Cw-3-Octen

This catalyst (1) is a selective catalyst for hydrogenation of 4-octyne to cw-4-octene (90% yield). If the product is left in contact with 1, it isomerizes to the trans-isomer. Since monoalkenes are hydrogenated slowly with this catalyst, cyclo-octene can be obtained from either 1,3- or 1,5-cyclooctadiene. Of more interest, benzene can be hydrogenated to cyclohexane (83% yield). One drawback is that the catalyst loses about 90% of its activity after one cycle. 

Reaction with alkenes. C6H5N3 and AICI3 (1 1.1) react with cyclohexene in CH2CI2 to give after neutralization 1 and 2 in about equal amounts. A similar reaction is observed with cyclopentene. However, in the reaction with cw-cyclo-octene, the aziridine 3 is isolated in 47% yield. These reactions probably involve an aziridinium-AlCl3 complex. 

This analysis suggests that in the double cross experiment the product of [Ci4]/[Ci2]—called —and [Ci4]/[Cig]—called rz—should be 4, and Fig. 1 shows that experimentally this is approximately true. A more accurate measure of this product at zero time can be achieved by multiplying ri and rj at the different times and extrapolating to zero time, as in Fig. 3. In a series of four such experiments, three using cyclooc-tene, c/s-2-butene, and cw-4-octene, and one using cyclooctene, trans-2-butene, and tra j-4-octene, the average value of ri x /-z at zero time was measured as 4.05 0.05 (66). 

The relative rates of lithium 2-aminoethylamide-catalyzed isomerization of /r Azs-4-octene, c/ s-4-octene, and 1-octene in ethylene diamine solutions at 25°C are 1, 3.5, and 90. Cw-2-octene was the major product from 1-octene, while trans- and m-3-octene were the principal initial products from cis- and /rtzAZ5-4-octene, respectively. 

The epoxidation of alkenes such as styrene, cw-cyclo-octene, tru 5-hept-2-ene, and norbornene with iodosobenzene catalyzed by a water-soluble diaquo-... 

Startg. m. hydrogenated with Lindlar catalyst in hexane at atmospheric pressure until the calculated volume of H2 is absorbed, the catalyst removed by filtration, the solvent evaporated, the residue dissolved in dioxane, added dropwise to a stirred suspension of LiAlH4 in dioxane, refluxed, and the product isolated after 38 hrs. tra j-4-octen-l-ol. Y 65%. F. e. s. A. Claesson, Acta Chem. Scand. B 28, 993 (1974) ethyl cw-(3,4-methylenedioxy)cinnamate by Lindlar hydrogenation s. B. B. Lurik, A. P. Golubova, and Y. P. Volkov, Khim.-Farm. Zh. 9 (6), 15 (1975) C. A. 83, 178 885... 

Other carbonyls cis-4-heptenal, trans,cw-2,6-nonadienal, 2,5-octadienal, 2,4,6-nonatrienal, 2,4,7-decatrienal, l-penten-3-one, l-octen-3-one,tra/ts,cw-3,5-octadien-3-one,3,5-undecadien-3-one, 1-octen-... 

In the same year the biotransformation of these monoterpenes by B. cinerea in model solutions was described by another group [41]. Although the major metabolites found were co-hydroxylation compounds, it is important to note that these authors only identified the -isomers in the extracts and that some new compounds were detected that were not described by the previous group, Fig. (9). Geraniol (20) was mainly transformed to (2 ,5 )-3,7-dimethyl-2,5-octadiene-l,7-diol (53), ( )-3,7-dimethyl-2,7-octadiene-l,6-diol (54) and (2 ,6 )-2,6-dimethyl-2,6-octadiene-1,8-diol (43), nerol (14) to (2Z,5 )-3,7-dimethyl-2,5-octadiene-1,7-diol (55), (Z)-3,7-dimethyl-2,7-octadiene-l,6-diol (56), and (2E,6Z) 2,6-dimethyl-2,6-octadiene-1,8-diol (47). Furthermore a cyclisation product (57) was formed which was not previously described. Finally citronellol (4) was converted to trans- (60) and cw-rose oxide (61) (a cyclisation product not identified by the other group), ( )-3,7-dimethyl-5-octene-l,7-diol (58), 3,7-dimethyl-7-octene-l,6-diol (59) and ( )-2,6-dimethyl-2-octene-1,8-diol (34). 

By using aroma extract dilution analysis (AEDA) of the volatile fractions of fresh and stored butter oil, Widder et al. (29) determined diacetyl, butanoic acid, 8-octalactone, skatole, 8-decalactone, cw-6-dodeceno-8-decalactone, l-octen-3-one, and l-hexen-3-one as potent contributors to the flavor of butter oil. The concentration of l-octen-3-one, trani-2-nonenal, and i-l,5-octadien-3-one increased during the storage of the butter oil at room temperature. 

Table 5 shows the sensory evaluation by Schieberle et al. (30) of the different kinds of butter, namely, Irish sour cream (ISC), cultured butter (CB), sour cream (SC), sweet cream (SwC), and farmer sour cream (ESC). It revealed ISC butter and ESC butter with the highest overall odor intensities. Table 5 shows that 19 odor-active compounds were detected by aroma extract dilution analysis (AEDA) in a distillate of the ISC butter. The highest flavor dilution (ED) factors have been found for 5-decalactone, skatole, i-6-dodeceno-y-lactone, and diacetyl followed by trany-2-nonenal, cw,c -3,6-nonadienal, c/i-2-nonenal, and l-octen-3-one. 

Under the same conditions, exo-8-bromobicyclo[5.1 0]octene-2 (5a) is converted into an approximately 1 1 mixture of two isomeric methoxycyclooctadienes, shown to be 3-methoxy-cw, mmr-cyclooctadiene-l, 4(6a) and 5-methoxy-rii, ram-cyclooctadiene-1,3 (7a).J A similar result is obtained with 8,8-dibromobicyclo[5.1.0i]octene-2 (5b), which... 

Rhodium (I)-catalyzed cyclizations of 6-octen-l-als bearing a (4R,6R)-di-methyl-l,3-dioxane group at different positions do not lead to hydroacylation ( 7.S.3) products, but lead instead to the products of formal ene reaction reactions [1244]. 3-Substituted aldehyde 6.79 (R,R = 4R,6R-1,3-dioxolanyl) gives trcms-cyclohexanols with a high selectivity (Figure 6.68), while 2-substituted analogs cyclize to cw-cyclohexanols in lower selectivities. 

Fio. 1. Plot of product composition as a function of extent of reaction for the reaction at 0°C of cyclooctene (5.44 mmoles), cw-2-butene (2.64 mmoles), and cis-4-octene (3.51 mmoles) with Mo[(CeH5)3P]2Cl2(NO)j (0.038 mmole) and (CHa)3Al2Cl3 (0.23 mmole) in chlorobenzene (2 ml). n-Heptane (352 mg) was the internal standard for the gas chromatographic analysis. Reprinted with permission from Katz and McGinnis (66) copyright by the American Chemical Society. The ordinate is labeled at the left for the solid curve and at the right for the dashed curve. 

Fig. 12.1 Aggregation pheromones of (a) Ips paraconfusus, three male-produced synergistic components - (+ )2-methyl-6-methylene-2,7-octadien-4-ol (ipsdienol) (-)2-methyl-6-methylene-7-octen-4-ol (ipsenol) and cw-verbenol. (b) Dendroctonus brevicomisj three attractive components, cxo-7-ethyl-5-methyl-6,8-dioxabicyclo-[3.2.1] octane (cxo-brevicomin) from the female l,5-dimethyl-6,8-dioxabicyclo-[3.2.1] octane (frontalin) from the male and myrcene released from the host tree. Verbenone and trans-verbenol, released after a male locates the female, interrupts response to the attractant blend.

Other oxymercuration studies include those on the monoepoxide of cw,c/5-cyclo-octa-l, 5-diene, with neighbouring group participation of the oxiran oxygen, bicyclo[2,2,2]octene, cis- and rranj -cyclo-octenes and cyclononenes, 1,3-diphenylpropenones, and the bicyclic systems (492) and (493). The kinetics of methoxymercuration of substituted cinnamic acids and many aliphatic olefins have been measured. 

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