WO2011150950A1 - 2-methyl-5-vinylpyridinium salts - Google Patents
2-methyl-5-vinylpyridinium salts Download PDFInfo
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- WO2011150950A1 WO2011150950A1 PCT/EP2010/003789 EP2010003789W WO2011150950A1 WO 2011150950 A1 WO2011150950 A1 WO 2011150950A1 EP 2010003789 W EP2010003789 W EP 2010003789W WO 2011150950 A1 WO2011150950 A1 WO 2011150950A1
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- vinylpyridine
- hydrogentartrate
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- 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
- C07D213/16—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 only one pyridine ring
- C07D213/18—Salts thereof
Definitions
- the invention relates to novel salts of 2-methyl-5-vinylpyridine (MVP), such as 2-methyl-5-vinylpyridinium hydrogentartrates, bromide, and phosphate, and a process for their production. It further relates to the use of said salts as a storage and transport form of MVP and a method for the purification of MVP via said 2-methyl-5-vinylpyridi- nium salts.
- MVP 2-methyl-5-vinylpyridine
- MVP is a toxic liquid which is produced by thermal dehydrogenation of 5-ethyl- 2-methylpyridine (MEP). MVP shows decomposition upon storage, leading to abatement of the product quality within months or a few years. Furthermore, MVP shows a highly exothermic decomposition behavior (enthalpy of decomposition: >400 J/g) with an onset temperature of ca. 145 °C. Consequently, transport of MVP is a major safety risk.
- MVP byproducts and residual starting material
- salts of 2-methyl-5-vinylpyridine are solid compounds having an enthalpy of decomposition that is substantially lower than that of the free base.
- crystallization and optional recrystallization of said salts results in a substantial reduction of the content of starting material of the 2-methyl-5-vinylpyridine synthesis (namely, 5-ethyl-2-methylpyridine) and unwanted byproducts.
- said salts can be easily re-converted into the free base 2-methyl-5-vinylpyridine by adding a strong base such as an alkali or alkaline earth hydroxide.
- X- is an anion selected from the group consisting of D-hydrogentartrate, L-hydrogentartrate, DL-hydrogentartrate, /ttesohydrogentartrate, bromide, and dihydro- genphosphate (H2P0 4 ), are provided.
- X " is D-hydrogentartrate, L-hydrogentartrate, or DL-hydrogentartrate (the latter being a 1 :1 mixture of D-hydrogentartrate and L-hydrogentartrate).
- Another embodiment of the invention is the use of a 2-methyl-5-vinylpyridinium salt as defined above for the storage and/or transport of 2-methyl-5-vinylpyridine.
- Still another embodiment of the invention is the preparation of a 2-methyl-5-vinylpyri- dinium salt of formula
- X- is an anion selected from the group consisting of D-hydrogentartrate, L-hydrogentartrate, DL-hydrogentartrate, esohydrogentartrate, bromide, and dihydro- genphosphate, by a process comprising the steps of
- the expression "the acid corresponding to the required anion” means D-tartaric acid for the D-hydrogentartrate, L-tartaric acid for the L-hydrogentartrate, DL-tartaric acid ("racemic acid”) for the DL-hydrogentartrate, /77esotartaric acid for the meso - drogentartrate, hydrobromic acid for the bromide, and phosphoric acid for the dihydro- genphosphate.
- the process for the preparation of the 2-methyl-5-vinylpyridinium salts of the invention can be conducted in any solvent wherein the starting materials are soluble without undergoing interfering reactions. It is also possible to use different solvents for both starting materials or employing one or both starting materials in neat form (e.g., gaseous hydrogen bromide). Suitable solvents include water and polar organic solvents such as lower alcohols or ketones, without being limited thereto.
- the solvent comprises a alkanol, namely, methanol, ethanol, 1-propanol, isopropyl alcohol (2-propanol), 1-butanol, seobutyl alcohol (2-bu- tanol), isobutyl alcohol (2-methyl-1 -propanol), tert-b Xy alcohol (2-methyl-2-propanol), or mixtures thereof.
- alkanol namely, methanol, ethanol, 1-propanol, isopropyl alcohol (2-propanol), 1-butanol, seobutyl alcohol (2-bu- tanol), isobutyl alcohol (2-methyl-1 -propanol), tert-b Xy alcohol (2-methyl-2-propanol), or mixtures thereof.
- the solvent is selected from methanol, ethanol, isopropyl alcohol, and mixtures thereof.
- the acid is selected from D-tartaric acid, L-tartaric acid, DL-tartaric acid, mesotartaric acid, and mixtures thereof.
- Another object of the invention is a method for purifying 2-methyl-5-vinylpyridine containing 5-ethyl-2-methylpyridine and/or isomeric methylvinylpyridines, said method comprising the steps of
- the 2-methyl-5-vinylpyridinium salt of formula I is recrystailized before liberating the 2-methyl-5-vinylpyridine.
- Example 1 The invention is further illustrated by the following non-limiting examples: Example 1
- DL-Tartaric acid 53.66 g, 357 mmol
- hot (50 °C) ethanol 600 ml
- the solution was added to a solution of crude 2-methyl-5-vinylpyridine (70.8 wt% MVP, 22.2 wt% MEP; 40.07 g, 238 mmol) in ethanol (20 ml) at 20-25 °C over a period of 1 h.
- the resulting suspension was aged at 20 °C for 30 min, cooled to 5 °C over a period of 60 min, and aged at 5 °C for another 30 min.
- the precipitated product was filtered and washed with cold (5 °C) ethanol (40 ml). After drying over night (35 °C, 20-100 mbar), 2-methyl-5-vinylpyridinium DL-hydrogentartrate was obtained as a white solid.
- GC 85.4 area% MVP, 14.1 area% MEP.
- the molar ratio tartrate/pyridines was assessed by 1 H NMR to be 1.0:1.0.
- the product was further purified by recrystallization from ethanol: 60.0 g MVP DL-tar- trate obtained as described above were dissolved in ethanol (330 ml) at 60 °C. After cooling to 25 °C over a period of 30 min, followed by cooling to 0 °C over a period of
- GC 90.8 area% MVP, 9.0 area% MEP.
- the molar ratio tartrate/pyridines was assessed by 1 H NMR to be 1.0:1.0.
- L-Tartaric acid (53.76 g, 358 mmol) was dissolved in hot (60 °C) isopropyl alcohol (400 ml). The solution was added to a solution of crude 2-methyl-5-vinylpyridine (71.1 wt% MVP, 22.0 wt% MEP; 40.10 g, 239 mmol) in isopropyl alcohol (30 ml) at 30-35 °C over a period of 30 min. The resulting suspension was aged at 35 °C for 1 h, cooled to 20 °C over a period of 60 min and aged at 20 °C for another 30 min. The pre- cipitated product was filtered and washed with isopropyl alcohol (40 ml). After drying over night (35 °C, 20-100 mbar), 2-methyl-5-vinylpyridine L-tartrate was obtained as white to slightly bluish solid.
- the molar ratio tartrate/pyridines was assessed by 1 H NMR to be 0.9:1.0.
- the product was further purified by recrystallization from isopropyl alcohol: 2-Methyl- 5-vinylpyridine L-tartrate (86.4 area% GC; 45.0 g), obtained as described above, was dissolved in isopropyl alcohol (350 ml) at 75 °C. After cooling to 20 °C over a period of 60 min, the mixture was aged at 20 °C for 60 min. The recrystallized product was filtered off, washed with isopropyl alcohol (30 ml), and dried to obtain 2-methyl-5-vinyl- pyridine L-tartrate as white to slightly bluish solid.
- the molar ratio tartrate/pyridines was assessed by 1 H NMR to be 1.0:1.0.
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Abstract
Disclosed are novel salts of 2-methyl-5-vinylpyridine (MVP), such as hydrogentartrates, bromide, and dihydrogenphosphate. In contrast to the free base, these salts are crystalline and stable and can be safely stored and transported. The salts can also be used to purify MVP, in particular to reduce its content of 5-ethyl-2-methylpyridine and unwanted isomers.
Description
2-Methyl-5-vinylpyridinium Salts
The invention relates to novel salts of 2-methyl-5-vinylpyridine (MVP), such as 2-methyl-5-vinylpyridinium hydrogentartrates, bromide, and phosphate, and a process for their production. It further relates to the use of said salts as a storage and transport form of MVP and a method for the purification of MVP via said 2-methyl-5-vinylpyridi- nium salts.
MVP is a toxic liquid which is produced by thermal dehydrogenation of 5-ethyl- 2-methylpyridine (MEP). MVP shows decomposition upon storage, leading to abatement of the product quality within months or a few years. Furthermore, MVP shows a highly exothermic decomposition behavior (enthalpy of decomposition: >400 J/g) with an onset temperature of ca. 145 °C. Consequently, transport of MVP is a major safety risk.
During production of MVP, the removal of byproducts and residual starting material (MEP) is only partially possible. The impurities, the physical properties of which are rather similar to those of MVP, can have negative influence in downstream chemistry and are a major source of byproducts.
Accordingly, it has been an object of the present invention to provide a stabilized form of MVP that can be stored over prolonged periods of time and has an increased onset temperature for decomposition and/or reduced enthalpy of decomposition. It has also been an object of the invention to provide a method for reducing the MEP content of MVP obtained by dehydrogenation of MEP.
According to the invention, these objects have been achieved by the hydrogentartrate, bromide, and phosphate salts of MVP and the method of producing said salts and reconverting them into MVP free base.
Applicants have found that certain salts of 2-methyl-5-vinylpyridine, in particular the hydrogentartrates, the bromide and the dihydrogenphosphate, are solid compounds having an enthalpy of decomposition that is substantially lower than that of the free base. Moreover, the crystallization and optional recrystallization of said salts results in a substantial reduction of the content of starting material of the 2-methyl-5-vinylpyridine synthesis (namely, 5-ethyl-2-methylpyridine) and unwanted byproducts. Applicants have further found that said salts can be easily re-converted into the free base
2-methyl-5-vinylpyridine by adding a strong base such as an alkali or alkaline earth hydroxide.
According to the invention, 2-methyl-5-vinylpyridinium salts of formula
wherein X- is an anion selected from the group consisting of D-hydrogentartrate, L-hydrogentartrate, DL-hydrogentartrate, /ttesohydrogentartrate, bromide, and dihydro- genphosphate (H2P04), are provided.
In a preferred embodiment, X" is D-hydrogentartrate, L-hydrogentartrate, or DL-hydrogentartrate (the latter being a 1 :1 mixture of D-hydrogentartrate and L-hydrogentartrate).
Another embodiment of the invention is the use of a 2-methyl-5-vinylpyridinium salt as defined above for the storage and/or transport of 2-methyl-5-vinylpyridine.
Still another embodiment of the invention is the preparation of a 2-methyl-5-vinylpyri- dinium salt of formula
wherein X- is an anion selected from the group consisting of D-hydrogentartrate, L-hydrogentartrate, DL-hydrogentartrate, esohydrogentartrate, bromide, and dihydro- genphosphate, by a process comprising the steps of
(i) providing a solution of 2-methyl-5-vinylpyridine and a solution of the acid corresponding to the required anion,
(ii) combining said solutions in a molar ratio of acid to 2-methyl-5-vinylpyridine of at least 1 :1 ,
(iii) allowing the formed 2-methyl-5-vinylpyridinium salt of formula I to crystallize, and
(iv) isolating said salt of formula I.
Herein, the expression "the acid corresponding to the required anion" means D-tartaric acid for the D-hydrogentartrate, L-tartaric acid for the L-hydrogentartrate, DL-tartaric acid ("racemic acid") for the DL-hydrogentartrate, /77esotartaric acid for the meso - drogentartrate, hydrobromic acid for the bromide, and phosphoric acid for the dihydro- genphosphate.
The process for the preparation of the 2-methyl-5-vinylpyridinium salts of the invention can be conducted in any solvent wherein the starting materials are soluble without undergoing interfering reactions. It is also possible to use different solvents for both starting materials or employing one or both starting materials in neat form (e.g., gaseous hydrogen bromide). Suitable solvents include water and polar organic solvents such as lower alcohols or ketones, without being limited thereto.
In a preferred embodiment, the solvent comprises a
alkanol, namely, methanol, ethanol, 1-propanol, isopropyl alcohol (2-propanol), 1-butanol, seobutyl alcohol (2-bu- tanol), isobutyl alcohol (2-methyl-1 -propanol), tert-b Xy alcohol (2-methyl-2-propanol), or mixtures thereof.
More preferably, the solvent is selected from methanol, ethanol, isopropyl alcohol, and mixtures thereof.
In another preferred embodiment of the process for the preparation of the 2-methyl- 5-vinylpyridinium salts of the invention, the acid is selected from D-tartaric acid, L-tartaric acid, DL-tartaric acid, mesotartaric acid, and mixtures thereof.
Another object of the invention is a method for purifying 2-methyl-5-vinylpyridine containing 5-ethyl-2-methylpyridine and/or isomeric methylvinylpyridines, said method comprising the steps of
(i) preparing a 2-methyl-5-vinylpyridinium salt of formula I as described above, (ii) liberating the 2-methyl-5-vinylpyridine by addition of a strong base, and
(iii) recovering the 2-methyl-5-vinylpyridine by extraction or distillation.
In a preferred embodiment of said method for purifying 2-methyl-5-vinylpyridine, the 2-methyl-5-vinylpyridinium salt of formula I is recrystailized before liberating the 2-methyl-5-vinylpyridine.
The invention is further illustrated by the following non-limiting examples:
Example 1
2-Methyl-5-vinylpyridinium DL-hydrogentartrate
DL-Tartaric acid (53.66 g, 357 mmol) was dissolved in hot (50 °C) ethanol (600 ml). The solution was added to a solution of crude 2-methyl-5-vinylpyridine (70.8 wt% MVP, 22.2 wt% MEP; 40.07 g, 238 mmol) in ethanol (20 ml) at 20-25 °C over a period of 1 h. The resulting suspension was aged at 20 °C for 30 min, cooled to 5 °C over a period of 60 min, and aged at 5 °C for another 30 min. The precipitated product was filtered and washed with cold (5 °C) ethanol (40 ml). After drying over night (35 °C, 20-100 mbar), 2-methyl-5-vinylpyridinium DL-hydrogentartrate was obtained as a white solid.
Yield: 68.90 g (92%).
GC: 85.4 area% MVP, 14.1 area% MEP.
The molar ratio tartrate/pyridines was assessed by 1H NMR to be 1.0:1.0.
The product was further purified by recrystallization from ethanol: 60.0 g MVP DL-tar- trate obtained as described above were dissolved in ethanol (330 ml) at 60 °C. After cooling to 25 °C over a period of 30 min, followed by cooling to 0 °C over a period of
90 min, the mixture was aged at 0 °C for another 60 min. The recrystallized product was filtered off, washed with cold (5 °C) ethanol (30 ml) and dried.
Yield: 48.7 g (86%) white solid.
GC: 90.8 area% MVP, 9.0 area% MEP.
The molar ratio tartrate/pyridines was assessed by 1H NMR to be 1.0:1.0.
Onset temperature of decomposition (DSC): 147 °C.
Enthalpy of decomposition (DSC): 192 J/g.
W NMR (DMSO-de, 400 MHz): δ 8.50 (d, 1 H), 7.82 (dd, 1 H), 7.24 (d, 1 H), 6.73 (dd, 1 H), 5.90 (dd, 1 H), 5.33 (d, 1 H), 4.34 (s, 2H), 2.46 (s, 3H).
13C NMR (DMSO-de, 126 MHz): δ 173.0, 157.2, 147.1 , 133.3, 132.9, 129.8, 123.0, 1 15.4, 72.1 , 23.6.
Example 2
2-methyl-5-vinylpyridine L-tartrate
L-Tartaric acid (53.76 g, 358 mmol) was dissolved in hot (60 °C) isopropyl alcohol (400 ml). The solution was added to a solution of crude 2-methyl-5-vinylpyridine (71.1 wt% MVP, 22.0 wt% MEP; 40.10 g, 239 mmol) in isopropyl alcohol (30 ml) at 30-35 °C over a period of 30 min. The resulting suspension was aged at 35 °C for 1 h, cooled to 20 °C over a period of 60 min and aged at 20 °C for another 30 min. The pre- cipitated product was filtered and washed with isopropyl alcohol (40 ml). After drying over night (35 °C, 20-100 mbar), 2-methyl-5-vinylpyridine L-tartrate was obtained as white to slightly bluish solid.
Yield: 70.60 g (95%).
GC: 86.4 area% MVP, 12.5 area% MEP.
The molar ratio tartrate/pyridines was assessed by 1H NMR to be 0.9:1.0.
The product was further purified by recrystallization from isopropyl alcohol: 2-Methyl- 5-vinylpyridine L-tartrate (86.4 area% GC; 45.0 g), obtained as described above, was dissolved in isopropyl alcohol (350 ml) at 75 °C. After cooling to 20 °C over a period of 60 min, the mixture was aged at 20 °C for 60 min. The recrystallized product was filtered off, washed with isopropyl alcohol (30 ml), and dried to obtain 2-methyl-5-vinyl- pyridine L-tartrate as white to slightly bluish solid.
Yield: 37.0 g (90%).
Assay (GC): 94.7 area% MVP, 5.0 area% MEP.
The molar ratio tartrate/pyridines was assessed by 1H NMR to be 1.0:1.0.
Onset temperature of decomposition (DSC): 139 °C.
Enthalpy of decomposition (DSC): 193 J/g.
1H NMR (DMSO-de, 400 MHz): δ 8.50 (d, 1 H), 7.82 (dd, 1 H), 7.24 (d, 1 H), 6.73 (dd, 1 H), 5.90 (dd, 1 H), 5.33 (d, 1 H), 4.33 (s, 2H), 2.46 (s, 3H).
13C NMR (DMSO-de, 126 MHz): δ 173.0, 157.2, 147.1 , 133.3, 132.8, 129.8, 122.9, 115.3, 72.1 , 23.6.
Example 3
2-Methyl-5-vinylpyridinium bromide
Crude 2-methyl-5-vinylpyridine (65.3 wt% MVP and 28.2 wt% MEP;100 g, 0.49 mol MVP) and acetone (500 ml) were charged into a jacketed vessel equipped with overhead stirrer. Aqueous hydrobromic acid (62%; 216.6 g, 1.67 mol) was added to the MVP solution via dropping funnel over a period of 30 min at a temperature of 20 °C. The resulting suspension was stirred for 15 min at 20 °C, cooled to -5 °C within 60 min, and aged at this temperature for 180 min. The precipitated product was filtered off on a glass filter and washed with cold (5 °C) acetone (30 ml). Drying for 24 h provided 2-methyl-5-vinylpyridinium bromide as a brownish solid.
Yield: 60.9 g (calcd. based on NMR assay: 54%).
Analytics:
Bromide (titr.): 39.6 wt%.
Assay (NMR): 57.4 wt% MVP.
MEP relative to MVP (GC): 3.4% (88% reduction).
Sum of impurities except MEP (GC): 0.4 area%.
Onset temperature of decomposition (DSC): 113 °C.
Enthalpy of decomposition (DSC): 280 J/g.
1H NMR (DMSO-de, 400 MHz): δ 8.96 (d, 1 H), 8.69 (dd, 1 H), 7.94 (d, 1 H), 6.91 (dd, 1 H), 6.26 (dd, 1 H), 5.65 (d, 1 H), 2.74 (s, 3H).
13C NMR (DMSO-de, 126 MHz): δ 152.4, 141.5, 138.9, 133.6, 130.3, 127.5, 120.4, 19.1.
Example 4
2-Methyl-5-vinylpyridinium dihydrogenphosphate
Crude 2-methyl-5-vinylpyridine (65.3 wt% MVP, 28.2 wt% MEP; 100.0 g, 0.49 mol) and methanol (50 ml) were charged into a jacketed vessel with overhead stirrer. To the MVP solution was added via dropping funnel a solution of aqueous phosphoric acid (85% H3P04;116.1 g, 1.0 mol) in methanol (900 ml) over a period of 60 min at a temperature of 20-25 °C. The solution was stirred for 60 min at 20 °C, cooled within 75 min to -5 to 0 °C, and aged for 45 min. The product was filtered on a G4 glass filter and washed with cold (5 °C) methanol (50 ml). Drying under vacuum for 4 days provided 2-methyl-5-vinylpyridinium dihydrogenphosphate as a brownish solid.
Yield: 78.7 g (calcd. based on assay by NMR): 34%.
Analytics:
Phosphorus: 15.8 wt% (ICP)
Molar ratio H3P04:pyridines: 1.1 :1.
Assay (NMR): 28.4 wt% MVP.
MEP relative to MVP (GC): 15.0% (47% reduction).
Sum of impurities (except MEP, detd. by GC): 0.5 area%.
Onset temperature of decomposition (DSC): 72 °C.
Enthalpy of decomposition (DSC): 155 J/g.
1H NMR (DMSO-de, 400 MHz): δ 10.0-9.1 (br. s), 8.50 (d, 1 H), 7.84 (dd, 1 H), 7.25 (d, 1H), 6.73 (dd, 1 H), 5.90 (dd, 1 H), 5.33 (d, H), 2.46 (s, 3H).
3C NMR (DMSO-de, 126 MHz): δ 157.1 , 146.9, 133.2, 133.0, 129.9, 123.0, 115.5, 23.5.
Example 5
2-Methyl-5-vinylpyridine from 2-methyl-5-vinylpyridinium DL-hydrogentartrate
Aqueous sodium hydroxide (10 wt.%, 88.5 g) was added over a period of 40 min to a suspension of 2-methyl-5-vinylpyridinium DL-hydrogentartrate (GC: 91 area% MVP, 9 area% MEP; molar ratio tartrate/pyridines (NMR) = 1.01 ; 26.94 g) in methyl fe/f-butyl ether (150 ml). After stirring the mixture at 21-24 °C for 30 min, the aqueous phase was separated. The organic phase was washed with water (10 ml) and filtered in order to remove any insoluble matter. The clear filtrate was concentrated under reduced pressure (up to 50 °C @ 30 mbar). 2-Methyl-5-vinylpyridine (91 % MVP, 9% MEP) was obtained as a slightly yellow oil.
Yield: 11.03 g (93%).
Claims
1. A 2-methyl-5-vinylpyridinium salt of formula
wherein X- is an anion selected from the group consisting of D-hydrogentartrate, L-hydrogentartrate, DL-hydrogentartrate, mesohydrogentartrate, bromide, and dihydrogenphosphate.
2. The 2-methyl-5-vinylpyridinium salt of claim 1 , wherein X" is D-hydrogentartrate, L-hydrogentartrate or DL-hydrogentartrate.
3. Use of a 2-methyl-5-vinylpyridinium salt according to claim 1 or 2 for the storage and/or transport of 2-methyl-5-vinylpyridine.
4. A process for the preparation of a 2-methyl-5-vinylpyridinium salt of formula
wherein X- is as defined in claim 1 , comprising the steps of
(i) providing a solution of 2-methyl-5-vinylpyridine and a solution of the acid corresponding to the required anion,
(ii) combining said solutions in a molar ratio of acid to 2-methyl-5-vinylpyridine of at least 1 :1 ,
(iii) allowing the formed 2-methyl-5-vinylpyridinium salt of formula I to crystallize, and
(iv) isolating said salt of formula I.
5. The process of claim 4, wherein the solutions of 2-methyl-5-vinylpyridine and acid comprise a alkanol as solvent.
6. The process of claim 5, wherein the C1-4 alkanol is selected from methanol, ethanol, isopropyl alcohol, and mixtures thereof.
7. The process of any of claims 4 to 6, wherein the acid is selected from D-tartaric acid, L-tartaric acid, DL-tartaric acid, mesotartaric acid, and mixtures thereof.
8. A method for purifying 2-methyl-5-vinylpyridine containing 5-ethyl-2-methylpyri- dine and/or isomeric methylvinylpyridines, said method comprising the steps of
(i) preparing a 2-methyl-5-vinylpyridinium salt of formula I according to any of claims 4 to 7,
(ii) liberating the 2-methyl-5-vinylpyridine by addition of a strong base, and (iii) recovering the 2-methyl-5-vinylpyridine by extraction or distillation.
9. The method of claim 8, wherein the 2-methyl-5-vinylpyridinium salt of formula I is recrystallized before liberating the 2-methyl-5-vinylpyridine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977005A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | 2,3,5-trimethylpyridine purification method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2716120A (en) * | 1952-01-03 | 1955-08-23 | Phillips Petroleum Co | Separation of alkenylpyridines from alkylpyridines |
| GB844981A (en) * | 1958-04-03 | 1960-08-17 | Phillips Petroleum Co | Process for the purification of polymerizable heterocyclic nitrogen compounds |
| JP2008222593A (en) * | 2007-03-09 | 2008-09-25 | Koei Chem Co Ltd | Method for purifying alkylaminopyridine |
-
2010
- 2010-06-24 WO PCT/EP2010/003789 patent/WO2011150950A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2716120A (en) * | 1952-01-03 | 1955-08-23 | Phillips Petroleum Co | Separation of alkenylpyridines from alkylpyridines |
| GB844981A (en) * | 1958-04-03 | 1960-08-17 | Phillips Petroleum Co | Process for the purification of polymerizable heterocyclic nitrogen compounds |
| JP2008222593A (en) * | 2007-03-09 | 2008-09-25 | Koei Chem Co Ltd | Method for purifying alkylaminopyridine |
Non-Patent Citations (4)
| Title |
|---|
| DATABASE HCAPLUS [online] ACS; XP002632737, retrieved from STN Database accession no. 89:111068 (DN) * |
| DATABASE WPI Week 200872, Derwent World Patents Index; AN 2008-M23531, XP002632739 * |
| SALAMONE, J.C. ET AL.: "POLYMERIZATION OF VINYLPYRIDINIUMSALTS. VII. FORMATION OF HIGH MOLECULARWEIGHT POLYVINYLPYRIDINIUM SALTS BY SPONTANEOUS POLYMERIZATION", J. POLYMER SCI.: SYMPOSIUM, vol. 45, 1974, pages 51 - 64, XP002632740 * |
| VILKOVA, S.A. ET AL., PLASTICHESKIE MASSY, no. 5, 1978, pages 23 - 25, XP008135081 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977005A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | 2,3,5-trimethylpyridine purification method |
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