CH515200A - Alkyl-substd bicyclo-decanol-3 prodn - by reacting bicyclo-decanone-3 with grignard reagent and hydrolysing - Google Patents

Abstract

Alkyl substd. bicyclo-decanol-3-prodn. - by reacting bicyclo-decanone-3 with Grignard reagent and hydrolysing Compounds having the formula (I) (where one of X's is H and the other is an alkyl, or both represent H, and R is an alkyl) are produced by reacting the corresponding bicyclodecanone-3 with RMY (where M is pref. Mg and Y is a halogen) and hydrolysing the resulting product. Some of these cpd. are novel. These cpds. have organoleptic properties and can be used in perfumery, prodn. of synthetic aromatic additives for foodstuffs, drinks or tobacco, or in pharmacology.

Description

  

  
 



  Process for the preparation of oxygenated bicyclic derivatives
 The present invention relates to a process for the preparation of oxygenated alicyclic compounds of decalin of formula:
EMI1.1
 in which one of the X represents hydrogen and the other an alkyl residue, for example methyl, or hydrogen, and
R represents an alkyl residue, for example methyl. It has been discovered that the compounds of formula I, some of which are new, are endowed with very interesting organoleptic properties and therefore are useful as perfuming agents in the perfume industry, as ingredients in the preparation of synthetic flavors and as agents. flavoring agents for human and animal foods, beverages, pharmaceutical preparations and tobacco.



   According to the invention, the compounds of formula I are prepared by treating a ketone compound of formula:
EMI1.2
 in which the X have the same meaning as above, with an organometallic compound and the resulting product is then hydrolyzed.



   Said organometallic compound is a compound of formula R - ME where ME represents a metallic function, such as Li or MgWhalogen, and R has the meaning defined above. Preferably, a halogenomagnesium agent is used and the operation is carried out under the conditions of a Grignard reaction.



   The compounds of formula II, in which one of
X represents hydrogen and the other an alkyl residue, can be prepared by alkylation in the presence of a proton eliminator of the compounds of formula:
EMI1.3

 As the alkylating agent, the usual alkylating agents, such as, for example, halides or alkyl sulphates, can be employed, and as proton scavengers a strong base such as, for example, NaH can be employed.



   The compounds of formula II b:
EMI1.4
 in which X represents an alkyl residue, for example methyl or ethyl, or hydrogen, can be obtained by cyclization, by means of an acidic cyclizing agent, acetylenic and / or allenic compounds of formula:
EMI1.5
  and or
EMI2.1
 respectively containing a double bond in one of the positions indicated by the dotted lines and in which X has the same meaning as above. As the cyclizing agent, an acid such as, for example, H2SO4, H3PO4, HC104 or F8C - COOH can be employed. Preferably, -H2SO4 is used for economic reasons. Compounds III and IV can be cyclized either simultaneously or individually.

  The cyclization of
III generally provides higher yields than cyclization of IV. However, it is generally more economical to cyclize a mixture of III and IV directly resulting from synthesis rather than separating m and IV beforehand. The above cyclization is based on a new principle which has no analogy in chemistry so far.



   Compounds m and IV can be prepared from dihydro-α-ionone (methylated or not) according to the usual means [see for example Bull. Soc. Chim.



  481 (1924); Angew. Chem. 72, 400 (1962); Ber. deutsch.



  chem. Ges. 74, 1474 (1941); J. Russ. Phys. Chem. Soc.



  19, 553 (1887); J. Prakt. Chem. 371 (2), 417 (1888); Ann.



  Chim. 105-144, (1965/10); Bull. Soc. Chia. 978 (1963)].



  The following diagram (A) illustrates this method of preparation in which chlorination takes place and then the treatment of the resulting chlorides with a strong base such as, for example, KOH, NaNH 2, lithium ethylene diamide.



  Diagram A
EMI2.2
    Dihydro-u-ionone (methylated or not)
 (X = H, Me)
EMI2.3


<tb> <SEP> PCl5
<tb> x <SEP> x <SEP> C1
<tb> <SEP> Cl
<tb> Cl <SEP> Cl
<tb> <SEP> Base
<tb> <SEP> III <SEP> + <SEP> IV
<tb>
 The example which follows serves to better illustrate the invention.



  In said example, temperatures are given in degrees centigrade.



   Example
 To a suspension of 2.6 g of Mg turnings in 20 ml of anhydrous ether, 9.5 g of methyl bromide dissolved in 10 mol of ether are added dropwise.



  When the addition is complete, the mixture is heated for 1/2 hour at reflux, then 19.4 g of 1,7,7-tri methylbicyclo [4.4.0] decanone- (3), prepared according to the method are added dropwise. described below, dissolved in 50 ml of ether. The mixture is kept for two more hours at reflux, then the mixture is poured into an ice-cold saturated solution of NH4Cl.



  Extracted with ether then neutralized, washed and dried the extract. After concentration of the extract under reduced pressure, the residue is distilled and 18.5 g of 1,3,7,7 tetramethylbicyclo [4.4.0] decanol - (3), Eb. 80-850 / 0.001
Torr. which crystallizes after standing in the cold. By recrystallization from hexane, an analytical sample is prepared, mp 95-70. Analytical constants: IR spectrum (CCl4) 3610, 3480, 1455, 1385, 1378, 1365 cm-1. NMR spectrum (CCl4): 0.84 (3H, s), 0.87 (3H, s), 1.1 (6H, s), 1.2-2.0 (complex bands) 6 ppm. Mass spectrum: 210, 177, 43, 69, 83, 195, 57, 109, 95.



   The bicyclic ketone used as the starting material in the preparation indicated above can be prepared as follows:
 With stirring, 21.6 g (0.1035 mole) of phosphorus pentachloride are introduced in 20 g (0.1085 mole) of dihydroionone over 30 minutes at 0-50. Then the brown-red solution was stirred without cooling so that the temperature rose to 20-250 ° C. The reaction mixture was then poured onto ice and the extract with pentane. The extract is washed with a saturated solution of NaHCO and NaCl and dried over MgSO4. After filtration and concentration of the extract, 23 g of a red oil are obtained, consisting essentially of a mixture of chlorides of the dihydroionone.



   140 ml of ethylenediamine are heated under argon in a 4-necked flask at 100-1100C, then dissolved therein while stirring 1.4 g of lithium (0.2 mol) in pieces. After the blue color has disappeared, the reaction mixture is cooled to 200 ° C. At this temperature, 23 g of the mixture of chlorides dissolved in 40 ml of ethylenediamine are introduced, while cooling with a water / ice bath, over 15 min. The reaction mixture is stirred for 30 min at room temperature, poured onto ice and extracted with pentane. The extract is then washed with water, dried over MgSO4, filtered and concentrated.

  13.2 g of a product consisting of 2,6,6-trimethyl- 1 - [butyn- (3) .yl- (1)] - cyclohexene- (1 and 2) and 2,6.6 are obtained. -trimethyl-1-allenylmethyl-cyclohexene- (1 and 2) in a weight ratio of about 7: 1. Eb point. product weight: 35-380 C / 0.08 mm.



  Yield: 65%, based on the dihydro-a-ionone.



   A flask is charged with 100 ml of formic acid (98 0 / o), 5 ml of concentrated sulfuric acid and 10 ml of water.



  While stirring, 2.71 g of the mixture of acetylenic and allenic compounds (7: 1) are introduced at 50,600 ° C. over 10 min.



  The reaction mixture was then stirred for 3 t / 2 h at 600, then poured onto ice and extracted with pentane. The extract is washed with water and with saturated NaHCO3 solution, dried over MgSO4, filtered and concentrated. 1.8 g of 1,7,7-trimethylbicyclo [4.4.0] decanone (3) are obtained in the form of a mixture of isomers.
A and B. Eb. of the mixture: 700 C / 0.001 mm. The mixture yield is 60 o / o. The isomers are separated by gas chromatography on a TCEP column (Tricyanoethoxypropane 15 0 / o) at 150 ° C., helium speed 40 ml / min. This gives 51.1 o / o of the isomer A, F.



     59-600 C, and 48.9 O / o of isomer B, F. = 71-720 C.



   The conditions for cyclization of the mixture of acetylenic and allenic compounds (7: 1) can be varied, for example as shown in the table below.

 

  Board
EMI3.1


<tb> <SEP> Composition <SEP> of <SEP> mixture <SEP> of <SEP> isomers
<tb> <SEP> Agent <SEP> <SEP>
<tb> of <SEP> cyclization <SEP> Medium <SEP> Temperature <SEP> Duration <SEP> A <SEP> and <SEP> B
<tb>
H2SO4 CH3COOH / H2O 350 C 5 h 51.1 o / o 48.9 0 / o
H2SO4 CH3COOH / H2O 500 C 15 h 51.8 o / o 48.2%
HClO4 CH3COOH / H2O 40-500 C 15 h 51.0% 49.0 O / o CF3COOH H2O 35-400 C 4 h 1/2 42.2% 57.8 O / o
Amberlite CH3COOH 800 C 15 h 59.0 O / o 41.0 O / o

 

Claims (1)

CLAIM Process for the preparation of compounds of the formula: EMI3.2 in which one of X represents hydrogen and the other an alkyl residue, or hydrogen, and R represents an alkyl residue, characterized in that a ketone compound of formula is treated: EMI3.3 in which the X have the same meaning as above, by an organometallic compound of formula R-ME, where ME represents a metallic function and R has the meaning defined above, and the resulting product is then hydrolyzed. SUB-CLAIM Process according to claim, characterized in that a genomagnesium halo is used as organometallic compound.