Methylcyclohexane derivatives

The cis-to-trans ratios of the isomeric 4-tert-butyl-l-methylcyclohexanes derived from treatment of 4- < r(-butyl-l -methylenecyclohcxanc with trifluoroacetic acid vary with the steric features of the organosilicon hydrides that are used (Eq. 76).204 The ratio is 0.04 with n-butylsilane, 0.09 with diethylsi-lane, 0.11 with triethylsilane, 0.10 with triisopentylsilane, and 0.19 with either tri-.s< c-butylsilanc or di-tert-butylsilane. 

The 2-methylcyclohexane derivative X, the norbornane derivative XV, the tert.leucine (I) and the N-trimethylglycine (XVI) provide information about the structural preconditions for sweet taste in the vicinity of ammonium and carboxylate groups (cf. Fig. 4 and 5). 

Karahana ether (196), isolated from Japanese hops, is also a 1,1,2,3-tetra-methylcyclohexane derivative, and has been synthesised by Coates and Melvin by a route that they suggest may resemble the biogenetic pathway.Their synthesis consists in cyclising geranyl acetate (194) with benzoyl peroxide in the presence of cupric saltsand hydrolysing the resulting mixture to the corresponding diols, from which the cis-diol (195) is separated and converted to the ether with p-toluenesulphonyl chloride in pyridine at room temperature. 

Several substituted cyclohexane derivatives may also be obtained by the reduction of a benzenoid precursor. Partial reduction of resorcinol, for example, and subsequent methyla-tion yields 2-methylcyclohexane-I,3-dione, which is frequently used in steroid synthesis (M.S. Newman, 1960 see also p. 71f.), From lithium-ammonia reduction of alkoxybenzenes l-alkoxy-l,4-cyclohexadienes are obtained (E.J. Corey, 1968 D). 

The consequences of this point are developed for a number of monosubstituted cyclo hexane derivatives in the following section beginning with methylcyclohexane... 

Derive an expression for the rate of toluene formation, assuming that the reactions occur in the forward direction only and that the surface coverage of toluene is much larger than that of methylcyclohexane, while desorption of toluene determines the overall rate. 

Likewise it is possible to differentiate between substituted and unsubstituted alicycles using inclusion formation with 47 and 48 only the unbranched hydrocarbons are accommodated into the crystal lattices of 47 and 48 (e.g. separation of cyclohexane from methylcyclohexane, or of cyclopentane from methylcyclopentane). This holds also for cycloalkenes (cf. cyclohexene/methylcyclohexene), but not for benzene and its derivatives. Yet, in the latter case no arbitrary number of substituents (methyl groups) and nor any position of the attached substituents at the aromatic nucleus is tolerated on inclusion formation with 46, 47, and 48, dependent on the host molecule (Tables 7 and 8). This opens interesting separation procedures for analytical purposes, for instance the distinction between benzene and toluene or in the field of the isomeric xylenes. 

This procedure differs from those outlined for the bromo and chloro derivatives in that an appreciable excess of (dimethyl-amino) diflu orophosphine cannot be used because it is difficult to separate from iododifluorophosphine by fractional condensation. Typically, (dimethylamino)difluorophosphine (6.38 mmol) and hydrogen iodide (12.76 mmol) are condensed into a 500-ml. reaction bulb and allowed to warm slowly to 25°. As reaction ensues, f the white solids are discolored by formation of red phosphorus triiodide which probably results from a disproportionation 3PF2I —> 2PF3 + PI3. Thus, when the products are separated by fractional condensation through —126° (methylcyclohexane slush) to —196°, an appreciable amount of... 

Treon JF, Crutchfield WE Jr, Kitzmiller KV The physiological response of animals to cyclohexane, methylcyclohexane, and certain derivatives of these compounds. J Ind Hyg Toxicol 25-323-3 7, 1943... 

The enthalpy of fomation of two such species has been measured, namely the cyclopropane and cycloheptane derivatives. The difference between the values for these two species, both as solids, is 238.1 kJmol . Is this difference plausible Consider the difference between the enthalpies of formation of the parent cycloalkanes as solids, 194 kJ mol . The ca 44 kJ mol discrepancy between these two differences seems rather large. However, there are idiosyncracies associated with the enthalpies of formation of compounds with three-membered rings and almost nothing is known at all about the thermochemistry of compounds with seven-membered rings. Rather, we merely note that a seemingly well-defined synthesis of cycloheptyl methyl ketone was shown later to result in a mixture of methyl methylcyclohexyl ketones, and superelectrophilic carbonylation of cycloheptane resulted in the same products as methylcyclohexane, namely esters of 1-methylcyclohexanecarboxylic acid. The difference between the enthalpies of formation of the unsubstituted alicyclic hydrocarbons cycloheptane and methylcyclohexane as solids is 33 kJmol . This alternative structural assignment hereby corrects for most of the above 44 kJ mol discrepancy in the enthalpies of formation of the two oximes. More thermochemical measurements are needed, of oximes and cycloheptanes alike. 

The yield determined in a certain type of experiment usually strongly depends on the assumptions made about the formation mechanism. In the older literature, the excited molecules were often assumed to be produced solely in neutral excitations [127,139-143] and energy-transfer experiments with Stern-Volmer-type extrapolation (linear concentration dependence) were used to derive G(5 i). For instance, by sensitization of benzene fiuorescence, Baxendale and Mayer established G(5 i) = 0.3 for cyclohexane [141]. Later Busi [140] corrected this value to G(5 i) = 0.51 on the basis that in the transfer, in addition to the fiuorescing benzene state S, the S2 and S3 states also form and the 82- 81 and 83 81 conversion efficiencies are smaller than 1. Johnson and Lipsky [144] reported an efficiency factor of 0.26 0.02 per encounter for sensitization of benzene fluorescence via energy transfer from cyclohexane. Using this efficiency factor the corrected yield is G(5 i) = 1.15. Based on energy-transfer measurements Beck and Thomas estimated G(5 i) = 1 for cyclohexane [145]. Relatively small G(5 i) values were determined in energy-transfer experiments for some other alkanes as well -hexane 1.4, -heptane 1.1 [140], cyclopentane 0.07 [142] and 0.12 [140], cyclooctane 0.07 [142] and 1.46 [140], methylcyclohexane 0.95, cifi-decalin 0.26 [140], and cis/trans-decalin mixture 0.15 [142]. 

Chandross and Ferguson64 find that the absorption spectra of dimers, produced65 by photolytic cleavage of photodimers of anthracene and mono-derivatives in a rigid methylcyclohexane glass at 77°K, are consistent with a symmetrical sandwich configuration these dimers also emit the characteristic excimer fluorescence. On the other hand, it is necessary to assume a 60° rotation of one component about the intermolecular axis of the 9,10-di-chloroanthracene dimer (as in the crystalline compound) to account for the observed resonance splittings of both absorption bands.64... 

A facile intramolecular carbomagnesiation becomes possible by inserting one more carbon between the reactive magnesium center and the double bond. For example, when a 6-chloro-l-heptene was refluxed with magnesium, 1,2-dimethylcyclopentane (cis/trans = ca 1/4) was obtained in 88% yield after hydrolysis (Scheme 47) °. The cyclization shows a 5-exo-trig selectivity and the product derived from 6-endo-trig cyclization (methylcyclohexane) is not observed. 

The photochemistry and photophysics of trans-stilbene derivatives (24) have been utilized by Whitten and co-workers to understand the relaxation characteristics of media such as micelles, monolayers, and LB films [144,145]. For example, the d>,rans to Cis for stilbene derivatives show the following trend solvent system methylcyclohexane > SDS micelle multilayer assemblies (with arachidic acid). In fact, no isomerization is observed in multilayer assemblies. This is the trend expected on the basis of how readily the media can respond to stilbene shape changes during isomerization process. 

Transition-metal-catalyzed hydroboration, a reduction using B H bonds, of styrene derivatives has been demonstrated to occur in supercritical carbon dioxide using tunable Rh(I) complexes as catalysts. In the case of vinyl anisole (eq. 2.5), significantly higher regioselectivities were reported for the reaction in this medium than in THF or perfluoro(methylcyclohexane) (Carter et ah, 2000). 

Enantioselective photocyclization of 2-(arylthio)-3-methylcyclohexan-l-ones (75) to dihydrobenzothiophene derivatives 77 was also achieved in inclusion crystals using chiral host molecules. Photoirradiation of the 1 1 inclusion crystals of 75g with (-)-12b as a water suspension gave the corresponding photocyclization product (+ )-m-77g of 82% ee in 83% yield. Similar photoirradiation of the... 

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