as well as the solvent, which is sucked-off in a water-jet vacuum at the end of the reaction, are collected in a cooling trap, which is cooled to -120"C (liquid nitrogen/pentane), and determined gas-chromatographically. The collected amount of ethane amounts to 0.49 g (86.90/, of theory). The residue which remains in the flask is freed from solvent residues for 2 hours at 400C on an oil pump at 10-2 Torr. Thereafter, the bromo(l0-undecenoato)ethyl-aluminium is obtained in the form of a slightly yellowish, semi-crystalline mass. Yield 5.6 g (93.5% of theory).

The following compounds are manufactured in an analogous manner by varying the two starting materials (aluminium alkyl or halide): a) Bromo(10-undecenoato)isobutylaluminium, a slightly yellowish, semicrystalline mass. Yield: 91.4%.

b) Chloro(10-undecenoato)hexylaluminium, a white, crystalline mass. Yield: 93.1%.

c) Chloro(l0-undecanoato)ethylaluminium, a white powder Yield: 91%.

Example 5 38.3 g of diisobutylaluminium cetyl alcoholate, 56.7 g of isobutylaluminium dicetyl alcoholate and 13.3 g of anhydrous aluminium chloride are added under an inert gas atmosphere to a 250 ml three-necked flask which is provided with a stirred thermometer and apparatus for the throughput of argon. The mixture is warmed to 90"C while stirring for 5 hours. During this time, the colourless oily Chloro(hexadecyloxy)isobutyl-aluminium described in Example I forms quantitatively from the heterogeneous mixture.

Example 6 39.7 g of diisobutylaluminium palmitate, 59.5 g of isobutylaluminium dipalmitate and 13.3 g of anhydrous aluminium chloride are reacted together in a manner analogous to that described in Example 5 and in an apparatus of the kind described in Example 5. After stirring for 4 hours at 85DC, the chloro(hexadecenoato)isobutylaluminium described in Example 2 has formed quantitatively.

Example 7 19.8 g of triisobutylaluminium and 13.3 g of anhydrous aluminium chloride are added to an apparatus of the kind described in Example 5 and warmed to 80"C while stirring under an inert gas atmosphere for 2 hours. The mixture is then left to cool to room temperature, 75.1 g of aluminium tricetyl alcoholate are added and the resulting mixture is warmed to 80"C while stirring for a further 3 hours. There is obtained quantitatively the chloro(hexadecyloxy)isobutylaluminium described in Example 1.

Example 8 In an apparatus of the kind described in Example 5, 19.8 g of triisobutylaluminium and 13.3 g of anhydrous aluminium chloride are reacted together for a period of 2 hours at 800C in a manner analogous to that described in Example 7. 79.3 g of aluminium tripalmitate are then added at room temperature.

After warming to 80"C for 3 hours while stirring, there is obtained quantitatively the chloro(hexadecanoato)isobutyl-aluminium described in Example 2.

Example 9 38.3 g of diisobutylaluminium cetyl alcoholate in 500 ml of n-heptane are placed in a 1 litre four-necked flask which is provided with a reflux condenser, stirrer, gas-inlet tube and apparatus for working under an inert gas atmosphere.

The solution is cooled down to --100C and 3.65 g of dry hydrogen chloride gas are conducted into the apparatus through the gas-inlet tube with intensive stirring over a period of 0.5 hour. The solution is stirred at --100C for a further hour and subsequently at 600C for a further 2 hours. After removal of the volatiles in a receiver which is cooled down to70 C, there are identified 5.5 g of isobutane (94.6% of the calculated amount). The residue in the apparatus i h) Chloro(tetradecanoato)isobutylaluminium 5.0 g n-Hexane 10.0 g "Isopar" Cosmetic 9.0 g Propellant gas mixture q.s. ad 100.0 g i) Chloro(hexadecanolato)isobutylaluminium 2.5 g Chloro(octadecanolato)isobutylaluminium 0.5 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g j) Chloro(hexadecanolato)isobutylaluminium 1.0 g Chloro(mentholato)octylaluminium 2.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g k) Chloro(hexadecanolato)isobutylaluminium 0.8 g Chloro(tetradecanoato)isobutylaluminium 1.2 g Chloro(2-ethylhexanolato)isobutylaluminium 1.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g 1) Chloro(ethanolato)ethylaluminium 3.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g m) Bromo(10-undecenoato)ethylaluminium 2.0 g n-Hexane 10.0 g Perfume 0.3 g Propellant gas mixture q.s. ad 100.0 g n) Chloro(sorbato)isobutylaluminium 3.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g o) Chloro(phenoxy)isobutylaluminium 15.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g p) Chloro(octadecanolato)isobutylaluminium 3.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g The essential active ingredient or essential active ingredients is/are dissolved in the solvent and introduced into a suitable aerosol container under nitrogen gasification. The remaining additives are added and the container is again flushed with nitrogen. Subsequently, the mixture is made up to 100 g with the propellant gas mixture.

In the foregoing compositions, the essential active ingredient(s) mentioned can be replaced by other essential active ingredient(s) described in Examples 1 to 10 hereinbefore.

WHAT WE CLAIM IS: 1. An antiperspirant composition which contains as an essential active ingredient or essential active ingredients one or more organo-aluminium compounds of the general formula

wherein X represents a chlorine or bromine atom, R, represents an alkyl group and R2 represents an alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkanoyl, alkenoyl or aroyl group, whereby the alkyl, alkenyl, alkanoyl and alkenoyl groups denoted by R2 can each be substituted by optionally alkyl-substituted cycloalkyl, optionally alkyl-substitued cycloalkenyl, optionally alkyl- and/or alkoxy-substituted aryl, alkoxy, cycloalkoxy, cycloalkenyloxy, and/or aryloxy and the cycloalkyl, cycloalkenyl, aryl and aroyl groups denoted by R2 can each be substituted by alkyl, alkoxy and/or aryl and whereby two adjacent alkyl and/or alkoxy groups present on a phenyl group denoted by R2 can also be joined with one another with the formation of a 5-membered or 6-membered saturated ring, in association with a compatible cosmetic carrier.

2. An antiperspirant composition according to claim 1 wherein R, represents an alkyl group containing from 2 to 8 carbon atoms and R2 represents an alkyl or

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (21)

**WARNING** start of CLMS field may overlap end of DESC **. h) Chloro(tetradecanoato)isobutylaluminium 5.0 g n-Hexane 10.0 g "Isopar" Cosmetic 9.0 g Propellant gas mixture q.s. ad 100.0 g i) Chloro(hexadecanolato)isobutylaluminium 2.5 g Chloro(octadecanolato)isobutylaluminium 0.5 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g j) Chloro(hexadecanolato)isobutylaluminium 1.0 g Chloro(mentholato)octylaluminium 2.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g k) Chloro(hexadecanolato)isobutylaluminium 0.8 g Chloro(tetradecanoato)isobutylaluminium 1.2 g Chloro(2-ethylhexanolato)isobutylaluminium 1.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g 1) Chloro(ethanolato)ethylaluminium 3.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g m) Bromo(10-undecenoato)ethylaluminium 2.0 g n-Hexane 10.0 g Perfume 0.3 g Propellant gas mixture q.s. ad 100.0 g n) Chloro(sorbato)isobutylaluminium 3.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g o) Chloro(phenoxy)isobutylaluminium 15.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g p) Chloro(octadecanolato)isobutylaluminium 3.0 g n-Hexane 10.0 g Propellant gas mixture q.s. ad 100.0 g The essential active ingredient or essential active ingredients is/are dissolved in the solvent and introduced into a suitable aerosol container under nitrogen gasification. The remaining additives are added and the container is again flushed with nitrogen. Subsequently, the mixture is made up to 100 g with the propellant gas mixture. In the foregoing compositions, the essential active ingredient(s) mentioned can be replaced by other essential active ingredient(s) described in Examples 1 to 10 hereinbefore. WHAT WE CLAIM IS:

1. An antiperspirant composition which contains as an essential active ingredient or essential active ingredients one or more organo-aluminium compounds of the general formula

wherein X represents a chlorine or bromine atom, R, represents an alkyl group and R2 represents an alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkanoyl, alkenoyl or aroyl group, whereby the alkyl, alkenyl, alkanoyl and alkenoyl groups denoted by R2 can each be substituted by optionally alkyl-substituted cycloalkyl, optionally alkyl-substitued cycloalkenyl, optionally alkyl- and/or alkoxy-substituted aryl, alkoxy, cycloalkoxy, cycloalkenyloxy, and/or aryloxy and the cycloalkyl, cycloalkenyl, aryl and aroyl groups denoted by R2 can each be substituted by alkyl, alkoxy and/or aryl and whereby two adjacent alkyl and/or alkoxy groups present on a phenyl group denoted by R2 can also be joined with one another with the formation of a 5-membered or 6-membered saturated ring, in association with a compatible cosmetic carrier.

2. An antiperspirant composition according to claim 1 wherein R, represents an alkyl group containing from 2 to 8 carbon atoms and R2 represents an alkyl or

alkanoyl group containing from 8 to 18 carbon atoms or a cycloalkyl or cycloalkenyl group substituted by alkyl.

3. An antiperspirant according to claim 1 wherein the essential active ingredient or one of the essential active ingredients is chloro(hexadecanoato)isobuylaluminium.

4. An antiperspirant according to claim 1 wherein the essential active ingredient or one of the essential active ingredients is chloro(tetradecanoato)isobutylaluminium.

5. An antiperspirant according to claim 1 wherein the essential active ingredient or one of the essential active ingredients is chloro(hexadecanolato)isobutyaluminium.

6. An antiperspirant according to claim I wherein the essential active ingredient or one of the essential active ingredents is chloro(octadecanolato)isobutylaluminium.

7. An antiperspirant according to claim 1 wherein the essential active ingredient or one of the essential active ingredients is chloro(mentholato)- isobutylaluminium.

8. An antiperspirant according to claim 1 wherein the essential active ingredient or one of the essential active ingredients is chloro(mentholato)octylaluminium.

9. An antiperspirant according to claim 1 wherein the essential active ingredient or one of the essential active ingredients is chloro(2-ethylhexanolato)isobutylaluminium.

10. An antiperspirant according to claim 1 wherein the essential active ingredient or one of the essential active ingredients is chloro(isophytolato)isobutylaluminium.

11. An antiperspirant according to any of the foregoing claims wherein the essential active ingredient or essential active ingredients is/are present in an amount of between 1 and 30 weight percent.

12. An antiperspirant according to any of the foregoing claims wherein the essential active ingredient or essential active ingredients is/are present in an amount of between 2 and 5 weight percent.

13. Organo-aluminium compounds of the general formula

wherein X represents a chlorine or bromine atom, R, represents an alkyl group and R2, represents a cycloalkenyl, alkanoyl, alkenoyl or aroyl group, whereby the alkanoyl and alkenoyl -groups denoted by R2' can each be substituted by optionally alkyl-substituted cycloalkyl, optionally alkyl-substituted cycloalkenyl, optionally alkyl- and/or alkoxy-substituted aryl, alkoxy, cycloalkoxy, cycloalkenyloxy and/or aryloxy and the cycloalkenyl and aroyl groups denoted by R2, can each be substituted by alkyl, alkoxy and/or aryl.

14. Organo-aluminium compounds according to claim 13, wherein R, represents an alkyl group containing from 2 to 8 carbon atoms and R2 represents an alkanoyl group containing from 8 to 18 carbon atoms or a cycloalkenyl group substituted by alkyl.

15. Chloro(hexadecanoato)isobutylaluminium.

16. Chloro(tetradecanoato)isobutylaluminium.

17. A process for the manufacture of the organo-aluminium compounds of formula (I') given in claim 13, which process comprises: a) treating a compound of the general formula (R,)m--AII-X, (11) wherein m and n each stand for 1 or 2 with the proviso that the sum of m and n is 3, and R, and X have the significance given in claim 13, with a compound yielding the group -OR2, in which R2, has the significance given in claim 13; or b) reacting a compound of the general formula (R1)2-Al-OR2, (III) with a compound of the general formula R1-Al-(OR21)2 (IV) and a compound of the general formula AIX3 (V) wherein R1, R2, and X have the significance given in claim 13; or c) reacting a compound of the general formula (R,)3AI (Vl) with a compound of the general formula Al(OR2,)3 (VII) and a compound of the general formula AIX3 (V) wherein R1, R2, and X have the significance given in claim 13; or d) treating a compound of the general formula (R1)2A1-OR2, (sir) with a hydrogen chloride or hydrogen bromide.

18. A process according to claim 17, wherein the starting materials are used in stoichiometric amounts.

19. A process according to claim 17 or 18, wherein m stands for 2, n stands for 1 and the compound yielding the group -OR2, is a compound of the formula R2,OH.

20. A process for the manufacture of the organo-aluminium compounds of formula (I') given in claim 13, substantially as hereinbefore described with reference to any one of Examples 2, 4, 6, 8 and 10.

21. An organo-aluminium compound of formula (I') given in claim 13, when manufactured by the process claimed in any one of claims 17 to 20 inclusive or by an obvious chemical equivalent thereof.