7213-64-1

Upstream product

• 7605-04-1 exo-2-benzonorbornenyl chloride 
• 67-63-0 isopropyl alcohol 
• 31351-14-1 exo-2-benzonorbornenyl mesylate 
• 75-65-0 tert-butyl alcohol 
• 4453-90-1 1,4-dihydro-1,4-methanonaphthalene 
• 67-56-1 methanol 
• 70332-88-6 2,3-diaza-7,8-benzotricyclo<4.3.0.0^4,9>nona-2,7-diene 
• 4453-90-1 1,4-dihydro-1,4-methanonaphthalene 

Downstream Products

• 19770-38-8 spiro(cyclopropane-1,1'-<1H>-indene) 
• 4453-90-1 1,4-dihydro-1,4-methanonaphthalene 
• 24459-98-1 2-vinylindene 
• 80452-17-1 3a,7b-Dihydro-1H-cyclopenta[3,4]cyclobuta[1,2]benzene 
• 18511-42-7 (2aS,7aR)-7,7a-Dihydro-2aH-cyclobuta[a]indene 
• 3463-79-4 benzonorcaradiene 
• 74420-42-1 2-Phenyl-6,10b-dihydro-4H-2,3a,10c-triaza-cyclopenta[c]fluorene-1,3-dione 
• 91-20-3 naphthalene 
• 264-08-4 benzocycloheptatrien 
• 3463-79-4 2,3-benzonorcaradiene 
• 90-12-0 1-Methylnaphthalene 
• 4453-90-1 1,4-dihydro-1,4-methanonaphthalene 
• 78812-93-8 1-methyl-2-methoxy-1,4-dihydronaphthalene 

Relevant academic research and scientific papers

UNTERSUCHUNGEN ZUM THERMISCHEN UND PHOTOCHEMISCHEN VERHALTEN VON 8,9-DIAZA-4,5-BENZOTRICYCLO3,7>OCTA-4,8-DIEN

Die direkte Photolyse der Titelverbindung 1 verlaeuft erwartungsgemaess unter Stickstoffabspaltung zu 6.Dagegen fuehrt ihre Thermolyse und ihre sensibilisierte Bestrahlung zu den ueberraschenden Produkten 4 bzw. 8, deren spektroskopische Charakterisierung und moegliche Bildungsmechanismen diskutiert werden.

LIGHT-MEDIATED TRANSFORMATIONS OF OLEFINS INTO ALCOHOLS: REACTIONS OF HYDROXYL RADICALS WITH CYCLOALKENES

Reactions of hydroxyl radicals, generated by photodecomposition of hydrogen peroxide in acetonitrile, with a wide variety of cycloalkenes have been examined.The results show that the major reaction is the addition of hydroxyl radicals to the less substituted end of the double bond, furnishing the secondary alcohols.The reactivity pattern and the observed regio- and stereoselectivity clearly reveal that the steric parameters associated with the substrates play a dominant role in directing the addition reactions.More importantly, this study led to the development of a new methodology for the facile conversions of olefins essentially into secondary alcohols, and includes a few examples which demonstrate the potential of the method.

Photolytic Cleavage of Remote Functional Groups in Polyfunctional Molecules. Photolysis of exo- and endo-2-Benzonorbornenyl Chlorides and Methanesulfonates

The photochemistry and photophysics of the title compounds are reported.The exo chloride exhibits a facile cleavage of the C - Cl bond upon excitation of the aryl chromophore (eq 1 - 3).The reaction has a rate > 700-fold larger than that observed with the endo isomer, derives from the singlet excited state, and leads to the formation of "hot" carbocations as well as free radicals.The exo mesylate shows similar characteristics (eq 4).A mechanism (Scheme II) is suggested which incorporates both heterolytic fission as well as sequential homolytic fission (to a polarized radical pair), followed by electron transfer to form an ion pair.The stereoelectronically controlled activation of the C - Cl and C - OMs moieties is explaned by a correlation diagram (Figure 5) which depicts the ?,?* state as correlating with the diradical product state through an avoided crossing with the C - X ?,?* state.Calculations indicate that this avoided crossing is considerably larger (and the barrier to reaction therefore considerably smaller) when the C - X unit in the 2-benzonorbornenyl series is exo.

PHOTOCHEMISTRY OF BENZOTRICYCLO2,7>HEPTENE: SINGLET EXCITED STATE REACTIONS DERIVED FROM CYCLOPROPANE RING CLEAVAGE

Direct irradiation of the title hydrocarbon in cyclohexane affords 2-vinylindene and benzonorcaradiene as major primary photoproducts.Deuterium labeling is used to determine reaction mechanisms.

Generation of 2,3-Benzobicyclo<2.2.1)hept-2-ene-5,7-diyl Diradicals via Denitrogenation of Appropriate Azoalkanes and Their Mechanistic Implications in the Di-?-methane Rearrangement of Benzonorbornadienes

The azoalkanes 16a-c, prepared from the bicycloalkadienes 5a-c via dipolar cycloaddition with 4-methyl-1,2,4-triazoline-3,5-dione (MTAD) and subsequent oxidative hydrolysis, were submitted to thermal and direct and ketone-sensitized photochemical denitrogenation, with the intention of entering the diradical manifold postulated for the di-?-methane rearrangement.It is shown that in each case denitrogenation leads to the expected 2,3-benzobicyclohept-2-ene-5,7-diyl diradical 7.Diradical 7 mostly cyclizes into the corresponding tricycloalkene 8, and only a very small fraction (5percent) suffers retro-di-?-methane rearrangement into the bicycloalkadiene 5 via the cyclopropyl dicarbinyl radical 6.Stabilizing substituents such as benzhydryl and spirocyclopropyl groups in a position α to the rearranging radical site in 7 discourage retro-di-?-methane reaction.