First Room Temperature Ionic Liquids

Started by psi43, September 27, 2007 04:51 PM

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psi43

September 27, 2007 04:51 PM
Ionic Liquids
  A solidified ionic   liquid1)

 An ionic liquid is a salt in which the ions are poorly coordinated, which   results in these solvents being liquid below 100°C, or even at room temperature   (room temperature ionic liquids, RTIL\\\'s). At least one ion has a delocalized   charge and one component is organic, which prevents the formation of a stable   crystal lattice.

 The methylimidazolium and pyridinium ions have proven to be good starting   points for the development of ionic liquids:

 

 Properties, such as melting point, viscosity, and solubility of starting   materials and other solvents, are determined by the substituents on the organic   component and by the counterion. Many ionic liquids have even been developed for   specific synthetic problems. For this reason, ionic liquids have been termed   "designer solvents".

 One of the first RTILs was a mixture of [emim]Cl with AlCl3  forming a series of equilibria between [emim][AlCl4], [emim][Al2Cl7],   and [emim][Al3Cl10]. This RTIL is not water stable. The   discovery of water-insoluble RTILs such as [bmim][PF6] allowed the   development of new work-up methods, including the separation of water-soluble   byproducts by simple extraction. Some transition metal catalysts that are   soluble in ionic liquids may be recycled together with the ionic liquid, after   extraction with water and the non-polar organic solvent used for product   separation. The catalyst and ionic liquid may be recycled several times.

  In addition, the following RTIL, derived from fructose (a renewable   feedstock), is a promising solvent for implementing fully "green" chemistry   methods:

   
 S. T. Handy, M. Okello, G. Dickenson, Org. Lett., 2003, 5,   2513-2515.

 This ionic liquid was proven to be suitable for Heck Reactions:

   
 S. T. Handy, M. Okello, G. Dickenson, Org. Lett., 2003, 5,   2513-2515.

 The absence of volatility is one of the most important benefits of ionic   liquids, offering a much lower toxicity as compared to low-boiling-point   solvents. Ionic liquids can also make for safer  microwave synthesis methods, because   sudden pressure surges are not possible. The dipole characteristics of ionic   liquids translate into rapid excitation by microwaves, and consequently faster   reactions.



Reviews

 P. Wasserscheid, W. Keim, Angew. Chem. Int. Ed. Engl. 2000  , 39, 3772.  DOI

   Books

                           Ionic Liquids in Synthesis
       Peter Wasserscheid, Tom Welton        Hardcover, 364 Pages
       First Edition, November 2002
       ISBN: 3-527-30515-7 - Wiley-VCH

                                  Chemistry in Alternative Reaction      Media
    D. J. Adams, P. J. Dyson, S. J. Taverner     Paperback, 268 Pages
    First Edition, November 2003
    ISBN: 0-471-49849-1 - Wiley

         Recent Literature

 Display all abstracts

   
 In ionic liquids [Bmim][PF6] or [Bmim][BF4], a highly regioselective N-substitution of pyrrole with alkyl halides, sulfonyl chlorides, and benzoyl chloride gave substituted pyrroles in excellent yields. Michael addition of pyrrole with electrophilic olefins was completed in a highly regioselective manner to afford N-alkylpyrroles.
 Z.-G. Lea, Z.-C. Chen, Y. Hu, Q.-G. Zheng Synthesis,   2004,   1951-1954.

 
The coupling of vinyl bromides with thiols or diphenyl diselenide using copper(I) salts as catalysts in ionic liquids based on amino ­acids gives vinyl chalcogenides in good to excellent yields with retention of stereochemistry. The ionic liquids act as solvent, base, and excellent promoter for the copper-catalyzed coupling reactions.

Necronomitr0n

#1
September 27, 2007 04:51 PM
unf
<+fawx> im trying to animate a dick coming out of a toaster how do i go on about doing this
<~rtil> well fawx what you would do is delete the fla and do something productive instead
<+ansel> i lure children into my van with candy and then i read them passages from 'the origin of species'
<%ropesnake> billy con ends with billy raping his cat
<+billymonks> FUCK YOU BUG
<~rtil> ya one time i gave this hobo some cat food and he ate it like the animal he is it pleased me

psi43

#2
September 27, 2007 04:54 PM
Z. Wang, H. Mo, W. Bao, Synlett, 2007, 91-94.        
 An improved and rapid one-pot synthesis of 2,4,5-triaryl imidazoles in  a room temperature ionic liquid does not need any added catalyst. This  one-pot methodology offers excellent isolated yields, simple work up  procedures and efficient recovery and recycling of the ionic liquid.
 S. A. Siddiqui, U. C. Narkhede, S. S. Palimkar, T. Daniel, R. J. Lahoti, K. V.   Srinivasan, Tetrahedron, 2005,   61, 3539-3546.

     
 A selective cathodic reduction of carbon dioxide in CO2-saturated   room-temperature ionic liquid BMIm-BF4  solutions containing amines, followed by addition of EtI as an  alkylating agent allows an environmentally friendly, mild, and safe  synthesis of organic carbamates in good yields.
 M. Feroci, M. Orsini, L. Rossi, G. Sotgiu, A. Inesi, J. Org. Chem., 2007,  72, 144-149.

       
 A convenient and efficient oxidation of hydroxylated and methoxylated  benzaldehydes and acetophenones to the corresponding phenols uses  hydrogen peroxide and methyltrioxorhenium as catalyst in ionic liquids  [bmim]BF4   and [bmim]PF6.
 R. Bernini, A. Coratti, G. Provenzano, G. Fabrizi, D. Tofani, Tetrahedron, 2005,   61, 1821-1825.

       
 A convenient, efficient, and selective N-Alkylation of N-acidic  heterocyclic compounds with alkyl halides is accomplished in ionic  liquids in the presence of potassium hydroxide as a base. In this  manner, phthalimide, indole, benzimidazole, and succinimide can be  successfully alkylated.
 Z.-G. Le, Z.-C. Chen, Y. Hu, Q.-G. Zheng, Synthesis, 2004,   208-212.







 
Aldimines (generated in situ from aldehydes and amines) react readily with ethyl diazoacetate in the presence of 2 mol% of Bi(OTf)3 in [bmim]PF6   to produce the corresponding aryl aziridine carboxylates in high yields with   excellent cis-diastereoselectivity.
 J. S. Yaday, B. V. S. Reddy, P. N. Reddy, M. Shesha Rao, Synthesis,  2003, 1387-1389.

       
 The ionic liquid 1-butyl-3-methylimidazonium tetrafluoroborate [bmim]BF4 was used for ethylenediammonium diacetate (EDDA)-catalyzed Knoevenagel condensation between aldehydes or ketones with active methylene compounds. Catalyst and solvent can be recycled.
 C. Su, Z.-C. Chen, Q.-G. Zhen, Synthesis,  2003, 555-559.

       
 The functionalized ionic liquid 1-(2-hydroxyethyl)-3-methyl­imidazolium   tetrafluoroborate ([HEmim][BF4]) is an efficient and recyclable   reaction medium for palladium-catalyzed Heck reactions under phosphine-free   conditions.
 L. Zhou, L. Wang,  Synthesis, 2006, 2649-2652.

       
The basic ionic liquid 1-butyl-3-methylimidazolium hydroxide, [bmIm]OH, efficiently catalyzes the Knoevenagel condensation of various aliphatic and aromatic aldehydes and ketones with active methylenes at room temperature without requirement of any organic solvent.
 B. C. Ranu, R. Jana, Eur. J. Org. Chem., 2006, 3767-3770.

 
 Hydroformylation of alkenes can be carried out in a few minutes under  microwave activation at a relatively low pressure (2.7 atm) using  commercially available catalysts and ligands. After 4 min of microwave  irradiation, the corresponding aldehyde is formed in high yield.
 E. Petricci, A. Mann, A. Schoenfelder, A. Rota, M. Taddei, Org. Lett.,  2006,  8, 3725-3727.

 
The palladium acetate-catalyzed coupling reaction of aryl boronic acids with carboxylic anhydrides or acyl chlorides was carried out smoothly in water in the presence of PEG or [bmim][PF6] to give high yields of ketones. The   Pd(OAc)2-H2O-[bmim][PF6] catalytic system can   be recovered and reused.
 B. Xin, Yuhong Zhang, K. Cheng, J. Org. Chem., 2006,  71, 5725-5731.

psi43

#3
September 27, 2007 04:59 PM
    
 The first Corey-Chaykovsky epoxidation and cyclopropanation using  trimethyl sulfonium iodide/trimethyl sulfoxonium iodide and KOH as base  in the recyclable ionic liquid, (bmim)PF6 are described.
    S. Chandrasekhar, Ch. Narasihmulu, V. Jagadeshwar, K. Venkatram Reddy,  Tetrahedron Lett., 2003,  44, 3629-3630.


                 

 
 A microwave-assisted, palladium-catalyzed catalytic transfer  hydrogenation of different homo- or heteronuclear organic compounds  using formate salts as a hydrogen source was performed in ([bmim][PF6]. Essentially pure products could be isolated in   moderate to excellent yields by simple liquid-liquid extraction.
 H. Berthold, T. Schotten, H. Hönig, Synthesis,  2002, 1607-1610.

                   

       
 A new, base-stable, imidazolium room-temperature ionic liquid (RTIL)  has been prepared and applied to the addition of Grignard reagents to  carbonyl compounds to afford alcohol products in good to excellent  yield at ambient temperature. The RTIL can be easily recycled and  reused.
 S. T. Handy, J. Org. Chem., 2006,  71, 4659-4662

                     
 Brønsted acid-base ionic liquids (GILs) based on guanidine and acetic  acid are efficient and reusable reaction media for palladium-catalyzed  Heck reactions. These solvents play multiple roles: as strong bases and  as ligands to stabilize Pd species.
 S. Li, Y. Lin, H. Xie, S. Zhang, J. Xu, Org. Lett.,  2006,  8, 391-394.

Necronomitr0n

#4
September 27, 2007 05:00 PM
UNF
<+fawx> im trying to animate a dick coming out of a toaster how do i go on about doing this
<~rtil> well fawx what you would do is delete the fla and do something productive instead
<+ansel> i lure children into my van with candy and then i read them passages from 'the origin of species'
<%ropesnake> billy con ends with billy raping his cat
<+billymonks> FUCK YOU BUG
<~rtil> ya one time i gave this hobo some cat food and he ate it like the animal he is it pleased me

psi43

#5
September 27, 2007 05:01 PM
 
Ammonium salts that can act as hydrogen-bond donors exert a remarkable acceleration on the rates of the regioselective arylation of electron-rich olefins by aryl halides in ionic liquids and common solvents.
 J. Mo, J. Xiao, Angew. Chem. Int. Ed., 2006,  45, 4152-4157.

             
A mild method for the trimethylsilyl trifluoromethanesulfonate (TMSOTf) catalyzed one-pot synthesis of homoallyl ethers from aldehydes has been developed in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim] [OTf]). The advantages of this method include the use of a recyclable ionic liquid, facile product isolation without employing excess organic solvent and elimination of an aqueous waste stream.
 P. W. Anzalone, R. S. Mohan,  Synthesis, 2005, 2661-2663.

             
 The ionic liquid 1-methyl-3-pentylimidazolium fluoroborate, [pmIm]BF4, is an efficient catalyst as well as solvent for the stereoselective debromination of various vicinal-dibromides to the corresponding (E)-alkenes in high yields under microwave irradiation. This reaction does not require any conventional reducing agent, and the ionic liquid can be recycled.
 B. C. Ranu, R. Jana, J. Org. Chem., 2005,  70, 8621-8624.

                      
The utility of dicationic ionic liquids for high-temperature organic reactions such as Claisen rearrangement, isomerizations, and the Diels-Alder reaction was demonstrated. Advantages of these solvents are high thermal stability and recyclability.
           X. Han, D. W. Armstrong, Org. Lett.,  2005,  7, 4205-4208.



 
A series of tetrahaloindate(III)-based ionic liquids (ILs) have been produced by microwave-assisted synthesis. These ionic liquids have been examined as catalyst in the reaction of CO2 with a various epoxides to give cyclic carbonates. Tetrahaloindate(III)-based ILs are found to exhibit high catalytic activities. The effects of a variety of parameters (temperature, pressure, molar ratio of propylene oxide to catalyst), the mechanism, and the significant role of H-bonding interactions in the coupling reactions are discussed.
 Y. J. Kim, R. S. Varma, J. Org. Chem., 2005,  70, 7882-7891.

             
 The system Cu(ClO4)2/acetamido-TEMPO/DMAP catalyses the room-temperature aerobic oxidation of primary alcohols to aldehydes in the ionic liquid [bmpy]PF6. The catalysts can be recycled and reused.
 N. Jiang, A. J. Ragauskas, Org. Lett., 2005,  7, 3689-3692.

Necronomitr0n

#6
September 27, 2007 05:01 PM
OH GOD I'M CUMMING
<+fawx> im trying to animate a dick coming out of a toaster how do i go on about doing this
<~rtil> well fawx what you would do is delete the fla and do something productive instead
<+ansel> i lure children into my van with candy and then i read them passages from 'the origin of species'
<%ropesnake> billy con ends with billy raping his cat
<+billymonks> FUCK YOU BUG
<~rtil> ya one time i gave this hobo some cat food and he ate it like the animal he is it pleased me

psi43

#7
September 27, 2007 05:01 PM







Alright, I'm done!

Nadroj0711

#8
September 27, 2007 05:19 PM
Systek, what the hell is wrong with you
'ello gov'na

Necronomitr0n

#9
September 27, 2007 05:22 PM
Fuck, these pictures are sexy!
<+fawx> im trying to animate a dick coming out of a toaster how do i go on about doing this
<~rtil> well fawx what you would do is delete the fla and do something productive instead
<+ansel> i lure children into my van with candy and then i read them passages from 'the origin of species'
<%ropesnake> billy con ends with billy raping his cat
<+billymonks> FUCK YOU BUG
<~rtil> ya one time i gave this hobo some cat food and he ate it like the animal he is it pleased me

CoolDrMoney

#10
September 27, 2007 05:54 PM
From now on any topic I find boring or stupid will have a clown of my choosing posted in it, starting with this one.


http://cooldrmoney.deviantart.com/

"Hmmm...."
by: SpeedyPac
date: December 1, 2007
Wade is not gay, read his profile! It's sad that you would use sexual orientation as a joke, shows that you have no real sense of humor.

KingDavid

#11
September 27, 2007 07:35 PM
copy and paste is a wonderful thing
Quote from: taylor
Quote from: Sinitronit sucks ass okay

and muse isnt that great anyway
thanks ill use this comment to help myself improve

rtil

#12
September 27, 2007 07:37 PM
this is all lies

psi43

#13
September 27, 2007 08:05 PM
Quote from: rtilthis is all lies

ionic liquids can't talk. You are a lie.

Necronomitr0n

#14
September 28, 2007 01:52 AM
Quote from: taylorugh fuck systek

at first it just seemed like an SSAF rip off then it seemed like some NG BBS faggot gay thing
Nah

I was just acting stupid

besides, psi needed me to make some posts since he needed to post all those pictures
<+fawx> im trying to animate a dick coming out of a toaster how do i go on about doing this
<~rtil> well fawx what you would do is delete the fla and do something productive instead
<+ansel> i lure children into my van with candy and then i read them passages from 'the origin of species'
<%ropesnake> billy con ends with billy raping his cat
<+billymonks> FUCK YOU BUG
<~rtil> ya one time i gave this hobo some cat food and he ate it like the animal he is it pleased me

Nadroj0711

#15
September 28, 2007 02:59 AM
Ironic Liquids
'ello gov'na

jebxz

#16
September 28, 2007 03:01 AM
calm down there niño

steal kians jokes, ive stooped to a new low

billy

#17
September 28, 2007 05:42 PM
Quote from: rtilthis is all lies

We haven't forgotten that you're an alien, rtil.

And I'm still going to eat your skin.

psi43

#18
September 28, 2007 08:12 PM
Quote from: taylorugh fuck systek

at first it just seemed like an SSAF rip off then it seemed like some NG BBS faggot gay thing

I pm'd him and wanted him to post something so I could post more pictures.

also, look at how ugly rtil is!

Necronomitr0n

#19
September 28, 2007 10:15 PM
Quote from: Psi43
Quote from: taylorugh fuck systek

at first it just seemed like an SSAF rip off then it seemed like some NG BBS faggot gay thing

I pm'd him and wanted him to post something so I could post more pictures.

also, look at how ugly rtil is!


It looks like a cast for when you break your arm
<+fawx> im trying to animate a dick coming out of a toaster how do i go on about doing this
<~rtil> well fawx what you would do is delete the fla and do something productive instead
<+ansel> i lure children into my van with candy and then i read them passages from 'the origin of species'
<%ropesnake> billy con ends with billy raping his cat
<+billymonks> FUCK YOU BUG
<~rtil> ya one time i gave this hobo some cat food and he ate it like the animal he is it pleased me
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