Diethyl Ether → beta-Ethenylidene-2-thiopeneethanamine

HRID 231557Notes

Reaction equation

HRID 231557 reaction equation
CC[O:3]CC.C[Si](C)(C)[N:8]([CH2:13][C:14]#[C:15][CH2:16]OC)[Si](C)(C)C.[S:21]1[CH:25]=[CH:24][CH:23]=[C:22]1[Mg]Br.[NH4+].[OH-]>Cl[Ni]Cl.C(OC(=O)C)C>[NH4+:8].[OH-:3].[C:15](=[C:14]([C:22]1[S:21][CH:25]=[CH:24][CH:23]=1)[CH2:13][NH2:8])=[CH2:16]

Participants

8

Reactant 4

HCID 3283Diethyl EtherHCID 14923Ammonium HydroxideHCID 13161121N,N-bis(trimethylsilyl)-4-methoxy-2-butynylamineHCID 178418438HCID 178418438, compound

Product 2

HCID 14923Ammonium HydroxideHCID 14518110beta-Ethenylidene-2-thiopeneethanamineYield 87%

Reagents, catalysts & solvents 2

HCID 24385Nickel DichlorideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

NiCl2 (dppp) catalyst (170 mg; 3M %) was added to dry ether (30 ml) in a 100 ml 3-necked flask with mechanical stirrer, thermometer and nitrogen bubbler. III (2.47g, 10.2 mM) was added via syringe with stirring and immediately thereafter 3M thienylmagnesium bromide (7 ml, 21 mM) was added via syringe. After stirring at room temperature for 20 hours the reaction was complete as shown by G C analysis. The silylated product was isolated by shaking with dilute NH4OH and extraction into ethylacetate (three times, each into 100 ml). After drying over K2CO3 and concentration, 2.68 g crude product was obtained. Purification and desilyation by flash chromatography (300 g silica gel, eluted with CHCl3, then CHCl3 :MeOH:conc. NH4OH 100:10:1) gave 1.22 g (87%) of the desired product as a light tan oil after drying under high vacuum.

Workup

  1. stirringAfter stirring at room temperature for 20 hours the reaction
  2. customThe silylated product was isolated
  3. dry with materialAfter drying over K2CO3 and concentration
  4. custom2.68 g crude product was obtained
  5. customPurification and desilyation by flash chromatography (300 g silica gel
  6. washeluted with CHCl3

Sources & evidence

ORD record
ord-1675d6007a9b4d018e3fc7e039de8aac
Source dataset
uspto-grants-1989_07
Patent number
US04847288

Reaction notes

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