Lithium Hydroxide → (1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid

HRID 1821126ノート

反応式

HRID 1821126 の反応式
C([O:3][C:4]([C:6]1[S:13][C:12]([CH3:14])=[C:11]2[C:7]=1[CH2:8][C@H:9]1[C:15]([CH3:17])([CH3:16])[C@H:10]12)=[O:5])C.[Li+].[OH-]>C(O)C.O>[CH3:16][C:15]1([CH3:17])[C@@H:9]2[CH2:8][C:7]3[C:11]([C@H:10]12)=[C:12]([CH3:14])[S:13][C:6]=3[C:4]([OH:5])=[O:3]

参加物

5

反応物 2

HCID 3939Lithium HydroxideHCID 57892442(1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid ethyl ester

生成物 1

HCID 57892448(1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid収率 76.4%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 962Water溶媒

反応条件

温度
70 °C

実験手順

To a solution of crude (1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid ethyl ester (10.3 g, 41.2 mmol) in ethanol (200 mL) a solution of 2N aq. LiOH (300 mL) is added. The resulting mixture is stirred at 70° C. for 1 h, cooled to rt and diluted with water (250 mL). The aq. solution is extracted three times with DCM (125 mL) before it is acidified to pH 3 by adding citric acid. The acidified solution is extracted twice with DCM (2×250 mL). These second extracts are combined, dried over Na2SO4, filtered and evaporated to leave (1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid (7.0 g) as a yellow solid. LC-MS: tR=0.95 min, [M+1]+=223.00. 1H NMR (CDCl3): δ3.04-2.92 (m, 1H), 2.83 (d, J=19.3 Hz, 1H), 2.39 (s, 3H), 1.91-1.87 (m, 2H), 1.13 (s, 3H), 0.73 (s, 3H).

後処理

  1. temperaturecooled to rt
  2. extractionThe aq. solution is extracted three times with DCM (125 mL) before it
  3. additionby adding citric acid
  4. extractionThe acidified solution is extracted twice with DCM (2×250 mL)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customevaporated

出典と根拠

ORDレコード
ord-91d40d4808574e80b30f5e4b55ff0792
出典データセット
uspto-grants-2009_10
特許番号
US07605269B2

反応ノート

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