Hydrochloric Acid → HCID 23172753、化合物

HRID 1770309ノート

反応式

HRID 1770309 の反応式
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

参加物

10

反応物 5

HCID 313Hydrochloric AcidHCID 21253610HCID 21253610、化合物HCID 212536202-Benzyloxy-3-bromopropionitrileHCID 21253638HCID 21253638、化合物HCID 86748431HCID 86748431、化合物

生成物 1

HCID 23172753HCID 23172753、化合物

試薬・触媒・溶媒 4

HCID 887Methanol溶媒HCID 962Water溶媒HCID 3283Diethyl Ether溶媒HCID 8058Hexane溶媒

反応条件

温度
-10 °C

実験手順

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 δ 3.80 (3H, s), 4.63 (1H, d, J 3 Hz), 4.83 (2H, s), 5.37 (1H, d, J 3 Hz), 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.

後処理

  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

出典と根拠

ORDレコード
ord-1624827ff2ea4dc9b9ae462f6bb3dfe7
出典データセット
uspto-grants-1995_01
特許番号
US05385996

反応ノート

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