Olefin using

Ziegler-Natta polymerization Stereospecific polymerization of olefines using a Ziegler catalyst. See titanium(IIl) chloride. 

The reaction product is cooled to room temperature, is washed with 10 ml of H2O to the purpose of removing lithium iodide and is then dehydrated over NaiS04. 3.57 g is obtained of dimethoxy-phenylacetone (III), as determined by gas-chromatographic analysis with an inner standard of 4,4 -dimethoxybeniophenone. The yield of ketone (III) relative to the olefin ( ) used as the starting material is of 87.1%. 

Shell Higher Olefin Process) plant (16,17). C -C alcohols are also produced by this process. Ethylene is first oligomerized to linear, even carbon—number alpha olefins using a nickel complex catalyst. After separation of portions of the a-olefins for sale, others, particularly C g and higher, are catalyticaHy isomerized to internal olefins, which are then disproportionated over a catalyst to a broad mixture of linear internal olefins. The desired fraction is... 

The introduction of metallocene and single-site polyethylene catalyst systems may eventually change the demand for higher olefins used as comonomers. Some sources indicate that their use will increase the demand for comonomers, but others feel that they will reduce comonomer use. At any rate, it is not expected that their introduction will have a significant effect on comonomer growth rates for the period 1992—1996 (see Olefin polymers). 

Detergents. The detergent industry consumes a large quantity of a-olefins through a variety of processes. Higher olefins used to produce detergent actives typically contain 10—16 carbon atoms because they have the desired hydrophobic and hydrophilic properties. 

The 0x0 process is employed to produce higher alcohols from linear and branched higher olefins. Using a catalyst that is highly selective for hydroformylation of linear olefins at the terminal carbon atom. Shell converts olefins from the Shell higher olefin process (SHOP) to alcohols. This results in a product that is up to 75—85% linear when a linear feedstock is employed. Other 0x0 processes, such as those employed by ICI, Exxon, and BASE (all in Europe), produce oxo-alcohols from a-olefin feedstocks such alcohols have a linearity of about 60%. Enichem, on the other hand, produces... 

By-products include ozonides (17). Other peroxidic products including polymeric peroxides and polymeric ozonides can form, depending on reaction conditions, solvent, and olefin used. A variety of cycHc diperoxides (4) have been obtained by ozonolysis of olefins. Both cis- and... 

Commercial Antioxidants Table 4 includes the main classes of antioxidants sold in the United States and the suppHer s suggested apphcations. Some of these are mixtures rather than single substrates. This is especially tme of alkylated amines and alkylated phenols. The extent of alkylation and the olefins used for alkylation can vary among manufacturers. Table 4 is not a complete listing of available antioxidants in the United States. 

The alkylate contains a mixture of isoparaffins, ranging from pentanes to decanes and higher, regardless of the olefins used. The dominant paraffin in the product is 2,2,4-trimethylpentane, also called isooctane. The reaction involves methide-ion transfer and carbenium-ion chain reaction, which is cataly2ed by strong acid. 

A new homogeneous process for hydroformylation of olefins using a water-soluble catalyst has been developed (40). The catalyst is based on a rhodium complex and utilizes a water-soluble phosphine such as tri(M-sulfophenyl)phosphine. The use of an aqueous phase simplifies the separation of the catalyst and products (see Oxo process). 

Garbonylation of Olefins. The carbonylation of olefins is a process of immense industrial importance. The process includes hydroformylation and hydrosdylation of an olefin. The hydroformylation reaction, or oxo process (qv), leads to the formation of aldehydes (qv) from olefins, carbon monoxide, hydrogen, and a transition-metal carbonyl. The hydro sdylation reaction involves addition of a sdane to an olefin (126,127). One of the most important processes in the carbonylation of olefins uses Co2(CO)g or its derivatives with phosphoms ligands as a catalyst. Propionaldehyde (128) and butyraldehyde (qv) (129) are synthesized industrially according to the following equation ... 

Manufacturing procedures for most branched-chain acids are well known. For example, oxo process acids are manufactured from branched-chain olefins using hydroformylation followed by oxidation (3) (see Oxo process). 

Neo acids are prepared from selected olefins using carbon monoxide and acid catalyst (4) (see Carboxylic Acids, trialkylacetic acids). 2-EthyIhexanoic acid is manufactured by an aldol condensation of butyraldehyde followed by an oxidation of the resulting aldehyde (5). Isopalmitic acid [4669-02-7] is probably made by an aldol reaction of octanal. 

Esters can be obtained from halogenated olefins using a metal carbonyl catalyst (87), eg, /n j -l-bromo-2-phenylethylene is treated with nickel carbonyl in the presence of methanol to afford the corresponding methyl cinnamate (see Cinnamic acid). 

SHARPLESS Asymmetric Oihydroxylation Enantioselecthfe syn dihyroxylation of olefins using AO-mn-p formed from phthalazine-... 

Conversion of a-haloketones to olefins using hydrazine (via enedlitnides C-C-N NH). Also reduction of o,3-epoxy ketones to allyl alcohols. 

A number of polymers have been produced from higher olefins using catalysts of the Ziegler-Natta type. 

In 1990, Jacobsen and subsequently Katsuki independently communicated that chiral Mn(III)salen complexes are effective catalysts for the enantioselective epoxidation of unfunctionalized olefins. For the first time, high enantioselectivities were attainable for the epoxidation of unfunctionalized olefins using a readily available and inexpensive chiral catalyst. In addition, the reaction was one of the first transition metal-catalyzed... 

Asymmetric Sharpless dihydroxylation of olefins using catalysts supported by polymers with heterocyclic fragments 98EJ021. 

Asymmetric olefination using optically active P,0-heterocycles as reagents 98YGK521. 

The olefins used are propylenes and butylenes ethylene is also produced from cracking operations but is not used in refinery processing. 

The most important olefins used for the production of petrochemicals are ethylene, propylene, the butylenes, and isoprene. These olefins are usually coproduced with ethylene by steam cracking ethane, LPG, liquid petroleum fractions, and residues. Olefins are characterized by their higher reactivities compared to paraffinic hydrocarbons. They can easily react with inexpensive reagents such as water, oxygen, hydrochloric acid, and chlorine to form valuable chemicals. Olefins can even add to themselves to produce important polymers such as polyethylene and polypropylene. Ethylene is the most important olefin for producing petrochemicals, and therefore, many sources have been sought for its production. The following discusses briefly, the properties of these olefmic intermediates. 

Table 6.7 Manganese sulfate-catalyzed epoxidation of olefins using aqueous H2O2 (30%).[al...

Copolymerization occurred when the olefin had a basicity lower than that of the aldehyde (with respect to the initiator used), but sufficiently high occasionally to displace a molecule of initiator and give rise to an active species this situation produced copolymers with varying proportions of ether units in the chain, depending on the monomers feed ratio and on the olefin used. Isopropenylbenzene gave the best results with alternate copolymerization over a fairly wide range of feed ratios rt = 0.03 0.03, r2 = 0.4 0.1 (2-furaldehyde = Mj) indene produced copolymers with lower 2-furaldehyde contents. 

C H2 OH>2 CHN02 (liq)+C H 3 COOHQiq) - (CH200CCH3)2CHN02 0iq), 3) selective oxidation to a mono ester olefin using mild conditions such as dil aq KMn04 ... 

Asymmetric versions of the cyclopropanation reaction of electron-deficient olefins using chirally modified Fischer carbene complexes, prepared by exchange of CO ligands with chiral bisphosphites [21a] or phosphines [21b], have been tested. However, the asymmetric inductions are rather modest [21a] or not quantified (only the observation that the cyclopropane is optically active is reported) [21b]. Much better facial selectivities are reached in the cyclopropanation of enantiopure alkenyl oxazolines with aryl- or alkyl-substituted alkoxy-carbene complexes of chromium [22] (Scheme 5). 

Effect of di monosulfonate ratio on IOS and VOS calcium tolerance. Similar trends were observed when studying internal olefinsulfonates (IOS) and vinylideneolefinsulfonates (VOS). These data are given in Table 7. The average carbon number of the olefins used to synthesize AOS 2024, IOS 2024, and VOS 2024 was nearly constant (21.2-21.6). Increasing the disulfonate content of IOS 2024 and VOS 2024 substantially increased the calcium ion tolerance. 

In 2008, Que and coworkers reported an asymmetric version of the dihydroxylation with a new type of ligands bearing bipyrrolidine as the chiral backbone [71]. The corresponding iron(II) complex showed general activity in the dihydroxylation of various olefins using H202- Satisfactory results are obtained with aliphatic as well as with aromatic olefins. For example, dihydroxylation of styrene gave styrene oxide and 1-phenylethane-1,2-diol in <1% and 65% yield, respectively (Scheme 10). 

D. L. Phillips, W.H. Fang, and X. Zheng, Isodiiodomethane is the methylene transfer agent in cyclopropanation reactions with olefins using ultraviolet photolysis of diiodomethane in solutions a density functional theory investigation of the reactions of isodiiodomethane, iodomethyl radical, and iodomethyl cation with ethylene. J. Am. Chem. Soc. 123(18), 4197-4203 (2001). 

Redox-type reactions show by far the worst performance in meeting the golden atom economical threshold. Three reductions meet this criterion with (AE)min values of 1 hydrogenation of olefins using the Lindlar catalyst (1952), Noyori stereoselective hydrogenation reaction (1985), and Zincke disulphide cleavage reaction (1911) whereas, oxidations... 

Scheme 2.19. Carbonyl Olefination Using Trimethylsilyl-Substituted Organo-... 

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