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

HRID 2087125노트

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HRID 2087125 반응식
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

참가 물질

8

반응물 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

생성물 1

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

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 8028Tetrahydrofuran용매3회

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온도
65 °C

실험 절차

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)+.

후처리

  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

출처 및 근거

ORD 기록
ord-719229510f6f4da48a7b3ba2879c843c
출처 데이터셋
uspto-grants-2004_04
특허 번호
US06727390B2

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