Propylene, direct reaction with

Allyl chloride is produced by direct chlorination of propylene further reaction with chlorine and water, by chlorohydrination and hydrolysis, yields epichlorhy-drin. 

Isobutylene oxide is produced in a way similar to propylene oxide and butylene oxide by a chlorohydrination route followed by reaction with Ca(OH)2. Direct catalytic liquid-phase oxidation using stoichiometric amounts of thallium acetate catalyst in aqueous acetic acid solution has been reported. An isobutylene oxide yield of 82% could be obtained. 

Telescope the Process by Combining Stages. This has been done successfully in the conversion of propylene to acrylonitrile by direct ammoxidation rather than oxidation to acrolein followed by reaction with ammonia in a separate stage, as was described in the earlier patent literature. The oxychlorination of ethylene and HC1 directly to vinyl chloride monomer is another good example of the telescoping of stages to yield an economic process. 

Kanofsky, J. R., and D. Gutman. Direct observation of the products produced by the 0-atom reactions with ethylene and propylene studied in high-intensity molecular beams. Chem. Phys. Lett. 15 236-239. 1972. 

A carbon-deposited film was prepared from the alumina film with 30-nm channels by the CVD technique using propylene. Fluorination was carried out by direct reaction of the film with dry fluorine gas (purity 99.7%). The film was placed in a nickel reactor and was allowed to react with 0.1 MPa of fluorine gas for 5 days at a predetennined temperature in the range of 50 to 200°C. Then the fluorinated carbon nanotubes were separated by dissolving the alumina film with HF. A schematic drawing of the fluorination process is given in Fig. 10.1.15. 

Reactions of the recoil C1] with several olefins have been studied, including ethylene, propylene, cyclopentene, and cfs-butene-2, as well as with several paraffins. The type of products observed indicated the existence of several general modes of interaction, such as CH bond insertion, interactions with CC double bonds, formation of methylene-C11. The most important single product in all systems is acetylene, presumably formed by CH insertion and subsequent decomposition of the intermediate. Direct interaction with double bonds is shown by the fact that, for example, in the case of propylene, yields of stable carbon atom addition products were significantly higher than in the case of propane. The same was true for ethylene and ethane. 

After propylene CVD at 800°C over an AAO film with a channel diameter of 30 nm, its carbon-coated film surface was fluorinated by direct reaction of the film with elemental fluorine. 

Direct reaction of elemental silicon with hydrogen chloride and propylene in place of ethylene under the same reaction conditions gave isopropyldichlorosilane (22% selectivity) and /z-propyldichlorosilane (8% selectivity) along with other chlorosilanes (Eq. 21). 

Here, the phenyl radical once again attacks the unsamrated bond. However, the steric effect and larger cone of acceptance (the methyl group screens the p carbon atom and makes it less accessible to addition) direct the addition process of the radical center of the phenyl radical to the a carbon atoms of methylacetylene and propylene (the carbon atom holding the acetylenic hydrogen atom). Consequently, crossed beam reactions with complex hydrocarbon molecules can be conducted and valuable information on the reaction pathways can be derived if (partially) deuterated reactions are utilized. 

Olah (17a) has also reported the alkylation reactions (at -10 with 1 1 HS03F-SbF5) of n-butane with ethylene to yield 38 weight percent of hexanes and of n utane with propylene to yield 29 weight percent of heptanes. The former reaction has also been reported by Parker (31) at 60 , but the product in this case more nearly resembles polyethylene degradation products. In our work with 10 1 HF-TaF5 at 40 , in a flow system, ethylene (14.1 wt.%) reacted with rv-butane to form 3-methyl-pentane as the initial product of 94% selectivity (Scheme 6, path a). The alternative, i.e., the direct reaction of ethylene with a secondary-butyl cation (path b), can be ruled out since butane does not ionize under these conditions (vide supra). 

Polyether diols are obtained in the same way as polyether triols, with the difference that the starter is propylene glycol or DPG instead of glycerol or TMP. Because potassium hydroxide and water lead, by the reaction with PO, to polyether diols, it is not necessary to anhydrisate the initial mixture of starter - KOH (solid or aqueous solution). The polyether diols, homopolymers of PO, are obtained by direct propoxylation of a propylene glycol or DPG mixture with KOH (solid or aqueous KOH 40-50% solution). 

Although it is relatively easy to prepare high-molecular-weight polysulfides, these products have not yet found applications. This is mostly due to a lack of industrially applicable monomer preparation methods. Neither ethylene sulfide nor propylene sulfide can be prepared by direct reaction of the corresponding olefins with elemental sulfur. Moreover, it is difficult to obtain polyethylene sulfide) sufficiently stable at higher temperatures and its odour may become offensive. 

Catal54ic oxidations of hydrocarbons have relatively low selectivities. Reactions with interesting perspectives are the direct oxidation of propylene to propylene oxide, of benzene to phenol, and of propane to isopropanol and acetone. 

A process for the epoxidation of propylene with in situ generation of hydrogen peroxide was proposed in the 1990s by the Tosoh Corporation (283). The company suggested that PO could be made in a flow system via a direct reaction between H2 and O2 in the presence of propylene by using a catalyst made of palladium supported on crystaUine titanium sihcate. A propylene conversion of 0.8% was reported, with a selectivity to PO of 99%. ARCO (now Lyondell) described catalysts that produce PO with better selectivity and yield as compared with those reported earher (284). BASF has also claimed the use of framework metal-modifled TS-1 catalysts for this catalytic chemistry (266). Various catalyst compositions were described that can be... 

Direct oxidation of propylene to propylene oxide (PO) with high selectivity and activity is yet to be achieved in heterogeneous catalysis, as was already indicated in the description on the preparation of the An catalysts. Obviously, the most attractive reaction is the direct oxidation with oxygen, rather than using the previously discussed mixture of oxygen and hydrogen ... 

Photochemical and photophysical properties of a poly(propylene amine) dendri-mer (2) functionalized with -stilbene units have been studied [102]. Z-photoisome-rization and photocyclization of the Z-isomer of the stilbene units were investigated in air-equilibrated acetonitrile solutions. The quantum yields of the E Z photoisomerization reaction and the fluorescence quantum yield of the E were found to be equal to 0.30 and 0.014, respectively. Stilbene dendrimers prepared by coupling 4,4 -dihydroxystilbene with first-, second-, third-, or fourth-generation benzyl ether-type dendrons underwent photoisomerization with the same efficiency as that of 4,4 -dimethoxystilbene [103], The lifetime of the core structure was found to be shorter then 1 ns. According to [104], polyphenylene-based stilbene dendrimers, Gl, G2, and G3, underwent mutual cis-trans isomerization upon direct irradiation with 310 nm light at room temperature. In a solvent glass at 77 K, one-way cis-trans isomerization was observed for G2. 

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