Triethylamine → HCID 24879673, compound

HRID 1468736Notes

Reaction equation

HRID 1468736 reaction equation
[CH2:1]([O:8][C:9]([C@@:11]([OH:19])([CH2:16][CH:17]=[CH2:18])[CH2:12][C:13]([OH:15])=O)=[O:10])[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>C(Cl)Cl>[CH2:16]([C@:11]1([C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)=[O:10])[CH2:12][C:13](=[O:15])[O:19]1)[CH:17]=[CH2:18]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 27337032,4,6-Trichlorobenzoyl chlorideHCID 24879672HCID 24879672, compound

Product 1

HCID 24879673HCID 24879673, compoundYield 67.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of hydroxyacid 81 (1.02 g, 3.86 mmol, 1.00 equiv) and triethylamine (519 μL, 17.37 mmol, 4.50 equiv) in CH2Cl2 (77 mL) was added via syringe pump over 4 h to a solution of 2,4,6-trichlorobenzoyl chloride (904 μL, 5.79 mmol, 1.50 equiv) and N,N-dimethylaminopyridine (DMAP) (519 mg, 4.25 mmol, 1.10 equiv) in CH2Cl2 (39 mL). The solution was then allowed to stir for 30 minutes after complete addition after which it was quenched with H2O (100 mL). The phases were separated and the aqueous phase was extracted with CH2Cl2 (2×100 mL). The organic phases were combined, dried over MgSO4, and the solvent was removed via rotary evaporation to yield a black oil which was purified by silica gel column chromatography (CH2Cl2) to yield 82 (639 mg, 67%) as a yellow oil. Rf=0.52 (CH2Cl2); 1H NMR (500 MHz, CDCl3) δ 7.38 (m, 5H, aryl H), 5.76 (m, 1H, vinyl H), 5.26 (s, 2H, PhCH2), 5.22 (m, 2H, vinyl H), 3.65 (d, 1H, J=16.5 Hz, C(O)CH2), 3.42 (d, 1H, J=16.5 Hz, C(O)CH2), 2.89 (dd, 1H, J=14.6, 6.8 Hz, CHCH2), 2.80 (dd, 1H, J=14.6, 6.8 Hz, CHCH2); 13C NMR (125 MHz, CDCl3) δ 169.03, 165.61, 134.75, 129.10, 128.95, 128.89, 128.59, 121.82, 75.65, 68.17, 45.86, 39.06; IR (neat film) 3034 (w), 1843 (s), 1741 (s), 1644 (w), 1456 (m) cm−1; LRMS (ESI) calcd. for C14H14O4Na (M+Na+) 269.1, observed 269.1.

Workup

  1. additionafter complete addition after which it
  2. customwas quenched with H2O (100 mL)
  3. customThe phases were separated
  4. extractionthe aqueous phase was extracted with CH2Cl2 (2×100 mL)
  5. dry with materialdried over MgSO4
  6. customthe solvent was removed via rotary evaporation
  7. customto yield a black oil which
  8. customwas purified by silica gel column chromatography (CH2Cl2)

Sources & evidence

ORD record
ord-75c07f0793da48aca414c9bb765037c9
Source dataset
uspto-grants-2015_04
Patent number
US09006231B2

Reaction notes

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