3217-89-8

Upstream product

• 611-74-5 N,N-dimethylbenzamide 
• 4794-04-1 1,4-dihydrobenzoic acid 
• 3217-88-7 cyclohexadieneacetyl chloride 
• 124-40-3 dimethyl amine 

Downstream Products

• 3424-15-5 N,N-dimethyl-1,4-dihydrobenzylamine 
• 118226-40-7 N,N-dimethyl-1,4-dihydrobenzylamine oxide 

Relevant academic research and scientific papers

Cross-conjugated compounds: microwave spectrum and ring planarity of 3-methylene-1,4-cyclohexadiene

The unstable 3-methylene-1,4-cyclohexadiene, an isomer of toluene, has been prepared from benzoic acid.The hydrocarbon can be handled quite easily in the solid state, and in the gas phase at low pressures.Rotational transitions have been measured from 12

Bimolecular Reactions of 3-Methylene-1,4-cyclohexadiene (p-Isotoluene), 5-Methylene-1,3-cyclohexadiene (o-Isotoluene), 1-Methylene-1,4-dihydronaphthalene (Benzo-p-isotoluene), and 9-Methylene-9,10-dihydroanthracene (Dibenzo-p-isotoluene)

3-Methylene-1,4-cyclohexadiene, 1, 5-methylene-1,3-cyclohexadiene, 2, 1-methylene-1,4-dihydronaphthalene, 5, and 9-methylene-9,10-dihydroanthracene, 8, react with second-order kinetics in benzene solution.The activation parameters for the reaction of 1,5,and 8, especially the frequency factor, suggest a nonconcerted reaction with little orientational demand in the transition state.The frequency factor for the reaction of 2 suggests a concerted pathway.The product distribution from each compound reinforces the kinetic observations.The products from the pyrolysisof 1 could be rationalized by a radical cage intermediate, which could combine or disproportionate.The reaction products from 5 indicate a radical chain oligomerization.The reaction of 8 gives an insoluble solid. o-Isotoluene (2) gives ene dimers.

Birch Reduction and Reductive Alkylation of Benzonitriles and Benzamides

In contrast to literature suggestions, benzonitriles and N,N-dialkylbenzamides are excellent substrates for Birch reduction and reductive alkylations.Thus, o-methoxybenzonitrile (1a) and benzonitrile (1b) give 1,4-cyclohexadienes 2a-2d from alkali-metal reduction in NH3-THF with tert-butyl alcohol (1 equiv), followed by sequential addition of an alkyl halide and excess NH4Cl.The product of HCN elimination is obtained if NH4Cl is not added prior to an aqueous workup.Birch reduction of 1a followed by NH4Cl quench gives 2-cyano-1-methoxy-1,3-cyclohexadiene (4), while benzonitrile (1b) gives the dimeric dinitrile 8, isolated as a 7:5 mixture od diastereoisomers.Hydrogenation of the mixture, 8, gives chromatographically separable 9a and 9b; a single-crystal X-ray diffraction study provided the molecular structure of 9b.Birch reduction of N,N-dimethylbenzamide (12a) gives 1,4-cyclohexadiene 13a, while reductive benzylation gives 13b.The effect of alkali metal (type and quantity), the availability of a proton source, and variation in reaction temperature on the course of Birch reduction of N,N-dimethylbenzamide (12a) is reported.