US3461128A - Process for producing n:n'-dilower alkyl-4:4'-bipyridylium salts - Google Patents
Process for producing n:n'-dilower alkyl-4:4'-bipyridylium salts Download PDFInfo
- Publication number
- US3461128A US3461128A US550965A US3461128DA US3461128A US 3461128 A US3461128 A US 3461128A US 550965 A US550965 A US 550965A US 3461128D A US3461128D A US 3461128DA US 3461128 A US3461128 A US 3461128A
- Authority
- US
- United States
- Prior art keywords
- carbon
- halogen atom
- tetrahydrobipyridyl
- salts
- reaction
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title description 28
- 230000008569 process Effects 0.000 title description 26
- 150000003839 salts Chemical class 0.000 title description 21
- 125000005843 halogen group Chemical group 0.000 description 23
- 150000001722 carbon compounds Chemical class 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- KIEFQUXBBALVKN-UHFFFAOYSA-N 2-(1,2,3,4-tetrahydropyridin-2-yl)pyridine Chemical group N1C=CCCC1C1=CC=CC=N1 KIEFQUXBBALVKN-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- VFDYKPARTDCDCU-UHFFFAOYSA-N hexachloropropene Chemical compound ClC(Cl)=C(Cl)C(Cl)(Cl)Cl VFDYKPARTDCDCU-UHFFFAOYSA-N 0.000 description 3
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DOJXGHGHTWFZHK-UHFFFAOYSA-N Hexachloroacetone Chemical compound ClC(Cl)(Cl)C(=O)C(Cl)(Cl)Cl DOJXGHGHTWFZHK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 2
- 229950005228 bromoform Drugs 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- -1 tertiary alkylamides Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 1
- NDZFNTHGIIQMQI-UHFFFAOYSA-N 1-benzylpyridin-1-ium Chemical class C=1C=CC=C[N+]=1CC1=CC=CC=C1 NDZFNTHGIIQMQI-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IHUREIPXVFKEDT-UHFFFAOYSA-N dibromo(dichloro)methane Chemical compound ClC(Cl)(Br)Br IHUREIPXVFKEDT-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB22773/65A GB1077366A (en) | 1965-05-28 | 1965-05-28 | Production of n:n'-disubstituted bipyridylium salts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3461128A true US3461128A (en) | 1969-08-12 |
Family
ID=10184845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US550965A Expired - Lifetime US3461128A (en) | 1965-05-28 | 1966-05-18 | Process for producing n:n'-dilower alkyl-4:4'-bipyridylium salts |
Country Status (12)
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080160084A1 (en) * | 2004-12-22 | 2008-07-03 | Colarome, Inc. | Natural Water-Insoluble Encapsulation Compositions and Processes for Preparing Same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3227723A (en) * | 1966-01-04 | Process for preparing bipykibyils | ||
| US3272835A (en) * | 1966-09-13 | Process for the manufacture of bipyridyls |
-
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 BR BR179983/66A patent/BR6679983D0/pt unknown
- 1966-05-27 SE SE07331/66A patent/SE340099B/xx 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3227723A (en) * | 1966-01-04 | Process for preparing bipykibyils | ||
| US3272835A (en) * | 1966-09-13 | Process for the manufacture of bipyridyls |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080160084A1 (en) * | 2004-12-22 | 2008-07-03 | Colarome, Inc. | Natural Water-Insoluble Encapsulation Compositions and Processes for Preparing Same |
| US9687807B2 (en) | 2004-12-22 | 2017-06-27 | Colarome, Inc. | Natural water-insoluble encapsulation compositions and processes for preparing same |
| US10981136B2 (en) | 2004-12-22 | 2021-04-20 | Capol Inc. | Natural water-insoluble encapsulation compositions and processes for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| BE681786A (enrdf_load_stackoverflow) | 1966-11-28 |
| NL127059C (enrdf_load_stackoverflow) | |
| NL6607290A (enrdf_load_stackoverflow) | 1966-11-29 |
| ES327222A1 (es) | 1967-08-01 |
| DK117830B (da) | 1970-06-08 |
| AT264524B (de) | 1968-09-10 |
| DE1695246A1 (de) | 1972-04-20 |
| BR6679983D0 (pt) | 1973-09-06 |
| GB1077366A (en) | 1967-07-26 |
| SE340099B (enrdf_load_stackoverflow) | 1971-11-08 |
| CH487153A (de) | 1970-03-15 |
| IL25837A (en) | 1970-02-19 |
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