Iminium salts and methods of preparing electron deficient olefins using such novel iminium salts
A technology of electron-deficient olefins and imide salts, applied in chemical instruments and methods, preparation of organic compounds, preparation of carboxylic acid nitriles, etc., can solve the problems of no imide salts and/or ionic liquid applications, etc.
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Embodiment 1
[0076] PRIMENE imine ( figure 2 ,step 1)
[0077] Imines were prepared using PRIMENE TOA, 811-R and JM-T by reacting an amine with a stoichiometric equivalent of paraformaldehyde and removing the water of condensation. All imines formed were distillable liquids and existed as stable monomeric imines as demonstrated by: 1 HNMR 60MHz (CDCl 3 ) 2H D 7.16, 7.09ppm (TOA imine); 2H s (br) 7.45ppm (81-R imine) and (CD 3 COCD 3 )2H 6.86PPM (JM-T imine) and FTIR (1650cm for each -1 ).
[0078] PRIMENE iminium salt ( figure 2 , step 2)
[0079] The distilled imine was analyzed by Karl-Fischer titration and appeared to be essentially free of water (<20 ppm). These imines were treated with a stoichiometric equivalent of acid while cooling. Iminium salts are prepared from the following acids: methanesulfonic acid, benzenesulfonic acid, sulfuric acid and mixtures of some of these.
[0080] PRIMENE TOA iminium methane sulfonate forms a viscous liquid that begins to show signs of ...
Embodiment 2
[0092] In this example, various amines were synthesized and characterized using the following instruments: JNM-MY60 (60MHz for 1 hour) or Varian UNITY-300 (for 1 H is 300MHz, and for 13 C NMR was recorded at 75.5 MHz). Chemical shifts δ are given in ppm relative to the residual peak of the deuterated solvent and coupling constants J are given in Hertz. IR spectra were recorded on a Nicolet 380 FT-IR spectrometer and measured either as KBr particles or as oil between KBr flakes. GC / MS spectra were acquired on a PE-GCMS Clarus 500, Perkin Elmer GCMS spectrometer.
[0093] All amines (PRIMENE TOA, 81-R, JMT, MD from Rohm and Haas), acids (methanesulfonic acid, acetic acid, p-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid and phosphoric acid from Aldrich), solvents ( Toluene, benzene, ether, heptane, hexane, methylene chloride, chloroform from Aldrich), n-butyl lactoyl cyanoacetate (from Degussa), other chemicals (cyanoacetic acid, cyanide from Aldrich Ethyl acetate...
Embodiment 3
[0107] In this example, various iminium salts were synthesized from the imines prepared above.
[0108] Synthesis of PRIMENE 81-R Imine-MSA
[0109]Methanesulfonic acid (96 g, 1.0 mol) was added dropwise to freshly distilled PRIMENE 81-R imine (197 g, ~1.0 mol) with stirring at ice-water bath temperature and then warmed to room temperature. The pale yellow iminium salt formed was retained for further reaction.
[0110] Synthesis of other iminium salts
[0111] Follow the same procedure to prepare the following iminium salts: Table 1 Note: MSA = methanesulfonic acid; BSA = benzenesulfonic acid; LAS = dodecylbenzenesulfonic acid, NSA = 2-naphthalenesulfonic acid; s = solid; √ = ionic liquid. *Using 2 molar equivalents of acid.
[0112] iminium salt a purity b (%) Yield c (%) PRIMENE81-R MSA 95 73 PRIMENE 81-R H 2 SO 4 ＜20 10 PRIMENE 81-R MSA / H 2 SO 4 (1:1) 77 46 PRIMENE 81-R MSA / H 2 SO 4 (1∶4) 70 21 ...
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