Triethylamine → HCID 76764491, compound

HRID 1468732Notes

Reaction equation

HRID 1468732 reaction equation
[CH2:1]([O:8][C:9](=[O:21])[C:10]([OH:20])([CH2:15][CH:16]=[C:17]([CH3:19])[CH3:18])[CH2:11][C:12](O)=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.ClC1C=C(Cl)C=C(Cl)C=1C(Cl)=O.CCOC(C)=O>C(Cl)Cl.C(Cl)(Cl)Cl.CC(O)=O>[CH2:1]([O:8][C:9]([C:10]1([CH2:15][CH:16]=[C:17]([CH3:19])[CH3:18])[CH2:11][C:12](=[O:13])[O:20]1)=[O:21])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 27337032,4,6-Trichlorobenzoyl chlorideHCID 67043395HCID 67043395, compound

Product 1

HCID 76764491HCID 76764491, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of hydroxyester 75 (100 mg, 0.342 mmol, 1.00 equiv) and triethylamine (166 μL, 1.20 mmol, 3.50 equiv) in CH2Cl2 (14 mL) was added via syringe pump over 4 h to a solution of 2,4,6-trichlorobenzoyl chloride (80 μL, 0.51 mmol, 1.5 equiv) and N,N-dimethylaminopyridine (DMAP) (46 mg, 0.38 mmol, 1.1 equiv) in CH2Cl2 (3.4 mL). The solution was then allowed to stir for 1 h after complete addition after which time it was quenched with H2O (10 mL). The phases were separated and the aqueous phase was extracted with CH2Cl2 (2×10 mL). The organic phases were combined, dried over Na2SO4, and the solvent was removed via rotary evaporation to yield a red solid which was purified by silica gel column chromatography (CH2Cl2) to yield S10 (47 mg, 50%) as a pale yellow oil. Rf=0.79 (60:38:2 Hex:EtOAc:HOAc); 1H NMR (500 MHz, CDCl3) δ 7.37 (m, 5H, ArH), 5.25 (s, 2H, ArCH2), 5.09 (m, 1H, vinyl H), 3.61 (d, 1H, J=16.4 Hz, C(O)CH2), 3.36 (d, 1H, J=16.4 Hz, C(O)CH2), 2.79 (m, 2H, CHCH2), 1.70 (d, 3H, J=0.8 Hz, CH3), 1.60 (d, 3H, J=0.8 Hz, CH3); 13C NMR (100 MHz, CDCl3) δ 169.21, 165.84, 138.67, 134.67, 128.68, 128.38, 114.24, 76.28, 67.84, 45.56, 33.43, 25.87, 17.99; IR (neat film) 2966 (m), 2914 (m), 1842 (s), 1737 (s), 1452 (m) 962 (m) cm−1; HRMS (EI) m/z calcd for C16H18O4 (M+) 274.120509, observed 274.120646; [α]D=+1.2° (c 2.92, CHCl3).

Workup

  1. additionafter complete addition after which time it
  2. customwas quenched with H2O (10 mL)
  3. customThe phases were separated
  4. extractionthe aqueous phase was extracted with CH2Cl2 (2×10 mL)
  5. dry with materialdried over Na2SO4
  6. customthe solvent was removed via rotary evaporation
  7. customto yield a red solid which
  8. customwas purified by silica gel column chromatography (CH2Cl2)
  9. customto yield S10 (47 mg, 50%) as a pale yellow oil

Sources & evidence

ORD record
ord-40134173c87841c4ad97975966d1fb01
Source dataset
uspto-grants-2015_04
Patent number
US09006231B2

Reaction notes

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