Pivaloyl chloride → HCID 86719528, compound

HRID 713832Notes

Reaction equation

HRID 713832 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[P:8]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[Li]CCCC.[C:26](Cl)(=[O:31])[C:27]([CH3:30])([CH3:29])[CH3:28]>C1COCC1>[C:27]([C:26]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[P:8]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:31])([CH3:30])([CH3:29])[CH3:28]

Participants

5

Reactant 3

HCID 62493Pivaloyl chlorideHCID 112836(2-Bromophenyl)diphenylphosphineHCID 178418339Butyllithium

Product 1

HCID 86719528HCID 86719528, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (2-bromophenyl)diphenylphosphine (II-a) (0.50 mmol) in dry THF (2 mL) was added dropwise under argon at −78° C. n-BuLi (0.55 mmol). The resulting solution was stirred at this temperature during one hour and pivaloyl chloride (0.80 mmol) was then added dropwise. After stirring at room temperature overnight, the reaction mixture was quenched with water (10 mL) and extracted with methylene chloride (3×10 mL). The organic phases were dried over MgSO4, filtered and the solvent evaporated giving a residue which was purified by column chromatography on silica gel using petroleum ether/ethyl acetate 3:1 as eluent. White solid; Yield 78%; Rf 0.43 (petroleum ether/ethyl acetate 3:1); IR (neat) 3049, 2967, 2928, 2867, 1686, 1585, 1477, 1458, 1431, 1389, 1361, 1283, 1192, 967, 947, 778, 741, 691 cm−1; 1H NMR (300MHz, CDCl3) δ 1.35 (s, 9H, CH3), 7.18-7.22 (m, 1H, Harom), 7.25-7.40 (m, 13H, Harom); 13C NMR (75.5 MHz, CDCl3) δ 27.7 (d, J=3.3 Hz, CH3), 44.7 (C(CH3)3), 124.8 (d, J=8.6 Hz, Carom), 128.3 (Carom), 128.5 (d, J=4.9 Hz, Carom), 128.7 (Carom), 133.3 (Carom), 133.5 (Carom), 134.6 (d, J=15.8 Hz, Carom), 134.8 (d, J=2.2 Hz, Carom), 137.0 (d, J=10.4 Hz, Carom), 148.0 (d, J=35.8 Hz, Carom); 31P NMR (121 MHz, CDCl3) δ −10.4; HRMS calcd for C23H23PONa [M+Na]+369.1379, found 369.1382.

Workup

  1. stirringAfter stirring at room temperature overnight
  2. customthe reaction mixture was quenched with water (10 mL)
  3. extractionextracted with methylene chloride (3×10 mL)
  4. dry with materialThe organic phases were dried over MgSO4
  5. filtrationfiltered
  6. customthe solvent evaporated
  7. customgiving a residue which
  8. customwas purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-d4508becba854792ba212100de557d0c
Source dataset
uspto-grants-2015_11
Patent number
US09186661B2

Reaction notes

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