Patai S., Rappoport Z. 2000 The chemistry of functional groups. The chemistry of dienes and polyenes. V. 2 / 0481 544

O

N

264

N

N

Ph

O

(144)

(266)

9-Chlorocyclononatetraene 267 rapidly rearranges in liquid sulfur dioxide to 1-chloro- 8,9-dihydroindene 268, which forms the cycloadduct 269 with the triazolinedione 264 (equation 145)137. The vinylimidazole 270 affords the purine analogue 271 (equation 146)138.

A selection of the many applications of cycloaddition with the triazolinedione 264 follows.

The preparation of an optically active triazolinedione, compound 274, is shown in equation 147. Commercially available ( )-˛-methylbenzylamine hydrochloride is converted into the hydrazine derivative 272 by treatment with phosgene, followed by H2NNHCO2Et. Thermal cyclization gives the urazole 273, which is dehydrogenated to the product by means of dinitrogen tetroxide. The reagent has been used for the optical resolution of various 1,3-dienes. ˛-Phellandrene 275, for instance, forms the cycloadduct 276, which is separated into its diastereomeric components chromatographically. The chiral diene is then regenerated by alkaline hydrolysis, followed by treatment with manganese

Me C8H17

Me C8H17

Me

Me

AcO

(294)

XI. FORMATION OF FIVE-MEMBERED RINGS

The action of methanolic sodium methoxide on hydroxylamine O-sulfonic acid generates nitrene NH, which adds to butadiene in situ to give a low yield of 1H-pyrroline 295 (equation 154)146.

−2 MeOH

(295)

The formation of 1-chlorophospholene chlorides, e.g. 296, by the action of dichlorophosphines on 1,3-dienes (equation 155) was first reported by McCormack in 1953147.

Butadiene, isoprene, chloroprene and 2,3-dimethyl-1,3-butadiene add phosphorus trihalides to form 3-phospholene 1,1,1-dihalides, e.g. 297 from isoprene and phosphorus

Isoprene, 2,3-dimethylbuta-1,3-diene and other dienes (but not butadiene itself) readily furnish analogous 2,5-dihydroselenophene 1,1-dioxides, e.g. 306, on treatment with selenious acid in chloroform at room temperature (equation 161)153.

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