Sulfuric Acid → HCID 53649929, compound

HRID 2399098Notes

Reaction equation

HRID 2399098 reaction equation
[CH2:1]([Mg]Br)[CH3:2].[Mg].C(Br)C.[CH3:9][CH:10]([OH:13])[C:11]#[CH:12].[C:14]([O:28][C@@H]1C[C@@H](C)C(=O)C(C)(C)C1)([O:17][C@@H:18]1[CH2:23][C@@H:22]([CH3:24])[C:21](=[O:25])[C:20]([CH3:27])([CH3:26])[CH2:19]1)(C)[CH3:15].S(=O)(=O)(O)[OH:40]>O1CCCC1>[C:1]([O:13][CH:10]([C:11]#[C:12][C:21]1([OH:25])[C@H:22]([CH3:24])[CH2:23][C@@H:18]([O:17][C:14](=[O:28])[CH3:15])[CH2:19][C:20]1([CH3:26])[CH3:27])[CH3:9])(=[O:40])[CH3:2]

Participants

8

Reactant 6

HCID 1118Sulfuric AcidHCID 6332Ethyl BromideHCID 162393-Butyn-2-olHCID 5462224MagnesiumHCID 22793831HCID 22793831, compoundHCID 178418443HCID 178418443, compound

Product 1

HCID 53649929HCID 53649929, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Procedure

A solution of ethylmagnesium bromide in tetrahydrofuran (prepared in the usual manner from 18.2 g of magnesium, 81.8 g of ethyl bromide and 200 ml of tetrahydrofuran) is treated dropwise within 30 minutes at room temperature, with 26.6 g of but-3-yn-2-ol in 75 ml of tetrahydrofuran. The mixture is stirred under reflux conditions for 2 hours and subsequently treated dropwise with a solution of 11.1 g of [4R,4'R]-4,4'-(isopropylidenedioxy)-bis[[6R]-2,2,6-trimethylcyclohexanone] in 75 ml of tetrahydrofuran. The mixture is stirred for 12 hours under reflux conditions, subsequently acidified by the addition of 1-N aqueous sulphuric acid, then saturated with common salt and extracted with diethyl ether. The ether extract is washed to neutrality with an aqueous common salt solution, dried over sodium sulphate and evaporated under reduced pressure. The resulting oily 4-[[4R,6R]-1,4-dihydroxy-2,2,6-trimethylcyclohex-1-yl]-but-3-yn-2-ol is subsequently acetylated by treatment with acetic anhydride in the presence of pyridine. There is obtained 2-acetoxy-4-[[4R,6R]-1-hydroxy-4-acetoxy-2,2,6-trimethyl-cyclohex-1-yl]-but-3-yne as an oil, which is purified by adsorption on silica gel using n-hexane/diethyl ether (3:2 parts by volume) as the eluant.

Workup

  1. stirringThe mixture is stirred for 12 hours under reflux conditions
  2. extractionsaturated with common salt and extracted with diethyl ether
  3. extractionThe ether extract
  4. washis washed to neutrality with an aqueous common salt solution
  5. dry with materialdried over sodium sulphate
  6. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-d35c383b7e7f44b5a42b2c507b90bb56
Source dataset
uspto-grants-1977_05
Patent number
US04026949

Reaction notes

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