Solvents donors

The monomers are electron pair acceptors, and donor molecules are often able to split the dimeric halide molecules to form adducts thus, whilst the dimeric halides persist in solvents such as benzene, donor solvents such as pyridine and ether appear to contain monomers since adduct formation occurs. Aluminium halides, with the one exception of the fluoride, resemble the corresponding boron halides in that they are readily hydrolysed by water. 

W. R. Eppedy and J. W. Taunton, "Exxon Donor Solvent Coal Liquefaction Process Development," paper presented at Coal Dilemma II ACS Meeting, Colorado Spriags, Colo., Feb. 12, 1979. 

Iron(III) iodide [15600-49-4], Fefy, is prepared by the oxidative photodecarbonylation of diiodotetracarbonylkon(II) ki the presence of dkodine (7). The black soHd obtained is extremely hygroscopic, spariagly soluble only ki dichloromethane, and decomposes to kon(II) iodide and dkodine when exposed to donor solvents such as tetrahydrofuran, acetonitrile, water, or pyridine. It also decomposes when exposed to light. 

Direct Hydrogenation. Direct hydrogenation of lignitic and other coals has been studied by many investigators. Lignite can be slurried with an anthracene-oil solvent, heated to a temperature of 460—500°C with 1 1 CO H2 synthesis gas at pressures to 28 MPa (280 atm) in a 2 kg/h reactor. The product hquids are separated, and in a commercial process, a suitable hydrogen-donor solvent would be recycled (54). 

W. N. Mitchell, K. L. Trachte, md S. Zaczepinski, "Performance of Low-Rank Coals in the Exxon Donor Solvent Process," paper presented at / 0th Biennial Eignite Symposium, Grmd Porks, N.D., May 1979. 

T[[dotb]he nature of the initial attack by the water (eq. 10) is a matter of some controversy (205,206). Stereochemical and kinetic studies of model systems have been reported that support trans addition of external water (207,208) or internal addition of cis-coordinated water (209), depending on the particular model system under study. Other paHadium-cataly2ed oxidations of olefins ia various oxygen donor solvents produce a variety of products including aldehydes (qv), ketones (qv), vinyl acetate, acetals, and vinyl ethers (204). However the product mixtures are complex and very sensitive to conditions. 

Fig. 17. Schematic diagram of the coal hquefaction section of the Exxon donor solvent (EDS) process. To convert MPa to psi, multiply by 145.

Vanadium (IV) Chloride. Vanadium(IV) chloride (vanadium tetrachloride, VCy is a red-brown hquid, is readily hydrolyzed, forms addition compounds with donor solvents such as pyridine, and is reduced by such molecules to trivalent vanadium compounds. Vanadium tetrachloride dissociates slowly at room temperature and rapidly at higher temperatures, yielding VCl and CI2. Decomposition also is induced catalyticahy and photochemically. This instabihty reflects the difficulty in storing and transporting it for industrial use. 

Vanadium(III) Chloride. Vanadium(III) chloride (vanadium trichloride, VCl ) is a pink-violet sohd, is readily hydrolyzed, and is insoluble in nonpolar solvents but dissolves in donor solvents, eg, acetonitrile, to form coordination compounds. Chemical behavior of the tribromide (VBr ) is similar to that of VCl. ... 

Charge-Transfer Compounds. Similat to iodine and chlorine, bromine can form charge-transfer complexes with organic molecules that can serve as Lewis bases. The frequency of the iatense uv charge-transfer adsorption band is dependent on the ionization potential of the donor solvent molecule. Electronic charge can be transferred from a TT-electron system as ia the case of aromatic compounds or from lone-pairs of electrons as ia ethers and amines. 

Several processes progressed to demonstration scales but have not been commercialized, primarily because of economic inabiHty to compete with available petroleum products. The H-Coal process developed by Hydrocarbon Research, Inc. was demonstrated at Catiettsburg, Kentucky using a 545 t/d plant and DOE support. The Exxon donor solvent Hquefaction process was not commercialized either. 

The acid-base properties of isoxazole and methylisoxazoles were studied in proton donor solvents, basic solvents or DMSO by IR procedures and the weakly basic properties examined (78CR(Q(268)613). The basicity and conjugation properties of arylisoxazoles were also studied by UV and basicity measurements, and it was found that 3-substituted isoxazoles were always less basic than the 5-derivatives. Protonation increased the conjugation in these systems (78KGS327). 

Depending on its rank, coal can be dissolved in as little as one minute in the temperature range of 623 to 723 K (662 to S42°F) in suitable solvents, which are assumed to promote thermal cracking of the coal into smaller, more readily dissolved fragments. These fragments may be stabilized through reactions with one another or with hydrogen supplied either by a donor solvent or from a gas phase. 

Magnitudes of /cg, /cp, /c, and indicate the importance of direct reactions with coal, where and are for hydrocracking reactions in the conversion process. Data for and from the experiments with HPO indicate that oil production from coal is increased by the use of a good hydrogen donor solvent. 

H2/Pd-C. If hydrogenation is carried out in the presence of (BOC)20, the released amine is directly converted to the BOC derivative. H2/Pd-C, NH3, —33°, 3-8 h, quant.When ammonia is used as the solvent, cysteine or methionine units in a peptide do not poison the catalyst. Pd-C or Pd black, hydrogen donor, solvent, 25° or reflux in EtOH, 15 min-2 h, 80-100% yield. Several hydrogen donors, including cyclohex-... 

FIGURE 13.57 NOTE The importance of Solvent/column interaction using Jordi DVB columns cannot be over emphasized. We have found that a SOySO mbc of MeOH/ACN for the strong solvent Is adequate for many reverse phase separations and is better than either alone. We have now observed that the use of THF/ACN as strong solvent is often better than MeOH/ACN. In general Lewis bases (electron donor solvents) deactivate the aromatic rings and often dramatically increase column efficiencies. 

We consider first the Sn2 type of process. (In some important Sn2 reactions the solvent may function as the nucleophile. We will treat solvent nucleophilicity as a separate topic in Chapter 8.) Basicity toward the proton, that is, the pKa of the conjugate acid of the nucleophile, has been found to be less successful as a model property for reactions at saturated carbon than for nucleophilic acyl transfers, although basicity must have some relationship to nucleophilicity. Bordwell et al. have demonstrated very satisfactory Brjinsted-type plots for nucleophilic displacements at saturated carbon when the basicities and reactivities are measured in polar aprotic solvents like dimethylsulfoxide. The problem of establishing such simple correlations in hydroxylic solvents lies in the varying solvation stabilization within a reaction series in H-bond donor solvents. 

Ligands L, L can be drawn from virtually the full range of inorganic and organic neutral and anionic ligands and, indeed, the reaction severely limits the range of donor solvents in which B10H14 can be dissolved. The approximate sequence of stability is ... 

As noted above, there is no physical evidence for this equilibrium in pure N2O4, but the electrical conductivity is considerably enhanced when the liquid is mixed with a solvent of high dielectric constant such as nitromethane (e 37), or with donor solvents (D) such as MeC02Et, Et20, Mc2SO, or Et2NNO (diethylnitrosamdne) ... 

However, in electron-donor solvents, L, the vacant antibonding orbital of I2 acts as an electron acceptor thus weakening the I-1 bond and altering the energy of the electronic transitions ... 

Donor solvent Formation constant X(20°C)/1 mol- -AH / kJ moC Charge-transfer band W/nm fmax A VI/cm- 2 ... 

AHC(S1), p. 485 84CHEC-I(5)345], except that for both types of compounds the A-oxide forms 117b and 118b predominate in proton donor solvents (Scheme 47). 

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