Water → HCID 23451695, compound

HRID 1278448Notes

Reaction equation

HRID 1278448 reaction equation
[Cl-].[Li+].[C:3](=[C:6]([CH2:24][CH2:25]Cl)[CH2:7][C:8]1(C(OC)=O)[CH:13]([CH3:14])[CH2:12][C:11]([O:15][CH:16]([CH3:18])[CH3:17])=[CH:10][C:9]1=[O:19])([CH3:5])[CH3:4].O>CN(C)P(=O)(N(C)C)N(C)C>[C:3](=[C:6]1[CH2:24][CH2:25][C:8]2([CH:13]([CH3:14])[CH2:12][C:11]([O:15][CH:16]([CH3:17])[CH3:18])=[CH:10][C:9]2=[O:19])[CH2:7]1)([CH3:4])[CH3:5]

Participants

5

Reactant 3

HCID 962WaterHCID 433294Lithium ChlorideHCID 23451702HCID 23451702, compound

Product 1

HCID 23451695HCID 23451695, compoundYield 81.9%

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
130 °C

Procedure

Dry lithium chloride (3.8 g, 0.09 mol) and methyl 1-(2-isopropylidene-4-chlorobutyl)-2-oxo-4-isopropoxy-6-methyl-3-cyclohexene carboxylate (21.3 g, 0.06 mol) were mixed in anhydrous hexamethylphosphoric triamide (120 mL) under nitrogen. The solution was heated at 130° C. for 40 minutes and after cooling was poured into water (300 mL). The mixture was extracted with ether and the extract dried (Na2SO4). Solvent removal gave 15.2 g of crude spiroketones 1 and 2 (glc purity of 93%, spiroketones separated on HPLC). Crystallization from petroleum ether gave 12.9 g of 2-isopropylidene-8-isopropoxy-10-methylspiro[4.5]dec-7-en-6-one isomer 1 exclusively, mp 77°-77.5° C.

Workup

  1. temperatureafter cooling
  2. extractionThe mixture was extracted with ether
  3. dry with materialthe extract dried (Na2SO4)
  4. customSolvent removal
  5. customgave
  6. custom15.2 g of crude spiroketones 1 and 2 (glc purity of 93%, spiroketones separated on HPLC)
  7. customCrystallization from petroleum ether

Sources & evidence

ORD record
ord-c4f6d2ea8cad49eea23f1ef45d010230
Source dataset
uspto-grants-1981_07
Patent number
US04281204

Reaction notes

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