DE2249580A1 - COSMETIC AGENTS INHIBITING SWEATING, NEW COMPOUNDS AND METHODS OF PRODUCING THE SAME - Google Patents

Description

DF *. MOUNTAIN D ^ Fw-IH © PTAPF ρατεϊπάϊ; jyÄL'i fe

β MÜKCHSK GO. hiAUI-RKlRGKERSTR. -SS

Attorney's file 22 853 _y

t U «liftI ₁

L ¹ OREAL, Paris (France)

Cosmetic j anti-perspiration agents ₃ new compounds and methods of making them

The present invention relates to new cosmetic, the .sweat-inhibiting gowns, as well as new connections and the making of these compounds.

There have been seen numerous remedies based on 'different Starting materials to reduce perspiration caused by the sweat glands, suggested.

Series 131 - 2 -

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(OSIlJ S3 8? Tl W 70 "W3310 T.legramm"! EEkGSWFPATENT Mönch. "TOEX 05 24 SiO BERG d Bank ι bayeritdi" V "r" intbank MOndnn 453103 Pothklxdc: Mjmim "5343

, Aluminiumdibydroxyallantoinat, Aluoiiiaiumieopropjlat ijo \ i © different andare organieehe Altiminiiimverbindungea οάϋτ · combinations "like; among these basic chemicals eoiea in particular Aluminiumhydrochloriö, known as Naaen Cltljrhydrol, Aluminiumhydroxyohlorlaetat, known as seeds Cihloracel, Alumlnlumphenolsulfat, AluminiumhydroiEyohlorallantoll · ''? for example, ai & Komplexverbindtiüg voi aluminum "hydro3tyohlorid rait propylene glycol, known as Hehydrol called>

The inverse number of the befcr. nth Compounds mil; the perspiration inhibiting effect produced Means cause a significant decrease in the3. Sohwitaena, but there are certain inadequacies which makes their application difficult in many cases.

Sweat inhibiting agents are preferred applied in the form of an aerosol spray, wherein the active compounds must have good solubility in alcohol in order to ensure good atomization is.

Among the aforementioned compounds, some are insoluble in alcohol, making them unsuitable for this purpose are. On the other hand, some show a fairly good alcohol solubility, especially in ethanol, but it has been shown to be less effective in inhibiting perspiration.

Eb has now been found to be a certain class of heterocyclic Aluminum compounds make it possible to produce excellent antiperspirant agents which

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have all the advantages of the known means without your main concern have the utmost insufficiency.

Auseerdem n? Urä§ found DAS®, in the majority & qt felling © this means in terms of the best known, di @ Sciaweissbildung retardant much higher, aufweisan sweating verhindernd® properties "

The present invention relates to new "Schwsisabbildung" inhibitory agents, which are characterized by because they are in a suitable cosmetic! an active compound of the formula

Z Al-R (I) ρ

contain, where E is chlorine; or -OSOgl "means., S ^e group having 1-4 · C atoms, a phenyl, p-Hjydroxyphenyl-, p-iPolylgrupp® represents or (10) radical and Z

1) a best of the general formula

R, CH ₂ -

C (H)

Ka

in which H- ^

a> -COHj, where EaXIe E ^ represents a® methyl, R «is a methyl group, im. Fall® R ,.

represents a phenyl group _a 1 ' e & nm

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group or -COOR ^ iet, where R ^ means an · alkyl group 3 with 1 to 4 carbon atoms »

b) -COOR., noble In the case of R * dia, "Bodautung"_# R _{2 has} a methyl group, a -0 ■ K -O group 06er -COOR ^) 0) -NO ₂ I where R _{2 is} bromine or an «alkyl group with 1 to 3

C atoms means " 2) a reed of the general formula

(III),

OH-

where in case (I) R ^ is a methyl group, Rg and Rc -0-R ₈ represent, in which R _{g is an} alkyl group with 1 to 4 carbon atoms and in part (II) R _{7 is} a Waeeeretoffatom and Rg

e) -CORqr where Rc, in the case of Rq is a methyl group, «a Represents methyl or fhenyl group and in the case of Rg a Pfaeny! Group represents a methyl group 1st »

f) -COOR ₈ , where R- is a methyl or phenyl group or -0-R ₈ , where R _{8 has} the above meaning,

g) -CSN, where Rg represents -O-Rg meaning «

Among the means that can be used for the means according to the invention Compounds of the formula I are specifically mentioned!

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2-chloro- * 5 »5-bie- (ethoxyoarbonyl) -1.3 _r 2 ~ dioxalua» nn ·

C _o H _K 0C 2 5 "

2-chloro-5-oyan ~ 5-ethoxyoarbonyl-1,3,2-dioxalaomnne

'2 "5 \ Λ" Λ

X j ¹ - ⁰¹

H S C ^ \ ^ </

-l, 3 »2-dioxalueann ·

O ₂ H

2-chloro-4-ethoxy-5-ethboxyoartonyl-X, 3 * 2-dloxmlominn

C ₂ H ₅ OO A Al-Ol

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2-chloro-4-methyl-5-ethoxycarbony1-1,3 # 2-dloxalu ninne

CH ₃

(I A

Il

O ₂ H ₅ OC (f Äl-Cl

\ -. Qr

2-chloro-5-acety1-4-methy1-1,3, 2-dloxaluminn ·

CH,

CH

2-Ciethanaulfonyloxy-5i5-bi »- (ethioliocarbonyl) -l # 3,2-dioxalttiaanne

II C ₂ H ₅ OC

C ₉ H ₁ -OC

d 5 D

2-chloro-5-ethoxyoarbonyl-4-ph * nyl-1,3 »2-.aio3» lualan ·

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5 ■! J
Ö

AX-Eq

CH ₅₅

Al-Ol

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-1 _f 3? 2 ~

2-chloro-4-ethoxy-5-ethoxyoarbonyl-6-methyl-1 _f 3f2-dioaluminum

C ₂ H ₅ O

C ₉ H O-Q fl Al-Cl

5,5-Bi8- {ethoxycarbonyl) -2 * (p-toluene8ulfonyloxy) -l »3 _t 2-

-O ^ CH

-1.3 t2-

it CH - C

XI) ¹ - ⁰¹

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XZ) -

3 _ν 2

* G

Δ1-0Χ

O Il

C ₂ HgO-C

CH.

ix-ox

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The kotmetieohen. Means according to the invention included 0.2 to $ 30, pre-assigned 0.5 to 25 #, at least one active the protein growth inhibiting compound of the formula Ic

The anti-vision agents according to the invention

can be in various forms »in particular) in Form clay creams, pencils, in powder form or in the form of Aeroaol spray.

If the inventive means are ala creams, the concentration of active compound in the cream ▼ orssugevrelae is 0.5 to 20 wt .- #.

The creams and "oil-in-water" emulsions, which consist of about 10-30% oil and 90-70 $ water.

Among the oils, which are emulsions for the Olphaae

suitable aind, called aalen

Purcellin oil hydrocarbon oils, such as para fi n oil, / perhydroaqualene

and solutions from mlkrokrietallinaia Waohs in Ulan,

tlerlaehe or vegetable UIa, like aUaaee almond oil, Ayooado oil, Oallophyllum oil, Lanolin, Bioinua oil, horse fat, SohwalnaaohmalB and olive oil.

Mineral oils tob Siedebereioh at Atuoephärendruok 250 -410 ⁰ C.

Saturated eaters, such as iaopropyl palmitate, alkyl myratate, iaopropyl myratate, butyl myratate ₉ , cetyl myriate, headeoyl tearate, ethyl palmitate, triglyoerides of ootanic and decanoic acids and cetylrloinoleates «

Ala Olphaae can also be used in other oils.

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- Il

eon oils _? as Dime thy lpolysiloäsasi »M®tbyipä © aylp © 3, ysil © Kaii measured. Copolymare from Glykoleilifeom si »Amweatomg get ·

To the recording ö © y oil® s & ^ © gSastigeSi) team ii © tllig® phase too. Waxes * * sd © ö & SÄSULitoßöta ₉ OamäelXiXametie ₉ bees waohsj microcrystalline latte msit Os @ k @ s> it © Bttelt @ m ^

For the production of the "finä! Iageg®aäBs © ii creams köjamea fatty alcohol" t, like- stea ^ lal & ofeol ©
(1) or the like, furthermore oxätäsrlles ^ ef © t or the like for application succeeded

If the inventionsgeaIsesa Ättol M 3? Os? B vea donors are present ^ _ is Ii®
Precautionary white 0.5 to 10

The inventionsäeesB g-tifij © i © otsli © a eso Grow into which in Fora eäaos? Eismlai © m 0im © ulass ^ ig © ^ au: «= koholieche or hjöröiilkelaältsote Msmag ies» αΐ £ ^ έγο® ₅ 11® Sohweissbildung heminmdeii VdAiaimig oiagoteaefet \ 3 @ ιΊβΒ

Bb is also aSgli © is ₉ äffi ile W & Aeg © 1> @ iitisat® M of oil or fatty alcohols

In general, oil® are sis? Hes? St © llang i © s = © rfindiamgegeaässen pens usedaa Waobee _v oils imi 'alcohols like them. at the above btsetiristeem ^ a HfesrotatÜtiBg ü © t apply *

The BimlgiemltteX required for these products can be the usual ones, such as in particular Fettaaid @ ₉ ζ · Β; Mono «- ethanolamide from copra fatty acid» bioethanolamide from stearic acid or the like *

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In the case of pens according to the invention, egg G? iotrin · »proportion of a watery, alcoholic or hydroalcoholic solution of the agent inhibiting the formation of swallows 10 h \ i; SCfo in BQzng on the weight of the pen »,

Vieira the erfindungsgeniäesen means in the form of di Pn3.er _s "Compact", available _p the concentration he active Sohweieebildung the inhibiting compound is preferably from 5 to 25 percent, -96 u®b in BeBug on the total weight composition.

These powdery products contain talc, among other things or other similar substances, as well as a certain amount of a fat tea »to bind the powder obtained.

However, the coemetisobic agents according to the invention are preferably produced in the form of an aerosol spray.

These sprays can be alcoholic, dry or powdery.

In this special embodiment the concentration of active compound which inhibits the formation of vision white is generally between 1 and 3 weight percent relative to the total weight of the atomizing agent.

The alcoholic sprays in the form of aerosols contain in addition to the active compound which inhibits the formation of soot an anhydrous alcohol »such as ethanol, isopropanol, and at least one propellant gas, liquefied under pressure, such as halogen * hydrocarbon

Like the powders, the troking sprays also contain the

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active compound and the propellant liquefied under pressure talc or other similar substances as well as a certain amount of an oil or fatty alcohol *

All these embodiments of the agents according to the invention, such as creams, sticks and sprays, can also be used in others such products contain additives used in application »

The products according to the invention can furthermore contain substances that improve the stability or shelf-life, such as p-methyl hydroxybenzoate or p-propyl hydroxybenzoate and fragrances contain*

The present invention relates to further new compounds of the formula

in which E _{10 is} chlorine or -0-H "» where B ^{n can be} a methyl · ethyl, isopropyl or tertiary butyl group and -QSO ₂ R », where R ^{1 is} an alkyl group · with 1 to 4 carbon atoms Phenyl, p-chlorophenyl, p-hydroxyphenyl, p-tolyl group or a 2-03co-bornanyl (iO) "B" et sei "can, and Z (1) a heat of the formula

OH ₂ -

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-H-

in which H-

a) -COR ₅ , in which, in the case of H, is a methyl or ethyl group, R _{2 is} a methyl group, in the case of R _{5 is} a phenyl group, R _{2 is} a methyl or aoetyl group or -COOK. ', in which R ₄ represents an alkyl group with 1 to 4 carbon atoms,

b) -COQR ^, where in the case of R. has the above meaning,

R _{2 represents} a methyl group, a -CSH group or -COOR ₄ ,

c) -NO ₂ , in which case R _{2 is} bromine or an alkyl group with 1 to 3 carbon atoms and

(2) a radical of the formula

v (in)

CH- I

where in case (I) R ₇ denotes a methyl group, R ₆ denotes -COOR ₀ and B -0-R ₈ , in which R ₈ denotes an alkyl group having 1 to 4 carbon atoms and in case (II) R ₇ denotes a hydrogen atom can, and Rg has the following meaning:

e) -COR ₉ , where in the case of R _{9 is} a methyl group, R _{5 is} a methyl or phenyl group and in the case of B _{9 is} a phenyl group, R _{5 is} a methyl or phenyl group,

f) -COOR ₈ , where in the case of R _{8 has} the above meaning, R _{5 is} a methyl or phenyl group or -0-R ₈ , and

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g) -Qs -. 'Mρ where in this lall Hr means -Q-Rq.

Under d®? I si.au «a connections can in particular ι a ^r o- · led i ^ erdsni
2- "chlorine" 51 3 ~ Ms- (ethoxy carbonyl) -1 ₅ 3 ₄ 2-dio3caluraaane,

-l _s 3 _s 2

l _} 3,2-dioxalumimie ₅ 1,3,2-dioxaluiEinae * «4-methy 1-19 3,2-dioxaluminne ,

2-Matbaasulfony loxy-5 »5 ~ bis- (ethoxy oarbouyl) -1,3? 2 ~ di 5 # 5-Bls- (ethoxycarbony1) -2- (p-toluene-sulfonyloxy) -1 j3 «2 dloxalumann ©,. '

-Ί, 3,2-dioxalumanne,

2-chloro-5-yan-4-ätboxy-l, 3? 2-dioxalumian © "5-benzoyl-2-chloro-5-ethoxycarbos ^ ll, 3 ♦ 2" 2-chloro-5 "ethoxy carbonyl-5- inettayl-l _? 3 »2 2-chloro-5-ethoxycarbonyl-4-pbönyl-l, 3» 2-dioxaluminne _v 5-aoetyl-5-benzoyl-2-ohlor4il, 3 »2-dioxalunanne _t '

5-Acety1 ^ -cblor ^ -pbeny 1-1,3,2-dioxaluminne, 5-benzoyl-2-cbilor-4-methyl-> l, 3,2-dioxaluminne, 2-chloro-4-atlioxy -5-atlioxyoarbonyl-6-methyl-1,3} 2-dlos: aluminne _i 2-isopropoxy-5-bromo-5-nit S? OX »3,2-dioxalumanne

Q U-O-CH

Br / \ - O ^ S

2-Iaopropoxy-5-ethoxycarbonyl-4-ethoxy-1 _ff 3 _v 2 "aioxaluiaiaae

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5-Benzoyl-2 ~ iaopropoxy-4-methyl-l _l 3f2-dioxalumliine

5-Aoetyl-2-iaopropoxy-4-phenyl-1 »3» 2-dioxaluniiiin ·

"Ί-w

4-ethoxy-5-ethoxycarbonyl-2-isopropoxy-6-caethyl-1,3 _t 2-dioxaluminne

O ₂ H ₅ O

Al-O-CH

CH

CH ₃

S-cyano-S-ether carbonyl ^ -laopropoxy-1,3 ₁ 2-dioxalumanne

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is

O ₂ H ₅ OO _η 0 _s .

Nf ALOCH

y Al-O-CH NSC S \ _ <{

5-Oyan-4 ~ ethoxy ~ 2-iaopropo3: y ~ 1, 3 » 2-dioxaluminne

r, - \ ■

Έ a C // Al-O-CH

5-Ethoa: carbonyl-2-iaopropoxy-5-niethyl1,3,2-aio3calumanne

C ₂ H ₅ OC 1 O CH ₃

V Al-O-CH ^ CH ₃ - ^ V /

^ CH ₃ 5-A "thoxy carbonyl-2-isopropoxy-4-pheny 1-1,3» 2-dioxaluminnt

Al-O-CH

^ CH ₃

2 ₁ ^ -Dietlaoxy-S-ethoxycarbonyl-1,3 _# 2 «dioxalumione

Al-OC ₂ H ₅

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- 1β -

22Α9580

The present invention has, among other things The subject of the process is the production of the connections of the formula (IV), in which Z © inen radical of the formula (II) means and starting from a fl-glycol (1) according to the following 3ohema can be obtained.

SCHEME A

R _x CH ₂ OH R ₁ ^σΗ 2 "· ° \

^H 2 ^CH 2 ^OH

^ • OHj-O '

c Ai-O-SO ₂ R ¹ ; α Ai-ci

« ₂ CHg-O ^ (4)

R "a CH ₅ , C ₂ H ₅ , CH (CHj) ₂ or

In general, a ß-G; Ly.kol (1) with an aluminum alcoholate in equimolecular amounts in an anhydrous solvent or in a mixture of anhydrous solvents, depending on the solubility of the starting products was selected, brewed for reaction.

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~ 19 -

ß-glycols (1) used are accepted by the action of lormaldehyde on at least one Elelstrcmenacceptoreiij. produced as a compound containing carbonyl, cyano or Kltrogruppe "Mine number dieeer ß" Gly] cole are described in the literature:

R ₂ ρ

ι Organic synth., Vol.40, page (and passages cited there)

"COCH, and R ₂ = CO ₂ C ₂ Hc: Mc Murry, J.ChenuSoo, 1967, p.18O4

R ₁ ^ R ₂ = COCH ₃

R ₁ = COCH ₅ and R ₂ = CH ₅ or COC ₂ H ₅

R ₁ = NO ₂ and R ₂ = alkyl

R ₁ = CO ₂ CH ₃ and R ₂ * GH »

: Kennedy, J.Soc, Chem. 1969 * p.879 J Ardis et coil. _t JAC »S., 1950, 72,

p. 1305.

t Morgan, Chem. Ind., 1938, p.885 t Morgan, J.Ohem. Soc, 1932, p.2267

: Vanderbilt, Ind.Eng.Ohanu, 1940, 22 »34

Walker, "Formaldehyde", Reinhold, 1964 · p.291 » CA 68 P 60535 / S

It also seems unnecessary to isolate and purify the β-glycol if the groups R ₁ and E are electron acceptors, which is the case with active methylene compounds. the case is. In fact, the conversion of the active methylene compound to β-glycol of type (1) is practically completed

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quantitatively and the crude product of the reaction extracted by means of a suitable solvent is suitable in the most cases for the production of aluminum derivatives (2), (3) and (4). This procedure is particularly advantageous because it requires a minimum of work.

The reaction of an aluminum alcoholate (R ¹¹ O), Al with a compound (1) usually takes place at room temperature and is exothermic. However, it is often necessary to heat the reaction mixture to the boiling point of the solvent. The anhydrous solvents used in this reaction include: alcohols, aromatic hydrocarbons, chlorinated hydrocarbons, esters and ethers.

For the preparation of the compounds of the formula (3) and (4) it is not necessary to use the compound of the formula (2) isolate. The solutions of the compounds (2) in an anhydrous solvent can either directly by means of gaseous hydrochloric acid or dissolved in an anhydrous solvent lead to compounds of the formula (4).

These compounds of formulas (3) and (4) can be easily prepared by evaporating the one or more used in the reaction Solvent to be isolated.

The preparation of the compounds according to formula (IV), in which Z represents a group of the formula (III), where R ~ denotes a hydrogen atom, is carried out according to scheme B by initially using a compound of the formula (5) in

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Fermenting an aluminum alcoholate under the same boo
It is reacted for the preparation of the compounds of the formula (2). In this way the yerbuild of the formula (6) is obtained, which is released by simple E:. '&its; in the y bond (7) converts from formol.

SCHEME B

pG CH ₀ OH

⁵ 1 \ / ²

^υ C

I ₆ CH ₂ OH + (R ¹¹ O), Al

.o - o,

R _A -C "Al-O-Ä" HCl ⁶ \

- 0 (7)

Al-OSO ₂ R *

(9)

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The preliminary compounds of the formula (7) can usually be isolated or directly by reaction with hydrochloric acid in compounds of the formula (θ) or by means of sulfuric acid in Compounds of formula (9) are converted.

The preparation of compounds of formula (IV), in which Z represents a group of formula (III), where R _{7 is} a methyl group, is carried out according to scheme 0 by adding a compound of formula (10) in the presence of an aluminum alcoholate under the previously described conditions is reacted. This gives the compounds of the formula (11) which can be easily isolated or converted directly into compounds of the formula (13) by reaction with hydrochloric acid, or with sulfuric acid into compounds of the formula (13).

SCHEME C

^y ^ C-0 R.-CH + (R ⁿ 0), Al

CH-OH ■

(10)

i ⁵

C—— 0

Al-O-SO ₂ R 'H θ'

R _{7 7}

(13) (12)

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It must be noted that the preparation of the preconditions according to formula (IV), in which the group E ₁ ^ is chlorine, by reaction of compounds of the formula (IV) ₉ In v / which R ^ q is an alkoxy radical means with hydrochloric acid is often incomplete, effective on insufficient minimum 'dos chlorine is zurückssufuhren to the aluminum, after all S at the Umwandlungeprozentaatz always or. higher at least equal to 80 $ ·

As from the general formulas of these new compounds as well as from the following preparation instructions for the same can be determined, these connections show sweat education inhibiting effect on the special feature, in 5-position of the Dioxalumanne or Dioxaluminne ring at least one

Have a group like eater, keto, nitrile or Nitro groups act as electron acceptors.

These groups make it possible to use the products according to the invention to give excellent properties.

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In the following, the invention is explained in more detail on the basis of manufacturing regulations for the active compounds and application examples, without, however, being restricted thereto. General method of preparation of ß-slycol of formulas 1 and 5:

1 MoI of a compound having an active methylene group is mixed with 2 _f 2 to 3.0 moles of formaldehyde in a 30 # wäseerigen

Solution mixed and cooled to -? 0 ° to -10 °. At this point, 2 to B g of potassium carbonate dissolved in as little water as possible are added and the reaction mixture is kept at a temperature of 0 ° to -15 ° for 15 to 120 minutes with stirring Ether, extracted. After drying over anhydrous magnesium sulphate, the extraction solutions can be used directly for the reaction with an aluminum alcoholate according to one of the reaction elements A or B.
Manufacturing regulations

Regulation 1: Preparation of 2 ~ chloro-5,5-bis- (ethoxycarbonyl) -1,3 ₁ 2-dioxalumanne method A

A mixture of a solution of 20.4 g of aluminum isopropylate in 160 ml of benzene and a solution of? 2 g of bis (hydroxymethyl) ethyl malonate in 160 ml of methanol are refluxed for two hours with stirring. After cooling down to room temperature are 33.3 nil one to the gel obtained

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3n ~ Dissolution of dry sulphate water in the oil added and taught for an hour »

After Yer & SSSsiüig the pressure smnfen v? Ith a colorless trristellises product with a slightly yellowish reflex @ rhslt © Bo The BpotHiifet w ± ra with 1.2 mol of isopropanol as Kristsll © lk @ hol

Yield (g)
Al (m I
Cl (m

Am Gemiscli voa B ₉ Q g and 6.5 g Alm & ± miimäifi $ jlat den at lg.?iatsD.p®2?etai? geE 4.75n>-Iiös'uiiig iraa troeksaeg 'OIs added and 30 Mjnnte® & ai £ 55 ^q <S © sSai ^ ste -Is obtained at a

terhalfe 50 ⁰ C asur frookea ©

The obtained f © st © 1/2 mole of ethanol as

Yield (g) ■

Al (m Aqu / g)

Cl- (m e'q / g) "33 '

V ο r β e h r'i Π 2f aulfonyloxj-5 »5 bis (lithoxycarbonyl)» 1.3,

A Gsmiaoh from a solution voia 20 _? 4 g of aluminum iso-proteylate in 100 ml of benzene in a solution of 22 g of bis. "

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(hycii'oxyinethylj-fithylmalona-t in 100 ml of methanol. are refluxed for? hours.

Laugh, on cooling the gel obtained becomes a solution from. 9.6 g methanesulfonic acid in 50 ml methanol added. After constant stirring, it is evaporated to dryness, whereby a colorless crystalline product is obtained.

calculated * found

Yield (g). 34 34.7

Al in iQu / g) 2.94 2.90

Regulation 3 t production of 2 ~ (p-toluenesulfoxyloxy) -5 , 5 bis- (ethoxycarbonyl) ~ 1,3 »2-dioxaluiaaiine

A mixture of a solution of 22 g of bis (hydroxymethyl) ethyl malonate in 100 ml of chloroform with a solution of 20.4 g of alirainiumleopropoxide for 100 ml of chloroform is heated to 50 ° for 2 hours.

After cooling, a solution of 17.2 g becomes anhydrous p-Tcluolsulfonic acid in 300 ml of Bensol added and 1 hour touched. After evaporation to dryness «under reduced A solid white-yellowish product is obtained under pressure. Biases Product contains 1/2 mole of Ieopropanol as crystalline alcohol.

found reunited

Yield (g) 44.6 45.5.

Al (m JLqu / g) 2.20 2.22

Regulation 4i Preparation of 2-Ieopropoxy-5-ethoxycarbonyl-4-ethoxy-1,3,2-dioxmluainne A mixture of a portion of 22 g Sia-i ^ droxymet.hyl) -

Ethyl malonate in 200 ml of ketlianol and a solution of 20.4 g

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Aluminum amisopropylate in 200 ml of benzene is heated to reflux for two levels with stirring. "The mixture is then evaporated under reduced pressure" at about 0%, possibly sroeteene, and a farMoe ^ s crystalline product is obtained.

b ^ found on the right

Yield (g) 21A . _r ^ ⁶ » ⁸ -

Al (m eq / g). 3 _? β4 3 _S 64

Provision 5s producing won 2 »ÖIal © r" 5-ethoxycarbonyl ~ 4 ~ ethoxy-l ₁ 3 ₉ 2

To a suspension ~ ψ & ά 27 ₉ 4 g

carbonyl-4-ethoxy-lj3? 2 "-dioxElumiMi © in 100 ml of methanol, 50 ml of a 2N-IiQsrag tos teöokmaai ³ 0M.orwaas © raw acid in isopropanol are added and 3 times g © rtiliert _{or similar}

The solution obtained \ fird anselbii © ®send evaporated under verainäeip »tem pressure to frockeae ssid.s © © in fartloses,
crystalline product obtained with a slightly yellowish Heflex. The product contains 1/2 S201 isopropanol ale crystal alcohol. ·. *

calculated found

Yield (g) " 28.05 27.3

Al (m eq / g) 3 ^ 56 3 _f 52

Cl (m eq / g} 3.56 3.10

Regulation 6: Preparation of 2-isopoxy-5-bromo ~ 5-nitro _{-1,3 f} 2-dioxalumanne

A mixture of a solution of 20.4 g of aluminum isopropylate in 100 ml of benzene and a solution of 20 g of 2-bromo-2-nitro-propanediol (l, 3) in 100 ml of methanol is two hours

30 9.8 50/1270

uPß heated.

After -VerdE-mOfen the solvent under reduced A white powder is obtained in the drunk.

calculated found

Yield (g) 28.4 28.4

Al (m Aqu / g) 3.52 3, '38

Regulation Tt Production of 2-chloro-5-bromo-5-nitro-1,3,2-dioxalumanne

A mixture of a solution of 10.2 g of aluminum isopropoxide in 50 ml of berieol and a solution of 10 g of 2-bromo-2-nitro ~ propanediol- (1.3) in 50 ml of methanol is refluxed with stirring for 2 hours.

The reaction mixture is then brought to room temperature cooled down; 25 ml of a 2N solution are added to this mixture of dry hydrochloric acid in Ieopropanol added and stirred for 1 1/2 hours. After evaporation of the solvent under reduced pressure, a colorless product with a light beige reflex preserved. The product contains 1/2 mole of isopropanol as crystal alcohol.

found reunited

Yield (g) 14.52 14.98

Al (m eq / g) 3.44 3.35

Cl (m eq / g) 3.44 3.17

Procedure 8: Preparation of 2-chloro-5-athoxycarbonyl-A-methyl-1,3,2-dioxaluminne

A mixture of a solution of 190 g of 2,2-bis (hydroxymethyl) acetylethyl acetate in 1000 ml of methanol and a solution

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of 204 g of aluminum! soprοpylat in 1000 ml of benzene is 2 hours hoi room temperature stirred. After leaving the misery become 333 overnight? 3 Kl of a 3n ~ solution of drier Hydrochloric acid in isopropanol added and 2 hours touched. After this time, the solvent is reduced Pressure evaporated to give a yellow crystalline product. The product contains 1/2 mole of laopropanol as Crystal alcohol X.

calculated found

Yield (g) 250.5 255

Al (m eq / g) 3.98 3 »78

Cl (m Jtqu / g) 3.98 3.18

Rule 9: Preparation of 2-chloro-5-acetyl-4-methy1-1 _r 3,2-dioxaluminne

A mixture of a solution of 8 g -bis- (hydroxymethyl) -aüetylaceton in 80 ml of methanol and a solution of 10.2 g of aluminum: * se propylat in 80 ml of benzene is stirred for 5 hours at room temperature.

After this time, a 2N solution of added troil ener hydrochloric acid in isourorcanol and left standing over laughs. After evaporation to dryness, a hall-beige powder is obtained. The product contains 1/2 mole IsoTropanol as crystal alcohol.

calculated found

Yield (g} 11.02 11.5

Al in ÄCLu / g} 4.54 4 _? 32

Cl fm lqu / g) 4.54 3 _f 93 '*

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Before shrift lOi production of 2-chloro-5-cyano-5-ethoxycarbonyl-1,3 »2-dioxalumanne

A mixture of a solution of 204 g of aluminum isopropyl at in 1000 ml of benzene and a solution of 173 g of bis (hydroxymethyl) cyanäthylßcetat in 1000 ml of methanol is 2 hours at room temperature touched.

250 ml of a 4N solution of dry hydrochloric acid iii IeoprOT> anol added and stirring continued for an additional hour. After this time the product is completely dissolved. After evaporation of the A colorless crystalline product is obtained under reduced pressure. This product contains 1/2 mole Ieopröpanol as crystal alcohol.

calculated found

Yield (g) 263.5 268

Al (m eq / g) 3.79 3.70

Cl (m eq / g) 3.79 3.12

Regulation 11: Production of 5-cyano-5-ethoxycarbonyl-2-isopropoxy-dioxalumanne and 5-cyano-4-ethoxy-2-isopropoxy-dioxaXuminne

A mixture of a solution of 34.6 g of bis (hydroxymethyl) cyanoethyl acetate in 200 ml of methanol and a solution of 40.8 g of aluminum ioprodylate in 200 ml of benzene is stirred for 2 hours at cleared red temperature. After evaporation to dryness under reduced pressure, without ^{exceeding a temperature of 45 °} C., a solid, colorless product is obtained

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f Yield (g)
kl {m eqn / g) ■ calculated for Dioxalumin Dioxalum mannequin 45.4
4.40 51 _? 4th
3.86

found

49.3. 4.06

Ba a mixture is obtained which contains about 65 $ Bioxalumanne and 35 $ Dioxaluminne =
Conversion to dioxalumin

30 g of the mixture obtained in this way are in a botation evaporator at a pressure of 20 mm Hg for 2 hours 80 ° heated »

calculated found

27.72 27.18 4 _s 40 4.39

Regulation 12: Manufacture of 2-Qhlcr-5 » oys.n-4-äthozy-l, 3? 2-dioxaluminne

25.2 ml of a 1.74N solution of dry HCl in isopropanol are added to a suspension of 10 g of 2-iso-droOOxy-5-cyano-4-ethoxy-If 3t 2 ° dioxaluminum in 100 ml of methanol and stirred for one hour. After evaporation to: dryness under reduced pressure and drying at 80 °, a solid yellowish product is obtained which contains 1/2 mol of isopropyl alcohol as crystal alcohol.

calculated found

Yield (g) 10.25-10.52

Al (m eq / g) '4.27 4.08

Cl (m eq / g) 4.27 ■ 4.01

Yield (g) AI (m eq / g}

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- 52-

Regulation 13: Manufacture of 5-acetyl-2- chloro-5-methyl-1. 3t 2-dioxalumanne

A mixture of a solution of 28.8 g of 3,3-BiB- (hydroxy- * methyl) -butanone- {2) in 100 ml of chloroform and a solution of 36.7 g of aluminum isopropoxide in 100 ml of chloroform are 1 1/2 Heated at reflux for hours. After cooling, 85.7 ml added to a 2.1N solution of dry HOl in isopropanol and stirred for another hour. After evaporation to When dry, an orange-colored powder is obtained which contains 1/2 mol of isopronanol as crystal alcohol.

calculated found

Yield (g) 40 40

Al (m Xqu / g) 4.5 4.35

Cl (m eq / g). 4.5 4.22

Regulation 14t Production of 5-benzoyl-2-chloro-5-ethoxycarbonyl-1,3 »2-dioxalumanne

A mixture of a solution of 14, β g of 2,2-Bie- (hydroxymethyl) -3-oxo-3 »t) henyl ethyl propionate in 57 g of ethyl acetate (This solution is obtained by extracting the reaction product obtained from benzoyl ethyl acetate with formaldehyde, desüreohend the method used at the beginning of the manufacturing process for the production of ß-glycols was described) and one Solution of 11.94 aluminum isopropylate in 25 ml of chloroform are stirred for 2 hours at room temperature. Aneohlieeeend 12.4 ml of a 4.72N solution of dry HOl in ethanol added and stirred for another hour. After evaporation

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to dryness at reduced pressure and a temperature ^ a colorless powder is obtained. The product contains 1/2 mole Isopropanol as crystal alcohol.

calculated. found

Yield Cg) 20.1 20.5

Al (m A'q / g) 2.92 2.88

Cl (m eq / g) 2.92 2.87

Regulation 15s production of'5-ethoxycarbonyl " 2-isopropoxy-4-phenyl-1,3,2-dioxaluminne

A mixture of a solution of 7 »4 g of 2,2-bis (hydroxymethyl) -3-oxo-3-phenylethyl oroanoate in 29 g of ethyl acetate (this solution is obtained by extraction of the reaction product obtained from benzoyl ethyl acetate with formaldehyde, according to the method used at the beginning of the manufacturing process the production of ß-glycols was described) and one Solution of 5.98 g of aluminum isopropylate in 20 ml of chloroform is stirred for 2 hours at room temperature *

This mixture becomes dry under reduced pressure evaporated, the temperature should be ^ 40 °; it will obtained a white powder. ,,

found reunited

Yield (g) 8.96 9 »2

Al (m AWg) 3.26 3 * 19

Regulation 16: Preparation of 2-chloro-5-ethoxycarbonyl-4-phenyl-1,3,2-dioxaluminous method A:

To a solution of 6 g of S-ethoxycarbonyl - ^ - isopropoxy ^ -

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phenyl-l, 3,2-dioxaluminne in 15 ml of ethanol, 4.18 ml of a :: 4.7N solution of dry hydrochloric acid in ethanol was added. The mixture is stirred for 1 hour and then under reduced pressure at a temperature between 55 ° and 60 ° evaporated to dryness. It will be a white sea Powder obtained, the 1/2 hol Ieopropanol as crystal alcohol contains.

calculated found

Yield (g) 6.12 5.9

Al (m AWg) 3.20 3.23

01 (m Aqu / g) 3.20 2.93

Method B.

A solution of 2,2-bis (hydroxymetnyl) -3-oxo-3-phenylethylpropanoate in 40 ml of ether (this solution is obtained duroh extraction of the reaction product of benzoylethyl acetate old formaldehyde, according to the method as described at the beginning of Manufacturing props for the manufacture of fl-olycols described) and its solution of 19.2 β aluminum isopropylate in 50 ml of chloroform are extracted and 1 hour touched. Bs are 18.1 ml of a 5.2N solution of drier HIL added and stirring continued for 4 hours. Lake Oemisoh becomes under changed pressure and a temperature of 60 ° to the Trookene evaporated. The resulting colorless Powder contains 1/2 mole of isopropyl alcohol as crystal alcohol.

found reunited

Yield (g) 29.5 29t6

Al (m Aqu / g) 3.20 3.35

01 (m Aqu / g) 3.20 2.81

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- 55 -

Method Cs

IO g 2-chloro-5-ethoxycarbonyl-5-benzoyl-1,3j2-dioy.aluTnaiine are heated to a temperature of 65 ° under reduced pressure for 1 hour »9-2 g of a white powder are obtained (theoretical yield = .9 »13 g.) ·

found calculated -

Al (m eq / g) "3.20 3.1?

Cl (m eq / g) 3.20 2.82

Provision dioxalumanne 17 2-S Preparation of 5-Beti2oyl »2-isopropoxy-4-methyl-l, 3 _f and / or 5-Acetyl-2-isopropoxy-4-phenyl-l, 3" 2-dioxaluminne

A mixture of 12.98 g of Benzoylacetort, 24 g of a 30% aqueous solution of formaldehyde and''20 ml of dioxane is cooled to -10 °, then a solution of 0.4 g of potassium carbonate in 1 ml of water is added and the mixture If a temperature of 0 ° to -5 ° is maintained, the mixture is stirred for 1 hour = the solution obtained is saturated with .8 g of ammonium sulfate and extracted twice with ethyl acetate. The extract v / ith -But anhydrous magnesium sulfate to give 74 "6 g of an 25 _S # 8" · solution of 2 »2-bis (hydroxymethyl) -LT) henyl ~ butandioii- (l _f 3) in ethyl acetate is obtained.

30.1 g of this solution are kept at room temperature for 4 days Stir with a solution of 7 »15 g of aluminum isopropoxide in 15 ml Treated with chloroform. After evaporation to Sroekene under reduced pressure at a temperature of 50 °, a yellow Powder received.

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Yield 3 g) Al (m Ä

2249580 calculated ge f. and e 9.66 9-52 3.62 3.61

Prescription 181 Preparation of 5-benzoyl-2-chloro-4-methyl-1,3,2-dioxalumin and / or 5-acetyl-2-chloro: e-4-dhenyl-1,3,2-dioxaluminne

4.8 g of the product obtained according to regulation 17 are suspended in 10 ml of ethanol and 3.7 ml of a 4 _f 7N solution of dry HCl in ethanol are added. This mixture is stirred for 30 minutes and then evaporated to dryness under reduced pressure at a temperature of 60 °, v / o a yellow powder is obtained which contains 1/2 part of isopropanol as crystal alcohol.

calculated found

Yield (g) 4.92 5.09

Al (m eq / g) 3.54 3.46

Cl (m eq / g) 3.54 2.97

Regulation 19 «Production of 5-acetyl-5-benzoyl-2-chloro-1,3,2-dioxalumanne

A mixture of a solution of 30 _? 1 ml of 2,2-bis- (hydroxymethyl) -l-dhenyl-butanedione- (l, 3) in ethyl acetate according to regulation 17 and a solution of 7 _{t of} 15 g of aluminum isopropylate in 15 ml of chloroform is stirred for 4 days at room temperature. 7.45 ml of a 4.7N solution of dry hydrochloric acid in ethanol are added and stirring is continued for 1 hour. The solution obtained is evaporated to dryness under reduced pressure and at a temperature ^ 40 °;

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a yellow powder containing 1/2 mole of isopropanol is obtained contains as crystal alcohol. '

calculated . found

Yield (g) 10.94 10.86

Al (m eq / g) " 3.20 3.20

Cl (in eq / g) ■ ■ 3.26 2.82

Regulation 20: Preparation of 5-benzoyl-2-chloro-5-methyl-1,3,2-dioxalumanne

a) Production of β, β-bis (hydroxymethyl) priopiohenone

A mixture of 26.8 g of propiophenone, 45 g of a 40 # strength aqueous solution of formaldehyde, 40 ml of ethanol and 1 g of potassium carbonate is heated on a boiling water bath for 15 hours. The reaction mixture is then poured into 250 ml of water and extracted with methylene chloride. The organic extract is washed with water and dried over anhydrous magnesium sulfate. After evaporation of the solvent, 32.7 g of an oil are obtained which is purified by column chromatography on silicon dipoxide (Mallinckrodt 100 mesh). 11.8 g of a product are obtained in this way, which crystallizes from isopropyl ether in the form of white needles which melt at 78 °.

b) Production of 5 ~ benzoyl-2-chloro-5 ~ methyl-1,3,2-dioxalumanne

A mixture of a solution of 0.73 g $, ß-bis (hydroxymethyl ) -prox) iophenone in 100 Eil ethyl acetate and a solution 0.77 g of aluminum isopropoxide in 5 ml of chloroform is heated on a boiling water bath for one hour. Well that

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- 3β -

0.8 ml of a 4.75N solution of dry HCl in Ethanol added and after a reaction time of 30 minutes evaporated to dryness at reduced pressure; it will be a yellowish powder obtained because 1/2 mole of Ieopronanol as Contains crystal alcohol.

calculated found

Yield (g) 1.07 1.03

Al (m eq / g) 3.52 3.52

Cl (m eq / g) 3.52 3.32

Regulation 21: Preparation of 5-ethoxycarbonyl-2-ieoOropoxy-5-methyl-1,3,2-dioxalumanne

A mixture consisting of a solution of 2.93 E of 2,2-bis (hydroxymethyl) ethylT) ropionate in 20 ml of ethyl acetate and a solution of 3.7 g of aluminum isopropylate in 20 ml of chloroform is refluxed for 60 minutes.

After evaporation to dryness under reduced pressure a white powder is obtained.

calculated found

Yield (g) 4.45 4.20

Al (m eq / g) 4.06 4.23

Regulation 22 ι Production of 2-chloro-5-ethoxycarbonyl-5-methyl-1,3,2-dioxalumanne

A mixture consisting of a solution of 6.4 g of 2,2-bis- (hydroxymethyl) -äthylOrOT) ionate in 15 ml of ethyl acetate and a solution of 8.1 g of aluminum isoylate in 25 ml of chloroform refluxed for one hour. After cooling, 8.4 ml of a 4.75N solution of dry HCl in ethanol are added and

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! Hour stirred. After "evaporation to dryness" at reduced pressure, a solid, colorless product is obtained which Contains 1/2 mole of isopropanol as crystal alcohol.

calculated found

Yield (g) ^{10 10}

Al (m-eqxi / g) "3.95 '/ 4.02 -

Cl (m KqVg). . 3.95 -3.2?

Regulation 23: Preparation of 4 ~ ethoxy-5-ethoxycarbonyl-2-isoT> ropoxy-6-i> iethyl-1, 3 * 2-dioxaluminne

A solution of H, 8 g (1-hydroxyethyl) ethyl malonate (F. Gaudemar-Bardone and M. Gauderaar, BuXl.Soc.Chim., 1968, P. 2878, A. Eoesch, BulloSoc, 1937, p. 1643) and 11.8 g of aluminum isopropylate in 30 ml of chloroform is 2 hours at 50 ° heated »Connection takes place at reduced pressure and one Temperature of 80 to 85 ° to dryness Ibinedevampft, with a yellowish transT> arente semi-solid Snfestana is obtained.

calculated found

Yield (g) 16.7 x 16.8

Al (m eq / g) 3.4? 3.45

Regulation 24: Preparation of 2-chloro-4-ethoxy-S-ethoxycarbonyl-ö-methyl-l, 3,2-dioxaluminne

A solution of 14.6 g of that obtained according to regulation 23 Product in 50 ml of ethanol is stirred for 30 minutes with 10.7 ml of a 4.75N solution of drier HCl treated in ethanol. The solution obtained is at reduced Pressure and a temperature of 7.0 ° evaporated to dryness. A beige solid product is obtained,

3,098 50/1270

_ 40 -

which contains 1/2 mole of isopropanol as crystalline alcohol <,

calculated found

Yield (g) 14.7 14.0

Al (m eq / g) 3.4 3.53

Cl (m eq / g) 3.4 2.97

Regulation 25: Preparation of P, 4-D5äthoxj-5-ethoxycarbonyl-1,3,2-dioxaluminne

A mixture consisting of 4.4 g of 2,2-Bi8- (hydroxyr; ethyl} -äthylmalona-fc and 3.24 g of aluminum ethylate in 70 ml of ethanol is heated to boiling for 1 hour. After evaporation to dryness a colorless powder is obtained when the bridge is reduced.

calculated found

Yield (g) 5.20 5.21

Al (m eq / g) 3.85 3.86

309850/1270

22Λ9580

Execute exercise! games

Example 1: According to the invention there is a cream
with anti-icing effect of the following composition:

Stearyl alcohol oxyethylene with 15MoI ethylene oxide .... 1.2 g

Whale rat 4 g

XsOO propyl myristate 3 g

Silicone oil (density 25 ⁰ O = 1.05-1.08;

Calculation index ex = 1.485-1.495) <. 0.5g

p-hydroxymethyl benzoate ö, lg

p-hydroxypropyl benzoate "0.1g

Fropylene glycol ..... <, 2.0g

2-chloro-5,5-bis (ethoxycarbonyl) -1,3,2-dioxalumanne '... · 2, above

Fragrance 0.5g

Make up to 100 g with water

Example 2: According to the invention, a stick with perspiration-inhibiting effect is made of the following composition
prepares:

Stearyl alcohol 10 g

Microcrystalline wax 4 g

Paraffin 10 g

Monoethanolamide of copra fatty acids 10 g

Stearic acid diethanolamide ....... <,., XO g

2-octyl-dodecanol- (l) 10 g

ProBylene glycol ₀ "20 g

Ethyl alcohol 20 g

Fragrance .. *. "...... 1 g

2-chloro-5,5-bis (ethoxycarbonyl) -l, 3,2-dioxalumanne «■ ... 5 g

Example 3: A stick with perspiration-inhibiting effect of the following composition is inventive
prepares: \

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Stearic acid diethanolamide, 5, *;

One oxäthylenierte with 13 moles of ethylene oxide

Mixture of 30 # cetyl alcohol and 7O? 6 stearyl

alcohol ........ ₉ £ 10

Water 20 g

Microcrystalline wax , 5 g

Paraffin oil 10 g

Perhydrosqualene 3 g

Beeswax 5 g

Ethyl alcohol 36 g

? -Chlor-4-ethoxy-5-ethoxycarbonyl ~ 1,3t2-dioxaluminne _a 5 g

Fragrance 1 g

Example 4: For the production of an according to the invention The following mixture is prepared for alcoholic sprays:

Hexachlorophene,. " 0.1g

2-chloro-4-methyl-5-ethoxycarbonyl-1,3,2-dioxaluminne. 5.2g

Fragrance .... ο., ₀ , 1, Cg

absolute alcohol 93.7g

50 g of this mixture are conditioned with 50 g of dichlorodifluoromethane in an aerosol container.

In like manner an excellent alcoholic spray is obtained when the 2-chloro-4 '-πlethyl-5-äthoxycarbonyll, 3 _J 2-dioxaluminne in the preceding example, the following compounds replaced:

5,5-bis (ethoxycarbonyl) -2- (p-toluenesulfonyloxy) -1,3, 2- dioxalumanne

5-Benzoyl-2-chloro-4-ethyl-1,3 "2-dioxaluminne 2-chloro-4-ethoxy-5-ethoxycarbonyl-6-methyl-1,3 * 2 ~ dioxalumnne

Example 5: For the production of an inventive The following mixture is recommended for alcoholic sprays:

309850/1270

Yer-'oincLung the formula '

ei f / Ks * o - / ^ k σι

W W / ί ί

Cl - OH ν 0.15g

2 ~ chloro-5-acetyl-4-methyl-l _? 3 »2-dioxalumin. 4 »0 g

Fragrance 1.0 g.

oxethylated lanolin ..... *. ° ................. _o 0.5 g - ■

Make up with absolute alcohol to .. “100 g

35 g of this mixture are then mixed with 40 g of trichlorofluoromethane and .25 g of dichlorodifluoromethane conditioned in an aerosol container.

In the same way, an excellent alcoholic spray is obtained if in the previous example the 2-chloro-5-acetyl "4-methyl-1 _f 3,2-dioxaluminne is replaced by the following compounds"

2-chloro-4-ethoxy-5-ethox; y.carbonyl-6-methyl-1,3 * 2-dioxaluminous 5-acetyl-5-benzoyl-2-chloro-1,3? 2 «
5 »Asetyl-2-chloro-5-methyl-1, 3
5-Benzoyl ~ 2-chloro-5-ethoxyear "bon3rl-l» 3 »2-diöxalumaraie.

B e i s ό i e 1 6s for the production of a device according to the invention dry sprays with perspiration inhibiting effect the following mixture is prepared: '■

2-chloro ~ 5-cyano-5-nitro-1,3 »2-dioxalumanne. 35 g

Colloidal silica 3 g

Fragrance 7 g

Make up to 100 g with isopropyl palmitate

10 g of this mixture are mixed with 45 g of Sriohloxfluormethau and 45 g Diehl ord if luormethaa conditioned in an aerosol container »

3 0 9 8 5 0/1270

Example 7i for the production of a Trooke sprays with perspiration inhibiting effect the following mixture is prepared ";

5-acetyl-2-chloro-4-phenyl-1,312-dioxaluminne 35 g

Colloidal silica 3 g

Fragrance T g

With triglycerides of fatty acids with 8 to 12

Fill up the carbon atoms to 100 g

10 g of this mixture are then conditioned with 45 g Tr i chlorofluoromethane and 45 g of dichlorodifluoromethane in an aerosol container.

Example 8: To produce a dusty dry opray according to the invention, the following mixture is prepared:

5-Benzoyl-2-chloro-5-raethyl-l _f 3 _f 2-dioxalumanne 3.5g

Hexachlorophene * 0.1g

Talc 0.3g

Fragrance 0.2g Isopropyl Palmitate Ii2g Trichlorf luorraethane, 47 ₁ 35g Dichlorodifluoromethane 47 »35g

Example 9s The following mixture is used to produce a dusty dry spray according to the invention prepare!

2-chloro-5-ethoxycarbonyl-4-phenyl-1,3 »2-dioxaluminne .. 3 _f 5 g

Hexachlorophene O ₁ I g

Fragrance 0.2 g

Starch ester 0.3 g

Silicone oil Ir ² g

Trichlorofluoromethane 47.35g

Dichlorodifluoromethane «47.35g

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Example 10: To produce a dry spray according to the invention in the form of talc, a mixture is used as follows! ita composition prepares:. Trioleate of sorbitol (viscosity at 25 ° C = 250 cp *>, ratio of the hydrophilic and the lipophilic portion βϊΙ & / = 1.8) ♦ 4.0g

Isopropyl myristate «... 6.5g

Odorless kerosene 8.0g

Polyethylene glycol (P.M. = 400} 4.Ό3

Colloidal silica ₀ 4.0g

Mikrotalk (5 / u) 52, above

Fragrance 1.0g

2 ~ chloro-5-bromo-5-nitro-1 _f 3,2-dioxalumanne 20.0g

10 g of this mixture are then conditioned with 45 g of trichlorofluoromethane and 45 g of dichlorodifluoromethane in an aerosol container.

In the same way, an excellent dry spray is obtained if, in the previous example, the 2-chloro-5-bromo-5-nitro-1,3,2 "dioxalumanne with 2-Metfaftnsulfonyloxy-5,5-bis- (ethoxycarbonyl) -l _f 3 »2-dioxalumann is replaced.

Example lit For the preparation of a erfindungegemässesn stodorizing talc in the form of a spray the following mixture is prepared *

Sorbitol trioleate t ......... 4.0 g

Isox> ropylrr, yristate · ........ ·· «6.5 g

Odorless kerosene .... ,, 8.0 g

Polyethylene glycol (P.M. = 400) 4.0g

Colloidal silicon dioxide _c 4.0 g

Microtalk (5 / u). _β . _βο . _{0, 0,} 22.5 g

Fragrance. _0. <, .... * ... <> 1.0 8

2 ~ chloro-5 "cyano-4-ethoxy-1,3,2-dioxaluminne 50.0 g

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10 g of this mixture are then mixed with 45 g of tri) ilo: ■ fluoromethane and 45 g dichlorodifluoromethane in an aerosol container conditioned.

Example 12: For the production of a "Compakt" powder is prepared as follows:

Talk TO, Og

Lanolin 2.5g

Vaseline oil <> 2.0g

Fragrance 0.5g

2-chloro-5-ethoxycarbonyl-5-methyl-1,3,2-diox-

alumanne 25 »Og

309850/1270

Claims (2)

Claims 1. Cosmetic, anti-perspiration agent, gekennaeichnet in that it is in a cosmetic carrier substance at least one active compound of the formula Z Al-H (I), contains, where R is chlorine or -OSOgE ¹ , R ^{1 is} an alkyl group with 1-4 carbon atoms, a phenyl, p-chlorophenyl-e p-hydroxyphenyl, p-tolyl group or a 2-oxolsomaiiyl- (10) - represents rest and Z
1) a residue of the general formula OH ₂ T in which R ^ a) -COR ,, where in the case of R, a methyl or ethyl group represents, Rg is a methyl group, but in the case of R ~ represents a phenyl group, Rg a methyl or acetyl group or -COOR. where R ^ is an alkyl group with 1 to 4 carbon atoms, b) -COOR., where in the case of R, the meaning given above has, Rg is a methyl group, a -C Ξ N group or -COOR. 3,098 50/1270 ~ 48 - means,
c) -NO ₂ , where R "is bromine or an alkyl group with 1 to 3 carbon atoms means » 2} a residue of the general formula (Ill), CH- where in all (I) R ^ is a methyl group, Rg is -COORg and Rc is -0-R ₈ , where R _{8 is} an alkyl group with 1 to 4 0 atoms and in the case (II) R ^ is a hydrogen atom and Rg e) -CORgt where Rc »in all Hq is a methyl group, a Represents methyl or phenyl group and in the case of Rq a Represents a phenyl group, a methyl group let, f) -COOR ₈ , where R _{5 is} a methyl or phenyl group or -0-R ₈ , where R _{8 has} the above meaning, g) -C = I, where R ₅ denotes -0-B ₈ * represents 2. Agent naoh claim 1, characterized in that it contains at least one of the following active compounds: 2-chloro-5 »5-bis (ethoxycarbonyl) -1,3» 2-dioxalumanne 2-chloro-5-cyano-5 -äthoiycarbonyl-l, 3,2-dioialuinanne 2-chloro-5-bromo-5-nitro-l, 3 ₁ 2-dioaalueanne 2-CbloΓ-5-ätho * fevt-Butyloxycarbonyl 4-ethoxy-l, 3,2-dioxaluminne 309850/1270 22Λ9580 2 ™ Clilor'-5-a- £; hoxycarbonyi-4-niethyl ~ l. 3,2-äioxaluminne 2-chloro-5-acetyl-4-niethyl-l, 3, 2-dioxaluminne 2-Me-5,5-thaneulf onylozy Ms-C ethoxy carbonyl) -1 ₃ 3 »2 ~ dJ.oxaluBiam : .e 5 s 5-bis- {ethoxycarbonyl) -2-p- {toluenesulfonyloxy} -1.3 _? 2- diosalumanne 5-acetyl-2-chloro-5-niethyl-l _> 3 , 2-dioxalumanne 5 ~ benaoyl-2-chloro-5-metbyl-l, 3 »2-dioxaluoanne 2-chloro-5-cyano ~ 4-ätb, osy-l _i 3i2-dioxaliualnne 5-BQnzoyl-2-chloro-5-ethoxycarbonyl-l, 3 »2-dioxalumanne 2-chloro-5-ethoxy carbonyl-5 ~ iaetlQrl-l» 3 »2-dloxalumanne 2-0hlor- 5-a-thoxycarbonyl-4-phenyl-1, 3,2-aioxalumiBae 5-Acetyl-5-benzoy 1-2-chloro-1, 3 »2-aio3Ea ^ utBBBn · 5-Acetyl-2-chloro-4- phenyl-1 _f 3,2-5: ioxaluminne 5-benzoyl-2 ~ chloro-4-ethyl-l ₁ 3 »2-dloxftluainne 2-chloro-4-ethoxy-5-ethoxy carboc ^ l ~ 6-methyl-r 1,3,2-di oxaluminne 3. Composition according to one of claims 1 and 2, characterized in that the concentration of the active compound BWisehen 0.2 and 30 pounds, preferably between 0.5 and 25 $ . 4. Agent according to one of the preceding claims, characterized in that it is in the form of creams, sticks, powders or aerosol tablets * in the form of a cream, 5. Agent according to one of claims 1 to 4 / characterized in that that ea is preferably about 0.5 to -20 the active compound as an emulsion of the type "Wassep ™ in-Oil" contains. '' 309850/127 0 6. Composition according to claim 5, characterized in that the emulsion consists of about 10 to 30 ^ oil and 90 to 7OJt water consists. 7. Agent according to one of claims 1 to 4 in the form of pins, characterized in that it is preferably 0.5 to 10 wt. # Of the active compound in the form of an emulsion in aqueous, alcoholic or aqueous-alcoholic solution to which melted waxes have been added. 8. Agent according to one of claims 1 to 4 in the form of a • "Compact" powder, characterized in that it is preferred 5 to 25% by weight of the active compound in admixture with talc or another similar substance. 9. Agent according to one of claims 1 to 4 in the form of an aerosol spray, characterized in that it is preferably 1 to 5% by weight of the active compound and a propellant gas liquefied under pressure, such as halogenated hydrocarbons. 10. Means according to claim 9 »characterized in that It is also an anhydrous alcohol such as Xthanol or Contains isopropanol. in the form of a dry spray, 11. Means according to claim 9, / characterized in that it includes talc or another similar substance contains. New compound, characterized in that it corresponds to the following formula: 309850/1270 Z Al-E ₁₀ (I?) in which E ^ q is chlorine or -0-B ", where E" can be a methyl, ethyl, isopropyl or tertiary butyl group and. -OSO ₂ E ¹ , where E ^! an alkyl group with 1 to 4 carbon atoms can be a phenyl, p-chlorophenyl, p-hydroxyphenyl, p-tolyl group or a 2-oxo ~ bornanyl- (10) -Reate and 'Z (!) is a best Pormel H _k OH ₂ - '(II) _t OH ₂ - in which B ^ } a) -COB, where ia lall © £. © in® is a methyl or ethyl group, B _{2 is} a methyl group, in the case of IU is a phenyl group, E _{2 is} a methyl or acetyl group © or -COOB *, where B * is an alkyl group with 1 to 4 carbon atoms represents. b) -COOB. is, where in the case B _- , has the above meaning, E _{2 is} a methyl group, a -C = Η group or -C00E ^, c) -HO ₂ , where in this .Halle E _{2 is} bromine or an alkyl group with 1 to 3 carbon atoms and (2) a best of the formula 3Q9850 / 127Q C- CH- I (in) where in case (I) Ry is a methyl group, H _{6 is} -COOE ₈ and Rc is -O-Rq, where Rq is an alkyl group with 1 to 4 carbon atoms and in case (II) R «can be a hydrogen atom, and Rg has the following meaning: e) -CORq, where in the case of R «is a methyl group, E _{R is} a methyl or phenyl group and in the case of Rq is a phenyl group, R ^ is a methyl or phenyl group» f) -COORg, where in the case of Rq has the above meaning, Rc denotes a methyl or phenyl group or -O-Rq, and g) -C = H, in which case Hc is -O-Rg. 13 * Seue connections according to claim 12, 2-chloro-5,5-bis- (ethoxycarbonyl) -1,3,2-dioxalumanne 2-chloro-5-cyano-5-ethoxycarbonyl-1, 3,2-dioxalumanne 2-chloro-5-bromo-5- nitro-1,312-dioxalumin 2-Ohlor-5-ethoxycarbony1-4-ethoxy-1,3,2-dioxalumin 2-chloro-5-ethoxy carbonyl-4-methyl-1,3,2-dioxalumin 2-chloro-5 -acety1-4-methyl-1,3,2-dioxalumin 2-methanesulfonyloxy-5,5-bis (ethoxycarbonyl) - !, 3,2-dioxalumanne 2-isopropoxy-5-bromo-5-nltro-1,3 , 2-dioxalumin, 2-isopropoxy-5 ~ ethoxycarbonyl-4-ethoxy-l _t 3,2-dioxalumin 309850/1270 5,5-Bi β- {ethoxy carbonyl) -2- {p-toluenesulfonyloxy) -1,3,2-dioxalumanne 5-acetyl-a-chloro-S-methyi-l, 3,2-dioxalumanhe 5-benzoyl-2-chloro-5-methyl-1,3,2-dioxalumanne-2-chloro-5-cyano-4-ethoxy -l »3,2-dioxalurainne 5-benzoyl-2-chloro-5-ethoxycarbonyl-l, 312-dioxalumanne 2-0hlor-5-ethoxycarbonyl-5-methyl-l, 3 * 2-dioxalumanne 2-chloro-5- ethoxycarbonyl-4-phenyl-1,3 * 2-dioxaluminne S-acetyl-S-benzoyl ^ -chlor-1,3s2-dioxalumanne 5-acetyl-2-chloro-4-pbeny1-1,3,2-dioxaluminne 5 -Ben2oyl-2-chloro-4-methyl-1,3,2-dioxaluminne 2-chloro-4-ethoxy-5-ethoxyoarbonyl-6-methy1-1,3j2-dioxaluminne 5-benzoyl-2-isopropoxy-4-metbyl -l, 3 % 2-dloxaluminne S-acetyl ^ -ieopropoxy ^ -pbenyl-1,3 »2-dioxaluminne 4-Ä'ttaoxy-5 ~ ethoxycarbonyl ~ 2-isopropoxy-6-diethyl-1,3, 2r · dioxaluminum 5-cyano-5-äthoiycarbonyl-2-ieoprqpoxy-l, 3 * 2-dioxalumanne 5-0yan-4-ethoxy-2-isopropoxy-l, 3 "2-ethoxy-5 dioxaluminne parbonyl ^ -isopropoxy - ^ - methyl- 1.3 * 2-dloxaluminum 5-Xthoxyoarbonyl-2-isopropoxy-4-pheny1-1,3 »2-dloxaluminum 2,4-dlätboxy-5-ethoxycarbonyl-1,3,2-dioxaluminine. 14 · Process for the preparation of connections of the ormel IV according to claim 12, characterized in that ß-glycol or a ß-keto alcohol with an aluminum alcoholate in one anhydrous solvents or in a mixture of such solvents is brought to reaction and the reaction product 309850/1270 after any conversion carried out either is subjected to the action of dry hydrochloric acid or sulfuric acid. 15. The method according to claim 13, characterized in that preferably equimolecular amounts of ö-ßlykol or a ß-keto alcohol can be reacted with an aluminum alcoholate. 16. The method according to any one of claims 13 and 14, characterized in that the anhydrous solvent Alcohols, aromatic hydrocarbons, chlorinated hydrocarbons, esters and ethers are used. 17. The method according to any one of claims 14 to 16, characterized in that the ß-glycol is used in the form of an extraction solution of the reaction product formed by the action of an active methylene compound on formaldehyde. L'OREAL in Baris represented by: 2.10.72 / Ing.Kr / E 309850/1270