In various solvents

Figure A3.6.7. Viscosity dependence of reduced -decay rate constants of ers -stilbene in various solvents [90], The rate constants are divided by the slope of a linear regression to the measured rate constants in the respective solvent.

In homopolymers all tire constituents (monomers) are identical, and hence tire interactions between tire monomers and between tire monomers and tire solvent have the same functional fonn. To describe tire shapes of a homopolymer (in the limit of large molecular weight) it is sufficient to model tire chain as a sequence of connected beads. Such a model can be used to describe tire shapes tliat a chain can adopt in various solvent conditions. A measure of shape is tire dimension of tire chain as a function of the degree of polymerization, N. If N is large tlien tire precise chemical details do not affect tire way tire size scales witli N [10]. In such a description a homopolymer is characterized in tenns of a single parameter tliat essentially characterizes tire effective interaction between tire beads, which is obtained by integrating over tire solvent coordinates. 

Potential of mean force for the Cr+MeCl reaction in various solvents. (Figure redrawn from Chandrasekhar ] and W L Jorgensen 1985. Energy Profile for a Nonconcerted S>]2 Reaction in Solution. Journal of tho American Chemical Society 107 2974-2975.)... 

The former exhibits absorption tjrpical of an isolated keto group, whereas the latter shows a high intensity -band associated with the conjugated system HO—C=C—C=0. The proportions of the two forms under various conditions are readily determined from the ultraviolet spectra. The ultraviolet spectra in various solvents are shown in Fig. A, 7, 2. Since the absorption of the keto form is negligible, the percentage of enol present is 100(em/e ), where e is the observed extinction at 245 mp. and that of the pure enol. It was shown that in alcoholic solution is 1900 and the percentage of enol is 12. Thus e is ca. 16000, and use of this value permits the approximate evaluation of the enol content in different solvents. The results are collected in Table XII. 

NITRATION WITH DINITROGEN PENTOXIDE 4.3.1 The State of dinitrogen pentoxide in various solvents... 

Using a multiple linear regression computer program, a set of substituent parameters was calculated for a number of the most commonly occurring groups. The calculated substituent effects allow a prediction of the chemical shifts of the exterior and central carbon atoms of the allene with standard deviations of l.Sand 2.3 ppm, respectively Although most compounds were measured as neat liquids, for a number of compounds duplicatel measurements were obtained in various solvents. 

PARTIAL MOLAR EXCESS ENTHALPY AT INFINITE DILUTION OF THIAZOLE IN VARIOUS SOLVENTS AT SIS.IS K... 

Some studies on the quatemization of arylthiazoles have been published, among them the quatemization of 2-methyI-4-phenyl thiazole in various solvents (263). The order of reactivity is the following 2-methyl-4-phenyl > 2-methyI-4-(3-nitrophenyl) > 2-methyl-4-(2-chlorophenyl) > 2-methyl-4-(4-nitrophenyl). Introduction of a phenyl group in the... 

Relative Rate of Sn2 Displacement of 1-Biomobutane by Azide in Various Solvents ... 

The activation energies for the decomposition (subscript d) reaction of several different initiators in various solvents are shown in Table 6.2. Also listed are values of k for these systems at the temperature shown. The Arrhenius equation can be used in the form ln(k j/k j) (E /R)(l/Ti - I/T2) to evaluate k j values for these systems at temperatures different from those given in Table 6.2. 

Table 6. Swelling on Immersion in Various Solvents for the Commercial Parylenes at Room Temperature...

The products are Hquids, soluble in various solvents and stable over prolonged periods. Monochloroborane is an equiUbtium mixture containing small amounts of borane and dichloroborane complexes with dimethyl sulfide (81). Monobromoborane—dimethyl sulfide complex shows high purity (82,83). Solutions of monochloroborane in tetrahydrofuran and diethyl ether can also be prepared. Strong complexation renders hydroboration with monochloroborane in tetrahydrofuran sluggish and inconvenient. Monochloroborane solutions in less complexing diethyl ether, an equiUbtium with small amounts of borane and dichloroborane, show excellent reactivity (88,89). Monochloroborane—diethyl etherate [36594-41-9] (10) may be represented as H2BCI O... 

The selective monochlorination of hydroquinone by SOCI2 (84) or a combination of HCl and H2O2 (85) has been studied in various solvents. 

Table 3. Mark-Houwink Constants for PET in Various Solvents at 25°C...

Metals and Metal Derivatives, Silane reacts with alkah metals dissolved in various solvents, forming as the chief product the silyl derivative of the metal, potassium being the most commonly studied, eg, KSiH [13812-63-OJ (27—30). When 1,2-dimethoxyethane or bis(2-methoxyethyl)ether are used as solvents, two competing reactions occur, where M is an alkah metal. 

Hydrolysis of TEOS in various solvents is such that for a particular system increases directiy with the concentration of H" or H O" in acidic media and with the concentration of OH in basic media. The dominant factor in controlling the hydrolysis rate is pH (21). However, the nature of the acid plays an important role, so that a small addition of HCl induces a 1500-fold increase in whereas acetic acid has Httie effect. Hydrolysis is also temperature-dependent. The reaction rate increases 10-fold when the temperature is varied from 20 to 45°C. Nmr experiments show that varies in different solvents as foUows acetonitrile > methanol > dimethylformamide > dioxane > formamide, where the k in acetonitrile is about 20 times larger than the k in formamide. The nature of the alkoxy groups on the siHcon atom also influences the rate constant. The longer and the bulkier the alkoxide group, the lower the (3). 

Catalyst Cation. The logarithms of extraction constants for symmetrical tetra- -alkylammonium salts (log rise by ca 0.54 per added C atom. Although absolute numerical values for extraction coefficients are vastly different in various solvents and for various anions, this relation holds as a first approximation for most solvent—water combinations tested and for many anions. It is important to note, however, that the lipophilicity of phenyl and benzyl groups carrying ammonium salts is much lower than the number of C atoms might suggest. Benzyl is extracted between / -propyl and -butyl. The extraction constants of tetra- -butylammonium salts are about 140 times larger than the constants for tetra- -propylammonium salts of the same anion in the same solvent—water system. 

Another approach to processible bismaleimide resins via a Michael addition chain extension, is the reaction of bismaleimide, or alow melting mixture of bismaleimides, with aminobenzoic hydrazide to provide a resin that is soluble in various solvents, such as acetone [67-64-1methylene chloride [75-09-2] and dimethylform amide [68-12-2] (33). The idealized chemical stmcture for a 2 1 BMI—aminobenzoic hydrazide resin is as follows ... 

When heated to 120°C, AIBN decomposes to form nitrogen and two 2-cyanoisopropyl radicals. The ease with which AIBN forms radicals, and the fact that the rate of information does not vary much in various solvents has resulted in wide use of AIBN as a free-radical initiator. AIBN is used commercially as a catalyst for vinyl polymerisation (see Initiators). 

Photolysis of 1,4-diphenylphthalazine 2-oxide in various solvents gives 1,3-diphenyl-isobenzofuran (52) as the primary product. In the presence of oxygen, deoxygenation to 1,4-diphenylphthalazine and oxidation of the initially formed 1,3-diphenylisobenzofuran (52) to 1,2-dibenzoylbenzene also take place (Scheme 17). 

A number of studies on the NMR spectra of isoxazole has been compiled and this list includes the coupling constants in various solvents as well as the neat liquid. The N signal for isoxazole appears at 339.6 p.p.m. relative to TTAI and is at much lower field than in other azoles. Reports of spectra of substituted isoxazoles also abound (79AhC(25)147, p. 201). 

TABLE 23-7 Selected Absorption Coefficients for CO in Various Solvents in Towers Packed with Raschig Rings ... 

TABLE 2.6 Swelling Characteristics of Sephacryl HR in Various Solvents"... 

Two different sets of experimental conditions have been used. Buu-Hoi et al. and Hansen have employed the method introduced by Papa et using Raney nickel alloy directly for the desulfurization in an alkaline medium. Under these conditions most functional groups are removed and this method is most convenient for the preparation of aliphatic acids. The other method uses Raney nickel catalysts of different reactivity in various solvents such as aqueous ammonia, alcohol, ether, or acetone. The solvent and activity of the catalyst can have an appreciable influence on yields and types of compounds formed, but have not yet been investigated in detail. In acetic anhydride, for instance, desulfurization of thiophenes does not occur and these reaction conditions have been employed for reductive acetylation of nitrothiophenes. Even under the mildest conditions, all double bonds are hydrogenated and all halogens removed. Nitro and oxime groups are reduced to amines. 

The spectra of an organic compound in various solvents differ only in small detail so long as no serious interaction takes place between solute and solvent. Thus the spectrum of a substance in an aprotic solvent (e.g. cyclohexane) should be almost the same as that in water. When addition of water occurs across a C=N bond, the spectrum of the hydrate in water can be vastly different from the spectrum of the anhydrous substance in cyclohexane, and this test has been used on several occasions determine whether or not a neutral species... 

---