Ammonia → HCID 14721509, compound

HRID 2379787Notes

Reaction equation

HRID 2379787 reaction equation
Br[CH:2]1[C:7]([CH3:9])([CH3:8])[O:6][C:5]2[CH:10]=[CH:11][C:12]([S:14]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)(=[O:16])=[O:15])=[CH:13][C:4]=2[CH:3]1O.[NH3:24].C([OH:27])C>>[NH2:24][CH:3]1[CH:2]([OH:27])[C:7]([CH3:8])([CH3:9])[O:6][C:5]2[CH:10]=[CH:11][C:12]([S:14]([C:17]3[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=3)(=[O:16])=[O:15])=[CH:13][C:4]1=2

Participants

4

Reactant 3

HCID 222AmmoniaHCID 702EthanolHCID 14517462HCID 14517462, compound

Product 1

HCID 14721509HCID 14721509, compound

Procedure

A solution of 3-bromo-3,4-dihydro-2,2-dimethyl-6-phenylsulfonyl-2H-benzo[b]pyran-4-ol in ethanol is shaken under a pressure of 8 bar of NH3 at 50° in an autoclave for 8 hours. The mixture is cooled and then evaporated to dryness and recrystallized from ethyl acetate. 4-Amino-3,4-dihydro-2,2-dimethyl-6-phenylsulfonyl-2H-benzo[b]pyran-3-ol of melting point: 160°-163°C. is obtained and is immediately subjected to acylation with 4-chlorobutyryl chloride. For this purpose, the substance is dissolved together with the acid chloride in CH2Cl2 and stirred in a two-phase mixture with 2N sodium hydroxide solution at room temperature for 24 hours. The usual working up results in 4-(4-chlorobutyrylamino)-3,4-di-hydro-2,2-dimethyl-6-phenylsulfonyl-2H-benzo[b]pyran-4-ol of melting point 155°-157° C. Cyclization to give the title compound is carried out by dissolving the substance in tetrahydrofuran, addition of a stoichiometric amount of 80% NaH suspension in oil and stirring the mixture at room temperature for 24 hours. The final product is identical to the product obtained by process b). Melting point: 200°-201° C. If 4-amino-3,4-dihydro-2,2-dimethyl-6-phenylsulfonyl-2H-benzo[b]pyran-3-ol is subjected to racemate resolution, it is possible to obtain from its (+) enantiomer the pure (+) enantiomer from Example 5a with the data indicated there.

Workup

  1. temperatureThe mixture is cooled
  2. customevaporated to dryness
  3. customrecrystallized from ethyl acetate

Sources & evidence

ORD record
ord-9b7969234e674ff39efe890100e59247
Source dataset
uspto-grants-1994_11
Patent number
US05364878

Reaction notes

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