Sodium Methoxide → Allyl trans-2-[3-(7-Bromo-6-methylthioquinazolin-4(3H)-on-3-yl)-2-oxopropyl]-3-methoxy-1-piperidinecarboxylate

HRID 34616Notes

Reaction equation

HRID 34616 reaction equation
C(O)=O.[Br:4][C:5]1[CH:14]=[C:13]2[C:8]([C:9](=[O:15])[NH:10][CH:11]=[N:12]2)=[CH:7][C:6]=1[S:16][CH3:17].C[O-].[Na+].Br[CH2:22][C:23](=[O:39])[CH2:24][C@H:25]1[C@H:30]([O:31][CH3:32])[CH2:29][CH2:28][CH2:27][N:26]1[C:33]([O:35][CH2:36][CH:37]=[CH2:38])=[O:34]>CO>[Br:4][C:5]1[CH:14]=[C:13]2[C:8]([C:9](=[O:15])[N:10]([CH2:22][C:23](=[O:39])[CH2:24][C@H:25]3[C@H:30]([O:31][CH3:32])[CH2:29][CH2:28][CH2:27][N:26]3[C:33]([O:35][CH2:36][CH:37]=[CH2:38])=[O:34])[CH:11]=[N:12]2)=[CH:7][C:6]=1[S:16][CH3:17]

Participants

5

Reactant 3

HCID 10942334Sodium MethoxideHCID 86741991Allyl trans-2-(3-bromo-2-oxopropyl)-3-methoxy-1-piperidinecarboxylateHCID 1357451507-bromo-6-methylthioquinazolin-4(3H)-one formic acid salt

Product 1

HCID 86742319Allyl trans-2-[3-(7-Bromo-6-methylthioquinazolin-4(3H)-on-3-yl)-2-oxopropyl]-3-methoxy-1-piperidinecarboxylate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

Under a nitrogen atmosphere in a flame dried flask at room temperature and with magnetic stirring, a suspension of 0.43 g (0.00136 mol) of 7-bromo-6-methylthioquinazolin-4(3H)-one formic acid salt in 5 ml of methanol was treated with two equivalents of sodium methoxide in methanol (approximately 1N). After 15 minutes 0.53 g (0.0016 mol) of allyl trans-2-(3-bromo-2-oxopropyl)-3-methoxy-1-piperidinecarboxylate was added in one portion. After being stirred for an hour, the reaction mixture was evaporated under reduced pressure, and the residue was taken up in about 15 ml of water. The aqueous solution was extracted three times with 15 ml portions of dichloromethane. The combined extracts were dried over anhydrous sodium sulfate, filtered, and evaporated to afford the title compound: yield 0.61 g (86%). 1H-NMR(CDCl3): 1.3-2.0 ppm (multiplet, 4H, CH3OCHCH2CH2CH2N), 2.6 (singlet, 3H, CH3S), 2.8-3.0 (multiplet, 4H, COCH2CH and NCH2), 3.3 (broad singlet, 1H, CH2CHNCO), 3.4 (singlet, 3H CH3O), 4.0 (broad doublet, 1H, CHOCH3), 4.6 (broad doublet 2H, CH2CH=CH2), 4.8-5.1 (multiple peaks, 2H, NCH2CO), 5.2-5.4 (multiplet, 2H, CH2 =CH), 5.9 (octet, 1H, CH=CH2), 7.3 (singlet, 1H, aromatic H), 7.9 (singlet, 1H, aromatic H), 7.95 (singlet, 1H, N=CH--N).

Workup

  1. customUnder a nitrogen atmosphere in a flame dried flask at room temperature
  2. customthe reaction mixture was evaporated under reduced pressure
  3. extractionThe aqueous solution was extracted three times with 15 ml portions of dichloromethane
  4. dry with materialThe combined extracts were dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. customevaporated

Sources & evidence

ORD record
ord-4a11b9ad41c6471abd9f2f521e6410a2
Source dataset
uspto-grants-1988_08
Patent number
US04762838

Reaction notes

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