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

HRID 1924807Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1924807
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-]>CCO.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]

Komponenten

5

Edukt 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

Produkt 1

HCID 57892448(1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acidAusbeute 76,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 702EthanolLösungsmittelHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

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 EtOH (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 give (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): δ 3.04-2.92 (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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-8f27f003fc28447ab42daa4782b23e30
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08178562B2

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