Hydrochloric Acid → HCID 178527425, compound

HRID 343280Notes

Reaction equation

HRID 343280 reaction equation
C1(O)C=CC=CC=1.Cl[C:9]1[C:10]([C:19]2[CH:24]=[CH:23][C:22](O)=[CH:21][C:20]=2F)=[N:11][N:12](C)[C:13]=1OC(F)F.B(Br)(Br)Br.N([O-])=O.[Na+].C1(S)C=CC=CC=1.[ClH:42].[S:43](=[O:45])=[O:44]>O.C(O)(=O)C.[Fe].O.O.O.O.O.S([O-])([O-])(=O)=O.[Cu+2].[Cu](Cl)Cl>[NH:12]1[CH:13]=[CH:9][C:10]([C:19]2[CH:24]=[CH:23][C:22]([S:43]([Cl:42])(=[O:45])=[O:44])=[CH:21][CH:20]=2)=[N:11]1

Participants

13

Reactant 7

HCID 313Hydrochloric AcidHCID 996PhenolHCID 1119Sulfur DioxideHCID 7969ThiophenolHCID 25134Boron tribromideHCID 23668193Sodium Nitrite2×HCID 136066305HCID 136066305, compound

Product 1

HCID 178527425HCID 178527425, compound

Reagents, catalysts & solvents 5

HCID 23925IronCatalystHCID 24014Cupric ChlorideCatalystHCID 24463Copper sulfate pentahydrateCatalystHCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

Scheme 3A, above, illustrates how the phenol JO, for example, 4-(4-chloro-5-difluoromethoxy-1-methylpyrazol-3-yl)-3-fluorophenol, may be prepared. In one route, JO is obtained from HO by treatment with boron tribromide. Alternatively, HS can be reduced with iron powder and acetic acid in water, affording K. Compound K can then be diazotized with sodium nitrite under strong acidic conditions and treated with copper sulfate pentahydrate to yield the targeted intermediate JO. Examples 1 and 2 provide detailed descriptions of the preparation of these intermediates. To prepare the thiophenol JS, K can be diazotized with sodium nitrite and hydrochloric acid, then treated with copper(II) chloride and sulfur dioxide in acetic acid, to yield the corresponding 4-(pyrazol-3-yl)phenylsulfonyl chloride L. Compound L can then in turn be treated with tin(II) chloride in acetic acid, affording the targeted intermediate JS, for example, 4-(4-chloro-5-difluoromethoxyl-1-methylpyrazol-3-yl)thiophenol. Example 9 provides a detailed description of the preparation of this intermediate. ##STR12##

Workup

  1. customaffording K
  2. customto yield the targeted intermediate JO
  3. customExamples 1 and 2 provide
  4. customdescriptions of the preparation of these intermediates

Sources & evidence

ORD record
ord-3d54dd88b4ec41dba80ecb0c12d5c7b6
Source dataset
uspto-grants-1999_01
Patent number
US05861359

Reaction notes

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