Thionyl Chloride → HCID 14294197, compound

HRID 1381706Notes

Reaction equation

HRID 1381706 reaction equation
[CH2:1]([O:3][C:4](=[O:20])[CH2:5][CH2:6][S:7][C:8](=[N:14][NH:15]C(OC)=O)[CH2:9][C:10]([CH3:13])([CH3:12])[CH3:11])[CH3:2].[S:21](Cl)(Cl)=O>ClCCl>[CH3:11][C:10]([C:9]1[S:21][N:15]=[N:14][C:8]=1[S:7][CH2:6][CH2:5][C:4]([O:3][CH2:1][CH3:2])=[O:20])([CH3:13])[CH3:12]

Participants

4

Reactant 2

HCID 24386Thionyl ChlorideHCID 86742731HCID 86742731, compound

Product 1

HCID 14294197HCID 14294197, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of [1-[(3-ethoxy-3-oxopropyl)thio]-3,3-dimethylbutylidene]hydrazinecarboxylic acid, methyl ester, thionyl chloride and dichloromethane was heated at reflux for 40 hours and then quenched with ice water. The orange product was extracted twice into ether. The extracts were combined, washed with 0.1N sodium hydroxide twice, water twice, saturated sodium chloride twice, dried and concentrated in vacuo. The resulting orange liquid was evaporated onto 70 g of silica gel. The gel was dried and poured onto a column of silica gel packed in petroleum ether. The column was eluted with a gradient of 1-10% ethyl acetate in petroleum ether. The desired fractions were purified on silica gel preparative TLC plates eluting with 3% ethyl acetate in petroleum ether, giving 2.9 g of the desired compound as a light yellow oil. Proton nuclear magnetic resonance (δ[ppm], CDCl3) 90 MHz: 1.23 (t, 3H, J=7.0 Hz, CH3); 1.49 (s, 9H, t-butyl); 2.84 (t, 2H, J=7.0 Hz, CH2CO); 3.59 (t, 2H, SCH2); 4.14 (q, 2H, OCH2).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 40 hours
  3. customquenched with ice water
  4. extractionThe orange product was extracted twice into ether
  5. washwashed with 0.1N sodium hydroxide twice
  6. dry with materialwater twice, saturated sodium chloride twice, dried
  7. concentrationconcentrated in vacuo
  8. customThe resulting orange liquid was evaporated onto 70 g of silica gel
  9. customThe gel was dried
  10. additionpoured onto a column of silica gel
  11. washThe column was eluted with a gradient of 1-10% ethyl acetate in petroleum ether
  12. customThe desired fractions were purified on silica gel preparative TLC plates
  13. washeluting with 3% ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-8e78041b40644ff1bdb560e25f8b5f27
Source dataset
uspto-grants-1989_02
Patent number
US04803280

Reaction notes

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