Acetonitrile → 7-(2-Chloroethoxy)-8-methoxy-4-oxo-1,4-dihydrobenzo[g]quinoline-3-carbonitrile

HRID 2213802Notes

Reaction equation

HRID 2213802 reaction equation
C([Li])CCC.[C:6](#[N:8])[CH3:7].ClCCO[C:13]1[CH:14]=[C:15]2[C:20](=[CH:21][C:22]=1OC)[CH:19]=[C:18]([C:25](OCC)=O)[C:17](/[N:30]=C/N(C)C)=C2.[Cl:35][CH2:36][CH2:37][O:38][C:39]1[CH:48]=[C:47]2[C:42]([CH:43]=[C:44](/[N:54]=[CH:55]/N(C)C)[C:45]([C:49]([O:51]CC)=O)=[CH:46]2)=[CH:41][C:40]=1[O:59][CH3:60]>O1CCCC1>[N:8]1[C:15]2[C:20](=[CH:21][CH:22]=[CH:13][CH:14]=2)[CH:19]=[C:18]([C:17]#[N:30])[CH:25]=1.[Cl:35][CH2:36][CH2:37][O:38][C:39]1[C:40]([O:59][CH3:60])=[CH:41][C:42]2[CH:43]=[C:44]3[C:45]([C:49](=[O:51])[C:7]([C:6]#[N:8])=[CH:55][NH:54]3)=[CH:46][C:47]=2[CH:48]=1

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 178418339ButyllithiumHCID 178468532HCID 178468532, compoundHCID 178468534HCID 178468534, compound

Product 2

HCID 931773-QuinolinecarbonitrileHCID 116384657-(2-Chloroethoxy)-8-methoxy-4-oxo-1,4-dihydrobenzo[g]quinoline-3-carbonitrileYield 76%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

To 2.5 mL of dry tetrahydrofuran at −78° C. is added 1.8 mL of 2.5 M n-butyllithium (4.4 mmol). Then 0.24 mL of dry acetonitrile in 4.5 mL of dry tetrahydrofuran is added dropwise over 10 minutes. This is stirred and additional 15 minutes at −78° C., then the ethyl 6-(2-chloroethoxy)-3-{[(E)-(dimethylamino)methylidene]-amino}-7-methoxy-2-naphthoate and ethyl 7-(2-chloroethoxy)-3-{[(E)-(dimethylamino)methylidene]amino}-6-methoxy-2-naphthoate (1:1 mixture) is dissolved in 3 mL of tetrahydrofuran and added dropwise over 15 minutes. The reaction mixture is stirred for 30 minutes at −78° C., then quenched with 0.57 mL of glacial acetic acid, and warmed to room temperature. To the yellow mixture is added 10 mL of water. The solids are filtered, washed with water and dried to give 0.502 g of 8-(2-chloroethoxy)-7-methoxy-4-oxo-1,4-dihydrobenzo]quinoline-3-carbonitrile and 7-(2-chloroethoxy)-8-methoxy-4-oxo-1,4-dihydrobenzo[g]quinoline-3-carbonitrile (1:1 mixture) as a yellow green solid (76%), m.p. 260–73° C. dec.

Workup

  1. additionadded dropwise over 15 minutes
  2. stirringThe reaction mixture is stirred for 30 minutes at −78° C.
  3. customquenched with 0.57 mL of glacial acetic acid
  4. temperaturewarmed to room temperature
  5. additionTo the yellow mixture is added 10 mL of water
  6. filtrationThe solids are filtered
  7. washwashed with water
  8. customdried

Sources & evidence

ORD record
ord-8747ecffbcf84c2dbd2c5aa5a1a4f561
Source dataset
uspto-grants-2006_09
Patent number
US07105531B2

Reaction notes

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