Cyclodecene, reaction with

Synthesis (Freed and Potoski (American Home), 1971 Freed, 1973 Kleemann et al., 1999,) Dezocine is prepared through the following sequence The condensation of 1-methyl-7-methoxy-2-tetralone with 1,5-di-bromopentane by means of NaH or potassium tertbutylate affords 1 -(5-bromopentyl)-1 -methyl-7-methoxy-2-tetralone this product is cyclized with NaH to give 5-methyl-3-methoxy-5,6,7,8,9,10,11,12-octahydro-5,11 -methano-benzocyclodecen-13-one i. The ketone i, by reaction with hydroxylamine hydrochloride in pyridine, is converted into its oxime ii, which is reduced with H2 over Raney Ni to a mixture of isomeric amines which were separated by crystallization of the HCI salts giving 5-a-methyl-3-methoxy-5,6,7,8,9,11 a, 12-octahydro-5,11 -methanobenzo-cyclodecen-13p-amine, which is finally cleaved with concentrated HBr. 

Reaction with cyclic epoxides. The reaction of epoxides of medium-size rings with base (lithium di- -alkylamides) has been extensively studied by Cope and by Crandall (1, 610 611 2, 247). Two products are usually obtained an allylic alcohol formed by -elimination and a bicyclic alcohol derived from a carbene intermediate formed by a-elimination. Boeckman has now found that the ciirbcnc pathway is highly favored if n-butyllithium (3 equiv.) is used as base and if (he reaction is conducted at low temperatures, —78 to 25° in the case of cis-eyelooctene oxide (1) and m-cyclodecene oxide. The oxide of cyclododecene,... 

Probably, the dramatic distinction in stereo-selectivity between cometathesis products obtained from Z-cyclodecene and from cycloolefins C5-C9 (Table 3), is connected with the fact that Z-cyclodecene gives the cyclic transition state having eleven atoms in the cycle (10 C-atoms + 1 Mo-atom). Meanwhile, it is known that the thermodynamic stability of E-isomers in the range of unsaturated cycles of different size dramatically increases beginning from cycloundecene [33]. So, Z-cycloolefins C5, and C7-C9 in cometathesis reaction with a-olefins allow predominantly Z-isomer new double bonds to be obtained (in l,A-dienes). This radically differentiates them from cycloolefins with number of C-atoms of 10 and more, as well as from open-chain olefins. 

Diacylation of cycloalkenes such as cyclododecene and cyclodecene affords the corresponding pyrylium salts.° Whereas the diacetylation of cyclododecene (29) with acetic anhydride in the presence of 70% perchloric acid proceeds smoothly in satisfactory yield, the analogous reaction with cyclodecene (31) succeeds only with sulfoacetic acid (prepared by heating acetic anhydride with sulfuric acid under carefully controlled conditions), and the yield is lower than 10%. The central CH2 groups of the resulting 9,1 l-dimethyl-[7]-(2,6)-pyrylophanium perchlorate (32) and of the... 

Based on the successful series of transformations summarized in Scheme 1, Schreiber and Santini developed an efficient and elegant synthesis of periplanone B (1),8 the potent sex pheromone of the American cockroach, Periplaneta americana. This work constitutes the second total synthesis of periplanone B, and it was reported approximately five years after the landmark periplanone B synthesis by W.C. Still9 (see Chapter 13). As in the first synthesis by Still, Schreiber s approach to periplanone B takes full advantage of the facility with which functionalized 5-cyclodecen-l-one systems can be constructed via anionic oxy-Cope rearrangements of readily available divinylcyclohexanols.5 7 In addition, both syntheses of periplanone B masterfully use the conformational preferences of cyclo-decanoid frameworks to control the stereo- and regiochemical course of reactions carried out on the periphery of such ring systems.10... 

Group Migration Reactions.- Direct irradiation of cyclooctene (la) in pentane brings about CIS -trans isomerization as well as the formation of the bicyclic products (2a) and (3). These are formed via the carbene intermediates (4) and (5). The latter carbene (5) also affords methylenecycloheptene. cis -trans -Isomerization also arises with the cycloalkenes (lb) and (Ic). Product (2b) is formed from cyclodecene (lb) and... 

Room temperature rate constants and Arrhenius parameters for the gas-phase reactions of ozone with cw-2-butene, 2-methyl-2-butene and a number of cycloalkenes are shown in Table 1 together with the literature values. The rate coefficients for cw-2-butene and 2-methyl-2-butene are in excellent agreement with the data evaluation of Atkinson and Carter [3]. The reported room temperature rate constants for the reaction of ozone with cyclopentene and cyclohexene show a considerable degree of scatter. The present results for cyclopentene provide support for the recent determinations by Bennett et al [24], Nolting et al [25], and Green and Atkinson [21], while the value for cycloheptene is slightly lower than the reported values [20] and [25]. No previous kinetic studies have been carried out on the reactions of O3 with cw-cyclooctene and cw-cyclodecene. 

A ten-membered ring derivative was prepared by the reaction of allene 7.91 with N-chlorosulfonyl isocyanate to give -lactam 7.92.51 Removal of the sulfonyl group and acid hydrolysis gave 10-amino-l-cyclodecene-l-carboxylic acid, 7.93. Similar... 

A new cage molecule [263(1,4)3(1,3,5)2-bicyclophanehexaene (446) has result-ed from a multi-stage reaction sequence, and the [10]paracyclophanes (447) from a mixture of two inside-inside [10.2.2]hexadecadienes (448) and (449) obtained by cycloaddition of methyl propiolate with cyclodecene. 

The reaction of a substituted ylide with an aldehyde usually leads to dominant or exclusive formation of the trans-oxiran. Thus, tetra-methylenesulphoniumbenzylides reacted with substituted benzaldehydes to afford only the frans-oxirans (57)." Townsend and Sharpless" demonstrated that the cycle of reactions from trans-cyclodecene oxide to the hydroxysul-phonium salt (58) and back occurred with less than 3% crossover to the... 

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