Water → N-methoxy-1,3,3-trimethyl-2,2-dioxo-6-[1-(3-pyridyl)pyrazol-4 yl]pyrido[3,2-c]thiazin-4-imine

HRID 1478540Notes

Reaction equation

HRID 1478540 reaction equation
C([O-])([O-])=O.[Na+].[Na+].O.CC1(C)C(C)(C)OB([C:16]2[CH:17]=[N:18][N:19]([C:21]3[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=3)[CH:20]=2)O1.Br[C:29]1[CH:30]=[CH:31][C:32]2[N:33]([CH3:46])[S:34](=[O:45])(=[O:44])[C:35]([CH3:43])([CH3:42])[C:36](=[N:39][O:40][CH3:41])[C:37]=2[N:38]=1>C(#N)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:41][O:40][N:39]=[C:36]1[C:35]([CH3:43])([CH3:42])[S:34](=[O:45])(=[O:44])[N:33]([CH3:46])[C:32]2[CH:31]=[CH:30][C:29]([C:16]3[CH:17]=[N:18][N:19]([C:21]4[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=4)[CH:20]=3)=[N:38][C:37]1=2

Participants

7

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 574162183-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)pyridineHCID 1237441886-bromo-N-methoxy-1,3,3-trimethyl-2,2-dioxo-pyrido[3,2-c]thiazin-4-imine

Product 1

HCID 90044061N-methoxy-1,3,3-trimethyl-2,2-dioxo-6-[1-(3-pyridyl)pyrazol-4 yl]pyrido[3,2-c]thiazin-4-imine

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6342AcetonitrileSolvent2×

Conditions

Temperature
100 °C

Procedure

To Na2CO3 (180 mg, 1.68 mmol) was added water (1.5 ml) and acetonitrile (2 ml) and the solution was degassed for 5 min with argon. 3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazol-1-yl]pyridine (109 mg, 0.40 mmol), a solution of 6-bromo-N-methoxy-1,3,3-trimethyl-2,2-dioxo-pyrido[3,2-c]thiazin-4-imine (117 mg, 0.34 mmol) in acetonitrile (2 ml) and Pd(dppf)Cl2 (13 mg, 0.017 mmol) were added sequentially followed by rinsing the flask with acetonitrile (1 ml). The mixture was stirred at 100° C. for 1 h then allowed to cool to ambient temperature. Water and ethyl acetate were added then the phases were separated. The aqueous phase was extracted with ethyl acetate. The combined organic phases were dried over Na2SO4, filtered and concentrated in vacuo. Purification by chromatography afforded two oxime isomers of N-methoxy-1,3,3-trimethyl-2,2-dioxo-6-[1-(3-pyridyl)pyrazol-4 yl]pyrido[3,2-c]thiazin-4-imine.

Workup

  1. customthe solution was degassed for 5 min with argon
  2. washby rinsing the flask with acetonitrile (1 ml)
  3. temperatureto cool to ambient temperature
  4. additionWater and ethyl acetate were added
  5. customthe phases were separated
  6. extractionThe aqueous phase was extracted with ethyl acetate
  7. dry with materialThe combined organic phases were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customPurification by chromatography

Sources & evidence

ORD record
ord-6b01e1b0a7cd45fd84ce49d672fc5a4e
Source dataset
uspto-grants-2016_08
Patent number
US09403845B2

Reaction notes

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