Cyclohexane benzene alkylation with

Organolithium compounds can readily be prepared from metallic Li and this is one of the major uses of the metal. Because of the great reactivity both of the reactants and the products, air and moisture must be rigorously excluded by use of an inert atmosphere. Lithium can be reacted directly with alkyl halides in light petroleum, cyclohexane, benzene or ether, the chlorides generally being preferred ... 

The solubility of benzene and of cyclohexane in [AMIMJBFq with various lengths of the alkyl chain in the cation of the ionic liquid was reported (88). The results of Fig. 11 show that the solubility of benzene increases with an increase in the alkyl chain length, but, surprisingly, the solubility of cyclohexane is little affected by varying the chain length. 

Lithium butoxides increase the rate of reaction of lithium alkyls with olefins in cyclohexane or hexane but decrease it in benzene. The propagation rate is, however, decreased in both types of solvent [77, 78] according to information presently available. In fact, as far as is known, butoxides reduce rates where the mechanism has been suggested to be dissociative and increase them in the other cases. More data are still required to confirm that this always happens. The experiments with polystyryllithium [77] show that the polymer dimers in solution are not dissociated by lithium fert.-butoxide as would be expected if mixed aggregates of the type (PstLi. BuOLi ) were formed. In this case, at least, the rate effect appears to be caused by addition of butoxide to the polystyryllithium dimers. The reaction still shows half order characteristics, and the rate depression is almost complete at a 1 1 ratio of butoxide to polymer chains. The major species present in solution would seem to be (PstLi. BuOLi)2 at this point. Similar results have been obtained with polyisoprenyllithium in cyclohexane [78]. The nature of... 

Photolysis of alkyl carboxylic acids with lead (IV) acetates can generate alkyl radicals by decarboxylation and this has been used to place an aryl group on a cubane. Thus photolysis of a benzene solution of the cubane dicarboxylic acid (136) containing lead tetraacetate yields the phenyl cubane (137). A mechanistically related procedure uses iodosobenzene diacetate for the photochemical arylation of cyclohexane carboxylic acid with heteroaromatics such as pyridine or quinoline. 

Tris[3-tert-butyl-4-(hydroxybenzyl)]mesitylene (III) was synthesized starting from 2-fert-butyl-6-chlorophenol, which in turn was prepared by the method of Kolka et al. (10). The 2-ferf-Butyl-6-chlorophe-nol was alkylated with a1,a3,a5-(trihydroxyhexamethyl)benzene (Aldrich) with the use of boron trifluoride etherate catalyst (II). A mixture of I and II was obtained, separated by fractional crystallization from methyl-cyclohexane. The structures of the two products were assigned on the... 

The reaction of ( S)-1 with isobutyraldehyde in benzene provides a 92 8 mixture of cis-44 and trans-45, whereas the same reaction with pivaldehyde affords only cis-46 in 74% yield. The reaction of ( S)-1 with pivaldehyde dimethyl acetal in the presence of pyridinium p-toluenesulfonate in a refluxing mixture of cyclohexane-ethyl acetate provides a 97 3 cis trans mixture of 46, but in only 25% yield [10]. Treatment of 46 with LDA at —70 °C followed by alkylation with methyl iodide proceeds in 94% yield to provide a 93 7 mixture of cis, trans isomers. Potassium hydroxide hydrolysis affords (5)-( + )-atrolactic acid (47) possessing 85% ee (Scheme 9). 

Table 5 also summarizes the selectivities for the separation of hexane/benzene, cyclohexane/benzene, and hexane/hexene mixtures at T=298.15 K, which were calculated from the y values for the ILs under study and collected from literature. As presented in table 5, the trend in Sy values depends on the number of carbon atoms in the alkyl groups attached to the cation, most of the ILs with shorter alkyl chain have higher Sy values while those with longer alkyl chain have smaller Sy" values, e.g., [OMIM][BF4], 9 carbon atoms, Sy" (i = hexane,) = benzene) =10.4, Sy i = cyclohexane, j = benzene) = 6.8 [BMIM][BF4], 5 carbon atoms, Sy i = hexane, j = benzene) = 37.3, Sy i = cyclohexane, j = benzene) = 19.7 ... 

Isomerization. Isomerization is a catalytic process which converts normal paraffins to isoparaffins. The feed is usually light virgin naphtha and the catalyst platinum on an alumina or zeoflte base. Octanes may be increased by over 30 numbers when normal pentane and normal hexane are isomerized. Another beneficial reaction that occurs is that any benzene in the feed is converted to cyclohexane. Although isomerization produces high quahty blendstocks, it is also used to produce feeds for alkylation and etherification processes. Normal butane, which is generally in excess in the refinery slate because of RVP concerns, can be isomerized and then converted to alkylate or to methyl tert-huty ether (MTBE) with a small increase in octane and a large decrease in RVP. 

The dipole moment varies according to the solvent it is ca 5.14 x 10 ° Cm (ca 1.55 D) when pure and ca 6.0 x 10 ° Cm (ca 1.8 D) in a nonpolar solvent, such as benzene or cyclohexane (14,15). In solvents to which it can hydrogen bond, the dipole moment may be much higher. The dipole is directed toward the ring from a positive nitrogen atom, whereas the saturated nonaromatic analogue pyrroHdine [123-75-1] has a dipole moment of 5.24 X 10 ° C-m (1.57 D) and is oppositely directed. Pyrrole and its alkyl derivatives are TT-electron rich and form colored charge-transfer complexes with acceptor molecules, eg, iodine and tetracyanoethylene (16). 

AH commercial processes for the manufacture of caprolactam ate based on either toluene or benzene, each of which occurs in refinery BTX-extract streams (see BTX processing). Alkylation of benzene with propylene yields cumene (qv), which is a source of phenol and acetone ca 10% of U.S. phenol is converted to caprolactam. Purified benzene can be hydrogenated over platinum catalyst to cyclohexane nearly aH of the latter is used in the manufacture of nylon-6 and nylon-6,6 chemical intermediates. A block diagram of the five main process routes to caprolactam from basic taw materials, eg, hydrogen (which is usuaHy prepared from natural gas) and sulfur, is given in Eigute 2. 

In general, pyridazine can be compared with pyridine. It is completely miscible with water and alcohols, as the lone electron pairs on nitrogen atoms are involved in formation of hydrogen bonds with hydroxylic solvents, benzene and ether. Pyridazine is insoluble in ligroin and cyclohexane. The solubility of pyridazine derivatives containing OH, SH and NH2 groups decreases, while alkyl groups increase the solubility. Table 1 lists some physical properties of pyridazine. 

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). 

In contrast to the problems encountered on photolysis of alkyl- and aryl-sulphonyl azides, we have found that ferrocenylsulphonyl azide 74 is smoothly decomposed by 3500 A light in cyclohexane or in benzene to give ferrocene 15, ferrocenylsulphonamide 16 and the novel bridged [2]ferrocenophanethiazine 1,1-dioxide 17 24>. The yield of 17 varied with the nature of the solvent, being 13.3% in cyclohexane, 67% in benzene, and zero in dimethyl sulphoxide or DMSO/benzene 25>. 

Ealy [ 75 ] also used conversion to alkyl mercury iodides for the gas chromatographic determination of organomercury compounds in benzene extracts of water. The iodides were then determined by gas chromatograph of the benzene extract on a glass column packed with 5% of cyclohexane-succinate on Anakron ABS (70-80 mesh) and operated at 200 °C with nitrogen (56 ml min-1) as carrier gas and electron capture detection. Good separation of chromatographic peaks was obtained for the mercury compounds as either chlorides, bromides, or iodides. The extraction recoveries were monitored by the use of alkylmer-cury compounds labelled with 203 Hg. 

No systematic study is available on other parameters in triphase alkylation of phenylacetonitrile, but the following isolated observations may be significant. Both dilution of the organic phase with benzene or cyclohexane and use of 10% NaOH in place of 50% NaOH greatly reduced the rate 101). The benzyltrimethylammonium ion is attacked by hydroxide ion under the conditions of phenylacetonitrile alkylation. Repeated use of either Dowex ion exchange resins101) or 2 % CL, 16-50 % RS resins 103) gave reduced activity. 

A new commercial use for butadiene is its employment in the nylon synthesis joining furfural, benzene, and cyclohexane as raw materials for nylon salt components. Amother olefinic hydrocarbon, which has found large scale application in recent years, is propylene tetramer, widely employed in reaction with aromatic nuclei to yield an alkylated aromatic base used in synthetic detergent production. 

When cycloalkanes (cyclopentane, cyclohexane) alkylate benzene, cycloalkylben-zenes, as well as bicyclic compounds (indan and tetralin derivatives) and products of destructive alkylation, are formed.191192 Cyclohexane reacts with the highest selectivity in the presence of HF—SbF5 to yield 79% cyclohexylbenzene and 20—21% isomeric methylcyclopentylbenzenes.191... 

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