Dimethyl Sulfoxide → HCID 25054760, compound

HRID 2351124Notes

Reaction equation

HRID 2351124 reaction equation
C([Li])CCC.Br[C:7]1[CH:8]=[CH:9][C:10]2[CH2:16][CH2:15][C:14]3[CH:17]=[CH:18][CH:19]=[CH:20][C:13]=3[C:12](=[CH:21][CH2:22][CH2:23][N:24]([CH3:26])[CH3:25])[C:11]=2[CH:27]=1.[O:28]1[CH2:32]CCC1.CS(C)=[O:35]>>[CH3:26][N:24]([CH3:25])[CH2:23][CH2:22]/[CH:21]=[C:12]1/[C:13]2[CH:20]=[CH:19][CH:18]=[CH:17][C:14]=2[CH2:15][CH2:16][C:10]2[CH:9]=[CH:8][C:7]([C:32]([OH:28])=[O:35])=[CH:27][C:11]/1=2

Participants

5

Reactant 4

HCID 679Dimethyl Sulfoxide2×HCID 8028TetrahydrofuranHCID 54015509HCID 54015509, compoundHCID 178418339Butyllithium

Product 1

HCID 25054760HCID 25054760, compound

Conditions

Temperature
-70 °C

Procedure

A solution of n-butyl lithium (6 mmole) was added dropwise to an E/Z (1:1) isomeric mixture of 3-(3-bromo-10,11-dihydrodibenzo[a,d]cyclohepten-5-ylidene)-N,N-dimethylpropylamine (1.98 g., 5.6 mmole) in 100 ml. dry tetrahydrofuran at -70° C. under a nitrogen atmosphere. After the yellowish orange solution was stirred at -70° C. for an additional 10 minutes, gaseous carbon dioxide was bubbled through the reaction medium for 30 min. to give a pale yellow solution. The reaction mixture was allowed to warm gradually to room temperature, and was then concentrated under reduced pressure. The residue was dissolved in water, and then the solution was neutralized with 1N hydrochloric acid. The crude E/Z (1:1) mixture was chromatographed on a reverse phase PRP-1 semi-preparative column with 15% acetonitrile in water to give 0.05 g. of the E-isomer and 0.08 g. of the Z-isomer. Both isomers were obtained as lyophilized powders, without definitive melting points. Rechromatography of the resulting isomeric mixture (0.8 g.) yielded more pure E-isomer (0.09 g.), Z-isomer (0.16 g.) and also an E/Z (1:1) isomeric mixture (0.10 g). pmr (E-isomer) (DMSO/d6) δ: 7.79 (d, J=1.6 Hz, 1H, H4), 7.68 (dd, J=7.9, 1.6 Hz, 1H, H2), 7.12-7.29 (m, 5H, aromatic), 5.88 (t, J=7.2 Hz, 1H, CH=), 3.30 (m, 2H, CH2Ar), 2.85 (m, 2H, CH2Ar), 2.35-2.45 (m, 4H, NCH2CH 2), 2.10 (s, 6H, NMe2). pmr (Z-isomer) (DMSO/d6) δ: 7.78 (dd, J=7.8, 1.7 Hz, 1H, H2), 7.66 (d, J=1.5 Hz, 1H, H4), 7.36 (d, J=7.8 Hz, 1H, H1), 7.04-7.26 (m, 4H, aromatic), 5.86 (t, J=7.2 Hz, 1H, CH=), 3.32 (m, 2H, CH2Ar), 2.85, (m, 2H, CH2Ar), 2.10-2.44 (m, 4H, NCH2CH2), 2.07 (s, 6H, NMe2).

Workup

  1. customat -70° C.
  2. customgaseous carbon dioxide was bubbled through the reaction medium for 30 min.
  3. customto give a pale yellow solution
  4. temperatureto warm gradually to room temperature
  5. concentrationwas then concentrated under reduced pressure
  6. dissolutionThe residue was dissolved in water
  7. customThe crude E/Z (1:1) mixture was chromatographed on a reverse phase PRP-1 semi-preparative column with 15% acetonitrile in water
  8. customto give 0.05 g
  9. customBoth isomers were obtained
  10. customRechromatography of the resulting isomeric mixture (0.8 g.) yielded more pure E-isomer (0.09 g.), Z-isomer (0.16 g.)

Sources & evidence

ORD record
ord-a13fc6542a7044c798562d9c1728b5ac
Source dataset
uspto-grants-1989_10
Patent number
US04871865

Reaction notes

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