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

HRID 1650231
Notes
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Reaction equation

HRID 1650231 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, H8), 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-eeaf2781be5e43228d052a0fe47720c9
Source dataset
uspto-grants-1990_05
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04923892

Reaction notes

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On this pageParticipantsProcedureSources & evidenceReaction notes