Bicyclo hexyl

Pyridine, 3-amino, 30, 3 5-ETHYL-2-METHYL, 30, 41 4-Pyrimidol, 2,6-diamino-, 32, 45 Pyrogallol-1,3-dimethyl ether, 31, 92 Pyrolysis, of, V-a.zo-bis- -cyclohexane-nitrile to l,l -dicyano-l,l -bicyclo-hexyl, 32, 48... 

Deuterium label distributions in the deamination of exo- and e c/o-tricyclo[3.3.0.0 ] octyl-6-amine (7.122 and 7.123, respectively) were determined in a joint investigation of Bentley and Kirmse (Bentley et al., 1988). The results indicate that the bicyclo-hexyl-type bridged ion structure 7.124 and the open structure 7.125 are approximately equivalent with respect to energy level, but that the norbornyl-type ion 7.126 is not involved in the deamination, a result that is in accord with MM2 force field calculations (Scheme 7-37). 

Diethylamino) ethyl [bicyclohexyl]-1-carboxylate hydrochloride Bicyclo-hexyl]-l-carboxylic acid, 2-(diethylamino) ethyl ester, hydrochloride BP USP ... 

Similarly to the 2-norbornyl cation, comparison of calculated (IGLO/DZ//MP2/ 6-31G(d)) and experimental 13C NMR chemical shifts allowed to differentiate between the hypercoordinated 70 and the trivalent form 71 of the bicyclo[2.1.1.]hexyl cation.85 The experimental (157.8 ppm) and calculated (158.5 ppm) values for Cl and C2 (averaged signal) are reported to be nearly identical for the symmetrically bridged... 

A stable adduct of Cjq with an electron donor moiety in the side chain (Table 4.1, compound 7) [24] was synthesized by the cycloaddition of a rigid diene containing a polynorbornyl-bicyclo[2.2.0]hexyl bridge and a dimethoxybenzene (DMB) unit in toluene at reflux in 63% yield. The donor-acceptor interaction of the electron rich DMB unit and Cjq is indicated by the X-ray crystal structure. The adducts are paired... 

Trishomoaromatic Cations. Following Winstein s proposal1058 1061 of the formation of a trishomoaromatic cation in the solvolysis of s-bicyclo[3.1.0] hexyl tosylate, extensive effort was directed toward its generation under stable ion... 

Brexyl cation 296 8-Deltacyclyl cations 297 Bicyclo[2.1.1]hexyl cations 298... 

Another controversial ion, the bicyclo[2.1.1]hexyl cation, has also been restudied by Saunders et al. (1977a). This ion was first observed by Seybold et al. (1973) and was concluded to be a group of interconverting bridged... 

The first observation of the parent 2-bicyclo[2.1.1]hexyl cation [230] under stable ion conditions was made by Seybold et al. (1973) who prepared [230] and its 2-deuterio analogue [232] from the corresponding chlorides [231]. The H-nmr data showed that all six methylene protons in [230] were equivalent... 

The C-nmr spectrum of [230] recorded by Olah et al. (1976b) was very much like its proton spectrum in that it consisted of only three signals, with a two carbon resonance at S 157.8 ppm. It was not possible to freeze out the static ion [30] or [233]. The 2-methyl- [234] and 2-phenyI-2-bicyclo[2.l.l]hexyl [235] cations were prepared from the corresponding alcohols. The H-nmr spectrum of [234] was found to be temperature dependent. At low temperature (—100°C) three non equivalent types of methylene protons were observed, but at higher temperatures they equilibrate with each other via 1,2-carbon shifts. By comparison of the C-chemical shifts of [234] with those of the... 

Brown et al. (1977) applied the tool of increasing electron demand to this bicyclic system with the solvolysis of a series of 2-aryl-2-bicyclo[2.1.1]hexyl p-nitrobenzoates in 80% aqueous acetone. The excellent log k rj a+ relationship, gave a p+ of —4.31, a value more negative than for the related 2-aryl-2-e rfo-norbornyl system where a-participation is believed to be absent. Also no support for u-participation in secondary bicyclo[2.l.l]hexyl derivatives could be found. 

Winstein and coworkers have thoroughly studied the solvolysis of 3-bicyclo-[3.1.0]hexyl tosylates. These investigations provide strong evidence that ionization of the c/>isomer [240 R = OTs] proceeds primarily through the... 

Aminocarbonyl-1,4-dimethyl-4-hexyl-2-oxo- E16b, 538 (aus 3-Diazo-2,4-dioxo-pyrrolidin) l-tert.-Butyl-3-(cyan-ethoxycarbo-nyl-methyl)- E16c, 877 (0-S02-R -> CHR2) Bicyclo[4.1.0jheptan 7-(Nitro-... 

In other studies, Clark and Smale have investigated the effects of a-phenyl substitution in the solvolyses of endo- and exo-bicyclo[3.1.0]hexyl through [5.1.0]octyl chlorides. For the endo derivatives, where the solvolyses proceed by a favored, concerted disrotatory mechanism in the parent systems, replacement of hydrogen by phenyl gives a relatively small rate enhancement (kph/ H = 1 )- other hand with the exo[3.1.0]... 

Of all of the parent 2-bicyclo[n.l.Ojalkyl systems, the 2-bicyclo[3.1.0]hexyl has been studied with the greatest number of different leaving groups and solvents and in the most laboratories. Thus, the chlorides have been hydrolyzed in 70% aqueous acetone at 250C142, amines have been deaminated in 70% aqueous acetone at 25 the... 

The relative rates of hydrolysis of the endo- and exo-2-bicyclo[3.1.0]hexyl 3,5-dinitrobenzoates (58 and 59) together with some comparison rate data are given below. The observation that essentially identical rates and products for hydrolysis are... 

SCHEME 8. A comparison of the products of hydrolysis of different 2-bicyclo[3.1.0]hexyl derivatives under various conditions... 

In an investigation stemming from a deamination study in the same system, Kirmse and Alberti examined the solvolyses of the 1-isobutoxy exo and endo-2-bicyclo[3.1.0]hexyl 3,5-dinitrobenzoates (60 and 61) in 70 % aqueous acetone. No kinetics were measured, and the only product which could be identified in low yield was bicyclo[2.1.1 ]hexane-5-one (62). 

---