Triethylamine → 5-Bromo-3-(2-triethylsilylethynyl)pyrazin-2-amine

HRID 627784

反応式

HRID 627784 の反応式
[CH2:1]([Si:3]([CH2:8][CH3:9])([CH2:6][CH3:7])[C:4]#[CH:5])[CH3:2].C(N(CC)CC)C.Br[C:18]1[C:19]([NH2:25])=[N:20][CH:21]=[C:22]([Br:24])[N:23]=1>O1CCCC1.CCOC(C)=O.[NH4+].[OH-].[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Br:24][C:22]1[N:23]=[C:18]([C:5]#[C:4][Si:3]([CH2:8][CH3:9])([CH2:6][CH3:7])[CH2:1][CH3:2])[C:19]([NH2:25])=[N:20][CH:21]=1

参加物

9

反応物 3

HCID 8471TriethylamineHCID 6200042-Amino-3,5-dibromopyrazineHCID 637947(Triethylsilyl)acetylene

生成物 1

HCID 866757025-Bromo-3-(2-triethylsilylethynyl)pyrazin-2-amine収率 91%

試薬・触媒・溶媒 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒HCID 14923Ammonium Hydroxide溶媒

実験手順

Triethyl(ethynyl)silane (6.102 g, 7.793 mL, 43.49 mmol) followed by triethylamine (5.201 g, 7.164 mL, 51.40 mmol) was added to a thoroughly degassed suspension of 3,5-dibromopyrazin-2-amine (10 g, 39.54 mmol), copper(I) iodide (753.0 mg, 3.954 mmol) and Pd(PPh3)2Cl2 (2.775 g, 3.954 mmol) in tetrahydrofuran (200.0 mL) and the resulting solution stirred at ambient temperature over 18 hours. (On addition reaction mixture changes colour rapidly from yellow to orange to red to dark red and brown and then orange). Reaction mixture is cooled to ambient temperature and then diluted with EtOAc and 10% solution of NH4OH (100 mL) added and the layers separated. EtOAc layer washed once more with 10% NH4OH. Aqueous layer extracted further with EtOAc (×3) and combined organics dried over (MgSO4), filtered and concentrated in vacuo to a brown oil. Purified on Companion using a 330 g pre-packed silica column loading with DCM and eluting with 0-100% Petrol/DCM. Relevant fractions combined and concentrated in vacuo to give a brown oil (11.24 g, 91%). 1H NMR (400.0 MHz, DMSO) δ 0.67-0.74 (m, 6H), 0.99-1.03 (m, 9H), 6.72 (s, 2H) and 8.14 (s, 1H) ppm; MS (ES+) 314.06.

後処理

  1. addition(On addition reaction mixture changes colour rapidly from yellow to orange to red to dark red and brown and then orange)
  2. customReaction mixture
  3. temperatureis cooled to ambient temperature
  4. additionadded
  5. customthe layers separated
  6. washEtOAc layer washed once more with 10% NH4OH
  7. extractionAqueous layer extracted further with EtOAc (×3)
  8. dry with materialcombined organics dried over (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo to a brown oil
  11. customPurified on Companion
  12. washeluting with 0-100% Petrol/DCM
  13. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-a78d8768453449efab2750f672793513
出典データセット
uspto-grants-2016_04
特許番号
US09309250B2

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