Acetic Acid → HCID 178477428, compound

HRID 256105Notes

Reaction equation

HRID 256105 reaction equation
[C:1]([CH:4]1[C:9](=[O:10])[CH2:8][CH:7]([CH2:11][CH:12]([S:14][CH2:15][CH3:16])[CH3:13])[CH2:6][C:5]1=[O:17])(=O)[CH3:2].C(O)(=O)C.[Cl:22]/[CH:23]=[CH:24]/[CH2:25][O:26][NH2:27].[OH-].[Na+]>O.CCCCCC>[Cl:22]/[CH:23]=[CH:24]/[CH2:25][O:26][NH:27][C:1](=[C:4]1[C:9](=[O:10])[CH2:8][CH:7]([CH2:11][CH:12]([S:14][CH2:15][CH3:16])[CH3:13])[CH2:6][C:5]1=[O:17])[CH3:2]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 14798Sodium Hydroxide2×HCID 158058O-((2E)-3-Chloro-2-propen-1-yl)hydroxylamineHCID 140312922-Acetyl-5-[2-(ethylsulfanyl)propyl]cyclohexane-1,3-dione

Product 1

HCID 178477428HCID 178477428, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8058HexaneSolvent

Procedure

In this example, 29.5 g (0.1151 mol) of 2-acetyl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione; 1.7 g (0.0277 mol) of acetic acid, and 19.7 g (0.1369 mol) of 3-trans-chloroallyloxyamine in 62 ml of water were admixed to 37 ml of hexane. Aqueous 5 wt. % sodium hydroxide was slowly added dropwise over about 15 minutes until 5.5 g (0.1369 m+small excess) of sodium hydroxide had been added yielding a reaction mixture pH of about 6. The mixture was heated to and maintained at 40° C. for 21/2 hours and then cooled to room temperature. The organic (i.e., hexane) phase was separated and washed with 16 ml of aqueous 5 wt. % hydrochloric acid and then aqueous 6.25 wt. % sodium hydroxide added until pH12. The aqueous phase was separated and admixed with 35 ml of hexane at about 0° C. (ice bath) and the pH adjusted to 5 by the dropwise addition of aqueous 36 wt. % hydrochloric acid over an ice bath. A few mls of methylene chloride was then added. The organic phase was separated, dried over magnesium sulfate and then concentrated by evaporation affording 35.2 g of a crude product as an oil. The crude product was purified by column chromatography over silica gel eluting with hexane:methylene chloride mixtures affording 17.4 g of the purified title compound also as an oil. Elemental analysis carbon calculated 55.56%, found 54.43%; Hydrogen calculated 6.99%, found 6.53%; Nitrogen 4.05%, found 4.31%.

Workup

  1. additionhad been added

Sources & evidence

ORD record
ord-fdac2e7727b64795b15c043c495cb3e5
Source dataset
uspto-grants-1987_10
Patent number
US04701205

Reaction notes

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