17-Chloro-16-formylandrosta-5,16-dien-3beta-yl acetate → HCID 10597695, compound

HRID 1531702Notes

Reaction equation

HRID 1531702 reaction equation
[C:1]([O:4][C@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:19]2[CH2:18][CH2:17][C@@:15]2([CH3:16])[C@H:11]3[CH2:12][C:13]([CH:25]=[O:26])=[C:14]2Cl)[CH2:6]1)(=[O:3])[CH3:2].[NH:27]1[CH:31]=[N:30][N:29]=[N:28]1>>[C:1]([O:4][C@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:19]2[CH2:18][CH2:17][C@@:15]2([CH3:16])[C@H:11]3[CH2:12][C:13]([CH:25]=[O:26])=[C:14]2[N:28]2[N:29]=[N:30][CH:31]=[N:27]2)[CH2:6]1)(=[O:3])[CH3:2]

Participants

3

Reactant 2

HCID 1047470117-Chloro-16-formylandrosta-5,16-dien-3beta-yl acetate2×HCID 178418441HCID 178418441, compound

Product 1

HCID 10597695HCID 10597695, compoundYield 28.2%

Procedure

The method followed that described for Synthesis Example 7, but using 3β-acetoxy-17-chloro-16-formylandrosta-5,16-diene (Compound 3) (0.5 g, 1.329 mmol), 1H-tetrazole (187 mg, 1.59 mmol) and Li2CO3 (287 mg, 3.94 mmol) gave a crude product (520 mg). Flash column chromatography on elution with pet. ether/EtOAc, (5:1), gave firstly 3β-acetoxy-17-(2H-tetrazol-2-yl)-16-formylandrosta-5,16-diene (Compound 22) (92 mg, 28.2%), mp 170-172° C. (decomp.). 1H NMR (300 MHz, CDCl3): δ 1.1 (3H, s, 18-Me), 1.29 (3H, s, 19-Me), 2.04 (3H, s, 36-OAc), 4.62 (1H, m, 3α-H), 5.42 (1H, d, J=4.2 Hz, 6-H), 8.68 (1H, s, 5′-H) and 10.46 (1H, s, 16-CHO). Analysis calculated for C3H3%N4: C, 67.28; H, 7.37; N, 13.65. Found: C, 67.15; H, 7.61; N, 13.45. Further elution with p. ether/EtOAc/Et3N (7:3:0.3) gave 3β-acetoxy-17-(1H-tetrazol-1-yl) -16-formylandrosta-5, 16-diene (Compound 23) (146 mg, 44.6%), mp 196-198° C. (decomp.). 1H NMR (300 MHz, CDCl3): δ 1.09 (3H, s, 18-Me), 1.20 (3H, s, 19-Me), 2.04 (3H, s, 3f-OAc), 4.62 (1H, m, 1S 3α-H), 5.43 (1H, d, J=4.8 Hz, 6-H), 8.93 (1H, s, 5′-H) and 9.92 (1H, s, 16-CHO). Analysis calculated for C23H30O3N4: C, 67.28; H, 7.37; N, 13.65. Found: C, 67.05; H, 7.65; N, 13.45.

Workup

  1. customthat described for Synthesis Example 7
  2. customgave a crude product (520 mg)
  3. washFlash column chromatography on elution with pet. ether/EtOAc, (5:1),

Sources & evidence

ORD record
ord-8a22474b29224a7e9e10a120c0a22e9f
Source dataset
uspto-grants-2001_03
Patent number
US06200965B1

Reaction notes

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