Cyclododecene derivatives

S)-( )-l,2-Dimethylcycloundecene (27b) was also prepared by a similar method and was found to be optically stable, but preparation of the cyclododecene derivative 27c in an optically active modification was unsuccessful. 

Trichloro-l,2,4-triazine reacts with cycloheptene and cyclododecene to give 2,6-dichloropyridine derivatives (e.g., 10) via an intermediate dihydropyridine formed by Diels-Alder addition and loss of Nj <96JCS(P1)519>. 

Some novel bicyclic pyrylium salts arise when a dicarboxylic acid derivative is used. For example, although decanedioyl chloride did not diacylate isobutene, possibly because of strain inherent in the expected product, 1,12-dodecanedioyl chloride gave a very low yield of the pyrylium salt (658) (62T1079). A dilute solution of the reactants in nitromethane was used in order to favour the intramolecular reaction. In a similar vein, a macrocyclic alkene, such as cyclododecene, undergoes diacylation to the bicyclic salt (659) (68TL4643), whilst... 

Treatment of cm- and fraws-cycloundeoene and cyclododecene with perform acid likewise gives complex mixtures of products derivable by 1 abnormal formolysis of the corresponding epoxides.1401-14o By contrast, mothylenecyclooctane oxide yields no diole on treatment with formic acid and subsequent alkaline hydrolysis, the main product being formykycJooctame.1 2 ... 

TABLE 1. Percent incorporation of the Step 3 product and derivative into cyclododecene at 170°C. 

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,... 

There is strong evidence that the ring-opening polymerization of cycloolefins provides a convenient approach for the synthesis of poiyaikenamers with high trans or cis content [2, 3]. Except for polyhexen-amer, poiyaikenamers of predominantly trans structure have been obtained from cyclobutene to cyclododecene, and poiyaikenamers of predominantly cis structure from cyclobutene to cyclooctene. In addition, poiyaikenamers of high steric purity have been obtained from norbomene and its derivatives or from other bicyclic and polycyclic olefins. 

AICI3 can also catalyze the aliphatic Friedel-Crafts type reaction of propylene oxide with cyclic/acyclic alkenes [86]. As shown in Scheme 6.67, AICI3 promoted the reaction of propylene oxide with cyclododecene to proceed at — 30°C to give aldehyde (86) in 25% yield, furan derivatives (87) in 18% yield, and an F/2 mixture of unsaturated alcohols (88) in 24% yield. 

Benzene-sensitized photoisomerization of (Z)-cyclododecene (34Z) affords 34E in a 39 61 E/Z ratio at the photostationary state. Other triplet sensitizers such as benzophenone, acetophenone, and acetone, as well as copper salts, can also be used. Sensitized photoisomerization of 1,5,9-cyclododecatriene has also been studied. Direct irradiation of (E)-3-methylenecyclodecene (55E) affords 55Z, which further pho-toisomerizes to yield 56, 57, and 58. Triphenylene sensitization of 55E affords a photostationary-state mixture of 55E and 55Z in a ratio of 94 6. Doubly-bridged ethylene derivatives 59Z (n = 8, 10), i.e., (Z)-bicyclo[8.8.0]octadec-l(10)-ene and (Z)-bicyclo[10.8.0]eicos-l(12)-ene, isomerize to the (E)-iso-mers upon xylene-sensitized or direct irradiation. An E/Z ratio of 0.42 is given upon sensitization of the latter, while much higher E/Z ratios of 9 and 2 are attained upon direct irradiation at 254 nm of (Z)-bicyclooctadecene and (Z)-bicycloeicosene, respectively. ... 

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