Methane, dichloromethoxy- → HCID 16738489, compound

HRID 1844229Notes

Reaction equation

HRID 1844229 reaction equation
CCN(C(C)C)C(C)C.[Br:10][C:11]1[CH:16]=[C:15]([CH:17]2[O:21][CH2:20][CH2:19][O:18]2)[CH:14]=[CH:13][C:12]=1[OH:22].[CH3:23][O:24][CH:25](Cl)Cl>C(Cl)Cl>[Br:10][C:11]1[CH:16]=[C:15]([CH:17]2[O:18][CH2:19][CH2:20][O:21]2)[CH:14]=[CH:13][C:12]=1[O:22][CH2:23][O:24][CH3:25]

Participants

5

Reactant 3

HCID 21004Methane, dichloromethoxy-HCID 81531DiisopropylethylamineHCID 19701587HCID 19701587, compound

Product 1

HCID 16738489HCID 16738489, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

(iPr)2NEt (6.0 mL, 35.0 mmol) was added dropwise to a stirred and cooled (0° C.) solution of alcohol 3a (4.0 g, 16.3 mmol) in CH2Cl2 (50 mL). After 15 min methoxymethylene chloride (MOMCl) (1.6 mL, 28 mmol) was added dropwise over a period of 5 min, and stirring was continued for 1 h. The cold bath was removed, and stirring was continued for 12 h. The reaction mixture was diluted with water (10 mL) and extracted with CH2Cl2. The combined organic extracts were washed with brine, dried over Na2SO4, and evaporated. The residue was purified by flash chromatography using hexanes-ethyl acetate mixture (5:1) as eluent to give compound 4a (4.4 g, 94%) as a colorless liquid. Rf=0.48 (25% EtOAc-hexanes); IR (neat) 2956, 2889, 1606, 1497, 1246, 1100, 1043 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.64 (d, J=1.8 Hz, 1H), 7.31 (dd, J=8.7, 2.1 Hz, 1H), 7.10 (d, J=8.1 Hz, 1H), 5.70 (s, 1H), 5.21 (s, 2H), 4.02 (m, 4H), 3.46 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 154.2, 132.8, 131.4, 126.7, 115.5, 112.6, 102.5, 94.8, 65.1, 56.2; EIMS (m/z, rel intensity) 290 (M++2, 54), 288 (M+, 58), 259 (23), 257 (23), 209 (56), 73 (100).

Workup

  1. stirringstirring
  2. customThe cold bath was removed
  3. stirringstirring
  4. waitwas continued for 12 h
  5. additionThe reaction mixture was diluted with water (10 mL)
  6. extractionextracted with CH2Cl2
  7. washThe combined organic extracts were washed with brine
  8. dry with materialdried over Na2SO4
  9. customevaporated
  10. customThe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-4cdf1f0d97ba4d118ee5d657203f977a
Source dataset
uspto-grants-2015_02
Patent number
US08946287B2

Reaction notes

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