RU1356428C - 3beta- chloro-24s- ethyloholest -5beta-en -4beta -ol as a semi-product for synthesis of 3beta- chloro- 4beta- hydroxy- 24s- ethyle- 5beta- cholestane -6- one - Google Patents

Abstract

The invention relates to steroid substances, in particular 3E-chloro-245-ethyl cholest-5E-en-4E-ol (EC) intermediate in the synthesis of 3E-chloro-4E-hydroxy-245-ethyl-5E-hopestan-6-one (ECN) . exhibiting phytostimulatory activity in 2. over a wide range of concentrations, similar to phyto mountain gibberellin A and heteroauxin. The goal is to create new intermediates for the synthesis of active phytostimulants. Preparation of EC is carried out by oxidation of 33-chloro-245-ethylcholesthene with selenium dioxide in boiling dioxane. Yield 38%; tl 99 - 102 ° C, gross-ph-lg OS1 Preparation of ECN is carried out by oxidation of EC with trifluoronacetic acid in choride methyl environment. Yield 65%; tll. 194-196? C, gross-f-la С Н О С1 ECN has a better phytostimulating effect than its analogue.

Description

The invention relates to a new chemical compound, specifically to a 3 / -chloro-245-et1 / 1 L cholest-5 / en-4 / -ole of formula I

n

which is an intermediate in the synthesis of the new compound 3 / -chloro-4/3-hydroxy-243-ethyl-5; 5-cholestan-6-one of the formula II ,, ..P ..

Compound I exhibits phyto-stimulating activity over a wide concentration range, not inferior in this respect to the known hetero-auxin phytohormones-HKB-berellin AZI, and even surpasses them at some concentrations. The fluorine-stimulating activity of compound II is about 10 times higher than the activity of a-ecdisoia, which is close in structure (2D 3/3, 14a, 22R, 25-pentaoxy-5-cholest-7-en-6-one). Compound P is slightly toxic to warm-blooded animals (its LDH is more than 4500 mg / kg).

The aim of the invention is a new derivative of / 3-sitosterol III, which allows to obtain a new biologically active 3/5-chloro-4/3-hydroxy-243-octyl-5-cholestan-6-one (1) with improved properties;

. For a better understanding of the essence of the invention, the following specific examples are given.

Example. Preparation of 3 / -chloro-245-octyl-cholest-5u5-en-4/3-ol (I).

To a solution of 8.5 g (19.6 mol) of 3/3-chloro-243-ethyl cholest-5-ene with 250 ml of dioxane was added 4.0 g (36 mol) of selenium dioxide. The reaction mixture was refluxed for 3.5 hours; after cooling to room temperature, it was filtered through alumina. The filtrate was evaporated in vacuo and the residue was subjected to silica gel column chromatography, eluting with a mixture of hexane and ether (25: 1). 3.35 g (7.46 mmol, 38%) of 3 / -chloro-245-ethyl-cholest-6 / en-4 / -ol (1) are obtained; t. pl. 99-102 ° C (acetone).

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Found,%: M 77, 58; H 11. 17; C1 7.60; pier May. 449 cu

Calculated for C29H490C1,%: C 77, 55; H .11.00; Ci 7.89.

IR spectrum (KBr, cm): 3550 (OH).

PM R spectrum (100 MHz СОС1з, d, ppm): 0.66 (fc, ЗН, 18-Ме); 0.88 (s., ZN, 19-ME); 4.02 (m, Hz, 1H, Sz-Na); 4.17 (m, Hz, 1H, SI-1a); 5.73 (m, 1H, Sat-H).

PRI me R 2. Obtaining 3/3-chloro-4 / -oxy-243-ethyl-5; 3-cholestan-6-one.

To a solution of 0.78 g (1.7 mmol) of 3 D-chloro-243-ethyl-cholest-5 3-en-4/3-ol (1) in 20 ml of methylene chloride, a solution of trifluoroacetic acid, which was prepared by adding 1.7 ml (.15 mmol) of 30% hydrogen peroxide, to a solution of 2.4 ml (17 mmol) of trifluoroacetic anhydride and 10 ml of methylene chloride. The reaction mixture was stirred at room temperature for 1.5 hours, then filtered through alumina. The filtrate was evaporated in vacuo, the residue was subjected to silica gel column chromatography, eluting with a mixture of hexane and ether (50: 1). 0.51 g (1.1 mmol, 65%) of 3 / -chloro-4 / -oxy-243-ethyl-5 / -cholestan-6-one (P) is obtained; t. pl. 194-196 ° C (hexane).

Found,%: C 74.90; H 10.60; C1 7.80; pier May. 465.16 c.u.

Calculated for C29H.902Ci,%: C, 74.88; H 10.62; C 7.62.

IR spectrum (KBr, see); 3550 (OH); 1712 ().

PMR spectrum (360 MHz, СОС1з, d ppm): 0.69 (s.З., 18-iV1e); 1.04 (s., ZN, 19-Me); 0.99 (d, 1-6.6 Hz, ZN, 21-Me); 0.84 (d, 6 Hz, 6H. 26/27-Me), 0.83 (t, J-6.7 Hz, ZN, 29 Me); 4.32 (m, Hz, 1H, C3-H2); 4.51 (dd, J, 60 Hz;, 56Hz, 1H, C4-H2).

Thus, through the described compound, a new derivative of 5/3-cholestane was obtained, which has a greater phyto-stimulating effect than the structural analogue.

(56) Carlisle D. B., Osborne D. J., Ellis P. E., Moorhouse J. E. Recfprocal effects of insect and plant grovjth substances-Nature, 1963, V. 200, N; 4912, p. 1230.

USSR copyright certificate No. 1110150. cl. C 07 J 9/00, 1982.

Sorrey C. W. Steroids and Walden inversion. IV. Derivatives of 6-ketositostane and 6: 17-diketoandrostane-J. Chem. Zoe .. 1948. No. 7, p. 1043-1045.

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Claims (1)

The claims “„ as an intermediate in the synthesis of 3/3 | 3-Chloro-245-ethyl cholest-en-4D-olchloro-4 / S-hydroxy-245-ethyl-5 /-cholestan-6 formulas. m jfn fW