Thermal reflux

Phenothiazines are well-known as intermediates for pharmaceuticals, and are also active as insecticides and antioxidants. These compounds are usually prepared by the thiation of diphenylamines with elemental sulfur. In this context, the group of Toma has elaborated a synthesis of 3-phthalimidophenothiazine, as shown in Scheme 6.265 [455]. Using a variety of high-boiling solvents under conventional thermal reflux conditions, low isolated yields of the desired product were obtained. The highest conversion and isolated product yield (55%) was achieved by microwave irradiation of a mixture of the starting N-(4-phenylaminophenyl)phthalimide with... 

Because of the very large enrichments required in heavy water production, cascades taper markedly. In the upper stages the relative advantage of chemical exchange over water distillation vanishes. Most heavy water plants carry out the last portion of the enrichment by distillation (from 20% or 30% D to 99.85%). Accordingly both exchange and distillation will be briefly treated below. First, however, to clarify the important distinction between chemical and thermal reflux we treat an example of isotope separation using chemical reflux. 

The only chemical exchange processes which have been developed for large scale production are either parasitic processes or ones for which thermal reflux has been adapted to the chemical exchange process. Two... 

Figure 11. Use of chemical association and dissociation for thermal reflux in a chemical exchange separation (BF anisole process)...

The domain of the search for an improved separation process was defined by certain criteria (a) isotopic fractionation should be achieved by means of a two-phase, chemical exchange reaction which was amenable to countercurrent operation in a multistage contactor at ambient temperature and pressure (b) the single-stage isotopic fractionation factor for the reaction should be appreciably larger than that for the distillation of Me20 BF3 (c) the molecular species in each process stream should be thermally refluxable—i,e, convertible from one species to the other by the addition or removal of heat alone (d) process materials should be more stable with respect to irreversible decomposition than those used in the (CH3)20 process and (e) the chemical form of the product should permit a ready, quantitative conversion of the separated isotopes to the elemental state. 

Figure 3. Exchange column, thermal refluxer, and reflux reactor for the NO-N2O3 solvent carrier system. The parts of the system are discussed in the text. X and Y indicate the positions to which connections are made when two columns are operated in cascade...

Dehydrochlorination of chlorinated derivatives such as 1,1,2-trichloroethane may be carried out with a variety of catalytic materials, including Lewis acids such as aluminum chloride. Refluxing 1,1,2-trichlorethane with aqueous calcium hydroxide or sodium hydroxide produces 1,1-dichloroethylene in good yields (22), although other bases such as magnesium hydroxide have been reported (23). Dehydrochlorination of the 1,1,1-trichloroethane isomer with catalytic amounts of a Lewis acid also yields 1,1-dichloroethylene. Other methods to dehydrochlorinate 1,1,1-trichloroethane include thermal dehydrochlorination (24) and by gas-phase reaction over an alumina catalyst or siUca catalyst (25). 

Anhydro-3-hydroxy-2-phenylthiazolo[2,3-6]thiazolylium hydroxide (407) underwent ready thermal reaction with alkynic and alkenic dipolarophiles in refluxing toluene. With the former dipolarophile sulfur was lost from the intermediate 1 1 cycloadduct (408) to give the substituted 5H-thiazolo[3,2- i]pyridin-5-ones (409). With the latter, the intermediate (410) lost H2S, also forming (409). 

The relative volatiHties Ot) are defined by Eq. (13-33), is the mini-mum-reflux ratio (L v + i/D)min,. nd q describes the thermal condition of the feed (e.g., 1.0 for a bubble-point feed and 0.0 for a saturated-vapor feed). The Xi p values are available from the given feed composition. The 0 is the common root for the top-section equations and the bottom-section equations developed by Underwood for a column at minimum reflux with separate zones of constant composition in each section. The common root value must fall between 06/, and Ot/, where hk and Ik stand for heavy key and light key respectively. The key components are the ones that the designer wants to separate. In the butane-pentane splitter problem used in Example 1, the light key is /1-C4 and the heavy key is i-C. ... 

The thermal quality of the solvent feed has no effect on the value of (S/F)mjn, but does affect the minimum reflux to some extent, especially as the (S/F) ratio increases. R nax occurs at higher values of the reflux ratio as the upper-feed quality decreases a subcooled upper feed provides additional refluxing capacity and less external reflux is required for the same separation. It is also sometimes advantageous to introduce the primary feed to the extractive distillation column as a vapor to help maintain a higher solvent concentration on the feed tray and the trays immediately below... 

Foam Breaking It is usually desirable to collapse the overflowing foam. This can be accomphshed by chemical means (Bikerman, op. cit.) if external reflux is not employed or by thermal means [Kishi-moto, Kolloid Z., 192, 66 (1963)] if degradation of the overhead product is not a fac tor. 

Underwood minimum reflux constant XjF = Mol fraction of component i in the feed XjD = Mol fraction of component i in the distillate q = Thermal condition of the feed Bubble point liquid q =1.0 Dew point vapor q =0 General feed q = (Ls - Lr)/F... 

Heptafluora-l-naphthylmagnesium bromide shows unusual thermal stability even after refluxing in diethyl ether for 7 h On carbonation, a 50% yield of the acid IS obtained [26] (equation 6)... 

The fluoride [NS(0)F]3 is more stable thermally and towards nucleophilic reagents than the corresponding chloride. For example, 8.15a is hydrolyzed by water to NH(S02NH2)2, whereas sulfanuric fluoride is unaffected by cold water. In warm water, however, hydrolysis occurs to give the [N3S304F2] anion. All three fluorine atoms in [NS(0)F]3 can be replaced by primary or secondary amines at 80-90°C in the absence of a solvent. Mono- or diphenyl derivatives can be prepared by treatment of [NS(0)F]3 with PhLi in diethyl ether at -70°C, while the Friedel-Crafts reaction with benzene at reflux in the presence of AICI3 gives two isomers of [NS(0)Ph]3. ... 

Due to the commercial availability of EMME in good purity, there has not been a need to develop new methods to prepare 3-anilino-acrylates therefore, only a few alternatives have been reported. One approach described thermal carbene generation from 37, and rearrangement to form 38. Cyclization in refluxing 1,2-dichlorobenzene (1,2-DCB) provided the 2, 3, 4-trisubstituted quinolines. An electron-withdrawing group (EWG) on the carbene carbon was required for this reaction, and therefore led to the EWG substitution in the 2-position of the quinoline. 

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