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Sodium Carbonate → 6,7-Difluorobenzo[B]thiazolo[3,4-D][1,4]oxazine-1(4H)-thione

HRID 1382737
Notes
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Reaction equation

HRID 1382737 reaction equation
[OH:1][CH2:2][C:3]1[N:4]([C:9]2[CH:14]=[CH:13][C:12]([F:15])=[C:11]([F:16])[C:10]=2F)[C:5](=[S:8])[S:6][CH:7]=1.[H-].[Na+].C(=O)([O-])[O-].[K+].[K+].C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.C(#N)C.CN(C)C=O>[F:16][C:11]1[C:10]2[O:1][CH2:2][C:3]3=[CH:7][S:6][C:5](=[S:8])[N:4]3[C:9]=2[CH:14]=[CH:13][C:12]=1[F:15]
ParticipantsProcedureSources & evidenceReaction notes

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 11430Potassium CarbonateHCID 24758Sodium hydrideHCID 146733094-hydroxymethyl-3-(2,3,4-trifluorophenyl)-2(3H)-thiazolethione

Product 1

HCID 146733106,7-Difluorobenzo[B]thiazolo[3,4-D][1,4]oxazine-1(4H)-thione

Reagents, catalysts & solvents 3

HCID 6228
Dimethylformamide
Solvent
HCID 6342AcetonitrileSolvent
HCID 312751,4-DioxaneSolvent

Procedure

That is, first the compound (VI) is obtained from the compound (V) in the same manner as in the process (a). The compound (VI) is then reacted with 1-acetoxy-3-halogenoacetone in an organic solvent such as chloroform, methylene chloride or a lower alcohol to give 3-acetoxy-2-oxopropyl N-(2,3,4-trifluorophenyl)dithiocarbamate (XVI). The compound (XVI) is then heated with an inorganic acid such as hydrochloric acid or sulfuric acid in a lower alcohol such as ethanol to give 4-hydroxymethyl-3-(2,3,4-trifluorophenyl)-2(3H)-1,3-thiazolethione (XVII). The compound (XVII) is then reacted with an inorganic base such as sodium hydride, potassium carbonate or sodium carbonate in an aprotic organic solvent such as N,N-dimethylformamide, acetonitrile or dioxane to give 6,7-difluoro-1H,4H-thiazolo[4,3-c][1,4]benzoxazine-1-thione (XVIII). The compound (XVIII) is then reacted with a lower alkyl halide such as methyl iodide or ethyl iodide in a polar organic solvent such as N,N-dimethylformamide, acetonitrile or ethanol to give 6,7-difluoro-1-alkylthio-4H-[1,4]benzoxazino[4,3-c]thiazolium halide (XIX). The compound (XIX) is then reacted with di(lower alkyl) malonate sodium salt, which is prepared from di(lower alkyl) malonate and sodium hydride, in an organic solvent such as tetrahydrofuran or dioxane to give di(lower alkyl) (6,7-difluoro-1H,4H-thiazolo[4,3-c][1,4]benzoxazin-1-ylidene)malonate (XI), which is treated in the same manner as in the process (a) to give the compound (II).

Sources & evidence

ORD record
ord-19c1a99ed3254571a5b94bd9e3203c42
Source dataset
uspto-grants-1989_02
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04808584

Reaction notes

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