Bicyclo dodecanes

Dodecahydro-5a,9-diaza-cyclohe- rv xn 4-Thia-bicyclo[5.4.1]dodecane... 

Zur Demethylierung von quartaren Trimethylammonium-Salzen laBt sich auch 1,4-Diaza-bicyclo[2.2.2]octan in siedendem Ethanol oder Dimethylformamid verwenden. Aus den quartaren Ammonium-Salzen erhalt man auf diese Weise z. B. N,N-Dimethyl-anilin (92%) und 1-Dimethylamino-dodecan (68 %)2 ... 

Among bicyclic cyclohex-2-enones, the formation of tricyclo[4.4.2.01,6]dodecane-2,7-dione from bicyclo[4.4.0]dec-l(6)-ene-2,7-dione and ethene proceeds in 95% yield,101 and that of 8-mcthyl-tricyclo[6.4.0.01,4]dodecan-5-ones from 6-methylbicyclo[4.4.0]dec-l(2)-en-3-one and ethene in 77% yield,102 respectively. Steroids containing cyclohex-2-enone subunits,103 e.g. 17/ -acetoxy-5a-androst-1 -en-3-one,104 often afford /raw-fused cycloadducts with alkenes. When such reactions are performed on silica gel, complete reversal of stereochemistry to that observed in solution can occur.105... 

Interestingly, Lewis acid catalyzed rearrangement of 6-methyltricyclo[8.2.0.0, 6]dodecan-9-one gave the spiroannulated triquinane ketone (l/ , 5/ )-l-methylspiro[bicyclo[3.3.0]octane-2,lf-cyclopentane]-6-one as the major product (70%).85... 

Perfluorinations of cyclooctane, -decane, -dodecane and -octadecane with cobalt(III) fluoride at 130-300°C give mainly rearranged products.47 For example, cyclooctane at 200°C gives perfluoro(bicyclo[3.3.0]octane)(2%), perfluoro bicyclo[3.3.0]oct-1(5)-ene (8 %), perfluo-ro(ethylcyclohexane) (26%), perfluoro(methylcycloheptane) (33%), and perfluorocyclooctane (31 %). A small amount of 177-pentadecafluorocyclooctane is also isolated. 

Figure 11. Molecules that are chiral in the excited state only, (a) (lS,3R,7R,9S)-tricyclo-[7.3.0.03 7]dodecane-5,11 -dione in the electronic ground state, (RS), and in locally excited n ->Jt states, (.RS ) and (RS).5S (b) 3-(1nJt )-(lS,6R)-bicyclo[4.4.0.]decane-3,8-dione prepared by thermal decomposition of enantiopure 1,2-dioxetanes. 56...

Intramolecular Diels-Alder reactions. The Lewis acid-catalyzed intramolecular Diels-Alder reaction is useful for construction of cw-fused bicyclo[6.4.0]dodecanes. Thus... 

Bicyclo[8.2.0 dodecan 1-Hydroxy-12-methylen- Vl/la, 2, 782 Bicyclo 5.1.0 octan 3-Ethyliden-2-hydroxy-1,5,5-trimethyl- E17b, 1730 (2-Oxo - 2-H/2-OH) Cyclohexan... 

TRIMETHYL-o-(2-HYDROXY-3-(l-PYRROUDINYL)PROPYL)OXIME (1R,4R)-BICYCLO(2.2.1)HEPTAN-2-ONE see TLT763 TRIMETHYL-e-LACTONE (mixed isomers) see TLYOOO 4,11,11-TRIMETHYL-8-METHYLENE-5-OXATRICYCLO(8.2.0.0(4,6))DODECANE see CCNIOO TRIMETHYLNITROSOHARNSTOFF (GERMAN) see TLU750... 

Ether cleavage.1 Treatment of the keto ether (1,9-oxatricyclo[4.3.3.0]dodecane-3-one) with acetic anhydride and pyridine hydrochloride (reflux 5.5 hr.) yields the diacetate (2, 4-acctoxy-l-(2-acetoxyethyl)bicyclo[4.3.0]nonadiene-4,6) in 93% yield. 

The cis or trans configuration of the annulated system normally is not changed in nucleophilic substitution. Such a cisitrans isomerization, however, has been observed in a few nucleophilic substitution reactions of various bicyclo[9.1.0]dodecane derivatives. ... 

Bicyclic cyclopropanone aminals with a succinimido moiety as iV-substituent allow displacement of succinimide by hydrogen by heating with triethylammonium formate giving 1. A ratio 3 1 of formate to aminal gave the best results. This reduction could not be applied to bicy-clo[3,1.0]hexane or bicyclo[9.1.0]dodecane systems due to ring-opening reactions under these conditions. ... 

Bis-[diisopropylamino]-methylseleno-3063,3112 C H330Si Bicyclo 9.1,0 dodecane 11-Methyl-1-trimethylsilyloxy- 23S8 Bicyclo[4.1, OJheptane 7-(l-Hydroxy-hexyl)-7-trimelhylsilyl-1371, 1496... 

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