Acetaldehyde → HCID 68725455, compound

HRID 1471408Notes

Reaction equation

HRID 1471408 reaction equation
C(NC(C)C)(C)C.[Li]CCCC.CCCCCC.[CH3:19][C:20]1[CH:21]([C:30](=[O:32])[CH3:31])[C:22]2([CH:27]=[CH:28][CH:29]=1)[CH2:26][CH2:25][CH2:24][CH2:23]2.C=C1C=CCC2(CCCC2)[CH:35]1[C:44](=[O:46])C.CC1C=CCC2(CCCC2)C=1C(=O)C.C(=O)C.Cl>C1COCC1>[OH:46][CH:44]([CH3:35])[CH2:31][C:30]([CH:21]1[C:20](=[CH2:19])[CH:29]=[CH:28][CH2:27][C:22]21[CH2:23][CH2:24][CH2:25][CH2:26]2)=[O:32]

Participants

10

Reactant 8

HCID 177AcetaldehydeHCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 8058HexaneHCID 68722789HCID 68722789, compoundHCID 68723086HCID 68723086, compoundHCID 68723713HCID 68723713, compoundHCID 178418339Butyllithium

Product 1

HCID 68725455HCID 68725455, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

At −70° C. under N2, a solution of diisopropylamine (0.91 ml, 6.5 mmol) in anhydrous THF (10 ml) was treated dropwise with a solution of 1.6M n-BuLi in hexane (4 ml, 6.5 mmol). The resulting solution was stirred for 20 min., and treated dropwise with a solution of a 3:90:7 mixture of 1-(7-methylspiro[4.5]deca-7,9-dien-6-yl)ethanone, 1-(7-methylenespiro[4.5]dec-8-en-6-yl)ethanone, and 1-(7-methylspiro[4.5]deca-6,8-dien-6-yl)ethanone (0.94 g, 4.98 mmol) in anhydrous THF (4 ml). The resulting solution was stirred for 45 min. at −50° C., treated with a solution of acetaldehyde (1.2 ml, 20 mmol) in anhydrous THF (4 ml). The resulting solution was stirred at −40° C. for 1 h, poured into a mixture of ice and 2N HCl, and extracted three times with MTBE (25 ml). The combined organic phases washed with a saturated aqueous solution of NaCl, dried (MgSO4), and concentrated. FC (40 g SiO2, hexane/MTBE 10:1) of the crude product (1.3 g) gave 3-hydroxy-1-(7-methylenespiro[4.5]dec-8-en-6-yl)butan-1-one (0.788 g, 68%, 3:1 diast. mixture)

Workup

  1. stirringThe resulting solution was stirred for 45 min. at −50° C.
  2. stirringThe resulting solution was stirred at −40° C. for 1 h
  3. extractionextracted three times with MTBE (25 ml)
  4. washThe combined organic phases washed with a saturated aqueous solution of NaCl
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-a5bda63b36e446ca8c446e2b3c529194
Source dataset
uspto-grants-2015_04
Patent number
US09012391B2

Reaction notes

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