Hydrochloric Acid → HCID 23172753, compound

HRID 1584521Notes

Reaction equation

HRID 1584521 reaction equation
Cl.C(OC(CBr)C#N)C1C=CC=CC=1.C(OC(CBr)C(N)=O)C1C=CC=CC=1.[CH2:29]([O:36][CH:37]([CH2:42]Br)[C:38]([O:40][CH3:41])=[O:39])[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.C1CN2C(=NCCC2)C1.C(=O)([O-])[O-].[K+].[K+]>CO.CCOCC.CCCCCC.O>[CH2:29]([O:36][C:37](=[CH2:42])[C:38]([O:40][CH3:41])=[O:39])[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 21253610HCID 21253610, compoundHCID 212536203-Bromo-2-(phenylmethoxy)propanenitrileHCID 21253638HCID 21253638, compoundHCID 86748431HCID 86748431, compound

Product 1

HCID 23172753HCID 23172753, compound

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Conditions

Temperature
-10 °C

Procedure

A slow stream of hydrogen chloride gas was passed for 4 h through a solution of 2-benzyloxy-3-bromopropionitrile (16.75 g) in methanol (2.38 g) and ether (66 ml) which was maintained at -10° C. The mixture was allowed to stand at 5° C. overnight, and then ice was added in small portions to the mixture at 0° C. After 20 min of stirring, the mixture was poured into water and the product was extracted with ether, washed with water and aqueous sodium bicarbonate, and dried (MgSO4). After the solvent was removed, the crude product was recrystallized from ether/CH2Cl2 to afford, after a first crop of crystals of 2-benzyloxy-3-bromopropanamide, the required intermediate, methyl 2-benzyloxy-3-bromopropanoate. This bromoester was treated with DBN/potassium carbonate as described above to yield methyl α-benzyloxyacrylate, mp 44.5-45.5° C. (from hexane); 1H NMR δ3.80 (3H, s), 4.63 (1H, d, J 3 Hz), 4.83 (2H, s), 5.37 (1H, d, J 3Hz), 7.33 (5H, s); IR 1740 cm-1. Ketals of alkyl pyruvates, prepared according to the directions in The Journal of Organic Chemistry, 1967, 32,1615, also may be converted to α-alkoxyacrylates by an acidic catalyst, as described in Chemische Berichte, 1911, 44, 3514.

Workup

  1. additionice was added in small portions to the mixture at 0° C
  2. extractionthe product was extracted with ether
  3. washwashed with water and aqueous sodium bicarbonate
  4. dry with materialdried (MgSO4)
  5. customAfter the solvent was removed
  6. customthe crude product was recrystallized from ether/CH2Cl2
  7. customto afford

Sources & evidence

ORD record
ord-24b5934ed5aa4e5bb3131e4e3a1ae943
Source dataset
uspto-grants-1999_08
Patent number
US05932675

Reaction notes

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