2294-41-9

Upstream product

• 156-59-2 cis-1,2-Dichloroethylene 
• 542-92-7 cyclopenta-1,3-diene 
• 70887-53-5 1-Chlortetracyclo<3.2.0.0^2,7.0^4,6>heptan 
• 694-98-4 norborn-5-en-2-one 
• 59975-41-6 5,6-dichloronorbornene 
• 128780-25-6 C₇H₇K 

Downstream Products

• 82204-55-5 C₁₅H₁₂ClN₃O₂ 
• 82204-57-7 C₁₅H₁₂ClN₃O₂ 
• 82204-56-6 C₁₅H₁₂ClN₃O₂ 
• 82204-58-8 5-chloro-N-phenyl-2,3-diazabicyclo<4.2.1>-nona-4,7-diene-2,3-dicarboximide 
• 82209-62-9 C₁₅H₁₁ClN₄O₄ 
• 82204-59-9 C₁₅H₁₁ClN₄O₄ 
• 82204-62-4 C₁₅H₁₁ClN₄O₄ 
• 128780-26-7 2-bromo-3-chlorobicyclo[2.2.1]hepta-2,5-diene 
• 128780-19-8 C₂₇H₂₀O 

Relevant academic research and scientific papers

Cycloaddition Behavior of 2-Substituted Norbornadienes towards 4-Phenyl-1H-1,2,4-triazole-3,5-dione (PTAD): Homo Diels-Alder Reactivity versus Insertion, Rearrangement, and Cycloaddition

The reaction of PTAD with 2-trimethylsilyl-, 2-chloro-, 2-cyano-, and 2-methoxycarbonylnorbornadienes 1 a-d, respectively, was investigated.In all cases homo Diels-Alder adducts were obtained, for 1a the unexpected regioisomer, the 1-trimethylsilyl derivative 2a, and for other norbonadienes 1 b-d the usual cyclopropane-substituted products 2 b-d.Except for the trimethylsilyl sytem 1a, for which also the dicarboximides 4a and 4'a, respectively, (rearrangement urazoles) were obtained, the other norbornadienes 1b-d afforded the insertion products 5 b-d.With increasing electron-withdrawal by the 2-substituents the insertion products 5 b-d increased at the expense of the homo Diels-Alder adducts 2 b-d.These results are mechanistically rationalized in terms of stepwise cycloaddition via 1,5-dipolar intermediates.In the case of 2-chloronorbornadiene (1b), besides the homo Diels-Alder 2b, the rearrangement urazole 4b and the insertion product 5b, also the cycloadduct 3b was formed.

Nucleophilic Exchange Reactions at 1-Chloroquadricyclane: 1,5- and 1,7-Dehydroquadricyclane as Reactive Intermediates.

Quadricyclane was metalated at position 1 to 1b in high yield by the complex of butyllithium and tetramethylethylenediamine or by a mixture of butyllithium and potassium tert-butoxide.Numerous 1-substituted quadricyclanes were accessible via 1b.Nuclophilic substitution products were obtained by the reaction of 1-chloroquadricyclane with organolithium compounds, lithium amides, and with lithium ethylthiolate (in the presence of a bulky strong base), which could be isomerized to the corresponding norbornadienes.Mechanistic investigations have shown that 1,7- and 1,5-dehydroquadricyclane (4 and 5) were involved as reactive intermediates.The nucleophilic substitution of optical active 1-chloroquadricyclane with lithium dimethylamide proceeded with 96percent racemization.This result is in accord with an elimination-addition mechanism passing over 4 and 5.