Water → HCID 14552443, compound

HRID 1761678Notes

Reaction equation

HRID 1761678 reaction equation
N[C:2]1[S:3][C:4]2[CH2:13][C@H:12]3[C@@H:7]([CH:8]=[C:9]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:10][N:11]3[CH2:14][CH2:15][CH3:16])[CH2:6][C:5]=2[N:22]=1.N([O-])=O.[Na+].O.[PH2](O)=O>P(=O)(O)(O)O>[CH2:14]([N:11]1[C@@H:12]2[C@H:7]([CH2:6][C:5]3[N:22]=[CH:2][S:3][C:4]=3[CH2:13]2)[CH:8]=[C:9]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:10]1)[CH2:15][CH3:16]

Participants

6

Reactant 4

HCID 962Water2×HCID 4124402Phosphinic AcidHCID 18632325HCID 18632325, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 14552443HCID 14552443, compoundYield 100.1%

Reagents, catalysts & solvents 1

HCID 1004Phosphoric AcidSolvent

Procedure

A solution of 0.5 g (1.5 mmole) of ethyl 2-amino-5-propyl-trans-4,4a,5,6,8a,9-hexahydrothiazolo[4,5-g]quinoline-7-carboxylate (Example 3) in 50 ml of 85% phosphoric acid was cooled to 0° C. Then 110 mg (1.8 mmole) of sodium nitrite dissolved in as small an amount of water as possible was slowly added under the surface of the reaction mixture. The resulting mixture was added dropwise to 50 ml of 50% hypophosphorous acid (H3PO2) at 0° C. The mixture was stirred at room temperature until gas evolution ceased. This took about 1 hour. The mixture was poured onto ice, and the hydrogen ion concentration of the mixture was adjusted to pH 11. Water was added to dissolve the precipitate that formed; then the product was extracted into a solution of CHCl3 /i-PrOH (3:1). This solution was dried using sodium sulfate and evaporated to give 0.46 g of the title product.

Workup

  1. additionas possible was slowly added under the surface of the reaction mixture
  2. customThis took about 1 hour
  3. additionThe mixture was poured onto ice
  4. dissolutionto dissolve the precipitate that
  5. customformed
  6. extractionthen the product was extracted into a solution of CHCl3 /i-PrOH (3:1)
  7. customThis solution was dried
  8. customevaporated

Sources & evidence

ORD record
ord-4edd8f6df1394ab59f7ab91f1b4ff660
Source dataset
uspto-grants-1989_05
Patent number
US04826986

Reaction notes

Loading…