Ammonium Chloride → 3-(4-Bromobutyl)-4'-hexyl-2,2'-bithiophene

HRID 85349노트

반응식

HRID 85349 반응식
C([O-])(O)=O.[Na+].Br[C:7]1[S:8][CH:9]=[CH:10][C:11]=1[CH2:12][CH2:13][CH2:14][CH2:15][Br:16].[CH2:17]([C:23]1[CH:24]=[C:25](B2OCC(C)(C)CO2)[S:26][CH:27]=1)[CH2:18][CH2:19][CH2:20][CH2:21][CH3:22].[NH4+].[Cl-]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.COCCOC>[Br:16][CH2:15][CH2:14][CH2:13][CH2:12][C:11]1[CH:10]=[CH:9][S:8][C:7]=1[C:25]1[S:26][CH:27]=[C:23]([CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[CH:24]=1

참가 물질

7

반응물 4

HCID 25517Ammonium ChlorideHCID 516892Sodium BicarbonateHCID 58419406HCID 58419406, 화합물HCID 668235992-Bromo-3-(4-bromobutyl)thiophene

생성물 1

HCID 668239393-(4-Bromobutyl)-4'-hexyl-2,2'-bithiophene수율 45%

시약·촉매·용매 2

HCID 178418397HCID 178418397, 화합물촉매HCID 80711,2-Dimethoxyethane용매

반응 조건

온도
80 °C

실험 절차

A mixture of a saturated solution of NaHCO3 (115 ml) and DME (230 ml) was sparged with argon for 45 minutes. 2-bromo-3-(4-bromobutyl)thiophene (10.4 g, 35 mmol) and 2-(4-hexylthiophen-2-yl)-5,5-dimethyl-1,3,2-dioxaborinane (9.9 g, 35 mmol) were added, followed by addition of Pd(PPh3)4. After warming up to 80° C., the mixture became first bright yellow, and then dark orange. After stirring at 80° C. for 18 h, a saturated solution of NH4Cl (aq, 210 ml) was added, and the mixture was extracted with ether. The organic phase was washed with water, a saturated solution of NaHCO3 and brine. After drying over magnesium sulfate and solvent removal, the dark orange oil was purified by column chromatography using hexanes as the eluent. The product (6.07 g, 45% yield) was isolated as a pale yellow oil and used without further purification. 1H-NMR (ppm, CDCl3): 0.87 (3H, t, J=6.96 Hz), 1.25-1.36 (6H, m), 1.61 (2H, m), 1.76 (2H, m), 1.88 (2H, m), 2.58 (2H, t, J=8.52 Hz), 2.76 (2H, t, J=7.56 Hz), 3.38 (2H, t, J=6.72 Hz), 6.86-6.93 (3H, m), 7.14 (1H, d, J=5.2 Hz); 13C-NMR (ppm, CDCl3): 14.1, 21.2, 22.3, 29.0, 29.2, 30.5, 30.7, 31.0, 31.1, 31.8, 121.2, 123.6, 128.1, 129.8, 132.0, 135.5, 137.1; ESI-MS (m/z) found: 385.06, [M+H], calculated: 385.06.

후처리

  1. customwas sparged with argon for 45 minutes
  2. extractionthe mixture was extracted with ether
  3. washThe organic phase was washed with water
  4. dry with materialAfter drying over magnesium sulfate and solvent removal
  5. customthe dark orange oil was purified by column chromatography

출처 및 근거

ORD 기록
ord-5753652ada8f436ebc212a6e28532d51
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08847068B2

반응 노트

불러오는 중…