Hexachlorobutadiene → 1,4-Bis(dimethylaminodimethylsilyl)butadiyne

HRID 1006073

反応式

HRID 1006073 の反応式
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl.[CH3:16][N:17]([Si:19]([CH3:22])([CH3:21])Cl)[CH3:18]>>[CH3:16][N:17]([Si:19]([CH3:22])([CH3:21])[C:1]#[C:2][C:3]#[C:4][Si:19]([N:17]([CH3:18])[CH3:16])([CH3:22])[CH3:21])[CH3:18]

参加物

4

反応物 3

HCID 6901HexachlorobutadieneHCID 87511Silanamine, 1-chloro-N,N,1,1-tetramethyl-HCID 178418339Butyllithium

生成物 1

HCID 219242541,4-Bis(dimethylaminodimethylsilyl)butadiyne収率 96%

反応条件

温度
-78 °C

実験手順

Synthesis of 1,4-bis(dimethylaminodimethylsilyl)butadiyne—A flame dried 250 mL Schlenk flask containing diethyl ether (20 mL) was cooled to −78° C. and n-butyl lithium (20 mL of 2.4 M in hexane, 48.0 mmol) was added by syringe. After several minutes, hexachlorobutadiene (1.88 mL, 12.0 mmol) was added drop wise via syringe over a 10 minute period. After completion of addition, the cold bath was removed and the mixture stirred at room temperature for 3 hours. The resulting 1,4-dilithio-1,3-butadiyne was used without further purification. The flask was then recooled to −78° C. and dimethylaminodimethylchlorosilane (3.6 mL, 24 mmol) was added by syringe. The flask was removed from the cold bath and the reaction mixture stirred at room temperature for 16 hours. At this time, 1H NMR analysis indicated complete disappearance of dimethylaminodimethylchlorosilane and formation of 1,4-bis(dimethylaminodimethylsilyl)butadiyne 206. Diethyl ether was removed in vacuo, and the mixture taken up in a minimum amount of pentane and filtered. Pentane was removed in vacuo to give 2.91 g (96%) of 1,4-bis(dimethylaminodimethylsilyl)butadiyne 206 as a viscous red liquid. IR (cm−1) 2074 (s), (—C≡C—C≡C—). 1H NMR (ppm) 2.44 (s), (N(CH3)2), 0.20 (s), (Si(CH3)2). 13C NMR 87.6, 84.4, (—C≡C—C≡C—) 37.7, (N(CH3)2), −1.2, (Si(CH3)2).

後処理

  1. temperatureflame
  2. customdried 250 mL Schlenk flask
  3. additioncontaining diethyl ether (20 mL)
  4. waitAfter several minutes
  5. additionAfter completion of addition
  6. customthe cold bath was removed
  7. customThe resulting 1,4-dilithio-1,3-butadiyne was used without further purification
  8. customwas then recooled to −78° C.
  9. customThe flask was removed from the cold bath
  10. stirringthe reaction mixture stirred at room temperature for 16 hours
  11. customDiethyl ether was removed in vacuo
  12. filtrationfiltered
  13. customPentane was removed in vacuo

出典と根拠

ORDレコード
ord-93b592e9ac7a4cb9884307d43a054e25
出典データセット
uspto-grants-2004_09
特許番号
US06787615B2

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