GB1107881A - Fluorinated pyridines - Google Patents

Fluorinated pyridines

Info

Publication number
GB1107881A
GB1107881A GB1038164A GB1038164A GB1107881A GB 1107881 A GB1107881 A GB 1107881A GB 1038164 A GB1038164 A GB 1038164A GB 1038164 A GB1038164 A GB 1038164A GB 1107881 A GB1107881 A GB 1107881A
Authority
GB
United Kingdom
Prior art keywords
give
reaction
tetrafluoropyridine
converted
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB1038164A
Inventor
Richard Dickinson Chambers
John Hutchinson
William Kenneth Rodge Musgrave
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Research Development Corp UK
Original Assignee
National Research Development Corp UK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Research Development Corp UK filed Critical National Research Development Corp UK
Priority to GB1038164A priority Critical patent/GB1107881A/en
Priority to NL6503014A priority patent/NL6503014A/xx
Priority to DE1965N0026355 priority patent/DE1620068A1/en
Priority to FR8623A priority patent/FR1432872A/en
Priority to BE660873D priority patent/BE660873A/xx
Priority to CH341965A priority patent/CH454142A/en
Publication of GB1107881A publication Critical patent/GB1107881A/en
Priority to AU19164/70A priority patent/AU1916470A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/69—Two or more oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C07D213/77—Hydrazine radicals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Abstract

Pentachloropyridine or tetrafluoropyridine are heated with anhydrous KF in the absence of a solvent to give fluorinated pyridines. Pentachloropyridine gives pentachloropyridine, 3-chlorotetrafluoropyridine and 3,5-dichlorotrifluoropyridine. Mixed tetrachloropyridines give 3 - chloro - 2,4,6 - trifluoropyridine, two isomeric dichlorodifluoropyridines, one of which is 3,5 - dichloro - 2,6 - difluoropyridine, and two isomeric trichloromonofluoropyridines. The starting materials are obtained by reacting pyridine with PCl5 to give di-, tri-, tetra- and penta-chloropyridines. The fluoropyridines produced by the above process may be subsequently reacted with ammonia, hydrazine or an alkali metal alkoxide to give a product containing, respectively, an amino, hydrazino or alkoxy group at position 2 and/or at position 4. The compounds produced according to the above processes may undergo further reactions to give other substituted polyfluoropyridines. Thus:- (a) Pentafluoropyridine reacts at position 4 with pentafluorophenyl magnesium bromide to give 4 - (pentafluorophenyl) - tetrafluoropyridine. (b) An amino group may be converted to bromo by the Sandmeyer reaction. (c) 4 - Bromo - tetrafluoropyridine may be treated with copper to give octafluoro-4,41-bipyridyl. (d) Compounds containing no fluorine at position 4 react at positions 2 and/or 6 with ammonia, alkali metal hydroxides and alkali metal alcoholates to give the corresponding amino, hydroxy or alkoxy compounds. (e) A hydrazino group at position 4 may be converted to an amino group by reaction with aqueous hydriodic acid, or to a hydrazone by reaction with a carbonyl compound. (f) An amino group at position 2 or 4 may be converted to -NO2 by reaction with H2O2 and trifluoroacetic anhydride. (g) 4 - Bromo - compounds may be converted to the corresponding magnesium bromides which then undergo the normal reactions of Grignard reagents. (h) Bromine may be replaced by hydrogen by treatment with copper (cf. reaction (c) above). (i) Methoxy groups may be converted to hydroxy by treatment with aqueous hydriodic acid. (j) Reaction of 4-hydrazino-tetrafluoropyridine with calcium hypochlorite and benzene gives 4 - phenyl - tetrafluoropyridine. (k) Reaction of pentafluoropyridine with phenyl-lithium gives 4-phenyl-tetrafluoropyridine. (l) 3,5 - Dichloro - trifluoropyridine is reacted with magnesium and ethylene dibromide, and the Grignard product is hydrolysed to 3-chloro-2,4,6-trifluoropyridine. Reference has been directed by the Comptroller to Specification 1,059,231.
GB1038164A 1964-03-11 1964-03-11 Fluorinated pyridines Expired GB1107881A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
GB1038164A GB1107881A (en) 1964-03-11 1964-03-11 Fluorinated pyridines
NL6503014A NL6503014A (en) 1964-03-11 1965-03-09
DE1965N0026355 DE1620068A1 (en) 1964-03-11 1965-03-10 Process for the preparation of fluorinated pyridine derivatives
FR8623A FR1432872A (en) 1964-03-11 1965-03-10 Fluoropyridines and process for their preparation
BE660873D BE660873A (en) 1964-03-11 1965-03-10
CH341965A CH454142A (en) 1964-03-11 1965-03-11 Process for the preparation of fluoropyridines and substituted fluoropyridines
AU19164/70A AU1916470A (en) 1964-03-11 1970-08-25 Preparation of fluorinated pyridines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1038164A GB1107881A (en) 1964-03-11 1964-03-11 Fluorinated pyridines
GB28065 1965-01-04

Publications (1)

Publication Number Publication Date
GB1107881A true GB1107881A (en) 1968-03-27

Family

ID=26235816

Family Applications (1)

Application Number Title Priority Date Filing Date
GB1038164A Expired GB1107881A (en) 1964-03-11 1964-03-11 Fluorinated pyridines

Country Status (7)

Country Link
AU (1) AU1916470A (en)
BE (1) BE660873A (en)
CH (1) CH454142A (en)
DE (1) DE1620068A1 (en)
FR (1) FR1432872A (en)
GB (1) GB1107881A (en)
NL (1) NL6503014A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ299678B6 (en) * 1999-03-31 2008-10-15 Basf Agro B.V., Arnhem (Nl), Wädenswil-Branch Process for preparing arylamine compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ299678B6 (en) * 1999-03-31 2008-10-15 Basf Agro B.V., Arnhem (Nl), Wädenswil-Branch Process for preparing arylamine compounds

Also Published As

Publication number Publication date
AU1916470A (en) 1970-10-29
NL6503014A (en) 1965-09-13
FR1432872A (en) 1966-03-25
DE1620068A1 (en) 1970-05-14
CH454142A (en) 1968-04-15
BE660873A (en) 1965-07-01

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