DE1543065B1 - 7-acetyl-2a, 3,4,5-tetrahydro-1,1,5,5-tetramethylacenaphthene, process for its production and use as a musk fragrance - Google Patents

Description

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It has been found that the new compound can be removed by the 7-acetyl-2a, 3,4,5-tetrahydro-l, l, 5,5-tetramethylace formula:
naphtha have a strong, musky odor
and is well suited for use in perfume compositions. 5 ..,

The process for producing the aforementioned Ace- y ^x \

naphthens is a four step process. It consists of ₍ \ ,;

that 1,1-dimethyltetrahydronaphthalene in itself _χ '\

known way with sulfuryl chloride, N-chlorine or

-Bromo-succinimide, N-chloro- or -Bromo-phthalimide, ίο £ "V <tt

tert-butyl hypochlorite or molecular chlorine or ^{3 3}

Bromine at about 25 to 60 ⁰ C and under action

free radical forming agents for 1,1-dimethyl- _{reproduced; in which} χ _{chlorine or bromine means} 4-chloro or -bromo-tetrahydronaphthalm reacts, which _{in the next stage deg according to the invention}

_{The received halogenated connection is disconnected} and the result is i, i. _D imethylhalogentetralin with MethmitMethallyl-magnesmni chloride or bromide to _a i _ _{Iylmagnesmmchlorid or bromide,} for example a known manner, the U-DimethyM-methaHyl- _dnem ^& _G rignard reagent reacted. Preferably produces tetrahydronaphthalm, the separated meth _is ^ _Grignard . _{Reagent uses chloride} . Al ylverbmdungm known per se with sulfur _{The reaction is most} expediently by random acid or polyphosphoric acid as cyclization ao _{fee deg Halo} ^s _{gentetralins in e} in the middle of the reaction solution to 2a, 3,4,5-tetrahydro-1,1,5,5-tetramethyllace - converts ^^ ^ _be ispielsweise diethyl ether or Tetranaphthen, these compounds are separated _{hvdrGfuran and} \ _ngdähr i_ _{to unge} ferry 4stündiges and one manner known per se with a Acetylionen _{cooking Mischl ng} of although it is not f _{under Rücki} f _USS performed, providing compound m the presence of is essential, but a Über-Fnedel-Crafts catalyst for the 7-acetyl derivative * _{5 shot of} the Grignard reagent is used to ensure conversion. as complete as possible implementation of the expensive

In the first reaction stage, 1,1-dimethyl _{entetralins is used} .

tetralin m the 4-position with one of the mentioned ^ _{6 on diege ψξ} . _The compound produced is a halogenating _agent, which replaces a hydrogen atom on an allyl carbon atom for a hydrogen atom
cause a halogen atom, halogenated. All these

Halogenating agents react after a free CH ₃

Radical trending mechanism, the ^;

Radical by light, a peroxide, or other CJj ₂ C = <

known means is generated. The reaction 35 j

can therefore be referred to as free radical halogenation \ /

will. j ^

Preferably the chlorine compound is prepared: j

because they are easy in good yield from without difficulty- / X, /

available halogenating agents 40 / \

can be. CH ₃ CH ₃

Tert-butyl hypochlorite is preferably used to produce the chlorine compound. The implementation
will be with or without a opposite of the reaction

inert organic solvent carried out. Will be played 45. She can come in after anyone If such a solvent is used, it may be separated from conventional processes, do not have any hydrogen atoms which are

tion conditions are substitutable. The preferred lins for the formation of 2a, 3,4,5-tetrahydro-l, l, 5,5-tetra-wise used solvents are aromatic methylacenaphthene is brought about by sulfur or poly compounds, such as benzene or fully phosphoric acid. Preferably 80 to constantly halogenated solvents, such as 95 ° / _o sulfuric acid used. Carbon tetrachloride. In a preferred embodiment, the

proceed with a large excess of dimethyltetralin product the reaction described above is carried out with no solvent. The dimethyl such a rate of 88 ° / _o by weight Schwetetralin exerts the function of both a reactor 55 feisäure added such that the reaction mixture tion component as well as a ^ solvent at a temperature of about 5 to about 15 ⁰ C, from. if necessary by using external cooling,

The reaction time and temperature are not kept critical. Response time isn't critical to it table, as the best yields are obtained immediately after combining, if the reactant produces some product. To 60 the reaction mixture after a further 1 to 4 hours Achievement of satisfactory yields in practice after addition of the product is stirred, is, however, a reaction between about 25 and The amount of cyclizing agent is not critical

about 6O ⁰ C for a period of 1 to table. Preferably, however, equal weight hours are preferred. The most economical amounts of sulfuric acid and starting compound apply process conditions to achieve high yields. Up to 100 weight percent excess of lie with a reaction time of about 2 hours concentrated sulfuric acid, based on the overall and a temperature of 30 to 40 ⁰ C. weight of the starting compound, may also for

The product that can be used after any of the usual to get good results.

ORIGINAL INSPECTED

3 4

The product obtained can be processed according to one of the customary processes used in the cosmetic industry to be isolated. It has the formula: most diverse media is not changed. Of the

Fragrance according to the invention can therefore perfumes,

^a soaps, detergents and various lotions

5 can be added. Its importance lies above all in the fact that it makes a new class of musk fragrances accessible to the perfume chemist, which differ in character and odor nuances from the products currently on the market. The perfume manufacturer therefore has a new odor-CH ₃ CH ₃ component through the compound according to the invention, which offers him the possibility of novel

To produce fragrance mixtures.

In the final procedural stage, the.

Product of the reaction described above 15 Example

under Friedel-Crafts conditions with an acetyl A. In a 500 ml three-necked flask fitted with a

Ion-supplying compound, for example with acetyl thermometer, stirrer and funnel (which is acetylated against chloride or acetic anhydride. The reaction is protected from light), 265 g of dimethyltione are conveniently presented in a manner related to the tetralin. The flask is irradiated by means of a reaction inert organic solvent through a 20 60 watt bulb passed approximately 1 cm from the flask, for example, hydrocarbons, nitro-attached, are removed. The dimethyltetralin hydrocarbons or halogenated hydrocarbons are ^{heated to 40 0} C; with vigorous stirring materials such. B. 2-Nitropjopan, Nitrobenzol, Tetra, 52 g of tert-butyl hypochlorite within a chlorocarbon or ethylene dichloride are suitable. Added hour in small amounts. The carbon disulfide reaction can also be used. 25 is slightly exothermic, the temperature is preferably kept at 30 to 40 ⁰ C with the help of the organic reaction parts of a water bath. After the addition of the selected solvents has ended, the reaction mixture is further taken, whereupon the Friedel-Crafts catalyst is stirred for 45 minutes. The excess Dimethylbeispielsweise aluminum chloride or boron trifluoride, in tetralin is added by fractionation at a Temgeringen amounts, the temperature-maintained for 30 temperature in the top of the column of 73 ⁰ C and a temperature of about -5 to about 10 ° C temperature in the distillation vessel of 96 ° C for one. The reaction time depends on the amount of pressure removed from 1 mm Hg, with the desired reactant. Product is obtained as a residue. This product is

When the addition of the catalyst is complete, the crude chlorodimethyltetralin becomes.

Mix the mixture for a further 1 to 4 hours to complete the reaction. The reaction is stirred thoroughly with dry nitrogen. A slight excess of rinsed 2-1 three-necked flask, which is provided with a stirrer, acetylating agent can be added to ensure a thermometer, reflux condenser and funnel as complete conversion as possible, 30 g of magnesium turnings, 300 g of this excess is however not essential. In all- ether and 7 g methallyl chloride given. Is common after the beginning approximately one in respect to the forward 40 the implementation of the flask is cooled to ⁰ C 3, lying Acenaphthenmenge equimolar catalyst used and a solution of 93 g of methallyl chloride in quantity. 470 g of ether over a period of 4 hours

The compound prepared in this way will be added at a temperature of 0 to 5 ° C, according to one of the Friedel-Crafts reactions known- The reaction mixture is at this temperature th procedure isolated. It is given by the formula: 45 another 7 hours and then overnight at

Stirred at room temperature. Transfer the Grignard reagent to another flask under nitrogen (Excess magnesium is removed) and a solution of 76 g of the crude chlorodimethyltetralin 50 (obtained by the method described under A) in 500 ml of ether for a period of time added under reflux for 1 hour. The reaction mixture is taking a further 2 hours Maintained reflux, cooled, and poured into a stirred solution of 750 ml of water, 500 g of crushed ice and poured 200 g of ammonium chloride. The aqueous layer is removed and extracted with 250 ml of ether, reproduced. The united layers of ether become with one

The compound according to the invention can be washed onto the 10% strength ammonium chloride solution, whereupon the solvent is removed in the same way as other musk-like compounds. The residue is fertilized alone or in admixture with other stocks - distilled at 2 mm; 61 g of 1,1-dimethyl parts are used here. You can get, for example, in 4-methallyltetralin: nf - 1.5275, boiling point perfumes, lotions, powders, soaps, etc. a 106 ° C / 0.4mmHg.

or contain several odorous or aromatic substances- C. With vigorous stirring, 59 g of the after

the substances are used. 65 B obtained product at 8 to 10 ⁰ C during a

The compound according to the invention has a time span of 4 hours to 200 g of 88% sulfur especially strong musk-like scent of long acid added. The reaction mixture becomes a lasting effect, which is also stirred by the multitude for more hours at this temperature and

then poured into a mixture of 100 g of water and 100 g of ice. The organic layer is removed and the water layer extracted with 75 ml of benzene. The combined organic layers are washed successively with 20 ° / ₀ sodium chloride solution, 10% sodium carbonate and 20% sodium chloride solution. The solvent is removed and the residue is distilled to obtain 44 g of 2a, 3,4,5-tetrahydro- 1,1,5,5-tetramethylacenaphthene, nf = 1.5316, boiling point 116 ° C / 4.8 mm Hg .

D. To a solution of 54 g of 2-nitropropane, 13.5 g of acetyl chloride and 27 g of the product obtained according to C, ^{small amounts of aluminum chloride are added every 15 minutes at 0 to 5 °} C. with vigorous stirring for a period of 2 hours (the total amount of aluminum added is 20 g). The reaction mixture is stirred for a further 2 hours at 8 to 1O ⁰ C and then poured into a cold solution of 100 ml of water and 27 g of concentrated hydrochloric acid. The mixture is stirred for 15 minutes and then separated. The organic layer is washed twice with concentrated hydrochloric acid and then successively with brine, 10% sodium carbonate and brine. The solvent is stripped off and the residue is ^{distilled at 141 °} C. at a pressure of 1 mm Hg. The distillate is recrystallized from aqueous ethanol. The recrystallized ketone has a melting point of 117 to 118 ° C and has a strong, musky odor.

Claims (3)

Patent claims: 1. 7 - Acetyl - 2a, 3,4,5 - tetrahydro-1,1,5,5 - tetramethyl-acenaphthene. 2. A process for the preparation of 7-acetyl-2a, 3,4,5-tetrahydro-1,1,5,5-tetramethyl-acenaphthene, characterized in that 1,1-dimethyltetrahydronaphthalene is added in a manner known per se with sulfuryl chloride, N-chloro- or -bromo-succinimide, N-chloro- or -bromo-phthalimide, tert-butyl hypochlorite or molecular chlorine or bromine at about 25 to 6O ⁰ C and under the action of free radical-forming agents to 1,1-dimethyl-4 -chloro- or -brometrahydronaphthalene, the halogenated compound obtained is separated off and 1,1-dimethyl-4-methallyltetrahydronaphthalene is prepared therefrom with methallyl magnesium chloride or bromide in a manner known per se, and the methallyl compound separated off in a manner known per se Sulfuric acid or polyphosphoric acid as a cyclizing agent is converted to 2a, 3,4,5-tetrahydro-l, l, 5,5-tetramethylacenaphthene, this compound is separated off and in a manner known per se with a compound which provides acetyl ions in the presence of a Friedel-Crafts catalyst converts to the 7-acetyl derivative. 3. Use of 7-acetyl-2a, 3,4,5-tetrahydro-l, l, 5,5-tetramethyl-acenaphthene as a musk fragrance.