Diazald → HCID 13475830, compound

HRID 1981112Notes

Reaction equation

HRID 1981112 reaction equation
[N+](=C)=[N-].[CH3:4]N(N=O)S(C1C=CC(C)=CC=1)(=O)=O.[C:18]([O:21][C@H:22]1[CH2:43][CH2:42][C@@:41]2([CH3:44])[C:24](=[CH:25][CH2:26][C@@H:27]3[C@@H:40]2[CH2:39][CH2:38][C@@:37]2([CH3:45])[C@H:28]3[CH2:29][CH2:30][C@@H:31]2[C@@H:32]([C:34]([OH:36])=[O:35])[CH3:33])[CH2:23]1)(=[O:20])[CH3:19]>>[CH3:4][O:35][C:34]([C@H:32]([C@@H:31]1[C@:37]2([CH3:45])[C@H:28]([C@H:27]3[C@H:40]([CH2:39][CH2:38]2)[C@:41]2([CH3:44])[C:24]([CH2:23][C@@H:22]([O:21][C:18](=[O:20])[CH3:19])[CH2:43][CH2:42]2)=[CH:25][CH2:26]3)[CH2:29][CH2:30]1)[CH3:33])=[O:36]

Participants

4

Reactant 3

HCID 6628DiazaldHCID 9550Diazomethane2×HCID 99460(2S)-2-[(3S,8S,9S,10R,13S,14S,17R)-3-acetyloxy-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-17-yl]propanoic acid

Product 1

HCID 13475830HCID 13475830, compoundYield 99.4%

Procedure

An ethanolic ethereal solution of diazomethane (CH2N2), generated from N-methyl-N-nitroso-p-toluenesulfonamide (CH3C6H4SO2N(CH3)NO; Diazald), was added dropwise to a suspension of (20S)-3β-acetoxy-5-pregnene-20-carboxylic acid (10.0 g, 25.7 mmole; m.p. 228°-231° C.) in 1:9 ethanol-ether at room temperature until all the solids dissolved and pale yellow color due to an excess diazomethane persisted. Excess diazomethane was removed with a stream of N2 until the solution became colorless. Removal of solvent provided the desired methyl ester, (20S)-3β-acetoxy-5-pregnene-20-carboxylic acid methyl ester (10.3 g; Rf 0.63 on silica gel in 3:7 ethyl acetate-hexane; m.p. 140°-142° C.) in 99.4% yield. Mass spectrum, m/e (relative intensity) 402 (M+, 0), 342 (100), 327 (10), 283 (4), 255 (6), 239 (5), 234 (11 ), 221 (12), 213 (5); NMR (CDCl3) δ0.70 (s, 18--H3), 1.02 (s, 19--H3), 1.19 (d, J=6.8 Hz, 21--H3), 2.03 (s, 3--OCOCH3), 4.60 (m, 3--H), 5.37 (br d, J=4.8 Hz, 6--H).

Workup

  1. dissolutiondissolved
  2. customExcess diazomethane was removed with a stream of N2 until the solution
  3. customRemoval of solvent

Sources & evidence

ORD record
ord-e1661a6287114965ac7c4ce5b77c2c1f
Source dataset
uspto-grants-1985_04
Patent number
US04512925

Reaction notes

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