Olefins alicyclic

Alder et al treated cyclopentene and cyclohexene with MA in benzene solution at 250°C. The products obtained were 2-cyclopentenylsuccinic anhydride 24 and 2-cyclohexenylsuccinic anhydride 25. The inherent symmetry of starting olefins prevented the observation of the double-bond migration initially. Agami et obtained only 3% yield of adduct 24 and 30% of 25 on heating a toluene solution of the reactants at 190°C for 24 h. The order of reactivity of alicyclic olefins as compared with aliphatic olefins is given below. Reactions of this type are not limited to carbocyclic compounds. 

Laporterie et obtained a 58% yield of product 27 from 1,1-dimethyl-l-silacyclo pentene-3 26 and MA at 150°C, thus suggesting the generality of the reactions. When the double bond in alicyclic olefins is not conjugated 

Alder and Dortmann also reported the reaction of 1-methylcy-clohexene 30 with MA and obtained a diastereomeric mixture of 31. An 

Alicyclic rings containing unconjugated diene and triene units have been examined. Alder and Munz obtained the expected bis-MA adduct 35, from 1,4-cyclohexadiene 34. 

Stumpf etal reacted MA with cis, trans, // (2 5-l,5,9-cyclododecatriene 36 in the presence of phenothiazine or thiamine as an inhibitor. The product cis, trans, /raAi5-2,5,9-cyclododecatrienylsuccinic anhydride 37 was obtained in yields as high as 76%. MA could be substituted in this reaction with maleic 

---

Azibenzil, in the presence of 02 and Pd(OAc)2 or PdCl2 2 PhCN, forms an intermediate metal-oxygen-carbene complex which is able to epoxidize aliphatic and alicyclic olefins azibenzil itself is transformed into benzil75). 

The hydroboration amination sequence in diglyme is a general procedure for the conversion of olefins to primary amines without rearrangement and with predictable stereochemistry.5 An alternative procedure, using tetrahydrofuran as solvent and either hydroxylamine-O-sulfonic acid or chloramine, is applicable with terminal olefins and relatively unhindered internal and alicyclic olefins.6 O-Mesitylenesulfonylhydroxylamine also gave desired amines in comparable yield.7 Alternative procedures for the hydroboration of olefins use commercially available solutions of di-borane in tetrahydrofuran8 or dimethylsulfide.9... 

In the case of aliphatic or alicyclic olefins only norbornene hydroformylation with Rh/(—VDIOP does not fit into the picture. The contrasting results between (Z)-2-butene and bicyclo[2.2.2]oct-2-ene obtained with Co/(—)-DIOP and Ru/ (—)-DIOP catalytic systems have been attributed to extensive isomerization of (Z)-2-butene to (E)-2-butene during hydroformylation16>. In the case of the only phenyl-substituted substrate investigated, the prediction of the unsaturated carbon atom preferentially formylated is not correct. This type of exceptions is found also for styrene, as it will be discussed later. 

The following regularities have been observed in allylic bromination of mono-, di-, and alicyclic olefins by NBS.352,354 In absence of activation methylene groups are brominated more easily than methyl groups, and these somewhat more easily than methine groups. Straight-chain and branched-chain olefins are brominated by NBS only once at each allyl position two bromine... 

The reactions of alicyclic olefins with Se02 have been extensively investigated. Heating cyclopentene with Se02 in acetic anhydride (acylating oxidation) oxidizes it to much monoacetoxy- and a little diacetoxy-cyclopentene but in a bomb tube at 90-100° much diacetate and little monoacetate are obtained.225 Thus the second methylene group next to the double bond is more or less attacked according to the reaction conditions. 

Phenanthraquinone (467) has been added photochemically to both alicyclic and bicyclic olefins. The nature of the products obtained is dependent upon the structure of the olefin. Thus with the bicyclic olefins (468—470) the keto-oxetans (471—473) are formed exclusively. The use of alicyclic olefins (474) as the addend... 

A mixture of 3,6-diphenyl-si/m-tetrazine, diphenylacetylene, and toluene refluxed 3 days 3,4,5,6-tetraphenylpyridazine. Y 86%.—A variety of unsatd. compounds, inch aliphatic and alicyclic olefins, styrenes, acetylenes, butadienes, and allene give the above reaction. 3,6-Bis(polyfluoroalkyl)-sym-tetrazines react with particular ease. F. e., also from ethylene derivatives via 1,4-dihydropyridazines, s. R. A. Garboni and R. V. Lindsey, Jr., Am. Soc. 81, 4342 (1959). 

---