Uncatalyzed

It is possible to prepare 1-acetoxy-4-chloro-2-alkenes from conjugated dienes with high selectivity. In the presence of stoichiometric amounts of LiOAc and LiCl, l-acetoxy-4-chloro-2-hutene (358) is obtained from butadiene[307], and cw-l-acetoxy-4-chloro-2-cyclohexene (360) is obtained from 1.3-cyclohexa-diene with 99% selectivity[308]. Neither the 1.4-dichloride nor 1.4-diacetate is formed. Good stereocontrol is also observed with acyclic diene.s[309]. The chloride and acetoxy groups have different reactivities. The Pd-catalyzed selective displacement of the chloride in 358 with diethylamine gives 359 without attacking allylic acetate, and the chloride in 360 is displaced with malonate with retention of the stereochemistry to give 361, while the uncatalyzed reaction affords the inversion product 362. 

The allyl-substituted cyclopentadiene 122 was prepared by the reaction of cyclopentadiene anion with allylic acetates[83], Allyl chloride reacts with carbon nucleophiles without Pd catalyst, but sometimes Pd catalyst accelerates the reaction of allylic chlorides and gives higher selectivity. As an example, allylation of the anion of 6,6-dimethylfulvene 123 with allyl chloride proceeded regioselectively at the methyl group, yielding 124[84]. The uncatalyzed reaction was not selective. 

The uncatalyzed addition of hydrogen to an alkene although exothermic is very slow The rate of hydrogenation increases dramatically however m the presence of cer tain finely divided metal catalysts Platinum is the hydrogenation catalyst most often used although palladium nickel and rhodium are also effective Metal catalyzed addi tion of hydrogen is normally rapid at room temperature and the alkane is produced m high yield usually as the only product... 

Carbonic anhydrase is an enzyme that catalyzes the hydration of carbon dioxide to bicarbonate The uncatalyzed hydration of carbon dioxide is too slow to be effective m transporting carbon dioxide from the tissues to the lungs and so animals have devel oped catalysts to speed this process The activity of carbonic anhydrase is remarkable It has been estimated that one molecule of this enzyme can catalyze the hydration of 3 6 X 10 molecules of carbon dioxide per minute... 

Figure 5.3 shows the data for the uncatalyzed polymerization of adipic acid and 1,10-decamethylene glycol at 161°C plotted according to Eq. (5.21). The various provisos of the catalyzed case apply here also, so it continues to be appropriate to consider only the final stages of the conversion to polymer. From these results, k is about 4.3 X 10" kg eq min at 161°C. 

Figure 5.3 Plot of (1 - p) (left-hand ordinate) and p (right-hand ordinate) versus time for an uncatalyzed esterification. [From S. D. Hamann, D. H. Solomon, and J. D. Swift, /. Macromol. Sci. Chem. A2 153 (1968).]...

Figure 5.4 Comparison of catalyzed (solid lines) and uncatalyzed (broken lines) polymerizations using results calculated in Example 5.2. Here 1 - p (left-hand ordinate) and n (right-hand ordinate) are plotted versus time.

Since Eqs. (5.15) and (5.21), respectively, give p as a function of time for the catalyzed and uncatalyzed polymerizations, the distributions discussed in the last few paragraphs can also be expressed with time as the independent variable instead of p. 

Graphically test whether these data indicate catalyzed or uncatalyzed conditions and evaluate the rate constant for polymerization at 270°C. Propose a name for the polymer. 

Uncatalyzed addition of hydrochloric acid is accompanied by replacement of one hydroxyl group, giving high yields of 2,4-dichloro-2-buten-l-ol (58) with mercuric or cupric salt catalysts, addition occurs without substitution (59,60). 

Anhydrous, monomeric formaldehyde is not available commercially. The pure, dry gas is relatively stable at 80—100°C but slowly polymerizes at lower temperatures. Traces of polar impurities such as acids, alkahes, and water greatly accelerate the polymerization. When Hquid formaldehyde is warmed to room temperature in a sealed ampul, it polymerizes rapidly with evolution of heat (63 kj /mol or 15.05 kcal/mol). Uncatalyzed decomposition is very slow below 300°C extrapolation of kinetic data (32) to 400°C indicates that the rate of decomposition is ca 0.44%/min at 101 kPa (1 atm). The main products ate CO and H2. Metals such as platinum (33), copper (34), and chromia and alumina (35) also catalyze the formation of methanol, methyl formate, formic acid, carbon dioxide, and methane. Trace levels of formaldehyde found in urban atmospheres are readily photo-oxidized to carbon dioxide the half-life ranges from 35—50 minutes (36). 

The hquid remaining after the solvent has been recovered is a heavy residual fuel called solvent-refined coal, containing less than 0.8 wt % sulfur and 0.1 wt % ash. It melts at ca 177°C and has a heating value of ca 37 MJ/kg (16,000 Btu/lb), regardless of the quaUty of the coal feedstock. The activity of the solvent is apparently more important than the action of gaseous hydrogen ia this type of uncatalyzed hydrogenation. Research has been directed to the use of petroleum-derived aromatic oils as start-up solvents (118). 

Equation 11 predominates in uncatalyzed vapor-phase decomposition and photo-chemicaHy initiated reactions. In catalytic reactions, and especially in solution, the nature of the reactants determines which reaction is predominant. 

Isomerization. Maleic acid is isomerized to fumaric acid by thermal treatment and a variety of catalytic species. Isomerization occurs above the 130 to 140°C melting point range for maleic acid but below 230°C, at which point fumaric acid is dehydrated to maleic anhydride. Derivatives of maleic acid can also be isomerized. Kinetic data are available for both the uncatalyzed (73) and thiourea catalyzed (74) isomerizations of the cis to trans diacids. These data suggest that neither carbonium ion nor succinate intermediates are involved in the isomerization. Rather, conjugate addition imparts sufficient single bond character to afford rotation about the central C—C bond of the diacid (75). 

The hydroxyl number can be deterrnined in a number of ways such as acetylation, phthalation, reaction with phenyl isocyanate, and ir and nmr methods. An imidazole-catalyzed phthalation has been used to measure the hydroxyl number for a number of commercial polyether polyols and compared (favorably) to ASTM D2849 (uncatalyzed phthalation) (99). The uncatalyzed method requires two hours at 98°C compared to 15 minutes at the same temperature. 

In plywood production with ureas, the spread veneers should be pressed as soon as possible. The time between spreading and pressing, usually called assembly time, should never exceed one hour. With some formulations, the permissible assembly time may be no longer than 15 rninutes. Melamine formulations and uncatalyzed melamine—urea combinations, however, can be spread and stored for as much as a week before use. 

En me Mechanism. Staphylococcal nuclease (SNase) accelerates the hydrolysis of phosphodiester bonds in nucleic acids (qv) some 10 -fold over the uncatalyzed rate (r93 and references therein). Mutagenesis studies in which Glu43 has been replaced by Asp or Gin have shown Glu to be important for high catalytic activity. The enzyme mechanism is thought to involve base catalysis in which Glu43 acts as a general base and activates a water molecule that attacks the phosphodiester backbone of DNA. To study this mechanistic possibiUty further, Glu was replaced by two unnatural amino acids. 

The processing methods for siHcone mbber are similar to those used in the natural mbber industry (59,369—371). Polymer gum stock and fillers are compounded in a dough or Banbury-type mixer. Catalysts are added and additional compounding is completed on water-cooled roU mills. For small batches, the entire process can be carried out on a two-roU mill. Heat-cured siHcone mbber is commercially available as gum stock, reinforced gum, partially filled gum, uncatalyzed compounds, dispersions, and catalyzed compounds. The latter is ready for use without additional processing. Before being used, sihcone mbber is often freshened, ie, the compound is freshly worked on a mbber mill until it is a smooth continuous sheet. The freshening process eliminates the stmcturing problems associated with polymer—filler interactions. 

Nitrobenzotrichloride is also obtained in high yield with no significant hydrolysis when nitration with a mixture of nitric and sulfuric acids is carried out below 30°C (31). 2,4-Dihydroxybenzophenone [131 -56-6] is formed in 90% yield by the uncatalyzed reaction of benzotrichloride with resorcinol in hydroxyHc solvents (32) or in benzene containing methanol or ethanol (33). Benzophenone derivatives are formed from a variety of aromatic compounds by reaction with benzotrichloride in aqueous or alcohoHc hydrofluoric acid (34). 

The characteristics of enzymes are their catalytic efficiency and their specificity. Enzymes increase the reaction velocities by factors of at least one million compared to the uncatalyzed reaction. Enzymes are highly specific, and consequendy a vast number exist. An enzyme usually catalyzes only one reaction involving only certain substrates. For instance, most enzymes acting on carbohydrates are so specific that even the slightest change in the stereochemical configuration is sufficient to make the enzyme incompatible and unable to effect hydrolysis. 

A. K. Galwey, Reactions in the Sohd State, in Bamford and Tipper, eds.. Comprehensive Chemical Kinetics, vol. 22, Elsevier, 1980. Galwey, A. K., Chemistry of Solids, Chapman and Hall, 1967. Sohn, H. Y, and W. E. Wadsworth, eds.. Rate Frocesses of Extractive Metallurgy, Plenum Press, 1979. Szekely, J., J. W. Evans, and H. Y. Sohn, Gas-Solid Reactions, Academic Press, 1976. Uhmann, ed., Enzyklopaedie der technischen Chemie, Uncatalyzed Reactions with Solids, vol.. 3, 4th ed., Verlag Chemie, 1973, pp. 395-464. 

Oxidation of trimethylene sulfide catalyzed by tungstic acid is preferred to the uncatalyzed reaction Yields are better and the reaction time... 

Molecular chlorine is believed to be the active electrophile in uncatalyzed chlorination of aromatic compounds. Simple second-order kinetics are observed in acetic acid. The reaction is much slower in nonpolar solvents such as dichloromethane and carbon tetrachloride. Chlorination in nonpolar solvents is catalyzed by added acid. The catalysis by acids is probably the result of assistance by proton transfer during the cleavage of the Cl-Cl bond. ... 

There is, however, no direct evidence for the formation of Cl", and it is much more likely that the complex is the active electrophile. The substrate selectivity under catalyzed conditions ( t j = 160fcbenz) is lower than in uncatalyzed chlorinations, as would be expected for a more reactive electrophile. The effect of the Lewis acid is to weaken the Cl—Cl bond, which lowers the activation energy for o-complex formation. 

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