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

HRID 85349Notes

Reaction equation

HRID 85349 reaction equation
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

Participants

7

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-5753652ada8f436ebc212a6e28532d51
Source dataset
uspto-grants-2014_09
Patent number
US08847068B2

Reaction notes

Loading…