Ethanol complexes

Silver perchlorate forms solid complexes with aniline, pyridine, toluene, benzene and many other aromatic hydrocarbons [1], A sample of the benzene complex exploded violently on crushing in a mortar. The ethanol complex also exploded similarly, and unspecified perchlorates dissolved in organic solvents were observed to explode [2], Solutions of the perchlorate in benzene are said to be dangerously explosive [3], but this may be in error for the solid benzene complex. The energy released on decomposition of the benzene complex has been calculated as 3.4 kJ/g, some 75% of that for TNT [4],... 

In refluxing decane, a mixture of Me3SiC=CC=CSiMc3 and Co(CO)2Cp gives cyclobutadiene (275a,b Scheme 59) and cyclopentadienone complexes (276), which could be protodesilylated with ethanolic Complexes 275 were... 

Single crystals of the ethanol complex of 1 were irradiated through Pyrex and the chiral photoproduct 2 was tested for optical activity by polarimetry and chiral HPLC. This indicated an enantiomeric excess of 89% (84% conversion at room temperature). 

Recrystallization of 27a from cyclohexane gave chiral crystals, and their photoirradiation in the solid state afforded optically pure cyclization product 28a [19]. Similarly, photoirradiation of the ethanol complex crystals of 27b in which 27b... 

Crystalline hexakis(ethanol) complexes of perchlorates, tetrn-fluoroborates, and nitrates of several metals, Zn, Mg, Mn, Fe, Co, and Ni, have been prepared from the hydrated salts by dehydration with triethyl orthoformate.8... 

Another Karl Fischer analysis should then be performed, and if water continues to persist, an additional 0.1-0.2 mole of triethyl orthoformate should be added and the refluxing continued for an additional hour. Upon concentration of the solution to a volume of 11., and then cooling it to 0° under nitrogen to exclude moisture, pastel-green hygroscopic needles of the tetrakis-(ethanol) complex (140 g., 22%f) form. These are collected and carefully dried under nitrogen on a Schlenk frit at 23°. Anal. Calcd. for C8H24C104Ni C, 30.61 H, 7.71 Cl, 22.59 O, 20.39 Ni, 18.70. Found C, 27.71 H, 6.95 Cl, 22.97 O, 20.82 Ni, 19.09. 

The tetrakis(ethanol) complex readily changes to a brown tris(ethanol) complex when it is dried at reduced pressure. Thermogravimetric analysis % shows ethanol is evolved from the tetrakis(ethanol) complex below 26° and this loss is complete at 113°. Two endotherms are observed on differential thermal analysis % during the final 4% loss in weight, at 80 and at 89°. 

DMF also appears to coordinate to [TPPFel] to form six-coordinate complexes, and the structmes and magnetic susceptibilities of two bis(ethanol) complexes of TPPFe salts and one OEPFe salt have been reported. The sttucture of [TPPFe(H20)2]C104 has also been reported the Fe-Np bond distances are 2.041 A and the Fe (aqua)... 

The reaction of 1,2-diaininocyclopropenylium perchlorates 14 with an equimolar amount of mercury(ll) acetate in dimethyl sulfoxide at 120 C afforded the cationic mercury complexes 15 as colorless crystals. The original cation salts 14 were recovered quantitatively when the complexes 15 were heated with perchloric acid in ethanol.Complexes 15 were also converted into l,2-diamino-3-iodocyclopropenylium ions 16 in 55% yield when treated with two molar equivalents of iodine in dichloromethane. Reaction of complexes 15 with sulfur in pyridine afforded the 2,3-diaminocyclopropenethiones 17 in 35% yield. 

Asymmetric induction in the di-jr-methane rearrangement is also of interest and studies on this have examined the influence of chiral esters. Thus the irradiation of 370 yields a cyclooctatetraene 371 and a diastereoisomeric mixture of the semibullvalenes 372 and 373 in a ratio of 60 40 in solution and 20 80 in the solid phase. The position of attachment is vital and the diastereoselectivity shown by the barrelene 374 is very poor and yields a 1 1 mixture of products . Further examples of the control exercised when dibenzobarrelenes are inadiated in the crystalline phase have used the derivatives 375 and 376 as the acid salts formed with chiral amines. Irradiation affords the products 377 and 378 respectively, obtained after esterification with MeOH, with an ee of >95% . The influence of a chiral crystal lattice on the outcome of the di-jr-methane reaction of achiral 379 has been studied. The irradiation in the crystalline phase gives two chiral di-TT-rnethane products 380 and 381. The former of these is racemic but the latter is obtained in high enantiomeric excess which, under the best conditions, i.e. at —20 °C, approaches 100%. The irradiation of ciystals of 345, as an ethanol complex, affords 382 with an ee of 94%. Carrying out the inadiation at temperatures lower than ambient enhances the specificity of the reaction . 

Synthesis and structural characterization of synthetic analogs of liver alcohol dehydrogenase (LADH) continued to be one of the most investigated fields of research. A number of ligands suitable for modeling LADH have been reported and their hydroxo zinc complexes also described.133-135 [Zn(TmMes)(HOMe)]+, for example, exhibits a coordination environment that resembles aspects of that in LADH.136 The ethanol complex [Zn(Tm Bu)(HOEt)]+ has been also isolated.137 [NS2] donor ligands, that feature thioether donors, also provide coordination environments that mimic the active site of LADH.138,139... 

In 1993, Kenji Matsuki reported an enantioselective reduction of the anhydride with Noyori s hinol-aluminium hydride-ethanol complex. [125]... 

As in the two-phase system, Mn(III) porphyrin is easily reduced by the conjugated Rh(III) complex in the presence of formate. In ethanol, complex 12 is capable of epoxidizing a-pinene with turnovers in the range of 300/h. The complex is much more stable under the applied reaction conditions than separate manganese porphyrin and rhodium bipyridine complexes and showed only a 10-20% loss of catalyst after 3h as followed by uv-vis spectroscopy. Further studies are being carried out to determine the scope and efficiency of this catalyst. 

Ethanol complex HexaiMi Hexanol complex of Ca -Mont Ca -Mont Ca -Mont... 

Because do not include water, these would be useful for the extraction of ethanol from aqueous solution. For example, when a mixture of (12.3 g, 56 mmol) and 80% ethanol (10 ml, equivalent to 137 mmol of ethanol) was kept at room temperature for 12 h, opaque turned to a 1 1 ethanol complex of transparent crystals gradually without dissolving. 

In 50% ethanol solution (10 ml, equivalent to 86 mmol ethanol), (1 g, 4.5 mmol) was dissolved by heating, and the solution was kept at room temperature for 12 h, to obtain the 1 1 ethanol complex of (0.96 g, 3.6 mmol, 80% based on 4 )- However, it was necessary to use organic solvent for dissolving in diluted ethanol solution, A solution of (2 g, 9 mmol) in ether-petroleum ether (1 1, 10 ml) was mixed with 15% ethanol solution (10 ml, equivalent to 26 mmol ethanol). The mixture was kept at room temperature for 12 h, to obtain the 1 1 ethanol complex of 4 (2,3 g,... 

Here K is a constant related to the apparent dissociation constant of the vanadium-hydroperoxide and vanadium-ethanol complexes and k is the limiting specific rate constant which could be observed when the intermediate complex concentration is maximal. 

Figure 15-8 shows the locations of cp and y values for cellulose la, ip, II, and IIIj. Also indicated are the values from the crystal structures of methyl cellotrioside (Raymond et al. 1995) and an ethanol complex of cellotetraose (Gessler et al. 1995). 

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