75503-82-1

Upstream product

• 95-09-0 5-chloromethyl-2-norbornene 
• 16745-72-5 p-Toluolsulfonsaeure-<6exo-methyl-2exo-norbornyl>ester 
• 42070-73-5 Toluene-4-sulfonic acid (1S,2R,4S)-1-bicyclo[2.2.1]hept-5-en-2-ylmethyl ester 
• 86646-41-5 (bicyclo[2.2.1]hept-5-en-2-yl)methyl methanesulfonate 
• 5453-80-5 5-Norbornene-2-carboxaldehyde 
• 95-12-5 5-hydroxymethyl-2-norbornene 
• 542-92-7 cyclopenta-1,3-diene 
• 106-95-6 allyl bromide 

Downstream Products

• 21681-47-0 8-methyltetracyclo<4.4.1^2,5.1^7,10.0^1,6>dodec-3-ene 
• 21681-47-0 8-methyltetracyclo<4.4.1^2,5.1^7,10.0^1,6>dodec-3-ene 
• 74-85-1 ethene 
• 542-92-7 cyclopenta-1,3-diene 

Relevant academic research and scientific papers

Thermal rearrangement of 7-methylbicyclo[3.2.0]hept-2-ene: An experimental probe of the extent of orbital symmetry control in the [1,3] sigmatropic rearrangement

The gas-phase thermal rearrangement of exo-7-methylbicyclo[3.2.0]hept-2-ene yields almost exclusively 5-methylnorbornene products. Inversion (i) of configuration dominates this [1,3] sigmatropic shift although some retention (r) is also observed. Because the [1,3] migration can only occur suprafacially (s) in this geometrically constrained system, the si/sr ratio of 7 observed for the migration of C7 in exo-7-methylbicyclo[3.2.0]hept-2-ene indicates that the orbital symmetry rules are somewhat permissive for the [1,3] sigmatropic migration of carbon.

Substituent Effects on 1H Chemical Shifts I-Complete 1H Chemical Shift Assignments of Methyl-Substituted Cyclic Systems

1H chemical shift assignments are presented for 2-methyladamantane, 2-methylnorbornane (endo and exo) and 2-methylnorbornene (endo and exo).Resonance assignment was achieved using a variety of 1D and 2D homo- and heteronuclear (1H-13C)experiments.The methyl group-induced substituent chemical shift (SCS) is derived and the SCS of protons vicinal to this group is discussed.KEY WORDS Norbornanes Norbornenes Adamantanes 1H NMR Substituent chemical shifts

Rearrangement and Cleavage of the Grignard Reagent from 5-(Chloromethyl)norbornene

The Grignard reagents 1-Mg and 2-Mg from endo- and exo-5-(chloromethyl)norbornene rearrange with ring cleavage on heating to yield an allylcyclopentenyl organomagnesium compound (3-Mg).This, in turn, undergoes competitively a variety of reactions, including an alternative cyclization to a bicyclooctene organomagnesium (4-Mg) and formal loss of hydrogen or propene to produce allylcyclopentadienyl- (5-Mg) and cyclopentadienylmagnesium compounds.Endo and exo isomers 1-Mg and 2-Mg rearrange at comparable rates and are partially interconverted, probably via their cleavage and recyclization.Mechanistic possibilities are discussed.

Chiroptical Studies of Bicyclic α-Diketones

On the basis of crystallographic analysis it was established that the α-diketone chromophore in bicycloheptane-2,3-diones is planar.C. d. studies of some bicyclic compounds show that the c. d. sign for long-wavelength transition is governed by the octant rule with signs opposite to that known for ketones.The vicinal effect of substituents with the same location in space strongly influences the magnitude of the Cotton effect, but not its sign.

Die Hydrolyse von 6exo-substituierten 2exo- und 2endo-Norbornylestern der p-Toluolsulfonsaeure

Hydrolysis of the 6exo-substituted 2exo- and 2endo-norbornyl p-toluenesulfonates 1b-l and 2b-l, respectively, in 70percent dioxane led to different amounts of the following products: Unrearranged 2exo-norbornanols 3 and norbornenes 5, accompained in somes cases by small amounts of the rearranged Rendo-epimers 4 and 6 and by nortricyclenes 7.When the 6exo-substituent was a nucleophile group as in 1e-l and 2e-l, various amounts of tricyclic products were also formed by endo-cyclozation.These results show that the 2exo- and 2endo-esters 1 and 2, respectively, react by way of different intermediates.In cases where the 6exo-substituent was an n-electron donor, as in 1m-r and 2m-r, quantitative fragmentation to (3-cyclopentenyl)acetaldehyde (13) occurred.