Trifluoroacetic acid → 2,4-Dibromo-5-(1-(cyclohexyloxy)ethoxy)phenyl acetate

HRID 1481839노트

반응식

HRID 1481839 반응식
[C:1]([O:4][C:5]1[CH:10]=[C:9]([OH:11])[C:8]([Br:12])=[CH:7][C:6]=1[Br:13])(=[O:3])[CH3:2].C(O[CH:17]1[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1)=C.F[C:24](F)(F)[C:25](O)=[O:26].C(N(CC)CC)C>C1(C)C=CC=CC=1>[C:25]([O:11][C:9]1[CH:10]=[C:5]([O:4][CH:1]([O:3][CH:17]2[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]2)[CH3:2])[C:6]([Br:13])=[CH:7][C:8]=1[Br:12])(=[O:26])[CH3:24]

참가 물질

6

반응물 4

HCID 6422Trifluoroacetic acidHCID 8471TriethylamineHCID 75129Cyclohexane, (ethenyloxy)-HCID 1178177972,4-Dibromo-5-hydroxyphenyl acetate

생성물 1

HCID 1178178392,4-Dibromo-5-(1-(cyclohexyloxy)ethoxy)phenyl acetate수율 669.8%

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

Under nitrogen, 2,4-dibromo-5-hydroxyphenyl acetate (4.00 grams, 12.9 millimoles, 1.0 equivalent) and cyclohexyl vinyl ether (2.74 milliliters, 19.3 millimoles, 1.5 equivalents) was dissolved in toluene (50 milliliters). Trifluoroacetic acid (0.10 milliliters, 1.29 millimoles, 0.10 equivalent) was added, and the mixture stirred at room temperature overnight (18-24 hours). The reaction was quenched by adding triethylamine (0.53 milliliters, 3.87 millimoles, 0.3 equivalent), and the volatiles were removed on the rotary evaporator. The resulting oil was taken up in diethyl ether (30 milliliters) and filtered through a plug of basic alumina. The product was rinsed through with additional ether (500 milliliters). The solvent was removed on the rotary evaporator and the resulting oil was pumped on for over 24 hours. The product was obtained as a racemate in the form of a slightly yellow oil (3.77 grams, 8.64 millimoles, 67%). 1H NMR (400 MHz, CDCl3) δ 7.76 (s, 1H), 7.00 (s, 1H), 5.48 (q, J=5.4 Hz, 1H), 3.69 (tt, J=9.1, 3.9 Hz, 1H), 2.34 (s, 3H), 1.94-1.63 (m, 4H), 1.55-1.48 (m, 1H), 1.52 (d, J=5.3 Hz, 3H), 1.44-1.02 (m, 5H); 13C NMR (101 MHz, THF-d8) δ 168.19, 154.65, 149.40, 136.68, 114.35, 111.79, 108.79, 100.94, 75.66, 34.45, 33.33, 26.69, 24.97, 24.85, 20.94, 20.55; FTIR (film) 647, 703, 725, 840, 891, 979, 1018, 1059, 1170, 1190, 1248, 1279, 1368, 1393, 1466, 1584, 1779, 2856, 2932 cm−1; UV/Vis 223, 232 (overlapping), 290 nm; ESI/MS/MS of m/z=459: 459 [M79Br/81Br+Na]+, 341, 281, 207, 151, 109 83 [C6H11]+; HRMS (ESI+): calc. for C16H20Br2NaO4+[M+Na]+456.9621, found 456.9628.

후처리

  1. customThe reaction was quenched
  2. customthe volatiles were removed on the rotary evaporator
  3. filtrationfiltered through a plug of basic alumina
  4. washThe product was rinsed through with additional ether (500 milliliters)
  5. customThe solvent was removed on the rotary evaporator
  6. customwas pumped on for over 24 hours

출처 및 근거

ORD 기록
ord-6a7a6f61a2474e62b8724d0da1a88cd7
출처 데이터셋
uspto-grants-2016_08
특허 번호
US09410016B2

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