2- Azabicyclo octane

Cycloadditions and Rearrangements. The addition of 2-oxyallyl cations to furan provides a route to oxabicyclo[3,2,l]octanes complementary to the cycloaddition of cyclopropanones to furan. Careful experimental studies have led to yields of preparative importance both with furan and with cyclopentadiene. Following the route to azabicyclo-octanes, dipolar addition to the pyrylium betaine (99) affords oxa-analogues (Scheme 23). Also reported are the addition of fiiran to 1-cyanonaphthalene, the formation of various cycloadducts of tropone and tropolone (Scheme 24), and the phototransformations of (100) (Scheme 25) and (101) (Scheme 26). Thermal addition gives (102) from (103) and similarly other 8-oxabicyclo-octanes are prepared from acyclic precursors. ... 

Monochloramine is also used in organic synthesis for preparation of amines, substituted hydrazines, etc. For example, reaction of NH2CI with 3-azabicyclo [3.3.0]octane [5661-03-0] yields A/-amino-3-azabicyclo[3.3.0]octane [54528-00-6] a pharmaceutical intermediate (38). 

Quinuclidines — see also l-Azabicyclo[2.2.2]octanes electron diffraction, 2, 117 microwave spectrum, 2, 107 NMR, 2, 121... 

Quinuclidine (l-azabicyclo[2.2.2]octane) 10.95. Crystd from diethyl ether. 

Heating 3,4-bis(phenylsulfonyl)furoxan with a solution of sodium butoxide in butanol followed by reduction with trimethyl phosphite gives furazan 281 (Scheme 183). Compound 281 was converted into dialkoxy derivative 282 with the lithium salt of ( )-l-azabicyclo[2.2.2]octan-3-ol in 33% overall yield (96W012711, 97EUP773021, 98JMC379). 

Therapeutic Function Miotic, cholinomimetic Chemical Name 1-Azabicyclo(2.2.2] octan-3-ol acetate Common Name 3-Quinuclidlnol Acetate... 

Chemical Name 3-(Diphenylmethoxy)-8-methyl-8-azabicyclo[3.2.1 ] octane methanesul-fonate... 

Benziloyloxy-1-azabicyclo[2.2.2] octane methobromide was prepared by adding 20 cc of a 30% solution of methyl bromide in ether to a solution of 2.5 g of 3-benziloyloxy-1-azabicyclo[2.2.2] octane in 20 cc of chloroform. After standing for 3 hours at room temperature and 15 hours at -i-5°C, a crystalline precipitate had formed. This was filtered off and recrystallized from a mixture of methanol, acetone, and ether prisms melting at 240° to 241°C. 

To a suspension containing 4.86 parts of 4-methylbenzenesulfonyl urethane (MP 80° to 82°C) and 36 parts of anhydrous toluene there are rapidly added 2.5 parts of N-amino-3-azabicyclo(3.3.0)octane (BP/18 mm = 86°C). The reaction mixture is heated under reflux for 1 hour. The resulting ciear solution crystallizes on cooling. The crystals are filtered, washed with 2 parts of toluene, then recrystallized from anhydrous ethanol. There are obtained 3.8 parts of the desired product, MP 180° to 182°C. 

A new class of bicyclic oxalactam, 8-oxa-6-azabicyclo[3.2.1]octan-7-one 61 was synthesized by intramolecular cyclization of 3,4-dihydro-2H-pyran- 2-carboxamide 62 using p-toluenesulfonic acid as a catalyst in an equivalent mixture of DMF and benzene at 100 °C for 4 hours57, S8. Corresponding conversion of 3-cyclohexane carboxamide 63 to bicyclic lactam 64 has never been accomplished54. ... 

Table 8. Bulk polymerization of 8-oxa-6-azabicyclo[3.2.1 ]octan-7-one 61S8 ...

To generate molecular libraries, a series of 5-oxo-2-azabicyclo[2.2.2]octane and triaza analogs were prepared via a stereospecific Diels-Alder reaction by reacting Wang-resin-bound diene 35 with a variety of dienophiles [28]. After removing the solid support with a strong acid, adducts 36 were isolated examples of reactions that have furnished the best yields are reported in Scheme 4.6. 

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