Temperature vapor phase reactions

Belter RK (2011) High temperature vapor phase reactions of nitrogen trifluoride with benzylic substrates. J Fluor Chem 132(5) 318-322... 

Reactions with Ammonia and Amines. Acetaldehyde readily adds ammonia to form acetaldehyde—ammonia. Diethyl amine [109-87-7] is obtained when acetaldehyde is added to a saturated aqueous or alcohoHc solution of ammonia and the mixture is heated to 50—75°C in the presence of a nickel catalyst and hydrogen at 1.2 MPa (12 atm). Pyridine [110-86-1] and pyridine derivatives are made from paraldehyde and aqueous ammonia in the presence of a catalyst at elevated temperatures (62) acetaldehyde may also be used but the yields of pyridine are generally lower than when paraldehyde is the starting material. The vapor-phase reaction of formaldehyde, acetaldehyde, and ammonia at 360°C over oxide catalyst was studied a 49% yield of pyridine and picolines was obtained using an activated siHca—alumina catalyst (63). Brown polymers result when acetaldehyde reacts with ammonia or amines at a pH of 6—7 and temperature of 3—25°C (64). Primary amines and acetaldehyde condense to give Schiff bases CH2CH=NR. The Schiff base reverts to the starting materials in the presence of acids. 

Mercaptals, CH2CH(SR)2, are formed in a like manner by the addition of mercaptans. The formation of acetals by noncatalytic vapor-phase reactions of acetaldehyde and various alcohols at 35°C has been reported (67). Butadiene [106-99-0] can be made by the reaction of acetaldehyde and ethyl alcohol at temperatures above 300°C over a tantala—siUca catalyst (68). Aldol and crotonaldehyde are beheved to be intermediates. Butyl acetate [123-86-4] has been prepared by the catalytic reaction of acetaldehyde with 1-butanol [71-36-3] at 300°C (69). 

Dehydrogenation of Propionates. Oxidative dehydrogenation of propionates to acrylates employing vapor-phase reactions at high temperatures (400—700°C) and short contact times is possible. Although selective catalysts for the oxidative dehydrogenation of isobutyric acid to methacrylic acid have been developed in recent years (see Methacrylic ACID AND DERIVATIVES) and a route to methacrylic acid from propylene to isobutyric acid is under pilot-plant development in Europe, this route to acrylates is not presentiy of commercial interest because of the combination of low selectivity, high raw material costs, and purification difficulties. 

In recent years alkylations have been accompHshed with acidic zeoHte catalysts, most nobably ZSM-5. A ZSM-5 ethylbenzene process was commercialized joiatiy by Mobil Co. and Badger America ia 1976 (24). The vapor-phase reaction occurs at temperatures above 370°C over a fixed bed of catalyst at 1.4—2.8 MPa (200—400 psi) with high ethylene space velocities. A typical molar ethylene to benzene ratio is about 1—1.2. The conversion to ethylbenzene is quantitative. The principal advantages of zeoHte-based routes are easy recovery of products, elimination of corrosive or environmentally unacceptable by-products, high product yields and selectivities, and high process heat recovery (25,26). 

Preparation. The simplest method of preparation is a combination of the elements at a suitable temperature, usually ia the range of 1100—2000°C. On a commercial scale, borides are prepared by the reduction of mixtures of metallic and boron oxides usiag aluminum, magnesium, carbon, boron, or boron carbide, followed by purification. Borides can also be synthesized by vapor-phase reaction or electrolysis. 

Thermal Cracking. Thermal chlorination of ethylene yields the two isomers of tetrachloroethane, 1,1,1,2 and 1,1,2,2. Introduction of these tetrachloroethane derivatives into a tubular-type furnace at temperatures of 425—455°C gives good yields of trichloroethylene (33). In the cracking of the tetrachloroethane stream, introduction of ferric chloride into the 460°C vapor-phase reaction zone improves the yield of trichloroethylene product. 

Reaction Mechanism. High temperature vapor-phase chlorination of propylene [115-07-17 is a free-radical mechanism in which substitution of an allyhc hydrogen is favored over addition of chlorine to the double bond. Abstraction of allyhc hydrogen is especially favored since the allyl radical intermediate is stabilized by resonance between two symmetrical stmctures, both of which lead to allyl chloride. 

Ethyl Vinyl Ether. The addition of ethanol to acetylene gives ethyl vinyl ether [104-92-2] (351—355). The vapor-phase reaction is generally mn at 1.38—2.07 MPa (13.6—20.4 atm) and temperatures of 160—180°C with alkaline catalysts such as potassium hydroxide and potassium ethoxide. High molecular weight polymers of ethyl vinyl ether are used for pressure-sensitive adhesives, viscosity-index improvers, coatings and films lower molecular weight polymers are plasticizers and resin modifiers. 

A third category of syn eliminations involves pyrolytic decomposition of esters with elimination of a carboxylic acid. The pyrolysis of acetate esters normally requires temperatures above 400° C and is usually a vapor phase reaction. In the laboratory this is done by using a glass tube in the heating zone of a small furnace. The vapors of the reactant are swept through the hot chamber by an inert gas and into a cold trap. Similar reactions occur with esters derived from long-chain acids. If the boiling point of the ester is above the decomposition temperature, the reaction can be carried out in the liquid phase, with distillation of the pyrolysis product. 

Photolytic. Based on data for structurally similar compounds, acenaphthylene may undergo photolysis to yield quinones (U.S. EPA, 1985). In a toluene solution, irradiation of acenaphthylene at various temperatures and concentrations all resulted in the formation of dimers. In water, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, 1,2-epoxyacenaphthylene, and 1-naphthoic acid. In methanol, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, methyl 8-formyl-1-naphthoate, and dimethoxyacetal 1,8-naphthalene dialdehyde (Chen et al., 1979). Acenaphthylene reacts with photochemically produced OH radicals and ozone in the atmosphere. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with OH radicals (500,000/cm ) at 25 °C are 8.44 x lO " cmVmolecule-sec and 5 h, respectively. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with ozone at 25 °C are... 

Photolytic. A carbon dioxide yield of 46.5% was achieved when aniline adsorbed on silica gel was irradiated with light (X >290 nm) for 17 h (Freitag et al., 1985). Products identified from the gas-phase reaction of ozone with aniline in synthetic air at 23 °C were nitrobenzene, formic acid, hydrogen peroxide, and a nitrated salt having the formula [CeHsNHsl NOs" (Atnagel and Himmelreich, 1976). A second-order rate constant of 6.0 x 10 " cmVmolecule-sec at 26 °C was reported for the vapor-phase reaction of aniline and OH radicals in air at room temperature (Atkinson, 1985). 

Photolytic. A photooxidation rate constant of 6 x 10 " cm /molecule-sec at room temperature was reported for the vapor-phase reaction of benzene with OH radicals in air (Atkinson, 1985). The reported rate constant and half-life for the reaction of benzene and OH radicals in the atmosphere are 8.2 x 10 M/sec and 6.8 d, respectively (Mill, 1982). Major photooxidation products in air include nitrobenzene, nitrophenol, phenol, glyoxal, butanedial, formaldehyde, carbon dioxide, and carbon monoxide (Nojima et al., 1975 Finlayson-Pitts and Pitts, 1986). 

When an aqueous solution containing 1,4-dichlorobenzene (190 pM) and a nonionic surfactant micelle (Brij 58, a polyoxyethylene cetyl ether) was illuminated by a photoreactor equipped with 253.7-nm monochromatic UV lamps, photoisomerization took place, yielding 1,2- and 1,3-dichlorobenzene as the principal products. The half-life for this reaction, based on the first-order photodecomposition rate of 1.34 x 10 /sec, is 8.6 min (Chu and Jafvert, 1994). A room temperature rate constant of 3.2 x lO cmVmolecule-sec was reported for the vapor-phase reaction of 1,4-dichlorobenzene with OH radicals (Atkinson, 1985). 

Photolytic. A rate constant of 3.7 x 10 L/molecule-sec was reported for the reaction of propylbenzene with OH radicals in the gas phase (Darnall et al, 1976). Similarly, a room temperature rate constant of 5.7 x lO cm /molecule-sec was reported for the vapor-phase reaction of propylbenzene with OH radicals (Atkinson, 1985). At 25 °C, a rate constant of 6.58 x 10 cmVmolecule-sec was reported for the same reaction (Ohta and Ohyama, 1985). 

Photolytic. Glyoxal, methylglyoxal, and biacetyl were produced from the photooxidation of 1,2,3-trimethylbenzene by OH radicals in air at 25 °C (Tuazon et al., 1986a). The rate constant for the reaction of 1,2,3-trimethylbenzene and OH radicals at room temperature was 1.53 x 10 " cmVmolecule-sec (Hansen et al., 1975). A rate constant of 1.49 x 10 L/molecule-sec was reported for the reaction of 1,2,3-trimethylbenzene with OH radicals in the gas phase (Darnall et al., 1976). Similarly, a room temperature rate constant of 3.16 x 10 " cm /molecule-sec was reported for the vapor-phase reaction of 1,2,3-trimethylbenzene with OH radicals (Atkinson, 1985). At 25 °C, a rate constant of 2.69 x lO " cm /molecule-sec was reported for the same reaction (Ohta and Ohyama, 1985). 2,3-Butanedione was the only products identified from the OH radical-initiated reaction of 1,2,4-trimethylbenzene in the presence of nitrogen dioxide. The amount of 2,3-butanedione formed decreased with increased concentration of nitrogen dioxide (Bethel et al., 2000). 

A third category of syn eliminations involves pyrolytic decomposition of esters with elimination of a carboxylic acid. The pyrolysis of acetate esters normally requires temperatures above 400° C. The pyrolysis is usually a vapor-phase reaction. In the... 

Chemical properties of iodine are quite similar to those of other halogens, especially chlorine and bromine. However, being less electronegative than chlorine and bromine, its reactivity towards most metals, nonmetals, and their compounds may differ vastly. All iodine reactions occur in vapor phase or aqueous media. Vapor phase reactions require elevated temperatures. 

The first synthesis of thieno[2,3-6]thiophene (7) was reported in 1886, by the reaction of citric acid and phosphorus trisulfide, although the product was formed in only 1% yield (Scheme 105). The yield was subsequently improved to 10% (76AHC(19)123). Vapor phase reaction of acetylene and sulfur at high temperatures is also reported to produce (7), along with many other products. 

The simplest vapor phase reaction of aliphatic carbonyl compounds in their triplet states is cleavage into acyl and alkyl radicals. The acyl radicals, especially at high temperatures, eventually decar-bonylate. 

Isobutyronitrile has been prepared by a number of catalytic vapor-phase reactions at elevated temperatures isobutylamine over copper 2 or nickel,3 isobutyramide over alumina,4 a mixture of ammonia and isobutyraldehyde over thorium dioxide,5 and a mixture of ammonia and isobutyl alcohol over copper. Isobutyronitrile also has been obtained by decarboxylation of 2-methyl-2-cyanopropanoic add 7 and from the reaction of iso-butyric acid with potassium thiocyanate.8 The above procedure is a modification of the method used by Walter and McElvain.9... 

The nitre paraffins (nitro methane am) nitmethane) became commercially available in the early 1440s. Several milhwn pounds arc produced annually by the vapor-phase reaction of propane and nitric acid ut elevated temperature ami pressure These compounds and ihcir derivatives find applications as fuels, solvents, and explosives. 

Oxidation rate constant k, for gas-phase second order rate constants, k0H for reaction with OH radical, kN03 with N03 radical and kG3 with 03 or as indicated, data at other temperatures see reference k 360 M-1 h 1 for singlet oxygen and k = 2.0 M 1 h-1 for peroxy radical at 25°C (Mabey et al. 1982) k0H < 1.0 x 10 11 cm3 molecule-1 s-1, estimated as toxic chemical residence time > 1160 d, loss < 0.1% in Id or 12 sunlit hours at 300 K in urban environments (Singh et al. 1981) t/2 = 213-2131 h, based on an estimated rate constant for the vapor phase reaction with hydroxyl radical in air (Howard et al. 1991)... 

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