Monoolefins

Formation of Carbon-Transition and Inner Transition Metal Bond 5.8.2.3. from Monoolefins 

Vogler, in Concepts of Inorganic Photochemistry, A. W. Adamson and P. D. Fleischauer, Eds., Wiley Interscience, New York, 1975, pp. 269-298. 

GeofFroy, M. S. Wrighton, Organometallic Photochemistry, Academic Press, New York, 1979. 

Fischer, M. Herberhold, in Essays in Coordination Chemistry, Birkhauser Verlag, Basel, 1965. 

Homogeneous Hydrogenation, John Wiley, New York, 1973. 

Quantum chemical investigations of the initial steps of the yttrium-mediated polymerization of ethylene and propene have been presented. The authors investigated the mechanistic details of the initial step of the polymerization brought about by a di(cyclopentadienyl)yttriumhydride catalyst using approximate DFT. In accord with the experimental 

A series of lanthanide metallocene catalysts are active in the regioselective ring-opening polymerization of strained f .vo-rnethylcnecycloalkanes to yield f . v -mcthylene-functionalizcd polyethylenes.9 a Methylenecyclobutane affords the polymer [-CH2CH2C112C( =CH2)-] under the catalytic action of [ 1,2- 

The experiments were usually performed in hydrocarbons at 80 °C. The ethylene reacted immediately and was consumed constant until the alkyl chain of the dialkyl magnesium compounds grew too long and the products began to precipitate. The treatment of the P-Mg-P1 compounds with C02 followed by hydrolysis gave acids with odd carbon chain lenghts of between 5 and 13 C atoms (FAB+-MS, m/z 101—213).915,915a 916 Direct alkylation of the 

Anionic or neutral allylic samarium or neodymium species as catalysts polymerize styrene without addition of any co-catalysts (catalyst/styrene ratio = 1 1000). Random syndiotactic-rich material was obtained from tetra(allyl)lantha-nates, whereas the neutral tris(allyl)lanthanides or anionic t -bis(cyclopentadienyl)bis(allyl)lanthanates afforded 

Recently, diphenylphosphine has been shown to be an efficient chain-transfer agent in organolanthanide-catalyzed ethylene polymerization, yielding phosphine-terminated polyethylenes. This reaction is a versatile, efficient way of incorporating an electron-rich functional group into an otherwise inert polymer.929 

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Process Technology. In a typical oxo process, primary alcohols are produced from monoolefins in two steps. In the first stage, the olefin, hydrogen, and carbon monoxide [630-08-0] react in the presence of a cobalt or rhodium catalyst to form aldehydes, which are hydrogenated in the second step to the alcohols. 

These reactions are appHcable to most monoolefins and are used to obtain a large number of commercial products. 

Uses. Fluorosulfuric acid serves as catalyst in the alkylation (qv) of branched-chain paraffins (53—58) and aromatic compounds (59), and in the polymeriza tion of monoolefins (60) and rosin (61). Addition of strong Lewis acids, such as SbF, TaF, and NbF, to fluorosulfuric acid markedly increases... 

Amylenes. Amylenes (C monoolefins) produce alkylates with a research octane in the range of 90—93. In the past, amylenes have not been used widely as an industrial alkylation charge, although in specific instances, alkylation with amylenes has been practiced (23). In the future, alkylation with amylenes will become more important as limits are placed on the vapor pressure and light olefin content of gasolines. 

Most of the industrially important alkyl aromatics used for petrochemical intermediates are produced by alkylating benzene [71-43-2] with monoolefins. The most important monoolefins for the production of ethylbenzene, cumene, and detergent alkylate are ethylene, propylene, and olefins with 10—18 carbons, respectively. This section focuses primarily on these alkylation technologies. 

HP Alkylation Process. The most widely used technology today is based on the HE catalyst system. AH industrial units built in the free world since 1970 employ this process (78). During the mid-1960s, commercial processes were developed to selectively dehydrogenate linear paraffins to linear internal olefins (79—81). Although these linear internal olefins are of lower purity than are a olefins, they are more cost-effective because they cost less to produce. Furthermore, with improvement over the years in dehydrogenation catalysts and processes, such as selective hydrogenation of diolefins to monoolefins (82,83), the quaUty of linear internal olefins has improved. 

Monoolefinic Hydwcarbons Ethylene Propylene 1 -Butene 1-Butane cis-2-Biitene trans-2-Biitene... 

Diolefms are hydrocarbon compounds that have two double bonds. Conjugated diolefins have two double bonds separated by one single bond. Due to conjugation, these compounds are more stable than mono-olefms and diolefms with isolated double bonds. Conjugated diolefins also have different reactivities than monoolefins. The most important industrial diolefmic hydrocarbons are butadiene and isoprene. 

Nonionic detergents are discussed in Chapter 7. Other uses of these alcohols are in the plasticizer field and in monoolefin production. 

Figure 10-9. The UOP (Detal) process for producing linear alkylbenzene (1) pacol dehydrogenation reactor, (2) gas-liquid separation, (3) reactor for converting diolefins to monoolefins, (4) stripper, (5) alkylation reactor, (6,7,8) fractionators.

DeFine selective hydrogenation from diolefins to monoolefins... 

The catalytic system used in the Pacol process is either platinum or platinum/ rhenium-doped aluminum oxide which is partially poisoned with tin or sulfur and alkalinized with an alkali base. The latter modification of the catalyst system hinders the formation of large quantities of diolefins and aromatics. The activities of the UOP in the area of catalyst development led to the documentation of 29 patents between 1970 and 1987 (Table 6). Contact DeH-5, used between 1970 and 1982, already produced good results. The reaction product consisted of about 90% /z-monoolefins. On account of the not inconsiderable content of byproducts (4% diolefins and 3% aromatics) and the relatively short lifetime, the economics of the contact had to be improved. Each diolefin molecule binds in the alkylation two benzene molecules to form di-phenylalkanes or rearranges with the benzene to indane and tetralin derivatives the aromatics, formed during the dehydrogenation, also rearrange to form undesirable byproducts. 

The problem of the diolefin formation was first solved with the introduction of the DeFine process, in which diolefins are hydrogenated to monoolefins by a contact (H-14). This catalyst was developed in 1984 and used on a large scale for the first time in 1986. With its help the diolefins are practically quantitatively removed and the monoolefin yield increased by about 4-5% [58]. The advantages of the DeFine step are [58,92] ... 

Contrary to expectations, only an unusually small part of the diene exists in the conjugated form. Furthermore the formation of cyclohexane derivatives is noticeable. Their formation can be explained with the compounds listed on row 4 in Table 9. During the alkylation the monoolefin reacts on one side to LAB, on the other side to oligomers, and, depending on the excess of benzene, in part to the dialkylbenzenes found as byproducts in the so-called heavy alkylate (the residues of the raw alkylbenzene distillation). 

The formation of DATs results from the presence of dichloroparaffins or diolefins in the alkylation process. In the chloroparaffin/AlCl3 process the ratio of dichloroparaffin to monochloroparaffin is about 1 10, and this results in a level of about 6-10% DAT in the product LAB. However, in the Pacol/HF process the ratio of diolefin to monoolefin is lower, resulting in a DAT level of about 1-2% [12]. When a DeFine unit is coupled to the Pacol olefin stream to further reduce diolefins, the level of DAT can be less than 1% [13]. 

F. Asinger, in Chemie und Technologie der Monoolefine, Akademie Verlag, Berlin, 1957. 

Products from very many other olefins have been detailed by Smidt et All monoolefins with at least one hydrogen atom on each carbon atom of the... 

Since the review by Lattes et al. on the amination of alkenes in 1983 [18] and our first review on the catalytic amination of monoolefins in 1989 [19], several review articles have appeared in the literature [13, 14, 17, 20-23]. The present review corresponds to an analysis of literature data up to the end of 1999. 

From a variety of differently substituted compounds, best results were obtained with the catalysts 195a-c in combination with /-methyl diazoacetate and monoolefins, cyclopropanes were obtained with a relatively high trans/cis ratio and enantiomeric excesses of 44-89% (Table 12). The absolute configuration at the catalyst s chiral center determines the enantioselectivity for both diastereoisomers. 

Enantioselective cyclopropanation of monoolefins 214 has also been performed. With the already mentioned chiral catalysts 195a and 209-213 rather high enantiomeric excess was achieved in some cases (Table 16), and the vinylcyclopropane structure was obtained in a subsequent dehydrohalogenation step. 

When a mixture of diazomethane and H2 was passed over Co, Fe, Ru, Ni or Pd surfaces, a mixture of hydrocarbons was produced (mainly Cj-C18, linear alkanes and monoolefins) whose composition varied with the metal, the temperature and the H2 partial pressure. The close similarity of this product mixture with that ob-... 

Triplet photoaddition of simple non-cyclic monoolefins is unknown. The sensitized dimerization of ethyl vinyl ether gives exclusively head-to-head adducts, Eq. 21, and probably should not be classed as an example of simple acyclic olefin. Usually the triplets have high energies and are severly twisted. 55> Some cyclic rigid molecules, Eq. 20, that do dimerize 63> do not incorporate substituents that allow regioselectivity to be determined. Butadiene gives principally head-to-head dimerization, Eq. 19, concordant with the PMO prediction, and so does indene, Eq. 22. The anti dimer that is formed would not be expected from a singlet excimer reaction. 

Forziati, A.F., Camin, D.L., Rossini, F.D. (1950) Density, refractive index, boiling point, and vapor pressure of eight monoolefin (1-alkene), six pentadiene, and two cyclomonoolefin hydrocarbons../. Res. Natl. Bur. Std. 45, 406 410. 

Ohta, T. (1984) Rate constants for the reactions of diolefins with OH radicals in the gas phase. Estimate of the rate constants from those for monoolefins. J. Phys. Chem. 87, 1209-1213. 

Verevkin, S.P., Wandschneider, D., Heintz, A. (2000) Determination of vaporization enthalpies of selected linear and branched C7, C8, C9, Cu and Cu monoolefin hydrocarbons from transpiration and correlation gas-chromatography methods. J. Chem. Eng. Data 45, 618-625. 

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