Alkenes continued reactions with

Syntheses of fluoro-substituted pyrazoles continue to be of interest. Both 3- and 5-fluoropyrazoles (44 and 45, respectively) can be prepared from 43 <96JOC2763>. Treatment of 43 with hydrazine followed by N-alkylation provides 44, whereas reactions with monosubstituted hydrazines afford 45. The 4-(trifluoromcthyl)pyrazoles 47 are obtained from J-trifluoromethyl vinamidinium salt 46 <96TL1829>. The 5-trifluoromethyl-3-carboethoxypyrazoles 49 are obtained from the 1,3-dipolar cycloadditions of trifluoromethyl alkenes 48 with ethyl diazoacetate <96T4383>. 

Additions to the double bond of phospha-alkenes continue to be explored. The reactions of (177) with aliphatic diazo compounds... 

During a 33 h continuous hydroformylation run using this set-up, no catalyst decomposition was observed and Rh leaching into the scC02/product stream was less than 1 ppm. The selectivity for the linear nonanal was found to be stable over the reaction time with n/iso = 3.1. During the continuous reaction, alkene, CO, H2 and C02 were separately fed into the reactor containing the ionic liquid catalyst solution. Products and unconverted feedstock dissolved in SCCO2 were removed from the ionic liquid. After decompression the liquid product was collected and analysed. 

The ability to form carbon—carbon bonds in a controlled manner around an alkene is the subject of continuing intense research [49,134—136], These compounds are stable and, due to the considerably different reactivities of the C—Zr and C—B bonds, allow for selective and sequential reactions with a variety of electrophiles. Temarotene 58 is a retinoid of interest [137] because it shows no sign of hypervitaminosis A and it is not teratogenic, presumably due to the lack of a polar group [138,139], The published synthesis of temarotene-type compounds is long and leads to mixtures of diastereo-isomers, from which the desired product is eventually isolated [140—142], However, the synthesis of temarotene 58 by the method of Srebnik et al. [130] is straightforward, as outlined in Scheme 7.18. 

Alkanes—Continued reactions—Continued with ozonide ions, 135 with superoxide ions, 134-35 role of oxygen ions in oxidation. 138-41 Alkenes, reactions with oxygen ions, 134 with ozonide ions, 135 with superoxide ions, 134-35 Aluminosilicate gels, alkali cations, 241... 

Reactions with Simple Alkenes and Aromatic Compounds.—A wide range of conditions continues to be used to form phosphorus-carbon bonds between halogeno-phosphines and alkenes or benzene derivatives. A selection of such reactions (Scheme 2) is outlined for the preparation of the compounds (17)—(23).22-26... 

Reactions of Phosphoranes.—The reactions of phosphorus pentachloride (101) with simple organic molecules continue to attract attention, notably in the Russian literature. For example, the preparative uses of alkene-addition reactions of (101) have been examined for a-methylstyrene (102), as outlined in Scheme 7.85... 

Supercritical hydrogenation is just one example of continuous reactions which can be carried out in SCCO2 solution. Other reactions which have been carried out successfully include Friedel-Crafts alkylation of aromatics by alcohols [64], the dehydration of alcohols to form ethers [65] (using acid catalysts), and the hydroformylation of alkenes [52] (using rhodium catalysts immobilized on Si02). In each of these reactions, it is possible to obtain a selectivity which is at least as good, and often better, than with conventional solvents. However, the precise role of the scCC>2 in these reactions is not as obvious as in supercritical hydrogenation. 

Vic-diols can thus be easily converted to alkenes through their reaction with A, A -thiocarbonyldimidazule. The reported synthesis of trans-cyclooctene is illustrative of the method [219]. It should be noted that continuous elimination of rrans-cyclooctene by a stream of argon was necessary to avoid isomerization to the cis isomer. The conversion of cis-cyclooctene to ww-cyclooctene through a trithiocarbonate is described in the same paper. 

Cycloaddition reactions of pyrylium salts with alkenes continue to be explored in the context of natural products synthesis, as shown in Schemes 12-14. In the example shown in Scheme 12, a pyrylium-ylide [5+2] cycloaddition was performed (128—> 129), allowing access to intermediates reminiscent of the core framework of the diterpene antibiotic, guanacastepene <2001TL4947>. 

Heterogeneous reactions lend themselves to continuous flow reactors, which are desirable as they minimise the reacting volume. This reduces operation risks, and allows smaller, more efficient plants to be built. Flow reactors designed for fluorous reactions with both liquid and gaseous substrates have been demonstrated to be effective, at least on a bench scale [49]. Fluorous solvents have also recently found applications as liquid membranes to control the rate of addition of reagents and so control exothermic reactions such as alkene bromination (Fig. 6), and demethylation of anisoles by reaction with boron tribromide [50], This has potential as a clean route as the kinetic control gives improved selectivity. 

A solution or suspension of the acid (1 mmol) in carbon tetrachloride (75 ml) containing DIB (0.55 mmol) and iodine (0.5 mmol) was irradiated with two 100 W tungsten-filament lamps for 45 min at reflux temperature. Another portion of DIB (0.55 mmol) was then added and irradiation was continued for 45 min at reflux. The reaction mixture was washed with dilute sodium thiosulphate and water, concentrated and chromatographed (silica gel column, 9 1 hexanes-ethyl acetate) to afford the alkyl iodide. Several steroidal acids with the carboxyl group attached at a 1° or 2° carbon atom gave the corresponding iodides in good yields. Acids with a 3° a-C instead of the iodide afforded alkenes similarly, alkenes were formed with a fivefold excess of DIB in the presence of cupric acetate. Aromatic acids also underwent iododecarboxylation, in moderate yields very effective was the otherwise difficult transformation of 1,8-naphthalenedicarboxylic acid to 1,8-diiodonaphthalene (80%) [68]. Cubyl and homocubyl iodides were also prepared in excellent yield [69]. 

Organometallic compounds are used widely as homogeneous catalysts in the chemical industry. For example, if the alkene insertion reaction continues with further alkene inserting into the M C bond, it can form the basis for catalytic alkene polymerisation. Other catalytic cycles may include oxidative addition and reductive elimination steps. Figure above shows the steps involved in the Monsanto acetic acid process, which performs the conversion... 

The regenerated bromine radical reacts with another molecule of the alkene, continuing the chain reaction. Both of the propagation steps are moderately exothermic, allowing them to proceed faster than the termination steps. Note that each propagation step starts with one free radical and ends with another free radical. The number of free radicals is constant, until the reactants are consumed, and free radicals come together and terminate the chain reaction. 

---