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WO2011150950A1 - Sels de 2-méthyl-5-vinylpyridinium - Google Patents

Sels de 2-méthyl-5-vinylpyridinium Download PDF

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Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
vinylpyridine
hydrogentartrate
mvp
acid
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.)
Ceased
Application number
PCT/EP2010/003789
Other languages
English (en)
Inventor
Meinrad Brenner
Stephan Elzner
Raimund Miller
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.)
Lonza AG
Original Assignee
Lonza AG
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 Lonza AG filed Critical Lonza AG
Publication of WO2011150950A1 publication Critical patent/WO2011150950A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C07D213/16—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.

Landscapes

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

Abstract

La présente invention a pour objet de nouveaux sels de 2-méthyl-5-vinylpyridine (MVP), tels que les hydrogénotartrates, le bromure, et le dihydrogénophosphate. Par contraste avec la base libre, ces sels sont cristallins et stables et peuvent être stockés et transportés en toute sécurité. Les sels peuvent aussi être utilisés pour purifier la MVP, en particulier pour réduire sa teneur en 5-éthyl-2-méthylpyridine et en isomères indésirables.
PCT/EP2010/003789 2010-06-02 2010-06-24 Sels de 2-méthyl-5-vinylpyridinium Ceased WO2011150950A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35069510P 2010-06-02 2010-06-02
US61/350,695 2010-06-02

Publications (1)

Publication Number Publication Date
WO2011150950A1 true WO2011150950A1 (fr) 2011-12-08

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/003789 Ceased WO2011150950A1 (fr) 2010-06-02 2010-06-24 Sels de 2-méthyl-5-vinylpyridinium

Country Status (1)

Country Link
WO (1) WO2011150950A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977005A (zh) * 2012-11-08 2013-03-20 安徽国星生物化学有限公司 2，3，5-三甲基吡啶的提纯方法

Citations (3)

* Cited by examiner, † Cited by third party
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 (ja) * 2007-03-09 2008-09-25 Koei Chem Co Ltd アルキルアミノピリジン類の精製方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
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 (ja) * 2007-03-09 2008-09-25 Koei Chem Co Ltd アルキルアミノピリジン類の精製方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977005A (zh) * 2012-11-08 2013-03-20 安徽国星生物化学有限公司 2，3，5-三甲基吡啶的提纯方法

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