DE2820657A1 - ALUMINUM ORGANIC COMPOUNDS - Google Patents

Description

The present invention relates to new compounds the general formula

X
R ₁ -Al-OR ₂ I.

wherein X is chlorine or bromine, R, alkyl and R _{2 is} alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkanoyl, alkenoyl or aroyl, the alkyl, alkenyl, alkanoyl and alkenoyl groups R ₂ each being optionally alkyl-substituted cycloalkyl , optionally alkyl-substituted cycloalkenyl, optionally alkyl- and / or alkoxy-substituted aryl, alkoxy, cycloalkoxy, cycloalkenyloxy and / or aryloxy can be substituted and the cycloalkyl, cycloalkenyl, aryl and aroyl groups R ₂

809847/0641

Hof / January 31, 1978

may in each case be substituted by alkyl, alkoxy and / or aryl, and furthermore two adjacent alkyl and / or alkoxy groups present on a phenyl radical R ~ also linked to one another to form a 5- or 6-membered, saturated ring could be.

The compounds of the formula I have the advantage that they have both a very excellent initial and a long lasting duration - have antiperspirant effects.

The present invention accordingly relates to new antiperspirants, characterized by a content of one or several organometallic compounds of the general formula I in admixture with a suitable one which is customary in cosmetics Carrier.

Those present in the above formula I with the meaning R2 Alkyl, alkoxy, alkenyl, alkarioyl and alkenoyl groups can be straight-chain or branched and are preferred up to 30 carbon atoms, with 2 to 20 carbon atoms are particularly preferred. Alkyl groups occurring as R, have the same meaning as the alkyl groups R-, but with the alkyl groups R, preferably carry from 2 to 8 carbon atoms, since the other compounds in particular the methyl compound are less accessible. Examples of alkyl groups R or R_ are methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, Neopentyl, n-hexyl, n-octyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-triacontyl. The alkoxy groups have an analogous meaning. Examples of Alkeny! Groups R_ are allyl, but-2-enyl, penta-2,4-dienyl,

Geranyl / B \ , nerolyl

809847/0841

Phytyl I ² ^ ^v ^ ^ ^ j ^ j J , 3,7-dimethyl-octa-2,6-

dien-1-yl. The alkanoyl groups R ~ carry at least 2 carbon atoms atoms. Examples are acetyl, propionyl, n-butyryl, isobutyryl, Pivaloyl, n-pentanoyl, n-hexanoyl, n-octanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl, n-octadecanoyl, n-eicosanoyl, n-triacontanoyl. Examples of alkenoyl groups R1 are acryloyl and but-2-enoyl (Crotonyl), penta-2,4-dienoyl, hexa-2,4dienoyl (sorbyl), undec-

(W

10-enoyl, geranoyl 1 \ octadec-9-enoyl (oleyl),

\ -fY J

Octadeca- ?, 12-dienoyl (linolyl), octadeca-9,12,15-trienoyl (linolenyl), eicos-5-enoyl.
15th

Cycloalkyl and cycloalkenyl groups R ₂ preferably have 5 or 6 carbon atoms, for example cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl.

The term "aryl" means an aromatic, mono- or polynuclear hydrocarbon radical, such as phenyl, naphthyl, Phenanthryl. "Aryloxy" and "aroyl" mean aryl-O- or Aryl-CO groups, in which "aryl" has the above meaning, e.g. phenyloxy, naphthyloxy, phenanthryloxy, benzoyl, naphthoyl, Phenanthroyl. Preferred aryl, aryloxy and aroyl groups are those with 1 or 2 aromatic rings.

The above-mentioned groups R ~ can optionally carry further substituents. Examples of such substituted Groups are the following:

Cycloalkyl-alkyl, for example cyclohexylmethyl, cyclopentylethyl; Cycloalkyl-alkeny1, for example cyclohexylallyl; Cycloalky1-alkanoyl, e.g. cyclopropylacetyl, cyclohexylacetyl ,

Cycloalkyl-alkenoyl, e.g., cyclohexylhexa-2,4-dienoyl;

809847/0841

-A-

Alkenyl substituted by alkyl-substituted cycloalkenyl, e.g. retinyl (such as all-trans-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, for example benzyl, phenethyl, naphthylmethyl, p-tolylmethyl, p-methoxyphenylethyl, p-methoxy-omethyl-phenylmethyl ;

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

Alkanoyl substituted by optionally alkyl- and / or alkoxy-substituted aryl, e.g. phenacetyl, ToIy! Acetyl, p-methoxyphenylacetyl;

Alkenoyl substituted by optionally alkyl- and / or alkoxy-substituted aryl, e.g. cinnamoyl, p-methoxy-cinnamoyl, 9- (4-methoxy-2,3,6-trimethylphenyl) -3,7-dimethyl-nona-2,4,6,8-tetraenoyl (e.g. the all-trans form:

9 30

Alkoxy-alkyl, e.g. 2-methoxyethyl, ethoxymethyl, 7-methoxy-3,7-dimethyl-octyl;

Alkoxy-alkenyl, e.g., 1-methoxyallyl, 7-methoxy-3,7-dimethyl-octa-2-enyl;

Alkoxyalkanoyl, e.g. ethoxyacetyl, 3-methoxypropionyl;

809847/0841

β - M.

Alkoxy-alkenoyl, e.g., 3-methoxy-acryloyl, 6-methoxy-hexa-2,4-dienoyl (6-methoxysorbyl);

Cycloalkoxy-alkyl, e.g. 2-cyclohexoxy-ethyl; Aryloxy-alkyl, e.g., 2-phenoxyethyl, 6-phenoxy-n-hexyl; Aryloxy-alkanoyl, e.g., phenoxyacety1;

Alky! -Cycloalkyl, e.g. 4-methyl-cyclohexy1, menthy1

Alkyl-aryl, e.g., o-, m- and p-tolyl; Alkyl-aroyl, e.g., o-, m- and p-toluoyl; Alkoxy-aryl, e.g., o-, m- and p-methoxyphenyl (anisyl) j Alkoxy-aroyl, e.g., o-, m- and p-methoxybenzoyl (anisoyl); Aryl-aryl, e.g., 4-phenyl-phenyl;

Aryl-aroyl, e.g., 4-phenyl-benzoyl.

In the above formula I, as mentioned, two adjacent alkyl and / or alkoxy groups present on a phenyl radical R "can also be linked to one another to form a 5- or 6-membered, saturated ring. This gives compounds of the formula I in which R »represents an indanyl, benzofuranyl, 1,3-benzodioxolyl, tetrahydronaphthyl, chromanyl or 1,4-benzodioxanyl radical linked to the oxygen atom via the benzene nucleus, which optionally passes through the benzene nucleus Alkyl and / or alkoxy and / or in the saturated nucleus can be substituted by alkyl. An example of this is the cc-tocopheryl radical
CH ₃

A preferred group of compounds of the formula I which can be used as Antxtranspirantxen are those where R, alkyl with 2 to 8 carbon atoms and R "

809847/0841

JS -

an alkyl or alkanoyl radical having 8 to 18 carbon atoms or an alkyl-substituted cycloalkyl or alkenyl radical represents.

The new organometallic compounds of the formula

X
I.

R ₁ -Al-OR ₂ I.

wherein X is chlorine or bromine, R, alkyl and R ₂

■ 10 represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkanoyl, alkenoyl or aroyl, the alkyl, alkenyl, alkanoyl and alkenoyl groups R ₂ each being replaced by optionally alkyl-substituted cycloalkyl,

■ j5 optionally alkyl-substituted cycloalkenyl, optionally alkyl and / or
alkoxy-substituted aryl, alkoxy, cycloalkoxy, cycloalkenyloxy and / or aryloxy
can be substituted and the cycloalkyl, cycloalkenyl, aryl and aroyl groups R ₂

can in each case be substituted by alkyl, alkoxy and / or aryl and furthermore two present on a phenyl radical R ",
Adjacent alkyl and / or alkoxy groups can also be linked to one another to form a 5- or 6-membered, saturated ring,

are manufactured according to the invention by a method which is characterized in that one

a) a compound of the general formula

in which m and η are each a number of
1 to 2, where the sum of
m and η represents 3, and R. and X represent the above

809847/0841

-J-

1 have meaning, with the group OR-

donating compounds, in which R "has the above meaning,
treated; or

b) a compound of the general formula

III

10 with a compound of the general formula

IV

and a compound of the general formula 15

in which R 1, R 1 and X have the above meaning, reacts; or
20th

c) a compound of the general formula

VI

25 with a compound of the general formula

VII

and a compound of the general formula 30

AlX ₃ V

wherein R,, R "and X have the above meaning, reacts; or
35

809847/0841

- JS -

d) a compound of the general formula

(R ₁ ) ₂ A1OR ₂ III

treated with hydrogen chloride or hydrogen bromide.

The inventive reaction of the starting compounds of formula II with the group -OR "releasing agents such as R ₂ OH, R ₂ O-alkali metal, (R ₂ O) ₂ -alkali earth metal or (R ₂ O) 3 ^A1 (process variant a) and the invention Reaction of the starting compounds of the formula III with hydrogen chloride or hydrogen bromide (process variant d) are preferably carried out in an inert organic solvent. The solvents used are, in particular, lower aliphatic and aromatic, optionally halogenated hydrocarbons, such as η-hexane, n-heptane, methylene chloride, benzene, toluene or chlorobenzene; as well as ethers such as diethyl ether, tetrahydrofuran or dioxane.

Although the above inert organic solvents are also used to carry out process variants b) and c) these processes are preferably carried out without a solvent.

In all process variants a) to d), the reaction temperature is not critical; however, it is preferably in a range between about room temperature and 90 ° C.

Because of the known sensitivity of organoaluminum compounds, e.g. to hydrolysis or oxidation, preferably all manufacturing processes a) to d) in dry equipment that is operated under an inert gas atmosphere (e.g. nitrogen, Argon etc.).

It is not necessary to strictly adhere to the stoichiometric proportions of the starting components in order to obtain a to obtain product falling under the formula I; much more

809847/0841

■ \, the proportions vary widely.

Preferably, however, stoichiometric amounts are purest Starting materials used because in the reactions listed above the desired end products in analytically pure form incurred and further costly cleaning operations are omitted.

The compounds of formula I are highly hygroscopic, IQ liquid or solid substances, generally without a defined melting point. Often they are viscous substances in accordance with the nature of organoaluminum compounds. They are usually readily soluble in inert organic solvents, e.g. in aliphatic and aromatic hydrocarbons, e.g. n-hexane, - | 5 n-heptane, benzene and toluene, and in ethers, e.g. diethyl ether, tetrahydrofuran, dioxane, 6-acetoxy-2,4 -dimethyl-1,3-dioxane, etc., or esters, for example ethyl acetate, isopropyl myristate.

To demonstrate the antiperspirant effect of the compounds of the formula I, representative representatives were examined on human volunteers checked.

For this purpose, a combined humidity-temperature measuring device (ROTRONIC HYGROSKOP T DT-2) was used, which measures the transpiration on the skin surface with the help of a special skin probe, its ohmic resistance changes with increasing humidity is allowed. During the measurement, the probe is placed on the surface of the skin in such a way that that no external air can penetrate into the measuring cell during the 4-minute measuring process. The humidity sensor (humidity feeling cell) works with an accuracy of + 2%. The measured values are qualitatively and quantitatively as Moisture increase or decrease indicated in percent. Of the Coupled linear recorder registers the measured values in the form of a perspiration curve at each measurement time. The exams are used in air-conditioned rooms without air flow at a room temperature of 36 ° C and a humidity of 50%

809847/0841

γ Ak

carried out.

Test material ; The active ingredients are tested in a concentration of 4% (% by weight). First they are dissolved in a suitable anhydrous aprotic solvent and filled into conventional spray cans. A dosing valve on the spray can allows precise dosing of 40 mg of substance per

Application on each 4 cm skin surface. The product on the market is used as the comparator preparation REXONA w (aluminum hydroxychloride) is used.

Test objects : 15 healthy test subjects (women and men) between the ages of 20 and 50 who are particularly suitable for these experiments (pre-selected).

Method : To determine the effectiveness of local anti-

perspiration is used on the inside of the skin on both front

2 arms. First, four to five 4 cm large areas of skin are marked with a stamp and the sweat secretion of these skin areas is measured over a period of 4 'with the ROTRONIC hygrometer and recorded in the form of a hygrometric curve. Shortly afterwards, the first test field is treated with one of the drug concentrations to be tested or the test preparations, and after an exposure time of 5-10 minutes, the second measurement of perspiration (measuring time 4 ¹ ) is carried out in order to determine the immediate effect of the antiperspirants or preparations. To determine the duration of action, a further measurement time is determined, namely 2 hours after application of the active ingredient or the test preparation. Three further test fields are treated one after the other with three other preparations in the same way one after the other and the perspiration of the skin is determined. One test field remains untreated and serves as a negative control. The order of the preparations within the test group must rotate so that the regional and individual differences in the sweat secretion on the inside of the forearm have no effect on the test results.

809847/0841

-YES-

evaluation

The percentage inhibition of perspiration compared to that of the untreated control field is at each measurement time determined. The individual measured values are expressed in absolute numbers as measured air humidity (in%) for the new active ingredients or the standard preparation (REXONAW) compiled below and with regard to both the strength and the duration of the antiperspirant activity of the evaluated various preparations.

Results

I) Substances that initially inhibit perspiration 75-100% and an inhibition after 2 hours of 15-25% caused:

Chloro (hexadecanolato) isobutyl aluminum, chloro (octadecanolato) isobutyl aluminum, chloro (hexadecanoato) isobutyl aluminum, chloro (tetradecanoato) isobutyl aluminum, chloro (mentholato) isobutyl aluminum, chloro (mentholato) aluminum
Chloro (2-äthylhexanolato) -isobutylaluminium, Chloro (isophytolato) -isobutylaluminium.

II. Substances that initially inhibit perspiration 50-75% and an inhibition after 2 hours of 10-15% caused:

Chloro (äthanolato) -isobutylaluminium, Chloro (2-phenoxyäthanolato) -isobutylaluminium, Chloro (2-phenoxyäthanolato) -äthylaluminium, Bromo (2-phenoxyäthanolato) -isobutylaluminium, Bromo (2-phenoxyäthanolato) -ätium [aluminum] -äthanolato) -bratoethylaluminium
Chloro (äthanolato) ethyl aluminum,

Bromo (ethanolato) isobutylaluminum.

809847/0841

Al

III. Substances that inhibit sweat at the beginning 30-50% and an inhibition after 2 hours of 5-10% caused:

Chloro (10-undecenoato) -isobutylaluminum, Chloro (phenoxy) isobutyl aluminum, chloro (benzoato) isobutyl aluminum, Bromo (10-undecenoato) -ethylaluminum, Bromo (10-undecenoato) -isobutylaluminium, Chloro (tert.-butoxy) -isobutylaluminum, bromo (tert.-butoxy) -isobutylaluminum, Chloro (sorbato) isobutylaluminum, Chloro (10-undecenoato) -hexylaluminum, Chloro (äthanolato) hexylaluminum, chloro (10-undecenoato) -ethylaluminium.

IV. Standard preparation

(xO

With the comparator preparation (REXONA v _ / - Sport) a An initial effect of 9% and an effect of 8.5% after 2 hours was observed.

As a carrier for the antiperspirants according to the invention The usual carriers used in cosmetics for antiperspirants come into consideration, such as powders, pencils, creams, Solutions, aerosols, etc. Suitable solvents are the anhydrous solvents mentioned above, which the common cosmetic additives can be added, e.g. additives to increase skin metabolism or skin elasticity, such as Pantenol or one of its lower alkyl ethers, e.g. the ethyl ether; bactericidal agents, e.g.

quaternary ammonium salts, and / or perfume. The agents are preferably used in aerosols, the propellant gas being the Usually used carriers come into consideration, e.g. low-boiling, liquefied, optionally halogen-substituted, in particular chlorinated and fluorinated alkanes, e.g. n-propane, η-butane, isobutane, η-hexane, dichlorodifluoromethane and dichlorotetrafluoroethane and mixtures thereof. A very purposeful

809847/0841

-IA-

-j massive propellant mixture consists of roughly equal parts Dichlorodifluoromethane and dichlorotetrafluoroethane, the invention Antiperspirants preferably contain between about 1 and 30 percent by weight, in particular between about 2 and 5 percent by weight active ingredient. In addition to the additives specified above, you can also use other, cosmetically valuable, e.g. antiperspirant or deodorant compounds contain.

The following examples illustrate the invention. The active ingredients listed in preparation examples 1 to 10 have been verified by correct microanalyses (determination the content of carbon, hydrogen and aluminum; Error limit 1-2%).

809847/0841

-IA-

■) 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 diisobutylaluminum chloride in 30 ml of absolute n-heptane is added dropwise from a dropping funnel with stirring over the course of half an hour. As a result of this addition, the temperature in the reaction vessel rises to 40 ^° C. The reaction mixture is then left to

Stir the mixture for 2 hours at 80 ° C. Then you get involved the solvent is removed from this temperature in a water jet pump vacuum. Contains the condensate collected in cold traps 2.35 g isobutane (98.6% of the calculated amount). The chloro (hexadecyloxy) isobutylaluminum remaining in the reaction flask is freed from the last residues of solvent for 2 hours at 80 C on the oil pump (10 Torr). The analytically pure The product is a colorless oily liquid. Yield: 15.0 g = 99.8% of theory. Theory.

The following are produced in an analogous manner:

a) Chloro (octadecyloxy) isobutylaluminum, a colorless one viscous oil. Yield 97.5% of theory

b) Chloro (mentholato) isobutylaluminum, a colorless oil. Yield: 96.3%.

c) Chloro (2-ethyl-l-hexyloxy) isobutylaluminum, colorless OeI. Yield: 97%.

d) chloro (3,7,11, lS-tetramethyl-l-hexadecen-S-yloxy) -isobutylaluminum, yellowish colored, rather viscous oil. Yield: 94.6%.

809847/0841

Example 2

9.1 g of diisobutylaluminum chloride in 100 ml of n-heptane are placed in a 500 ml four-necked flask at 70 ° C. while gassing with nitrogen. ^{A solution, kept at 70 °} C., of 13.2 g of palmitic acid in 80 ml of n-heptane is dropped from the dropping funnel into the flask over a period of about 20 minutes. The mixture is then left to stir for 3 hours at 90 ° C. and the solvent is then stripped off in vacuo (18 torr). The one caught in the cold traps

■ jO condensate contains 2.9 g isobutane = 96.9 d. calculated amount. The chloro (hexadecanoato) isobutylaluminum remaining in the flask is for 2 hours at 80 C on the oil pump

_2

10 Torr freed from the solvent residues. The resulting product is analytically pure: it is colorless, whole slightly cloudy oil. Yield: 18.8 g = 97.3%.

The following are produced in an analogous manner:

a) Chloro (tetradecanoato) isobutylaluminum, colorless Liquid. Yield: 92.8%.

b) Chloro (10-undecenoato) isobutylaluminum, viscous, almost colorless oil. Yield: 94.6%.

c) Chloro (benzoato) isobutylaluminum, colorless, viscous, slightly cloudy oil. Yield: 93.7%.

d) Chloro (sorbato) isobutylaluminum, slightly yellowish colored oil. Yield: 92.3%.
30th

Example 3

In a 250 ml four-necked flask, 1.54 g of anhydrous aluminum chloride and 50 ml given n-heptane. A solution of 8.47 g of tri-n-octylaluminium, dissolved in 25 ml of n-heptane and heated, is added dropwise with stirring for 1 hour at 50 ° C. The initially unsolved aluminum

809847/0841

- ve 92.

chloride dissolves in the process. A solution of 5.4 g of menthol in 50 ml of n-heptane now becomes the contents of the flask for about 15 minutes added dropwise and then heated to 80 C for 3 hours. The volatiles are then drawn off at 80 ° C. using a water jet pump. The condensate collected in the cold traps contains 3.7 g of n-octane, corresponding to 93.4% of theory. The one left in the flask Analytically pure chlorο (mentholato) octylaluminum is used during 3

_2
Freed from solvent residues on the oil pump at 10 torr for hours. The compound is a viscous, slightly cloudy oil. Yield: 94.1%.

In an analogous way, by varying all 3 starting materials (Aluminum organyls or halides or alcohols) the following compounds are produced:

a) Chloro (äthanolato) isobutylaluminum, colorless liquid. Yield: 92.1%.

b) chloro (2-phenoxyethanolato) isobutylaluminum, white Crystals, m.p. 101-102 ° C. Yield: 93.2%.

c) Chloro (2-phenoxyäthanolato) ethyl aluminum, white Crystals. Yield: 89.5%.

d) Bromo (2-phenoxyethanolato) isobutylaluminum, white Crystals. Yield: 93.2%.

e) Bromo (2-phenoxyäthanolato) ethylaluminum, white Crystals. Yield: 94.3%.

f) Bromo- (äthanolato) ethyl aluminum, colorless clear liquid (after removing solvent residues at 30 ° C and

_2
10 Torr). Yield: 91.6%.

g) Chloro (äthanolato) ethyl aluminum, clear colorless liquid (after removing solvent residues at 30 ° C and

_2
10 Torr). Yield: 90.4%.

809847/0341

-IfI-

- | h) Bromo (äthanolato) isobutylalurainiuin, colorless liquid. Yield: 92%.

i) chloro (phenoxy) isobutylaluminum, clear colorless oil. Yield: 97.1%.

k) chloro (tert-butoxy) isobutylaluminum, clear, colorless oily liquid. Yield: 96%.

1) Bromo (tert-butoxy) isobutylaluminum, very pale yellowish oily liquid. Yield: 94.3%.

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

Example 4

In a 500 ml four-necked flask are under argon gas 1.67 g of anhydrous aluminum bromide and 100 ml of abs. given n-hexane. For this purpose 1.43 g are added with stirring at room temperature Triethylaluminum dissolved in 100 ml of abs. η-hexane was added dropwise within 10 minutes. The onset of the reaction will make this Dissolved aluminum bromide; it is stirred for 2 hours at 50 ° C. and then cooled to room temperature.

In a second four-necked flask, which is also under an argon atmosphere, 3.46 g of undecylenic acid in 100 ml of abs. Submitted η-hexane. The solution of diethylaluminum bromide prepared in the first apparatus - as described above - is transferred into the dropping funnel of this second apparatus with the exclusion of air and moisture. This solution is now allowed to drip into the dissolved undecylenic acid over half an hour at room temperature. After the addition has ended, the mixture is left to stir at 50 ° C. for 2 hours. The formed during the reaction as well as the ethane solvent pump vacuum water was sucked off at the end of the reaction, are in cold traps that are cooled to -120 ⁰ C, collected (liquid nitrogen / pentane) and determined by gas chromatography. The captured

809847/0841

The amount of ethane is 0.49 g = 86.9% of theory The one in the flask

_2 remaining residue is 2 hours on the oil pump (10

Torr) at 40 ⁰ C freed from solvent residues. Then the bromo (10-undecenoato) ethylaluminum is obtained as a pale yellowish, semicrystalline mass. Yield 5.6 g = 93.5% of theory

In an analogous way, by varying the two output components Aluminum alkyls or halides produced the following compounds:

a) Bromo (10-undecenoato) isobutylaluminum, pale yellowish, semicrystalline mass. Yield: 91.4%.

b) Chloro (10-undecenoato) hexylaluminum, white, crystalline Dimensions. Yield: 93.1%.

c) Chloro (10-undecenoato) ethyl aluminum, white powder. Yield: 91%.

Example 5

In a 250 ml three-necked flask under an inert gas atmosphere, which is provided with a stirrer, thermometer and device for bypassing argon, 38.3 g of diisobutylaluminum acetyl alcoholate, 56.7 g of isobutyl aluminum dicetyl alcoholate and 13.3 g of anhydrous aluminum chloride were added. The mixture is heated to 90 ° C. for 5 hours while stirring. During this time, the heterogeneous mixture forms quantitatively the colorless oily chloro (hexadecyloxy) isobutylaluminum described in Example 1.

Example 6

In an apparatus specified in Example 5, the following are reacted analogously to this example: 39.7 g of diisobutylaluminum palmitate, 59.5 g isobutyl aluminum dipalmitate and 13.3 g anhydrous Aluminum chloride. After stirring for 4 hours at 85 ° C it has turned

809847/0841

quantitatively the chloro (hexadecanoato) already described in example 2 isobutylaluminum formed.

Example 7

In an apparatus described in Example 5 are

19.8 g triisobutyl aluminum and 13.3 g anhydrous aluminum chloride combined and heated to 80 ° C. for 2 hours with stirring under an inert gas atmosphere. Then it is left to room temperature cool, gives 75.1 g of aluminum tri-cetyl alcoholate to this and heated to 80 ° C. for a further 3 hours with stirring. The chloro- (hexadecyloxy) isobutylaluminum described in Example 1 is obtained quantitatively.

Example 8

In an apparatus described in Example 5, analogously to Example 7, 19.8 g of triisobutylaluminum and 13.3 g of anhydrous aluminum chloride are first reacted at 80 ° C. for 2 hours. Then 79.3 g of aluminum tri-palmitate are added at room temperature. After 3 hours of heating at 80 ⁰ C under stirring to obtain quantitatively the method described in Example 2 chloro (hexadecanoato) isobutylaluminum.

Example 9

In a 1 l four-necked flask equipped with a reflux condenser, Stirrer, gas inlet pipe and device for working under an inert gas atmosphere are provided, 38.3 g of diisobutylaluminum acetyl alcoholate are obtained presented in 500 ml of n-heptane. This solution is cooled to -10 ° C. and stirred vigorously 3.65 g of dry hydrogen chloride gas were passed through the gas inlet tube into the apparatus over half an hour. The solution is stirred for a further 1 hour at this temperature and then for a further 2 hours at 60.degree 5.5 g of isobutane = 94.6% of the calculated amount are detected in samples that have been cooled down to -70 ° C. Of the

809847/0841

The residue in the apparatus is kept at 60 ° C. for 2 hours

_2
freed of solvent residues at the oil pump (10 Torr).

The chloro (hexadecyloxy) isobutylaluminum formed precipitates practically quantitatively as a colorless oil. 5

Example 10

In the apparatus and procedure described in Example 9, 39.6 g of diisobutylaluminum palmitate are mixed with 3.65 g of hydrogen chloride brought to reaction. 5.3 g of isobutane (91.1% of the calculated amount) are detected in the condensate. Of the Residue in the apparatus is for 2 hours on the oil

_2

pump (10 Torr) freed of solvent residues. The chloro (hexadecenoato) isobutylaluminum formed practically falls quantitatively.

Example 11

The preparation of solutions or aerosols which can be used as antiperspirants or deodorants is illustrated below. A mixture of 40% dichlorodifluoromethane and 60% dichlorotetrafluoroethane is used as the propellant gas mixture for the aerosol preparation.

25 a) Chloro (hexadecanolato) -

isobutyl aluminum

Trichlorotrifluoroethane

Perfume

Isopropyl myristate
Propellant gas mixture gs ad

b) chloro (hexadecanoato) isobutylaluminum n-hexane
35 panthenol ethyl ether

Propellant gas mixture q.s. ad

809847/0841

4.0 G 20.0 G 0.1 G 0.3 G ιοο, ο G 2.0 G 20.0 G 0.2 G 100.0 G

c) Chloro (mentholato) -

isobutyl aluminum 5.0 g

η-hexane 10, Og

Cr)

Isopar Cosmetic ^ (Esso; aliphatic hydrocarbon used as solvent with predominantly 7 carbon atoms)
Propellant gas mixture qs ad

-JO d) Chloro (isophytolato) -isobutylaluminum trichlorotrifluoroethane
n-hexane

6-acetoxy-2,4-dimethyl-1,3-dioxane Propellant gas mixture q.s. ad

e) chloro (2-phenoxyethanolato) isobutylaluminum

n-hexane

Isopropyl myristate
Propellant gas mixture qs ad

f) Bromo (2-phenoxyethanolato) isobutylaluminum

n-hexane

Cr)
Isopar Cosmetic ^

Propellant gas mixture q.s. ad

g) Chloro (hexadecanolato) -

isobutylaluminum 1.2 g chloro (2-ethylhexanolato) -

isobutyl aluminum 1.8 g

Chloro (isophytolato) -

isobutyl aluminum 1.0 g

n-hexane 10.0 g

Perfume 0.3 g

Propellant gas mixture q.s. ad - 100.0 g

809847/0841

0.2 G 100.0 G 3.0 G 5.0 G 10.0 G 0.2 G 100.0 G 3.0 G 10.0 G 0.3 G 100.0 G 3.0 G 10.0 G 0.2 G 100.0 G

-ψι -

h) chloro (tetradecanoato) isobutyl aluminum n-hexane

Cr)

Isopar Cosmetic ^

Propellant gas mixture q.s. ad

i) Chloro (hexadecanolato) isobutylaluminum Chloro (octadecanolato) isobutylaluminum n-hexane
Propellant gas mixture qs ad

j) chloro (hexadecanolato) isobutylaluminum

Chloro (mentholato) octyl aluminum n-hexane

Propellant gas mixture q.s. ad

k) Chloro (hexadecanolato) isobutylaluminum Chloro (tetradecanoato) isobutylaluminum Chloro (2-ethylhexanolato) -isobutylaluminium
n-hexane

Propellant gas mixture q.s. ad

1) Chloro (äthanolato) ethyl aluminum

n-hexane
Propellant gas mixture qs ad

m) Bromo (10-undecenoato) ethylaluminum n-hexane
Perfume
Propellant gas mixture qs ad

n) chloro (sorbato) isobutylaluminum n-hexane

Propellant gas mixture q.s. ad

2820657 G 5.0 G 10.0 G 9.0 G ιοο, ο G 2.5 G 0.5 G 10.0 G 100.0 G 1.0 G 2.0 G 10.0 G 100.0 G 0.8 G 1.2 G 1.0 G 10.0 G 100.0 G 3.0 G 10.0 G ιοο, ο G 2.0 G 10.0 G 0.3 G 100.0 G 3.0 G 10.0 G 100.0

809847/0841

2820657 G 15.0 G 10.0 G 100.0 G 3.0 G 10.0 G 100.0

1 ο) chloro (phenoxy) isobutyl aluminum n-hexane propellant gas mixture q.s. ad

5 p) chloro (octadecanolato) isobutyl aluminum n-hexane propellant gas mixture q.s. ad

The active ingredient (s) is / are dissolved in the solvent and, while gassing with nitrogen, into a brought a suitable aerosol can. The other additives are added and the can is flushed again with nitrogen. Afterward is made up to 100 g with the propellant gas mixture.

15 In the above preparations, in addition to the specified Active ingredients, the other active ingredients described in Examples 1 to 10 above can also be used.

809847/0841

Claims (16)

/ "Λ 1J compounds of the general formula X
I.
R ₁ -Al-OR ₂ I. where X is chlorine or bromine, R, alkyl and R _{2 is} alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkanoyl, alkenoyl or aroyl, the alkyl, alkenyl, alkanoyl and alkenoyl groups R "each being optionally alkyl-substituted cycloalkyl , optionally alkyl-substituted cycloalkenyl, optionally alkyl- and / or - | 5 alkoxy-substituted aryl, alkoxy, cycloalkoxy, cycloalkenyloxy and / or aryloxy can be substituted and the cycloalkyl, cycloalkenyl, aryl and aroyl groups R _{2 can} each be substituted by alkyl, alkoxy and / or aryl and furthermore two Adjacent alkyl and / or alkoxy groups present in a phenyl radical R _{2 can} also be linked to one another to form a 5- or 6-membered, saturated ring. 2. Compounds according to claim 1, characterized in that R. is alkyl with 2 to 8 carbon atoms and R _{2 is} an alkyl or alkanoyl radical with 8 to 18 carbon atoms or an alkyl-substituted cycloalkyl or alkenyl radical. 3. Chloro (hexadecanolato) isobutyl aluminum. 4. Chloro (octadecanolato) isobutyl aluminum. 5. Chloro (hexadecanoato) isobutyl aluminum. 809847/0841 ORIGINAL INSPECTED 9t 6. Chloro (tetradecanoato) isobutyl aluminum. 7. Chloro (mentholato) isobutyl aluminum. 8. Chloro (mentholato) octyl aluminum. 9. Chloro (2-ethylhexanolato) isobutylaluminum. 10. Chloro (isophytolato) isobutyl aluminum. 809847/0841 11. Process for the preparation of compounds of the general formula X
R ₁ -Al-OR ₂ I. where X is chlorine or bromine, R, alkyl and R "is alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkanoyl, alkenoyl or aroyl, the alkyl, alkenyl, alkanoyl and alkenoyl groups R" each being optionally alkyl-substituted cycloalkyl , optionally alkyl-substituted cycloalkenyl, optionally alkyl- and / or alkoxy-substituted aryl, alkoxy, cycloalkoxy, cycloalkenyloxy and / or aryloxy can be substituted and the cycloalkyl, cycloalkenyl, aryl and aroyl groups R ₂ each by alkyl, alkoxy and / or aryl can be substituted and wherein two adjacent alkyl and / or alkoxy groups present on a phenyl radical R "can also be linked to one another to form a 5- or 6-membered, saturated ring, characterized in that one a) a compound of the general formula in which m and η each denotes a number from 1 to 2, the sum of m and η being 3, and R, and X have the above meaning, with the group OR ₂ donating compounds wherein R _{2 has} the above Has meaning
treated; or 809847/0841 b) a compound of the general formula (R ₁ ) ₂ -Al-OR ₂ III with a compound of the general formula TV and a compound of the general formula 10 wherein R ₁ , R ₃ and X have the above meaning, reacts; or c) a compound of the general formula (R ₁ J ₃ Al VI 20 with a compound of the general formula Al (OR ₂ ) ₃ VII and a compound of the general formula 25 AlX ₃ V wherein R ,, R_ and X have the above meaning, reacts; or
30th d) a compound of the general formula ₁₂₂ III 35 treated with hydrogen chloride or hydrogen bromide. 809847/0841 - 28 - 12. The method according to claim 11, characterized in that that the starting materials are used in stoichiometric amounts. 13. The method according to claim 11 or 12, characterized in that m is the number 2, η is the number 1 and the compound R “0H which donates _{the group OR 2 is.} 809847/0841 14. Antiperspirant, characterized by a content of one or more compounds of the formula I according to the Claims 1 to 10 in admixture with a suitable carrier customary in cosmetics. 15. Antiperspirant according to claim 14, characterized in that that the content of one or more compounds of the formula I is between 1 and 30 percent by weight. 16. Antiperspirant according to claim 15, characterized in that the content of one or more compounds of formula I is between 2 and 5 percent by weight. 809847/0841