Thermal Substitution

The second most important nucleophilic substitution in pyridazine A-oxides is the replacement of a nitro group. Nitro groups at the 3-, 4-, 5- and 6-position are easily substituted thermally with a chlorine or bromine atom, using acetyl chloride or hydrobromic acid respectively. Phosphorus oxychloride and benzoyl chloride are used less frequently for this purpose. Nitro groups in nitropyridazine A-oxides are easily replaced by alkoxide. The... 

When position 4 of the 5-benzothiazole moiety (e.g., 962) was substituted, thermal cyclization in refluxing Dowtherm A for 10-15 min led to the linear thiazolo[5,4-g]quinolinecarboxylate (963) in 81% yield [77JAP(K)125196 79CPB1],... 

The parameters (2 + 0.60 Re1/2 Sc1/3) and (2 -f 0.60 ReI/2Pr1/3) represent the Nusselt numbers for mass and heat transfer, respectively (87). Equation 3 derives from Froessling directly, while Spalding substituted thermal diffusivity for molecular diffusivity to establish the basis for Equation 4. 

Not only the Co(CN)sX3, but also tams-Co(CN)4 (S03XY)" (Y = OH2, OH-, S03-) complexes, seem to give photoreactivity patterns consistent with the fact that the dz2 orbital is populated in the lowest LF state.54) The photoreaction of frans-Co(CN)4(S03)(OH2)3- is particularly noteworthy in that S03 undergoes efficient photosubstitution, while it is inert to substitution thermally.57) In fact,... 

Complex (18) is commercially available and has been used extensively for the preparation of CpCo complexes. The CO ligands are substituted thermally or photochemically under conditions similar to those required for the substitution of Fe(CO)s (i.e. at about 100-120 °C). The products formed from irradiation of (18) under different conditions are depicted in Scheme 20. 

Substituting thermal diffusion for molecular diffusion allows the computation provided for liquid-solid mass transfer to be transferred to thermal diffusion using the following equation ... 

Consider now thermal coupling of the prefractionator arrangement from Fig. 5.116. Figure 5.16a shows a prefi-actionator arrangement with partial condenser and reboiler on the prefractionator. Figure 5.166 shows the equivalent thermally coupled prefractionator arrangement sometimes known as a Petlyuk column. To make the two arrangements in Fig. 5.16 equivalent, the thermally coupled prefractionator requires extra plates to substitute for the prefractionator condenser and reboiler. 

The problem of the synthesis of highly substituted olefins from ketones according to this principle was solved by D.H.R. Barton. The ketones are first connected to azines by hydrazine and secondly treated with hydrogen sulfide to yield 1,3,4-thiadiazolidines. In this heterocycle the substituents of the prospective olefin are too far from each other to produce problems. Mild oxidation of the hydrazine nitrogens produces d -l,3,4-thiadiazolines. The decisive step of carbon-carbon bond formation is achieved in a thermal reaction a nitrogen molecule is cleaved off and the biradical formed recombines immediately since its two reactive centers are hold together by the sulfur atom. The thiirane (episulfide) can be finally desulfurized by phosphines or phosphites, and the desired olefin is formed. With very large substituents the 1,3,4-thiadiazolidines do not form with hydrazine. In such cases, however, direct thiadiazoline formation from thiones and diazo compounds is often possible, or a thermal reaction between alkylideneazinophosphoranes and thiones may be successful (D.H.R. Barton, 1972, 1974, 1975). 

There also exists an acidregioselective condensation of the aldol type, namely the Mannich reaction (B. Reichert, 1959 H. Hellmann, 1960 see also p. 291f.). The condensation of secondary amines with aldehydes yields Immonium salts, which react with ketones to give 3-amino ketones (=Mannich bases). Ketones with two enolizable CHj-groupings may form 1,5-diamino-3-pentanones, but monosubstitution products can always be obtained in high yield. Unsymmetrical ketones react preferentially at the most highly substituted carbon atom. Sterical hindrance can reverse this regioselectivity. Thermal elimination of amines leads to the a,)3-unsaturated ketone. Another efficient pathway to vinyl ketones starts with the addition of terminal alkynes to immonium salts. On mercury(ll) catalyzed hydration the product is converted to the Mannich base (H. Smith, 1964). 

Benzylthio or 2-benzyloxy derivatives of A-2-thiazoline-5-one (224) are readily opened by amines to give the amide derivatives (225) (Scheme 115) (459. 471). Compound 225 can be cyclized thermally to the corresponding thiohydantoins (459). Similarly, treatment of 4-substituted-2-phenylthiazol-5(4H)-ones (226) with amino acids, peptides, or hydrazine affords the corresponding Nfcti-thiobenzamidoacetylated derivatives (227) (Scheme 116) (455). 

In agreement with the theory of polarized radicals, the presence of substituents on heteroaromatic free radicals can slightly affect their polarity. Both 4- and 5-substituted thiazol-2-yl radicals have been generated in aromatic solvents by thermal decomposition of the diazoamino derivative resulting from the reaction of isoamyl nitrite on the corresponding 2-aminothiazole (250,416-418). Introduction in 5-position of electron-withdrawing substituents slightly enhances the electrophilic character of thiazol-2-yl radicals (Table 1-57). 

The protons attached to C 2 of malonic acid are not directly involved m the process and so may be replaced by other substituents without much effect on the ease of decar boxylation Analogs of malonic acid substituted at C 2 undergo efficient thermal decar boxylation... 

By an assortment of thermodynamic manipulations, the quantities dn/dp and [N (d G/dp )o] can be eliminated from Eq. (10.48) and replaced by the measurable quantities a, /3, and dn/dT the coefficients of thermal expansion, isothermal compressibility, and the temperature coefficient of refractive index, respectively. With these substitutions, Eq. (10.48) becomes... 

Secondary amines give only a monosubstituted product. Both of these reactions are thermally reversible. The product with ammonia (3,3, 3 -nitrilottispropionamide [2664-61-1C H gN O ) (5) is frequently found in crystalline acrylamide as a minor impurity and affects the free-radical polymerisation. An extensive study (8) has determined the stmctural requirements of the amines to form thermally reversible products. Unsymmetrical dialkyl hydrasines add through the unsubstituted nitrogen in basic medium and through the substituted nitrogen in acidic medium (9)). 

Because of the high melt viscosity of polyolefins, normal spinning melt temperatures are 240—310°C, which is 80—150°C above the crystalline melting point. Because of the high melt temperatures used for polyolefin fiber spinning, thermal stabilizers such as substituted hindered phenols are added. In the presence of pigments, the melt temperature must be carefully controlled to prevent color degradation and to obtain uniform color dispersion. 

Properties. The ideal substitute should have identical or better performance properties than the CFG it replaces. The ideal CFG substitute must not harm the o2one layer, and must have a short atmospheric lifetime to ensure a low greenhouse warming potential (GWP). It also must be nontoxic, nonflammable, thermally and chemically stable under normal use conditions, and manufacturable at a reasonable pnce. The chemical industry has found substitutes that match many but not all of these cntena. 

Perfluoroepoxides have also been prepared by anodic oxidation of fluoroalkenes (39), the low temperature oxidation of fluoroalkenes with potassium permanganate (40), by addition of difluorocarbene to perfluoroacetyl fluoride (41) or hexafluoroacetone (42), epoxidation of fluoroalkenes with oxygen difluoride (43) or peracids (44), the photolysis of substituted l,3-dioxolan-4-ones (45), and the thermal rearrangement of perfluorodioxoles (46). 

Two classes of fat replacers exist mimetics, which are compounds that help replace the mouthfeel of fats but caimot substitute for fat on a weight for weight basis and substitutes, compounds having physical and thermal properties similar to those of fat, that can theoretically replace fat in all appHcations (46). Because fats play a complex role in so many food appHcations, one fat replacer is often not a satisfactory substitute. Thus a systems approach to fat replacement, which reHes on a combination of emulsifiers, gums, and thickeners, is often used. 

This mechanism not only accounts for the substitution of the more labile chlorine atom on the polymer chain, it also results in the elimination of a new potential initiation site by moving the double bond out of conjugation with any adjacent chlorine atoms. The newly formed C—O or C—S bonds, with AH > 484 kJ/mol (100 kcal/mol), are significantly more thermally stable than even the normal C—Cl bonds in PVC at about 411 kj/mol (85 kcal/mol) (11). 

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