EP1786761A1 - Procede de production de tricyanomethanides de cations organiques - Google Patents

Procede de production de tricyanomethanides de cations organiques

Info

Publication number
EP1786761A1
EP1786761A1 EP05772429A EP05772429A EP1786761A1 EP 1786761 A1 EP1786761 A1 EP 1786761A1 EP 05772429 A EP05772429 A EP 05772429A EP 05772429 A EP05772429 A EP 05772429A EP 1786761 A1 EP1786761 A1 EP 1786761A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
group
independently
aryl
halogen atoms
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.)
Withdrawn
Application number
EP05772429A
Other languages
German (de)
English (en)
Inventor
Christoph TÄSCHLER
Cornelia Zur Täschler
Andreas Breuer
Felix Previdoli
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
Priority to EP05772429A priority Critical patent/EP1786761A1/fr
Publication of EP1786761A1 publication Critical patent/EP1786761A1/fr
Withdrawn legal-status Critical Current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
    • C07D213/06—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
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/04—Preparation of carboxylic acid nitriles by reaction of cyanogen halides, e.g. ClCN, with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C255/05—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton containing at least three cyano groups bound to the carbon skeleton
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms

Definitions

  • the invention relates to a process for the preparation of ionic liquids of the formula
  • Q + is an organic cation containing at least one heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen.
  • the ionic liquids of formula I are Tricyanomethansalze or Tricyano- methanides.
  • Tricyanomethane metal salts and processes for their preparation are known from Schmidtmann, H., Ber. 29, 1896, 1172 and Trofimenko, S. et al., J. Org. Chem. 27, 1962, 433-438. From Batten, SR et al., Chem. Commun. 1998, 439-440 tri cyanomethan-metal salt complexes are also known with organic ligands.
  • metal tricyanomethanides for example Kaliumtricyanomethanid, according to Trofi ⁇ menko et al. From dibromomalononitrile, potassium cyanide and potassium bromide are formally reacted per mole of tricyanomethanide 1.5 mol Br 2 .
  • EP-A 0850 921 US Pat. No. 3,981,899, Jäger, L. et al., Z. Anorg. Chem. 611, 1992, 62-72, Cioslowski, J. et al., Chem. Phys. Lett. 170, 1990, 297-300, Elvidge, L.A. et al., J. Chem. Soc. Perkin Trans. 1, 8, 1983, 1741-1744 and Makhon'kov, D.I. et al., Zh. Org. Khim. 15, 1979, 2441-2445. However, these are solids only.
  • EP-A 0010396 discloses various liquid ammonium tricyanomethanides which are used as fungicides and herbicides.
  • Salts of organic cations have a low vapor pressure and often a low melting point. They are called ionic liquids when they are liquid at room temperature. Ionic liquids have become known in recent years as umwelt ⁇ friendly solvent for a "green chemistry" an ionic liquid and thus the temperature range as a solvent is influenced by variation of the anions and cations. Meanwhile, various ionic liquids are available for applications ranging from about -60 ° C to over 300 ° C.
  • the organic cations of ionic liquids are monovalent quaternary ammonium or phosphonium bases, or cations of aromatic, usually nitrogen-containing bases, which are optionally additionally substituted by alkyl groups, halogen atoms or cyano groups and may contain further heteroatoms such as phosphorus, sulfur or oxygen.
  • Examples of common organic cations are imidazolium, oxazolium, pyrazinium, pyrazolium, pyridazinium, pyrrolidinium, pyrimidinium, thiazolium and triazolium cations. Imidazolium and pyrrolidinium cations are the most commonly used.
  • the cations can be delocalized with a charge located on at least one heteroatom, or in the middle of a ring, or else in complex notation. All representations are used equivalently side by side.
  • Typical anions in ionic liquids are acetate, AlCl 4 " , AsF 6 -, BF 4 " , bromide, CF 3 SO 3 - (CFa) 2 PF 4 -, (CF 3 ) 3 PF 3 -, (CF 3 ) 4 PF 2 ⁇ , (CF 3) 5 PF, (CFa) 6 T, chloride, CN, "FeCIf, NO 3 -, PF 6" pyruvate, oxalate or SCIST. Most commonly AlCl 4 , AsF 6 , BF 4 and PF 6 " are used.
  • Q + is an organic cation selected from the group consisting of cations of the formula, a) [WR 1 R 2 R 3 R 4 ] "1" , wherein W represents a nitrogen or phosphorus atom, and i) wherein R 1 to R 3 are independently C 1-20 alkyl, and R 4 is C 1-2 o alkyl, C 3-10 cycloalkyl or C 6-10 aryl, wherein R 1 to R 4 independently of one another optionally contain one or more halogen atoms, or ii) wherein R 1 and R 2 together with W form a 5- to 7-membered ring, and wherein R 3 and R 4 are independently C 1-2 o-alkyl, wherein R 3 and R 4 independently of one another optionally contain one or more halogen atoms, or iii) in which R 1 and R 2 , and also R 3 and R 4 together with W form a 5- to 7-membered ring, or b) [NR 5 R
  • each of the optionally formed from R 1 to R 12 rings one or more substituents selected from the group consisting of C ⁇ o-alkyl groups, C 1-2 o-alkoxy groups, halogen and cyano be bound, the C 1-2 o-alkyl groups and C 1-20 -alkoxy groups independently of one another optionally contain one or more halogen atoms, and in which each of the rings formed from R 1 to R 12 optionally contains one or two further heteroatoms selected from the group consisting of nitrogen, May contain sulfur and oxygen, and / or may be fused to another aromatic or non-aromatic 5- to 7-membered ring comprising mixing malononitrile with a cyano compound of the formula RCN, wherein R is selected from the group consisting of chlorine, bromine , Iodine and cyano in the presence of a base, optionally in the presence of a solvent, and adding a salt (Q + ) n X n
  • malononitrile, the cyano compound of the formula RCN and the salt (Q + ) n X n ⁇ in the presence of a base, if appropriate in the presence of a further solvent, are mixed in an aqueous phase, wherein formation and exchange of the Tricyanomethanidanions take place in a one-pot reaction ,
  • Both the cyano compound of the formula RCN, and the base and / or the salt of the formula (Q + ) n X n " , wherein R, Q + , X n" and n are as defined above, may be in pure form, as well as a solution, for example in water and / or methanol.
  • Other suitable solvents and / or solubilizers can be selected from the group consisting of acetone, acetonitrile, C 1 .
  • the cyano compound RCN is selected from the group consisting of cyanogen chloride, cyanogen bromide and cyanogen, more preferably cyanogen chloride or cyanogen.
  • the molar ratio of malononitrile to the cyano compound of the formula RCN is in the range from 0.2: 1 to 2: 1, particularly preferably from 0.9: 1 to 1.1: 1, very particularly preferably at 0, 95: 1 to 1.05: 1.
  • Suitable bases in the process according to the invention can be selected from the group consisting of alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, ammonia, primary, secondary and tertiary amines.
  • the base is particularly preferably an alkali metal hydroxide and alkaline earth metal hydroxide, very particularly preferably sodium hydroxide and / or potassium hydroxide.
  • the pH is maintained at a value greater than 4 during the reaction, preferably at a value greater than 7, more preferably in the range from 7 to 9.
  • the halide as anion X n ⁇ of the salt of the formula (Q + ) n X n " may be selected from the group consisting of fluorine, chlorine, bromine and iodine, more preferably chloride.
  • pseudohalide anions X n " in the salt (Q + ) n X n ⁇ it is possible to use anions which consist of at least two electronegative atoms and which are chemically similar to the halogens.
  • Pseudohalide anions are preferably selected from the group consisting of CN " , OCN “. , SCN “ and N 3 " . Particularly preferred is CN " .
  • Suitable organic acid anions are, for example, anions of monobasic and dibasic nonaromatic and aromatic acids such as, for example, acetate, oleate, fumarate, maleate, pyruvate, oxalate and benzoate. Particularly preferred are acetate and pyruvate.
  • the tricyanomethane salts of formula I formed, wherein Q + is as defined above are separated from unreacted starting compounds and purified by extraction procedures.
  • the erfmdungsgemässe method allows the creation of ionic liquids with a very low chloride content.
  • An advantage of the method according to the invention is the possibility of providing largely chloride-free and sodium-free ionic liquids.
  • C 1-n -alkyl denotes an unbranched or branched alkyl group having 1 to n carbon atoms
  • C 1-20 -alkyl represents groups such as methyl, ethyl, propyl, isopropyl, butyl , Isobutyl, sec-butyl, tert-butyl, pentyl, 1,4-dimethyl-pentyl, hexyl, heptyl, octyl, 1,5-dimethyl-hexyl, nonyl, decyl, 4-ethyl-l, 5-dimethylhexyl, undecyl , Dodecyl, tridecyl, tetradecyl or eicosyl.
  • C 3-n -cycloalkyl means a cycloalkyl group having 3 to n carbon atoms.
  • C 3-1 o -cycloalkyl represents groups such as cyclopropyl, cyclobutyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl , Cyclononyl or cyclodecyl.
  • C 6-10 aryl means an aryl group having from 6 to 10 carbon atoms, for example, C 6-10 aryl represents groups such as phenyl, benzyl, methylphenyl, dimethylphenyl, ethylmethylphenyl, diethylphenyl or naphthyl.
  • C 1-n -alkoxy denotes an unbranched or branched alkoxy group having 1 to n carbon atoms
  • C 1-2O -alkoxy represents groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy , sec-butoxy, tert-butoxy, pentyloxy, 1,4-dimethyl-pentyloxy, hexyloxy, heptyloxy, Octyloxy, 1,5-dimethyl-hexyloxy, nonyloxy, decyloxy, 4-ethyl-l, 5-dimethylhexyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or eicosyloxy.
  • halogen means fluoro, chloro, bromo or iodo.
  • the cation Q + contains at least one 5- to 7-membered aromatic or non-aromatic ring.
  • an aromatic or non-aromatic ring in the organic cation Q + contains one to two further heteroatoms from the group consisting of nitrogen, sulfur or oxygen. More preferably, the cation Q + contains another nitrogen or sulfur atom.
  • one or more substituents from the group consisting of C 1-20 alkyl groups, C 1-20 alkoxy groups, C 3-1 o-cycloalkyl groups, C 6-1 can be attached to an aromatic or nonaromatic ring of the cation Q + o-aryl groups, halogen and cyano.
  • the C 1-6 -alkyl groups, C 1-20 -alkoxy groups, C 3-1- o-cycloalkyl groups, C 6-1O -aryl groups independently of one another optionally contain one or more halogen atoms.
  • the cation Q + is particularly preferably selected from the group consisting of organic ammonium, phosphonium and sulfonium cations, pyrrolidinium, pyrrolinium, pyrazolium, pyrazolium, imidazolium, tolazolium, oxazolium and thiazolium -, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,3-dioxolium, pyrylium, thiopyrylium, Azoniaspiro and Phosphoniaspirokationen.
  • the cation Q + is selected from the group consisting of N, N-di (C 1-2 o -alkyl) -N, N- (dimethyl) ammonium, N- (C 6-10 -) aryl) -N ⁇ N-tri (C 1-20 -alkyl) -arimionium, N, N-di (C 6-10 -aryl) -N ) iV ' - (dimethyl) - ammonium, tetramethylphosphonium, tetrabutylphosphonium , Trimethylsulfonium, tributylsulfonium, 1- (C 1-2 o -alkyl) -3-methylpyridinium, 1- (C 1-20 -alkyl) -3-cyano-pyridinium, 1- (C 1 -20 alkyl) - -methylpyrrolidinium- 1, 1- (C 1 - 20 - alkyl) - 1, 3 dimethyl pipe
  • Ionic liquids of the formula I in which Q + is as defined above may, if appropriate in a mixture with one or more other ionic liquids, water or organic solvents, be used as solvent and in particular as constituent of polar solvents.
  • the tricyano-methanides can be used particularly suitably as conductive solvents in the electrochemical or electrosynthesis, in which the addition of conductive salts can be reduced, or completely omitted.
  • ionic liquids based on tricyanomethanides The polarity of ionic liquids based on tricyanomethanides is lower than with conventional ionic liquids, but higher than with ordinary organic solvents, so that here new applications arise.
  • Ionic liquids based on tricyanomethanides are relatively nonpolar ionic liquids which have low water solubilities and low viscosities in comparison with other ionic liquids.
  • ionic liquids based on tricyanomethanides has the advantage over many other ionic liquids that no metal-containing residues are formed during thermal disposal.
  • the compounds obtained by the process according to the invention also have particularly low halide values.
  • Methylpyrrolidine (150 g, 1.76 mol) is initially introduced and mixed at room temperature with butyl chloride (163 g, 1.76 mol). The resulting reaction mixture is then heated under reflux for 24 h (reaction temperature about 77 ° C) with a slightly yellowish suspension forms. Thereafter, the reaction mixture is cooled to room temperature and filtered. The residue is washed with a little MTBE and then dried at 50 ° C. in vacuo to give pure 1-butyl-1-methylpyrrolidmium chloride (27 g, 0.09 mol, 8.6% conversion). The remaining material of the reaction mixture consists exclusively of the unreacted starting materials methylpyrrolidine and butyl chloride, which are completely recovered.
  • Example 2 1-Butyl-1-methylpyrrolidinium tricyanomethanide Malononitrile (17.8 g, 264 mmol) is initially charged in water (300 ml) and at 0 to 5 ° C cyanogen chloride (16.5 g, 0.268 mmol) is added to the Initiated reaction solution, wherein the pH of the reaction solution is kept during introduction to 8.5 by ent speaking addition of 30% sodium hydroxide solution. The reaction temperature of the solution is kept at 0 to 5 0 C during the introduction of cyanogen chloride for about 1 h. To the reaction mixture is added a mixture of 1-butyl-1-methylpyrrolidinium chloride (47.5 g, 0.267 mmol) in water (150 ml).
  • a solution of 1-ethyl-3-methylimidazolium chloride (178.4 g, 1.22 mol) in water (180 ml) is prepared as described in Example 2 to a mixture of malononitrile (84.6 g, 1.28 mol) and Cyanogen chloride (79.9 g, 1.30 mol) was added.
  • the resulting reaction mixture gives no phase separation and is first treated with activated carbon (3%) as in Example 2 and then extracted with dichloromethane (300 ml). The organic phase is then washed with water (2 x 200 ml).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Pyrrole Compounds (AREA)

Abstract

L'invention concerne un procédé de production de liquides ioniques à base de sels de tricyanométhane de formule (I), dans laquelle Q<sup
EP05772429A 2004-08-25 2005-08-20 Procede de production de tricyanomethanides de cations organiques Withdrawn EP1786761A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05772429A EP1786761A1 (fr) 2004-08-25 2005-08-20 Procede de production de tricyanomethanides de cations organiques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04020116A EP1634867A1 (fr) 2004-08-25 2004-08-25 Des sels de cations organiques du tricyanométhane
EP05772429A EP1786761A1 (fr) 2004-08-25 2005-08-20 Procede de production de tricyanomethanides de cations organiques
PCT/EP2005/009026 WO2006021390A1 (fr) 2004-08-25 2005-08-20 Procede de production de tricyanomethanides de cations organiques

Publications (1)

Publication Number Publication Date
EP1786761A1 true EP1786761A1 (fr) 2007-05-23

Family

ID=34926287

Family Applications (2)

Application Number Title Priority Date Filing Date
EP04020116A Withdrawn EP1634867A1 (fr) 2004-08-25 2004-08-25 Des sels de cations organiques du tricyanométhane
EP05772429A Withdrawn EP1786761A1 (fr) 2004-08-25 2005-08-20 Procede de production de tricyanomethanides de cations organiques

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP04020116A Withdrawn EP1634867A1 (fr) 2004-08-25 2004-08-25 Des sels de cations organiques du tricyanométhane

Country Status (7)

Country Link
EP (2) EP1634867A1 (fr)
JP (1) JP5019456B2 (fr)
KR (1) KR101198060B1 (fr)
CN (1) CN101010291B (fr)
HK (1) HK1106222A1 (fr)
SG (1) SG155204A1 (fr)
WO (1) WO2006021390A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009502738A (ja) * 2005-07-27 2009-01-29 株式会社日本触媒 反応用溶媒及びそれを用いた製造方法
EP2048131A4 (fr) 2006-07-27 2012-05-16 Nichicon Corp Composé ionique
WO2009021751A1 (fr) * 2007-08-16 2009-02-19 Lonza Ltd Procédé de fabrication et de purification de tricyanométhanures de métaux alcalins et alcalino-terreux
WO2010000357A2 (fr) * 2008-07-01 2010-01-07 Merck Patent Gmbh, Utilisation de liquides ioniques contenant des anions tricyanométhanure comme solvant pour l'extraction d'alcools à partir de solutions aqueuses
SG173153A1 (en) 2009-02-02 2011-08-29 Lonza Ag Novel tricyanoborates
EP2465849A1 (fr) 2010-12-08 2012-06-20 Lonza Ltd. Tricyanométhanides de 3-cyanopyridinium en tant que liquides ioniques

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981899A (en) * 1968-07-25 1976-09-21 The United States Of America As Represented By The Secretary Of The Army Triaminoguanidine cyanoformate
EP0010396A1 (fr) * 1978-10-24 1980-04-30 Fbc Limited Compositions fongicides et herbicides, certains dérivés de cyanométhane et de cyanoéthylène étant des agents actifs de celles-ci, la préparation de ces dérivés et procédés de lutte contre les champignons et les mauvaises herbes
CA2805188C (fr) * 1996-12-30 2015-12-08 Hydro-Quebec Utilisation d'un compose ionique derive du malononitrile comme photoinitiateur, amorceur radicalaire ou catalyseur dans les procedes de polymerisation, ou comme colorant cationique
JP4152773B2 (ja) 2003-03-03 2008-09-17 日信工業株式会社 ブレーキペダルの操作量に対応した操作フィーリングを演出するブレーキ操作量検出装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006021390A1 *

Also Published As

Publication number Publication date
KR20070047347A (ko) 2007-05-04
SG155204A1 (en) 2009-09-30
JP5019456B2 (ja) 2012-09-05
WO2006021390A1 (fr) 2006-03-02
CN101010291A (zh) 2007-08-01
HK1106222A1 (en) 2008-03-07
JP2008510753A (ja) 2008-04-10
KR101198060B1 (ko) 2012-11-07
EP1634867A1 (fr) 2006-03-15
CN101010291B (zh) 2010-12-22

Similar Documents

Publication Publication Date Title
EP1786761A1 (fr) Procede de production de tricyanomethanides de cations organiques
DE102005035103A1 (de) Verfahren zur Herstellung von Onium-Salzen mit Tetrafluoroborat-Anion mit reduziertem Halogenid-Gehalt
EP1928839B1 (fr) Procede pour produire des fluorures de l&#39;acide 5-fluoro-1,3-dialkyl-1h-pyrazol-4-carboxylique
EP1537126A1 (fr) Procede pour la production par voie organometallique d&#39;intermediaires organiques au moyen de bases aryllithium
DE1770670A1 (de) Verfahren zur Herstellung von 1-Aminoisochinolinverbindungen
DE2835157A1 (de) Verfahren zur herstellung von n-substituierten alpha -halogenacetaniliden
WO2005097749A1 (fr) Dicyanamides d&#39;alkylpyridinium et procede pour leur production
EP1831179B1 (fr) Procede de fabrication de sels d&#39;onium contenant des anions de tetrafluoroborate presentant une teneur reduite en halogenures
DE2627223C2 (fr)
DE2512498C2 (de) Verfahren zur herstellung von sulfonsaeurefluoriden
DE2661028C2 (fr)
EP1902004B1 (fr) Procede de production d&#39;alkylsulfonates d&#39;onium
DE10064423A1 (de) Verfahren zur Herstellung substituierter organischer Verbindungen und Verwendung von Katalysatoren für Substitutionsreaktionen
EP0222205B1 (fr) Procédé de préparation de dérivés d&#39;imidazolyl-méthane
DE102004060073A1 (de) Verfahren zur Hertellung von Onium-Salzen mit Tetrafluoroborat-Anion mit reduziertem Halogenid-Gehalt
DE68906449T2 (de) Herstellung von 2,6-dioxopiperidinderivate.
DE102004060076A1 (de) Verfahren zur Herstellung von Onium-Salzen mit Alkyl- oder Arylsulfonat-Anionen oder Alkyl- oder Arylcarboxylat-Anionen mit geringem Halogenid-Gehalt
DE102005032837A1 (de) Verfahren zur Herstellung von Onium-Alkylsulfiten
DE3434553C2 (fr)
DE2604248C2 (de) Verfahren zur Herstellung von Thienopyridinderivaten
DE102005032838A1 (de) Mischung von Onium-Alkylsulfonaten und Onium-Alkylsulfiten
EP4028390A1 (fr) Procédé amélioré de préparation d&#39;époxydes à partir d&#39;aldéhydes ou de cétones
EP0100498B1 (fr) Procédé pour la préparation de l&#39;acide dichlorolactique, du nitrile ou de l&#39;amide de l&#39;acide dichlorolactique
DE69819315T2 (de) Verfahren zur herstellung von piperidincarbonsäureamiden
DE102004060074A1 (de) Verfahren zur Herstellung von Onium Alkylsulfaten mit geringem Halogenid-Gehalt

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070326

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: HR YU

RAX Requested extension states of the european patent have changed

Extension state: YU

Payment date: 20070326

Extension state: HR

Payment date: 20070326

17Q First examination report despatched

Effective date: 20090806

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20140723