Pyridine → 9-(7-fluoro-4-propyl-2H-1,4-benzoxazin-3(4H)-on-6-yl)imino-8-thia-1,6-diazabicyclo[4.3.0]nonane-7-thione

HRID 1762025Notes

Reaction equation

HRID 1762025 reaction equation
[F:1][C:2]1[C:15]([NH:16][C:17]([N:19]2[CH2:24][CH2:23][CH2:22][CH2:21][NH:20]2)=[S:18])=[CH:14][C:5]2[N:6]([CH2:11][CH2:12][CH3:13])[C:7](=[O:10])[CH2:8][O:9][C:4]=2[CH:3]=1.N1C=CC=CC=1.[C:31](Cl)(Cl)=[S:32]>C(Cl)Cl>[F:1][C:2]1[C:15]([N:16]=[C:17]2[N:19]3[N:20]([CH2:21][CH2:22][CH2:23][CH2:24]3)[C:31](=[S:32])[S:18]2)=[CH:14][C:5]2[N:6]([CH2:11][CH2:12][CH3:13])[C:7](=[O:10])[CH2:8][O:9][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 1049PyridineHCID 10040ThiophosgeneHCID 14461655N-(7-fluoro-4-propyl-2H-1,4-benzoxazin-3(4H)-on-6-yl)aminothiocarbonylperhydropyridazine

Product 1

HCID 144616569-(7-fluoro-4-propyl-2H-1,4-benzoxazin-3(4H)-on-6-yl)imino-8-thia-1,6-diazabicyclo[4.3.0]nonane-7-thioneYield 87.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred, cold (-20°) solution of 12.0 g (0.0340 mole) of N-(7-fluoro-4-propyl-2H-1,4-benzoxazin-3(4H)-on-6-yl)aminothiocarbonylperhydropyridazine and 8.69 g (0.110 mole) of pyridine in 300 mL of methylene chloride was added dropwise 3.90 g (0.0340 mole) of thiophosgene. The resulting mixture was stirred at room temperature for approximately 18 hours. The reaction mixture was washed with dilute hydrochloric acid followed by an aqueous, saturated sodium chloride solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was treated with decolorizing charcoal and was filtered through a pad of silica gel. The filtrate was evaporated under reduced pressure leaving a solid residue. This residue (10.4 g) was combined with 3.6 g of a similar residue prepared in a similar manner. The resultant solid (14.0 g) was recrystallized from ethyl acetate and n-heptane to yield 11.7 g of 9-(7-fluoro-4-propyl-2H-1,4-benzoxazin-3(4H)-on-6-yl)imino-8-thia-1,6-diazabicyclo[4.3.0]nonane-7-thione, mp 112°-114° C. (corresponding to Compound 5 of Table 1).

Workup

  1. washThe reaction mixture was washed with dilute hydrochloric acid
  2. dry with materialThe washed organic phase was dried over anhydrous magnesium sulfate
  3. filtrationwas filtered
  4. additionThe filtrate was treated with decolorizing charcoal
  5. filtrationwas filtered through a pad of silica gel
  6. customThe filtrate was evaporated under reduced pressure
  7. customleaving a solid residue
  8. customprepared in a similar manner
  9. customThe resultant solid (14.0 g) was recrystallized from ethyl acetate and n-heptane

Sources & evidence

ORD record
ord-0575f981091747b3b0d3c5dfd9206f84
Source dataset
uspto-grants-1989_05
Patent number
US04830659

Reaction notes

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