Dichloromethane → HCID 86602905, compound

HRID 2252505Notes

Reaction equation

HRID 2252505 reaction equation
COC1C=CC(C[O:8][C@H:9]([C@H:58]([CH3:71])[CH2:59][C@@H:60]([CH3:70])[CH2:61][O:62][Si:63]([C:66]([CH3:69])([CH3:68])[CH3:67])([CH3:65])[CH3:64])[C@@H:10]([CH3:57])/[CH:11]=[CH:12]\[C@@H:13]([O:49][Si:50]([C:53]([CH3:56])([CH3:55])[CH3:54])([CH3:52])[CH3:51])[CH2:14][C@H:15]([O:41][Si:42]([C:45]([CH3:48])([CH3:47])[CH3:46])([CH3:44])[CH3:43])[C@@H:16]([CH3:40])/[CH:17]=[CH:18]/[CH2:19][O:20][C:21]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=CC=1.C(Cl)Cl.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>O>[Si:63]([O:62][CH2:61][C@H:60]([CH3:70])[CH2:59][C@@H:58]([CH3:71])[C@@H:9]([OH:8])[C@@H:10]([CH3:57])/[CH:11]=[CH:12]\[C@@H:13]([O:49][Si:50]([C:53]([CH3:56])([CH3:55])[CH3:54])([CH3:51])[CH3:52])[CH2:14][C@H:15]([O:41][Si:42]([C:45]([CH3:46])([CH3:47])[CH3:48])([CH3:44])[CH3:43])[C@@H:16]([CH3:40])/[CH:17]=[CH:18]/[CH2:19][O:20][C:21]([C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1)([C:66]([CH3:69])([CH3:67])[CH3:68])([CH3:65])[CH3:64]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 86602906HCID 86602906, compound

Product 1

HCID 86602905HCID 86602905, compoundYield 84%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

The above PMB alcohol 85 (2.90 g, 2.77 mmol) was added to CH2Cl2 (25 mL) and H2O (1 mL), and DDQ (0.94 g, 4.15 μmol) was added. After 1 h of stirring, the reaction mixture was quenched by adding sat'd NaHCO3 (200 mL). The organic phase was washed by sat'd NaHCO3 solution (3×100 mL) and brine, dried over MgSO4 and concentrated. Purification by flash column chromatography (EtOAc/hexane 5:95) furnished 86 (2.16 g, 84%) as a colorless oil: IR (CHCl3) 3477, 2956, 2928, 2856, 1471, 1386, 1254, 1088, 836, 774 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.55-7.52 (m, 6H), 7.38-7.25 (m, 9H), 5.92 (dd, J=15.7, 6.0 Hz, 1H), 5.62 (dt, J=15.7, 5.5 Hz, 1H), 5.52 (dd, J=11.1, 9.3 Hz, 1H), 5.35 (t, J=10.5 Hz, 1H), 4.63 (m, 1H), 3.97 (m, 1H), 3.63 (d, J=5.4 Hz, 2H), 3.51-3.36 (m, 2H), 3.18 (m, 1H), 2.68 (m, 1H), 2.47 (m, 1H), 1.71-1.59 (m, 3H), 1.42-1.27 (m, 2H), 1.17 (m, 1H), 1.08 (d, J=6.7 Hz, 3H), 1.04 (d, J=6.9 Hz, 3H), 0.99 (s, 9H), 0.97 (s, 9H), 0.96 (s, 9H), 0.91 (d, J=6.8 Hz, 3H), 0.84 (d, J=6.6 Hz, 3H), 0.18 (s, 3H), 0.16 (s, 3H), 0.15 (s, 3H), 0.13 (s, 3H), 0.12 (s, 6H); 13C NMR (75 MHz, CDCl3) δ 144.4, 135.2, 134.1, 131.1, 128.7, 127.7, 126.8, 126.4, 86.7, 79.8, 72.8, 69.6, 66.2, 65.2, 43.0, 42.1, 35.5, 33.7, 32.8, 32.5, 26.1, 26.0, 25.9, 18.4, 18.1, 17.6, 16.8, 16.3, 14.7, −2.9, −4.0, −4.15, −4.22, −5.3; LRMS (ESI) 951.7 [M+Na]+, 823.7, 577.4, 413.3, 328.4, 243.1; HRMS (ESI) calcd for C56H92O5Si3Na 951.6150 [M+Na]+, found 951.6165; [α]20D30.0 (c 3.6, CHCl3).

Workup

  1. additionwas added
  2. customthe reaction mixture was quenched
  3. additionby adding sat'd NaHCO3 (200 mL)
  4. washThe organic phase was washed by sat'd NaHCO3 solution (3×100 mL) and brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customPurification by flash column chromatography (EtOAc/hexane 5:95)

Sources & evidence

ORD record
ord-51def74f02054c24b54498db4b92761b
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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