Triethylamine → Tert-butyl(6-(2-(triethylsilyl)ethynyl)-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methylcarbamate

HRID 219093

反応式

HRID 219093 の反応式
Cl[C:2]1[CH:3]=[CH:4][C:5]2[N:6]([C:8]([CH2:11][NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[N:9][N:10]=2)[N:7]=1.[CH2:20]([Si:22]([CH2:27][CH3:28])([CH2:25][CH3:26])[C:23]#[CH:24])[CH3:21].C(N(CC)CC)C>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.[Cu](I)I.C(#N)C>[C:15]([O:14][C:13](=[O:19])[NH:12][CH2:11][C:8]1[N:6]2[N:7]=[C:2]([C:21]#[C:20][Si:22]([CH2:27][CH3:28])([CH2:25][CH3:26])[CH2:23][CH3:24])[CH:3]=[CH:4][C:5]2=[N:10][N:9]=1)([CH3:18])([CH3:17])[CH3:16]

参加物

7

反応物 3

HCID 8471TriethylamineHCID 637947(Triethylsilyl)acetyleneHCID 57691389tert-Butyl ((6-chloro-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methyl)carbamate

生成物 1

HCID 57691160Tert-butyl(6-(2-(triethylsilyl)ethynyl)-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methylcarbamate

試薬・触媒・溶媒 3

HCID 83717Copper iodide触媒HCID 178418807HCID 178418807、化合物触媒HCID 6342Acetonitrile溶媒

実験手順

A 1 L-round-bottomed flask flushed with argon was charged with tert-butyl (6-chloro-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methylcarbamate (12.00 g, 42.3 mmol), Pd(dppf)Cl2-CH2Cl2 adduct (3.45 g, 4.23 mmol), copper iodide (2.01 g, 10.6 mmol) at room temperature. Acetonitrile (400 mL) was added followed by triethyl(ethynyl)silane (37.9 ml, 211 mmol). Upon stirring the reaction mixture turned dark red. Triethylamine (177 ml, 1269 mmol) was added via cannula over five minutes. The first drops resulted in a change of color to light yellow/orange. At the end of the addition, the reaction mixture was dark red again. After stirring at 50° C. for one hour, the mixture was cooled to room temperature and concentrated in vacuo. Purification by MPLC (ISCO, EtOAc/MeOH: 100/0 to 90/10) afforded the desired product. The material was taken forward without further purification. MS m/z=388.3 [M+1]+. Calc'd for C19H29N5O2Si: 387.2.

後処理

  1. customA 1 L-round-bottomed flask flushed with argon
  2. customThe first drops resulted in a change of color to light yellow/orange
  3. additionAt the end of the addition
  4. stirringAfter stirring at 50° C. for one hour
  5. concentrationconcentrated in vacuo
  6. customPurification by MPLC (ISCO, EtOAc/MeOH: 100/0 to 90/10)

出典と根拠

ORDレコード
ord-1c06deba54cc4e058ee06469c7a1e1da
出典データセット
uspto-grants-2012_06
特許番号
US08198448B2

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