Conversion of olefins

TS-l/MCM-41 catalysts synttiesized by the dry gel conversion method are shown to have hexagonal mesopores. The catalytic activity of synthesized TS-l/MCM-41 catalysts was tested with qroxidation reaction of olefins to reved that both the conversion of olefins and selectivity to epoxide are higher than those of H-MCM-41,... 

Titanium containing hexagonal mesoporous materials were synthesized by the modified hydrothermal synthesis method. The synthesized Ti-MCM-41 has hi y ordered hexa rud structure. Ti-MCM-41 was transformed into TS-l/MCM-41 by using the dry gel conversion process. For the synthesis of Ti-MCM-41 with TS-1(TS-1/MCM-41) structure TPAOH was used as the template. The synthesized TS-l/MCM-41 has hexagonal mesopores when the DGC process was carried out for less than 3 6 h. The catalytic activity of synthesized TS-l/MCM-41 catalysts was measured by the epoxidation of 1-hexene and cyclohexene. For the comparison of the catalytic activity, TS-1 and Ti-MCM-41 samples were also applied to the epoxidation reaction under the same reaction conditions. Both the conversion of olefins and selectivity to epoxide over TS-l/MCM-41 are found hi er flian those of other catalysts. 

The ligands synthesized were also apphed to the isomerizing hydroformylation of more reactive 2-pentene. At 120 °C/ 20 bar quantitative conversion of olefin to aldehydes was achieved within 40 min. Trends similar to those described for internal octene hydroformylation were found. The regioselectivity obtained for the individual ligands tends to be 5% higher compared to that for the octenes. Thus, in the presence of 10 75% of n-hexanal were determined, compare Table 3. Obviously, 2-pentene is able to react more smoothly to the terminal isomer compared to olefins having the double bond in an more internal position. Illustrative for this effect are also literature results obtained for 2- and 4-octene.4,5... 

Minnie, O. R., Petersen, F. W., and Samadi, F. R. 2003. Effect of 1-hexene extraction on the COD process conversion of olefins to distillate. Paper presented at the South African Chemical Engineering Congress, Sun City, P083. 

Used industrially as an oxidizing agent especially in conversion of olefins to glycols, and in the preparation of chlorates, peroxides, and periodates as a biological stain for adipose... 

Scheme 17. Titanium-mediated metathesis strategy for the conversion of olefinic esters (118) to cyclic enol ethers (123) (Nicolaou et al.) [34]...

Scheme 18. The conversion of olefinic ester 125 to cyclic enol ether 127. (a) 4.0 equiv of Tebbe reagent (93), 25°C, 20 min then reflux, 5 h, 71% (b) 1.3 equiv of Tebbe reagent (93), 25°C, 20 min, 77% (c) 2.0 equiv of Tebbe reagent (93), 25°C, 20 min then reflux, 3 h, 65% (Nicolaou et al.) [34a]...

An analogous reaction is the conversion of olefins into primary amines by the consecutive action of BH3. THF and trimethylsilyl azide171. The observation172 that organoboranes and chloramine give primary amines is the basis of an amine synthesis in which olefins are treated with the complex BH3 THF, followed by aqueous ammonia and aqueous sodium hypochlorite173. Imines are reduced by the chiral dioxaborolidine 162 to yield optically active amines. 1-Imino-l-phenylpropane, for instance, affords 1-phenylpropylamine in 73% enantiomeric excess (equation 59)174. 

The 3/Rh catalyst formed in situ (P/Rh = 4 1, substrate/Rh = 1000 1) has been applied to the aqueous-organic biphasic hydroformylation of 1-decene. The conversion of olefin and yield of aldehyde were 99.5 and 99.0%, respectively, after 5 h at 120 °C and 5.0 MPa of synthesis gas. Recycling tests showed that the aldehyde yield was still higher than 94.0% even after the catalyst had been recycled 20 times. 

The use of zeolite-base catalysts have only emerged relatively recently. Mobil olefin to gasoline/disHllate (MOGD) developed by Mobil and conversion of olefin to disHllate (COD) of PetroSA use ZSM-5 zeolite to convert olefins to gasoHne and... 

Isopinocampheol has been prepared by hydrogenation of irams-pinocarveol with a neutral nickel catalyst at 70-100°. The hydroboration reaction provides a convenient procedure for the conversion of olefins to alcohols without rearrangement and with a predictable stereochemistry. The reaction has been applied to a large number of olefins of widely different structures. The results obtained support the proposed generaliza-tit)ii that hydroboration involves an anborane from the less hindered side of the double bond. ... 

Light hydrocarbons (Ci to C4) and aromatics (mainly Ce to Ce) were produced by ZSM-5 due to the the conversion of olefins and paraffins. Thus,these results provide evidence for cracking of olefins, paraffins and cyclization of olefins by ZSM-5 at 500 C. The steam deactivated ZSM-5 catalyst exhibited reduced olefin conversion and negligible paraffin conversion activity. 

By analogy between the oxo forms of vanadium(V) and iron(IV), the latter being the active species in oxidations by cytochrome P-450, the system constituted by vanadium oxide as the catalyst, and t-butylhydro-peroxide, as the oxidant, gives good results in the conversion of olefins to the corresponding epoxides. With the supported "clayniac" catalyst, in the presence of i-butyraldehyde as a sacrificial reducer, olefins are epoxidized in good yields by compressed air at room temperature, in a convenient procedure. 

The hydroboration amination sequence in diglyme is a general procedure for the conversion of olefins to primary amines without rearrangement and with predictable stereochemistry.5 An alternative procedure, using tetrahydrofuran as solvent and either hydroxylamine-O-sulfonic acid or chloramine, is applicable with terminal olefins and relatively unhindered internal and alicyclic olefins.6 O-Mesitylenesulfonylhydroxylamine also gave desired amines in comparable yield.7 Alternative procedures for the hydroboration of olefins use commercially available solutions of di-borane in tetrahydrofuran8 or dimethylsulfide.9... 

The Conversion of Olefins to 7-Lactones (Addition of Oxygen, Carbon)... 

Permanganate oxidations may be used for the direct conversion of olefins to a-hydroxy ketones and 1,2-diketones in moderate yields usually under acidic conditions.562"566... 

Conversion of olefins into epoxides has been achieved in a great ifnbfiT of cases through halohydrin intermediates generated by " kiition of hypoholous acids across the olefiiuc double bond (Eq, 127). 

Several peroxy acids are need in the conversion of olefins into epoxides. Their properties and preparations have been described by Swem.1<78>1878 Included among them are performio acid, peracetic arid, parbenzoio acid, monoperphthalic acid, and percamphoric acid, Mere recently trifluoroperacetic acid has attained some promi-nenee.S01>1I4fl-1778 Certain desirable features have been discovered in y-nitroperbenzoic arid as well.1 ... 

Earlier work in this laboratory showed that chromium oxide supported on alumina is a good catalyst for the conversion of olefins (ref. 1) as well as paraffins (ref. 2) to nitriles with high selectivities, by reaction of NO with the hydrocarbons (nitroxidation). Recent work (ref. 3) reported preliminary results of the nitroxidation of paraxylene as an extension of the use of C Oj-Al Oj to the catalytic synthesis of aromatic nitriles. It should be mentioned that only few data are available in the literature related to the nitroxidation of aromatic hydrocarbons. Teichner et al (ref. 4 ) reported interesting results of selective synthesis of benzonitrile by nitroxidation of toluene on NiO-AlgO catalysts. Improvements of the catalytic activity and selectivity in this reaction were reached by use of C Og-Al. which also exhibits striking properties in the synthesis of paratolunitrile by contact of NO with paraxylene (ref. 3). 

A new development is that electrochemical oxidation of ferrocyanide to ferricyanide can be coupled with AD to give a very efficient electrocatalytic process [37]. Under these conditions, the amount of potassium ferricyanide needed for the reaction becomes catalytic and Eqs. 6D.6 and 7 can be added following Eq. 6D.4. Summation of Eq. 6D.1-6D.4, 6D.6, and 6D.7 gives 6D.8, showing that only water in addition to electricity is needed for the conversion of olefins to asymmetric diols and that hydrogen gas, released at the cathode, is the only byproduct of this process. In practice, sodium ferrocyanide is used in the reaction and the amount of this reagent used in comparison with the potassium ferricyanide method mentioned above has been reduced from 3.0 equiv. to 0.15 equiv. (relative to an equivalent of olefin). 

Perbenzoic acid is used for the conversion of olefinic compounds into epoxides. 

Furthermore, the above change in the structure of the ligand causes in the case of 1-butene a great increase (about 5 times) and with (Z)- and (E)-2-butene an even larger decrease of the optical yield. Part of this effect might be connected with the different extents of isomerization of the substrates in the two cases in fact, with DIOP-DBP, a three times longer reaction time is required to reach the same conversion of olefin to aldehyde 48). 

Shell s version of the Oxo process is in use in several foreign countries as well as in the U.S. The first commercial use of this catalyst system was for the production of normal butanol and 2-ethylhexanol in 1963. It is ejected to continue to be Shell s primary process for the conversion of olefins to alcohols. This process has produced higher alcohols efficiently since its first commercial application in 1965. This is due to its simplicity, its high quality products and its flexibility to utilize many different feedstocks. 

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