Chlorotrimethylsilane → 1-Bromo-4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)benzene

HRID 2087125ノート

反応式

HRID 2087125 の反応式
Br[CH2:2][CH2:3][Br:4].Cl[Si](C)(C)C.[F:10][C:11]([F:31])([C:15]([F:30])([F:29])[C:16]([F:28])([F:27])[C:17]([F:26])([F:25])[C:18]([F:24])([F:23])[C:19]([F:22])([F:21])[F:20])[CH2:12][CH2:13]I.Br[C:33]1[CH:38]=CC(I)=[CH:35][CH:34]=1>C1COCC1.[Zn].[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Br:4][C:3]1[CH:35]=[CH:34][C:33]([CH2:13][CH2:12][C:11]([F:31])([F:10])[C:15]([F:29])([F:30])[C:16]([F:28])([F:27])[C:17]([F:25])([F:26])[C:18]([F:24])([F:23])[C:19]([F:22])([F:21])[F:20])=[CH:38][CH:2]=1

参加物

8

反応物 4

HCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 115221-Bromo-4-iodobenzeneHCID 748881,1,1,2,2,3,3,4,4,5,5,6,6-Tridecafluoro-8-iodooctane

生成物 1

HCID 114548901-Bromo-4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)benzene収率 56%

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
65 °C

実験手順

To a 250 mL three-neck flask equipped with dropping funnel was added zinc powder (9.50 g, 146.2 mmol) and dry THF (20 mL) under argon. 1,2-Dibromoethane (0.5 mL) was added and the mixture was heated at 65° C. for 2 min. The mixture was then cooled to room temperature. Chlorotrimethylsilane (0.5 mL) was added and the mixture was stirred at room temperature for 20 min. A solution of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl iodide (57.8 g, 126.6 mmol) in dry THF (100 mL) was added dropwise to keep the temperature of the solution at room temperature. The reaction mixture was stirred at room temperature for 12 h. The colorless solution was then transferred via canula to a solution of 1-bromo-4-iodobenzene (35.8 g, 126.6 mmol) and tetrakis(triphenylphosphine) palladium(0) (5.0 g, 4.3 mmol) in THF (60 mL). After 24 h at 45° C., the solvent was removed under vacuum. The residue was dissolved in methylene chloride (50 mL), extracted with FC-72 (50 mL) six times. The combined FC-72 layers were concentrated. Vacuum distillation of the residue gave 8 (34.3 g, 56%) as a colorless liquid. b.p. 79.1-80.9° C./0.03 mmHg; 1H NMR (300 MHz, CDCl3) δ2.36 (tt, J=18.3, 9.1 Hz, 2H), 2.86-2.92 (m, 2H), 7.11 (d, J=8.4 Hz, 2H), 7.45 (d, J=8.4 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ26.1, 32.9 (t, JFC=22.1 Hz), 105.5-123.2 (m, C6F13), 120.7, 130.1, 132.1, 138.3; 19F NMR (282.4 MHz, CDCl3) δ−125.6 (2F), −122.9 (2F), −121.7 (2F), −120.7 (2F), −113.4 (2F), −79.6 (3F); IR (CHCl3) 3065, 2954, 2879, 1490, 1237, 1145, 1013, 810 cm−1; EIMS m/z 502/504 (M+), 423, 169/171 (M—C6F13CH2)+.

後処理

  1. customTo a 250 mL three-neck flask equipped
  2. temperatureThe mixture was then cooled to room temperature
  3. customat room temperature
  4. stirringThe reaction mixture was stirred at room temperature for 12 h
  5. waitAfter 24 h at 45° C.
  6. customthe solvent was removed under vacuum
  7. dissolutionThe residue was dissolved in methylene chloride (50 mL)
  8. extractionextracted with FC-72 (50 mL) six times
  9. concentrationThe combined FC-72 layers were concentrated
  10. distillationVacuum distillation of the residue

出典と根拠

ORDレコード
ord-719229510f6f4da48a7b3ba2879c843c
出典データセット
uspto-grants-2004_04
特許番号
US06727390B2

反応ノート

読み込み中…