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Carbon Dioxide → (z)-11-(3-(Dimethylamino)propylidene)-6,11-dihydrodibenz[b,e]oxepin-9-carboxylic acid

HRID 2351122
Notes
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Reaction equation

HRID 2351122 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][O:10][C:9]3[CH:12]=[CH:13][CH:14]=[CH:15][C:8]=3/[C:7](=[CH:16]\[CH2:17][CH2:18][N:19]([CH3:21])[CH3:20])/[C:6]=2[CH:22]=1.O1CCCC1.C([Li])CCC.[C:33](=[O:35])=[O:34]>CCCCCC>[CH3:20][N:19]([CH3:21])[CH2:18][CH2:17]/[CH:16]=[C:7]1\[C:8]2[CH:15]=[CH:14][CH:13]=[CH:12][C:9]=2[O:10][CH2:11][C:5]2[CH:4]=[CH:3][C:2]([C:33]([OH:35])=[O:34])=[CH:22][C:6]\1=2
ParticipantsProcedureSources & evidenceReaction notes

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 8028TetrahydrofuranHCID 23053922(Z)-3-(9-Bromo-6,11-dihydrodibenz[b,e]oxepin-11-ylidene)-N,N-dimethylpropylamineHCID 178418339Butyllithium

Product 1

HCID 23053917(z)-11-(3-(Dimethylamino)propylidene)-6,11-dihydrodibenz[b,e]oxepin-9-carboxylic acid

Reagents, catalysts & solvents 1

HCID 8058
Hexane
Solvent

Procedure

Pure (Z)-3-(9-bromo-6,11-dihydrodibenz[b,e]oxepin-11-ylidene)-N,N-dimethylpropylamine (0.78 g., 2.2 mmole), in cold (-70° C.) dry tetrahydrofuran (50 mL), was treated with 2.4 mmole n-butyl lithium in hexane followed by gaseous carbon dioxide by the procedure of Example I, Step c. This provided the desired carboxylic acid which was recrystallized from water to yield 0.15 g. pure Z-isomer, m.p. >205° C. (decomp.) with melting at 210° C. pmr (CDCl3 /D2O) δ: 7.84 (d, J=1.8 Hz, 1H, H10), 7.81 (dd, J=6.4, 1.8 Hz, 1H, Hg), 6.94-7.35 (m, 5H, aromatic), 5.78 (t, J=6.9 Hz, 1H, CH=), 5.25 (s, 2H, CH2O), 3.20 (m, 2H, NCH2), 2.80 (s, 6H, NMe2), 2.50-2.90 (m, 2H, CH2).

Sources & evidence

ORD record
ord-6338fbc8ee924ed3bd3a26a21ca1ce03
Source dataset
uspto-grants-1989_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04871865

Reaction notes

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On this pageParticipantsProcedureSources & evidenceReaction notes