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Larger Bicyclics

The ion (785) predicted in 1971 to be stable has now been made. Reduction of bull-valene with Na-K alloy in dimethoxyethane gives a yellow precipitate of the dipotassium salt. The lithium salt was made by exchange and its spectra recorded in dimethoxyethane. Similar reduction of dihydrobullvalene did not lead to an isolable dianion (786) which would be homoantiaromatic and would not enjoy the stabilization that (785) obtains from the third it-system. Addition of dibromocarbene to [Pg.446]

A new cheap route to (787) is reported. Irradiation of butadiene in benzene gives a modest yield of (791) which can be doubly brominated (NBS) and reduced with zinc to (787) contaminated with a little bullvalene. If the dibromide is reduced with BujSnH, (791), (787), (792), and (793) are formed. Monobromination of (791) gives a mixture of two structurally isomeric allylic bromides and reduction of this with BujSnH gives (791)—(794). The formation of (792) and (793) implies that the initial radical (795) rearranges to (797) by a 1,2-alkenyl shift in which (796) might be an intermediate or a transition state.  [Pg.447]


The Prefix Nor Is Used to Denote a Ring System Devoid of Methyl Groups. The Identification Numbers for the Formulas Correspond to Those Used in Later Charts. The Orientations Shown in Column 1 are Only for Ready Recognition of the Corresponding Larger Bicyclic Carbon Skeletons Recommended in Chart 8. [Pg.36]

The intramolecular cyclopropanations of a-diazocarbonyl compounds have been extensively studied and recently reviewed . The reaction is satisfactorily accomplished when the diazo carbon atom is proximal to the double bond in the substrate. Thus, the construction of bicyclo[3.1.0]hexane and bicyclo[4.1.0]heptane skeletons has been achieved by this method, whereas the synthesis of bicyclo[5.1.0]octane or the larger bicyclic systems has usually been difficult (equation 73). Bicyclo[2.1.0]pentan-2-ones expected in the reaction of j8,y-unsaturated diazoketones are generally labile and readily undergo the ring cleavage to give jS,y-unsaturated ketenes. ... [Pg.333]

Phenylalanine and tryptophan have side chains that incorporate aromatic rings which are large and hydrophobic The aromatic portion of tryptophan is bicyclic which makes it larger than phenylalanine Tryptophan also has a more electron rich aromatic ring and is more polarizable than phenylalanine Its role is more specialized and it is less abundant m proteins than most of the other ammo acids... [Pg.1113]

Antidepressant activity is retained when the two carbon bridge in imipramine is replaced by a larger, more complex, function. Nucleophilic aromatic substitution on chloropyridine 31 by means of p-aminobenzophenone (32) gives the bicyclic intermediate 33. Reduction of the nitro group (34), followed by intramolecular Schiff base formation gives the required heterocyclic ring system 35. Alkylation of the anion from 35 with l-dimethylamino-3-chloropropane leads to tampramine 36 [8]. [Pg.203]

Another stereochemical feature of the Diels-Alder reaction is that the diene and dienophile partners orient so that the endo product, rather than the alternative exo product, is formed. The words endo and exo are used to indicate relative stereochemistry when referring to bicyclic structures like substituted norbornanes (Section 4.9). A substituent on one bridge is said to be exo if it is anti (trans) to the larger of the other two bridges and is said to be endo if it is syn (cis) to the larger of the other two bridges. [Pg.495]

Geometric considerations in cyclopolymerization are optimal for 1,6-dienes (see 4.4.1.1). Instances of cyclopolymerization involving formation of larger rings have also been reported (see 4.4.1.4), as have examples where sequential intramolecular additions lead to bicyclic structures within the chain (see 4.4.1.2). Various 1,4- and 1,5-dienes are proposed to undergo cyclopolymerization by a mechanism involving two sequential intramolecular additions (see 4.4.1.3). [Pg.186]

The yields of the tetrathia[6.6. l]propellane 60 and of the spirodithiabieyclo[5.4.0]-undecane 63 are only 25% and 18%, respectively. Perhaps this is the manifestation of the relative difficulty in formation of medium rings. It is not otherwise obvious why the yields should be so low. Of course propellanes with larger rings exist but the medium ring isn t cyclized at the bicyclic stage. It is already there 16). [Pg.14]

A different approach to 1 is available32,33 for somewhat larger quantities in good yields. The procedure (Scheme 2) is based upon the condensation of ethyl /f-bromomethacrylate (9) or its precursor, diethyl /i,/7 -dibromoisobutyr-ate, with the pyrrolidine enamine (10) of Af-toluene-p-sulfonylpiperid-4-one to afford the bicyclic intermediate (11). If the carbonyl group is modified... [Pg.82]

This free-energy difference between the anomers, which can be estimated by the ratios observed in glycosidation and anomerization equilibria, is larger in derivatives of 4 than in those of D-glucofuranose. This result can be attributed to the lessened conformational flexibility of bicyclic structures. [Pg.192]

Li 1839, Kirkpatrick Macmillan, a Scottish blacksmith, invented a much better bicycle. Macmillan s machine had tires with iron rims to keep them from getting worn down. He also used foot-operated cranks, similar to pedals, so his bicycle could be ridden at a quick pace. It didn t look much like the modern bicycle, though, because its back wheel was substantially larger than its front wheel. Although Macmillan s bicycles could be ridden easily, they were never produced in large numbers. [Pg.186]

About 20 years ago, Bohlmann and co-workers examined South American plants of the widespread Vemonia species and found the first and (until now) only naturally occurring endocydic allenes (Scheme 18.32) [97]. These are the bicyclic sesquiterpene lactones 100-102 bearing a 10-membered ring [98], in which the E-double bond of the larger ring can also be present in its oxidized form (101, 102). As in other cases, these fasdnating natural products have not been synthesized until now. [Pg.1017]

However, bicyclic dichloride 95 under the same conditions was converted into diene 96 and not to the rearrangement product 94 (equation 33). This result is explained by the larger size of the ring, which is far less strained than that in diene 9046. The gas-phase thermolysis of diene 91 at 126-186 °C afforded an almost equimolar mixture of bicyclic diene 92 and triene 93 which are formed, presumably, via the TMM-diradicals... [Pg.753]


See other pages where Larger Bicyclics is mentioned: [Pg.161]    [Pg.290]    [Pg.26]    [Pg.375]    [Pg.39]    [Pg.324]    [Pg.1176]    [Pg.79]    [Pg.1123]    [Pg.446]    [Pg.818]    [Pg.387]    [Pg.161]    [Pg.290]    [Pg.26]    [Pg.375]    [Pg.39]    [Pg.324]    [Pg.1176]    [Pg.79]    [Pg.1123]    [Pg.446]    [Pg.818]    [Pg.387]    [Pg.50]    [Pg.240]    [Pg.124]    [Pg.152]    [Pg.441]    [Pg.397]    [Pg.1408]    [Pg.251]    [Pg.146]    [Pg.107]    [Pg.349]    [Pg.611]    [Pg.107]    [Pg.187]    [Pg.79]    [Pg.187]    [Pg.46]    [Pg.1015]    [Pg.240]    [Pg.218]    [Pg.280]    [Pg.7]    [Pg.223]    [Pg.326]   


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