Low-temperature intermediates

Fluoromethyl sulfides are converted to fluoromethanesulfonyl chlorides by reaction with chlorine in waters at low temperatures, intermediate sulfoxides can be isolated [109] (equation 100)... 

Irradiation of a diazonium compound in EPA glass at 77°K and monitoring the reaction by UV revealed the presence of new absorption bands, which disappeared upon warming to room temperature. Little or no evolution of nitrogen occurred in these experiments. Hence the low-temperature intermediate has been proposed to be a rather stable triplet state of the diazonium compound. 

Burnham, 1962 Keller and Hanson, 1968 Rose, 1970 Lowell and Guilbert, 1970 Keller, 1963). These studies indicate that kaolinite can be formed by hydrothermal alteration at the surface as well as to depths of several kilometers. Although information is lacking for low temperatures, intermediate conditions of pressure and temperature are known to permit the stability of the potassic mica-beidellite mixed layered composition series which excludes the stable coexistence of K-feldspar and kaolinite. If one accepts the argument that both beidellite-sodic and potassic are... 

The 4-nitromethy (benzene arises from ipso attack of NOW at the isopropyl-substituted ring carbon. Unlike methyl, the isopropyl group is eliminated rapidly as propene. Can we say that the other products, 3 and 4, arise by direct substitution Evidently not, because nitration at 0° gives two other products, 5 and 6, which must be formed by ipso attack at the inelhyl-heanng carbon. At low temperatures, intermediate ion 7 is attacked by the weakly nucleophilic ethanoate ion to give 5 and 6. Both of these adducts solvolyze rapidly in 78% sulfuric acid to give 3 only ... 

This reaction clearly proceeds via an unstable low temperature intermediate, probably [CljCO-iAlBrj], which decomposes at 15 "C [2127]. 

Wolffenbuttel RF (1997) Low-temperature intermediate Au-Si wafer bonding eutectic or silicide bond. Sens Actuat A Phys 62 680-686... 

At low temperature, intermediate products having formula (13.79) were identified. 

The reaction of pincer triflato complex 37 with 2-(tributylstannyl)furan allowed isolating the transmetallation product 38 as a stable compound (Scheme 1.25) [216]. Furthermore, by performing the reaction at low temperature, intermediate 39 was observed in which the furan is -coordinated to the palladium center. 

MATERIALS SELECTION AND APPLICATION Cryogenic Low-Temperature Intermediate-Temperature High-Temperature... 

For example, when an N-methylthioacetamide (96), R, = R — Me, was condensed with chloroacetone, a 2,3,4-trimethylthiazolium chloride was obtained in quantitative yield. The reaction is usually run in aqueous or alcoholic solution at room temperature. At low temperature, with N-phenylthioacetamide (96), Rj = Me, R2 = Ph and chloroacetone, an acyclic intermediate (98) was isolated and characterized (Scheme 43). It was easily converted to 2,4-dimethyl-3-phenylthiazolium chloride (97), R, = Rs = Me, Rj -Ph, by heating (99,102, 145). 

This polymerization is carried out in the two stages indicated above precisely because of the insolubility and infusibility of the final product. The first-stage polyamide, structure [IX], is prepared in polar solvents and at relatively low temperatures, say, 70°C or less. The intermediate is then introduced to the intended application-for example, a coating or lamination-then the second-stage cyclization is carried out at temperatures in the range 150-300°C. Note the formation of five-membered rings in the formation of the polyimide, structure [X], and also that the proportion of acid to amine groups is 2 1 for reaction (5.II). 

High Pressure in the Chemical Industry. The use of high pressure in industry may be traced to early efforts to Hquefy the so-called permanent gases using a combination of pressure and low temperature. At about the same time the chemical industry was becoming involved in high pressure processes. The discovery of mauveine in 1856 led to the development of the synthetic dye industry which was well estabUshed, particularly in Germany, by the end of the century. Some of the intermediate compounds required for the production of dyes were produced, in autoclaves, at pressures of 5-8 MPa (725-1160 psi). 

Monsanto has disclosed the use of carbon dioxide—amine complexes which are dehydrated, at low temperatures, with phosphoryl chloride [10025-87-3] or thionyl chloride [7719-09-7] as a viable route to a variety of aUphatic isocyanates. The process rehes on the facile formation of the intermediate salt (30).REPLACEVariations of this process, in which phosgene is used as a dehydrating agent, have been reported earlier (84). Table 2 Hsts commercially available aUphatic isocyanates. 

Figure 2 illustrates the three-step MIBK process employed by Hibernia Scholven (83). This process is designed to permit the intermediate recovery of refined diacetone alcohol and mesityl oxide. In the first step acetone and dilute sodium hydroxide are fed continuously to a reactor at low temperature and with a reactor residence time of approximately one hour. The product is then stabilized with phosphoric acid and stripped of unreacted acetone to yield a cmde diacetone alcohol stream. More phosphoric acid is then added, and the diacetone alcohol dehydrated to mesityl oxide in a distillation column. Mesityl oxide is recovered overhead in this column and fed to a further distillation column where residual acetone is removed and recycled to yield a tails stream containing 98—99% mesityl oxide. The mesityl oxide is then hydrogenated to MIBK in a reactive distillation conducted at atmospheric pressure and 110°C. Simultaneous hydrogenation and rectification are achieved in a column fitted with a palladium catalyst bed, and yields of mesityl oxide to MIBK exceeding 96% are obtained. 

Mixtures of HNO, H2SO4, and SO also result in high concentrations of NO/, and toluene can be readily nitrated at —40 to — 10°C as a result (6). At these low temperatures, the formation of the meta-isomer of mononitrotoluene (MNT) is greatiy reduced. Such a reduction is highly desired in the production both of dinitrotoluenes (DNTs) employed to produce intermediates for polyurethane production and of trinitrotoluene (TNT), which is a high explosive. > -MNT results in the production of undesired DNT and TNT isomers (see Nitrobenzene and nitrotoluenes). 

There is evidence that dioxirane is an intermediate product in the low temperature ozonization of ethylene and is probably formed from the diradical resonance isomer of the 1,3-zwitterion (164). 

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