SU1594163A1 - Method of producing driman-8a-diol - Google Patents

Abstract

The invention relates to cycloaliphatic alcohols, in particular to the preparation of driman-8α, 11-diol, an intermediate product for the synthesis of biologically active compounds. The goal is to simplify the process and expand the resource base. The preparation is carried out by ozonization of neoabienol in the form of a mixture of Δ 13-cis and Δ 13-trans-isomers at (-70) - (- 65) ° С in absolute methanol (solvent), followed by reduction of the forming azonide with sodium borohydride. The process goes in two stages. 1 tab.

Description

.f 1 i-fSfKK

Vrea-:

The invention relates to an improved process for the preparation of drman-8c /, 1 1-diol, an intermediate product for the synthesis of valuable biological agents in plants and plants.

The goal of the invention is to simplify the process and expand the base.

The goal is achieved by ozonizing neoabia 1ola formula

xCH,

sn

-he

in the form of a mixture of u-twic and l-trans-isomers at (-70) - (-65) C in absolute methanol, followed by reduction of the ozo-iodide formed by sodium borohydride.

Example 1. Through a solution of 118 mg of a mixture of -Tjjic and / 1 - -trans-β-neoabienol in 11 ml of absolute methanol, a stream of ozonized 1sulfur is passed at (-70) - (-65) C until ozone breakthrough, at the outlet of the reactor calb. In the reaction mixture after it reaches room temperature, 52 mg of sodium borohydride are added in two doses, stirring the mixture each time for 1 hour.

The excess hydride is decomposed with sulfuric acid, diluted with water and extracted with sulfuric ether. The ethereal extract is washed with water, a saturated solution of NallCOa, water, and stained

if

IVnBfCtfi

3№NV

anhydrous and the solvent is distilled off under vacuum. With statak (103 mg) chromatographic on 3 g of alumina. A mixture of sulfur and immobilized ether (1: 4) was washed from the column with 73 mg (7A%) drimai-8o, 11-diol. A recrystallized product from petroleum ether gives crystals of mp. 121-122 ° C.

Found%: C, 75.14j; H, 11.73.

C, 11,, 0 /

Calculated,%: C 75.00; And 11.66.

,, in-СНз) 1.31 s (ЗН, Cg-CHpi

C 75.00;

IR spectrum, cm-: 1035, 3350 (OH). IiMP-cneKTp (CHClj) s /, MD: 0.78 s (3H) i 0.85 s (ZP) (0 (0113) 2) 1.1 s

(ZN, S

3.79 t (21, s „-CH,).

Examples 2-4. Carried out analogously to example 1, varying the ozonation temperature.

The results of the examples are given in the table.

The proposed method allows to simplify the process by reducing the number of stages from eight to two, eliminating hard-to-reach, toxic and expensive reagents and solvents: 2,3-dichloro-5,6-di-1-benzo-quinone, dioxane, as well as expanding the raw material for the synthesis of drimans -8c, 11-diol due to the use of a mixture of L – 1SHC and / 3 -trans-isomers of neoabienol — the available compounds contained in the vat residue after rectification of fir resin; and replacing it with the amberinolide used in the well-known method — an inaccessible and scarce substance ways

The papus of which is complex and which is k.I. itself is itself a valuable raw material for the synthesis of substances with an amber smell of perfumery purposes.

Formula I.3 gain

The method of obtaining driman-8o /, 1 1-di ol of the formula

ozonization of the oxygen-containing diterpene compound at a low temperature in an organic solvent followed by reduction of the resulting ozonide with sodium complex hydride in an organic solvent, which is described by the use of neoabienol formula to simplify and expand the raw material base

.sn s

C-CH3

he

A trans-mixture of 4-cis-and -isomers, ozonization is carried out at -70 .., -65 ° C, reduction is carried out with sodium borohydride, and absolute methanol is used as an organic solvent in both stages.

Claims (1)

Claim The method of obtaining driman-8o /, 1 1-diol of the formula SNOON ozonization of the oxygen-containing diterpene compound at a low temperature in an organic solvent, followed by reduction of the ozonide formed with complex sodium hydride in an organic solvent, characterized in that, to simplify the process and expand the raw material base, a neoabienol of the formula used as an oxygen-containing diterpene compound, in the form of a mixture of D * ^e- cis- and 45 ¹ ^ -trans ~ -isomers, ozonation is carried out at -70 ... -65 ° C, reduction is carried out with sodium borohydride, and absolute methanol is used as an organic solvent in both stages Example The amount of neoabienol mg Amount of solvent Meon, ml Reducing agent ozonide Temperature, ° С Time ozonation, h DRI OUT man-8 o (, -diol, one% one 118 'eleven Iavits (-70) - (-65) 60 74 2 118 1.1 ' ΒΗβΒΗ ₄ (-78) - (-75) 60 74 3 108 ten Iahn (-45) - (-40) 60 65 four 110 ten Iavn; four (-25) - (-20) 60 60