Dichloromethane → HCID 86602911, compound

HRID 2252507Notes

Reaction equation

HRID 2252507 reaction equation
[CH3:1][O:2][C:3](=[O:77])/[CH:4]=[CH:5]\[CH:6]=[CH:7]\[C@H:8]([CH3:76])[C@@H:9]([O:68][Si:69]([C:72]([CH3:75])([CH3:74])[CH3:73])([CH3:71])[CH3:70])[CH2:10][C@H:11]([O:60][Si:61]([C:64]([CH3:67])([CH3:66])[CH3:65])([CH3:63])[CH3:62])/[CH:12]=[CH:13]\[C@H:14]([CH3:59])[C@H:15]([O:51][Si:52]([C:55]([CH3:58])([CH3:57])[CH3:56])([CH3:54])[CH3:53])[C@H:16]([CH3:50])[CH2:17][C@@H:18]([CH3:49])[CH2:19][CH2:20][C@@H:21]([O:41][Si:42]([C:45]([CH3:48])([CH3:47])[CH3:46])([CH3:44])[CH3:43])[C@H:22]([CH3:40])[C@@H:23]([O:30]CC1C=CC(OC)=CC=1)[C@@H:24]([CH3:29])/[CH:25]=[CH:26]\[CH:27]=[CH2:28].C(Cl)Cl.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>O>[CH3:1][O:2][C:3](=[O:77])/[CH:4]=[CH:5]\[CH:6]=[CH:7]\[C@H:8]([CH3:76])[C@@H:9]([O:68][Si:69]([C:72]([CH3:75])([CH3:74])[CH3:73])([CH3:70])[CH3:71])[CH2:10][C@H:11]([O:60][Si:61]([C:64]([CH3:67])([CH3:66])[CH3:65])([CH3:62])[CH3:63])/[CH:12]=[CH:13]\[C@H:14]([CH3:59])[C@H:15]([O:51][Si:52]([C:55]([CH3:56])([CH3:57])[CH3:58])([CH3:54])[CH3:53])[C@H:16]([CH3:50])[CH2:17][C@@H:18]([CH3:49])[CH2:19][CH2:20][C@@H:21]([O:41][Si:42]([C:45]([CH3:46])([CH3:47])[CH3:48])([CH3:43])[CH3:44])[C@H:22]([CH3:40])[C@@H:23]([OH:30])[C@@H:24]([CH3:29])/[CH:25]=[CH:26]\[CH:27]=[CH2:28]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 86602912HCID 86602912, compound

Product 1

HCID 86602911HCID 86602911, compoundYield 83,882.5%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

The ester 96 (0.15 g, 0.14 μmol) was added to CH2Cl2 (5 mL) and H2O (0.2 mL) and DDQ (34 mg, 0.15 μmol) was added at 0° C. After 1 h of stirring at 0° C., the reaction mixture was quenched by adding sat'd NaHCO3 (5 mL). The organic phase was washed by sat'd NaHCO3 solution (3×10 mL) and brine, dried over MgSO4 and concentrated. Purification by flash column chromatography (EtOAc/hexane 1:9) furnished 97 (0.12 g, 90%) as a colorless oil: IR (CHCl3) 3540, 2956, 2929, 2856, 1641, 1601, 1471, 1462, 1407, 1379, 1361, 1255, 1174, 1089, 1004, 836, 773 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.33 (dd, J=15.5, 11.2 Hz, 1H), 6.61 (ddd, J=16.9, 10.5, 10.4 Hz, 1H), 6.51 (t, J=11.4 Hz, 1H), 6.17 (dd, J=15.5, 5.9 Hz, 1H), 6.07 (t, J=11.0 Hz, 1H), 5.54 (d, J=11.3 Hz, 1H), 5.45-5.37 (m, 2H), 5.28 (m, 1H), 5.18 (d, J=16.8 Hz, 1H), 5.09 (d, J=10.1 Hz, 1H), 4.51 (m, 1H), 3.91 (m, 1H), 3.74 (m, 1H), 3.69 (s, 3H), 3.45 (m, 1H), 3.23 (m, 1H), 3.76 (m, 1H), 2.56 (m, 2H), 2.29 (br, 1H), 1.68 (m, 1H), 1.56-1.41 (m, 3H), 1.34-1.17 (m, 3H), 1.02 (d, J=6.9 Hz, 3H), 0.97 (d, J=6.9 Hz, 3H), 0.94 (d, J=6.8 Hz, 3H), 0.90-0.84 (m, 40H), 0.81 (d, J=5.8 Hz, 3H), 0.77 (d, J=6.5 Hz, 3H), 0.76 (d, J=6.2 Hz, 3H), 0.08-0.01 (m, 24H); 13C NMR (75 MHz, CDCl3) δ 166.8, 147.3, 145.5, 135.3, 133.0, 132.3, 131.5, 129.9, 126.4, 117.6, 115.2, 81.3, 77.5, 76.7, 72.7, 66.4, 50.9, 42.9, 42.6, 40.1, 37.9, 36.1, 35.4, 35.2, 33.8,.32.2, 30.6, 26.2, 26.0, 25.9, 19.6, 19.0, 18.4, 18.10, 18.05, 17.7, 16.6, 14.4, 6.9, −2.8, −3.5, −3.6, −3.7, −4.1, −4.15, −4.21, −4.4; LRMS (ESI) 1043.7 [M+Na]+, 889.8, 757.6, 625.5, 544.3, 364.4; HRMS (ESI) calcd for C57H112O7Si4Na 1043.7383 [M+Na]+, found 1043.7433; [α]20D−40.3 (c 2.1, CHCl3).

Workup

  1. additionwas added at 0° C
  2. customthe reaction mixture was quenched
  3. additionby adding sat'd NaHCO3 (5 mL)
  4. washThe organic phase was washed by sat'd NaHCO3 solution (3×10 mL) and brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customPurification by flash column chromatography (EtOAc/hexane 1:9)

Sources & evidence

ORD record
ord-db8e62619ac7436faaa2b64ca0362072
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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