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
  • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
  • C07D213/22—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl

Definitions

• This invention relates to the production of bipyridylium salts and particularly to the production of bis-quaternary salts of 4:4-bipyridyl.
• N:N'-dibenzyl tetrahydrobipyridyl can be oxidised to an N:N'-dibenzyl bipyridylium salt by the action of iodine, but this process gives only poor yields of the bipyridylium salt, and much of the starting material is converted into benzyl pyridinium salts by fission of the bond connecting the two pyridine rings.
• N:N'-disubstit-utedtetrahydro-4:4-bipyridyls may be converted in good yield into N:N-disubstituted 4:4-bipyridylium salts by the action of compounds containing a labile halogen atom.
• tetrahydrobipyridyls which may conveniently be used in our process are those more fully described in the above mentioned U.K. applications, for example tetrahydrobipyridyls which carry alkyl or carbamyl alkyl, and particularly methyl or N:N-disubstituted carbamyl methyl substituents on the nitrogen atoms.
• tetrahydrobipyridyls which carry alkyl or carbamyl alkyl, and particularly methyl or N:N-disubstituted carbamyl methyl substituents on the nitrogen atoms.
• Other suitable N:N-disubstituted-tetrahydro-4:4 bipyridyls are those carrying inert substituents, for example alkyl groups, on the carbon atoms of the pyridine nuclei.
• the carbon compound containing a labile halogen atom may be any such compound which is capable of nited States Patent 3,461,128 Patented Aug. 12, 1969 removing hydrogen from the tetrahydrobipyridyl, for example a compound containing a carbon-to-halogen bond of dissociation energy less than about kcals./mole.
• Bromine and iodine atoms tend to be more labile than chlorine atoms when attached to carbon and compounds containing bromine and iodine will therefore tend to be more effective than those containing chlorine only.
• compounds containing bromine and iodine are relatively expensive and it is therefore economically desirable to use the cheaper compounds containing chlorine.
• a carbon tetrahalide which does not contain fluorine for example carbon tetrachloride, carbon tetrabromide, bromotrichloromethane or dichlorodibromo m e t h a n e.
• Other compounds which may be used in our invention are bromoform, iodoform, methylene iodide, hexachloroethane, hexachloropropene, 1:1:1 trifiuoro 2:2 dibromo-Z-chloroethane and hexachloroacetone.
• chloroform, methylene dichloride, benzotrichloride and monochlorobenzene tends to yield very little of the desired product.
• tetrahydrobipyridyl and the carbon compound containing the labile halogen atom may be interacted simply by mixing the two components, but this procedure tends to give rise to a vigorous reaction which may be difficult to control. We have therefore found it useful to moderate this reaction by carrying it out in solution in an inert solvent. Suitable solvents are those which will dissolve the N:N'-disubstituted-tetrahydro4:4-bipyridyl and also the carbon compound containing the labile halogen atom.
• solvents examples include ethers for example diethyl ether, tetrahydrofuran, 1:2 dimethoxyethane, bis (2- methoxyethyl) ether and 1:4-dioxane; ketones, for example acetone; hydrocarbons, for example benzene and hexane; organic bases, for example pyridine; halogenated hydrocarbons, other than those used to interact with the tetrahydrobipyridyl, particularly chlorinated hydrocarbons, for example chlorobenzene, chloroform and methylene dichloride; amides, particularly tertiary alkylamides, for example formamide; sulphoxides, for example dimethyl sulphoxide or nitriles, for example acetonitrile.
• ethers for example diethyl ether, tetrahydrofuran, 1:2 dimethoxyethane, bis (2- methoxyethyl) ether and 1:4-di
• the concentration of the tetrahydrobipyridyl may conveniently be above about 0.75 mole per litre and the concentration of the carbon compound containing a labile halogen atom, for example carbon tetrachloride, may be above about 0.25 mole per litre. Lower concentrations of either reagent necessitates the recovery of the N:N-disubstituted bipyridylium salts from large quantities of solvent and therefore tend to be inconvenient.
• Either reagent may if desired be used undiluted, the other reagent being dissolved in the chosen solvent, but if the reagents are Q used in high concentration care should be taken that the reaction does not become too vigorous and lead to some destruction of the desired product or to the production of unwanted by-products.
• Methylene iodide 200 200 35 1 13 Carbon tetrabromide 200 200 35 1 22 Hexachloropropene. 450 600 20 1. 30
• the temperature at which reaction is carried out will depend on the concentration of the reagents and on the particular reagents used. We have found that suitable temperatures are from about 55 C. to 70 C. and preferably from 0 C. to 50 C.; higher temperatures tend to cause decomposition of the tetrahydrobipyridyls and lower temperatures will necessitate cooling of the reactants.
• the most suitable time of reaction can be found by simple experiment and will depend on the reagents used and the temperature at which the reaction is earned out; we have however found that a minimum time of 20 to 30 minutes is generally necessary.
• the N:N-disubstituted bipyridylium salt may be recovered from the reaction mixture by conventional processes for example by extraction of the reaction mixture with water or with a dilute aqueous solution of a mineral acid such as sulphuric, hydrochloric or phosphoric acid.
• the N:N-bipyridylium salt may then be recovered from the aqueous phase, which has previously been separated from the organic phase, by evaporation of the water and crystallisation of the salt.
• a process for the production of an N:N-dilower alkyl-4:4-bipyridylium salt which comprises reacting in an inert solvent a N:N-dilower alkyl tetrahydro-4:4-bipyridyl with a linear alkyl or linear alkenyl carbon compound having less than 4 carbon atoms and containing a labile halogen atom selected from chlorine, bromine and iodine and the labile halogen atom is attached to carbon by a bond of dissociation energy less than about 70 kcal./mole.
• a process as claimed in claim 2 wherein the electron withdrawing group is a carbonyl group, a CHal group (where Hal represents chlorine, bromine or iodine), or a fluorine, chlorine or bromine atom.
• carbon compound is bromotrichloromethane, dichlorodibromomethane, bromoform, iododform, methylene iodide, hexachloropropene, hexachloroacetone or 1:1:1-trifiuoro-2:2- dibromo-Z-chloroethane.
• ether is diethyl ether, tetrahydrofuran or bis-(Z-methoxy ethyl) ether.
• a process as claimed in claim 9 wherein the solvent comprises diethyl ether, tetrayhdrofuran, 1:2-dimethoxyethane, bis-(Z-methoxyethyl) ether, 1:4-dioxane, acetone, benzene, hexane, pyridine, chlorobenzene, chloroform, methylene dichloride, formamide, dimethyl sulphoxide and acetonitrile.
• a process as claimed in claim 9 wherein the initial concentration of carbon compound in the reaction mixture is more than about 0.25 mole per litre.
• a process as claimed in claim 1 wherein the pro- 3,461,128 5 6 portion of carbon compound used is such that substanpyridyliurn salt is extracted from the reaction mixture by tially two labile halogen atoms are available for each water. molecule of tetrahydrobipyridyl. References Cited 16.
• a process as claimed in claim 1 wherein the inter- UNITED STATES PATENTS action is carried out at a temperature in the range 55 C to C 5 3,227,723 1/1966 Baines e1: a1. 260-296 17.
• a process as claimed in claim 1 wherein the inter- 3272835 9/1966 Dransfi 61d et 260296 action is carried out at a temperature in the range of 0 HENRY R. JILES Primary Examiner C. to 50 C.

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

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Cited By (1)

Citations (2)

• 0
  • NL NL127059D patent/NL127059C/xx active
• 1965
  • 1965-05-28 GB GB22773/65A patent/GB1077366A/en not_active Expired
• 1966
  • 1966-05-18 US US550965A patent/US3461128A/en not_active Expired - Lifetime
  • 1966-05-23 IL IL25837A patent/IL25837A/xx unknown
  • 1966-05-25 DE DE19661695246 patent/DE1695246A1/de active Pending
  • 1966-05-26 NL NL6607290A patent/NL6607290A/xx unknown
  • 1966-05-26 AT AT501266A patent/AT264524B/de active
  • 1966-05-27 BE BE681786D patent/BE681786A/xx unknown
  • 1966-05-27 SE SE07331/66A patent/SE340099B/xx unknown
  • 1966-05-27 BR BR179983/66A patent/BR6679983D0/pt unknown
  • 1966-05-27 ES ES0327222A patent/ES327222A1/es not_active Expired
  • 1966-05-28 DK DK277066AA patent/DK117830B/da unknown
  • 1966-05-31 CH CH782666A patent/CH487153A/de not_active IP Right Cessation

Patent Citations (2)

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