21113-62-2

Upstream product

• 32651-20-0 1,4-diphenylcyclohexane-1,4-diol 
• 75-07-0 acetaldehyde 
• 91925-45-0 1,4-diphenyl-2,3-dioxabicyclo<2.2.2>oct-5-ene 
• 120-92-3 cyclopentanone 
• 637-88-7 1,4-Cyclohexanedione 
• 591-51-5 phenyllithium 
• 74-85-1 ethene 
• 536-74-3 phenylacetylene 
• 3262-89-3 triphenylboroxine 
• 108-86-1 bromobenzene 
• 100-58-3 phenylmagnesium bromide 
• 67-64-1 acetone 
• 87433-33-8 1,4-diphenyl-2,3-diazabicyclo<2.2.2>oct-2-ene 

Downstream Products

• 78070-39-0 1,4-Diphenyl-bicyclo<2.2.2>oct-2-ene-5,6-dicarbonic acid-anhydride 
• 91925-45-0 1,4-diphenyl-2,3-dioxabicyclo<2.2.2>oct-5-ene 
• 91925-45-0 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]oct-5-ene 
• 114396-00-8 1,4-Diphenyl-2,3-dioxa-bicyclo[2.2.2]octane 
• 92-94-4 [1,1';4',1'']terphenyl 
• 1366368-88-8 (+/-)-2-hydroxy-5-oxo-2,5-diphenylpentanal 
• 495-71-6 phenacylacetophenone 
• 114880-21-6 1,4-Diphenyl-bicyclo<2.2.2>octane-2,3-dicarbonic acid anhydride 
• 123207-76-1 syn-1,2;3,4-bis(epoxy)-1,4-diphenylcyclohexane 

Relevant academic research and scientific papers

Generation of the 1,4-Diphenylcyclohexane-1,4-diyl Radical Cation by CeIV-catalysed Denitrogenation of the Azoalkane 1,4-Diphenyl-2,3-diazabicyclooct-2-ene and its Reluctance to undergo Cope Rearrangement

It is experimentally confirmed that the radical cation of 1,4-diphenylcyclohexane-1,4-diyl does not isomerize thermally to the radical cation of 2,5-diphenylhexa-1,5-diene, but is instead quantitatively dehydrogenated to p-terphenyl

Striking Contrast between Photoinduced and Non-photoinduced Electron-transfer Reactions of 1,4-Diphenyl-2,3-diazabicyclooct-2-ene

Photoinduced electron-transfer (PET) reactions of 1,4-diphenyl-2,3-diazabicyclooct-2-ene 1 result in a quantitative formation of 2,5-diphenylhexa-1,5-diene 2, in sharp contrast to the results of non-PET reactions and showing the importance of a back electron-transfer (BET) process in PET reactions.

Nickel-Catalyzed Direct Synthesis of Aryl Olefins from Ketones and Organoboron Reagents under Neutral Conditions

Nickel-catalyzed addition of arylboron reagents to ketones results in aryl olefins directly. The neutral condition allows acidic protons of alcohols, phenols, and malonates to be present, and fragile structures are also tolerated.

NbCl3-catalyzed [2+2+2] intermolecular cycloaddition of alkynes and alkenes to 1,3-cyclohexadiene derivatives

NbCl3(DME)-catalyzed [2+2+2] intermolecular cycloaddition of alkynes and alkenes was successfully achieved to give 1,4,5-trisubstituted-1,3- cyclohexadiene derivatives in good yields. The Royal Society of Chemistry 2009.

A radical-anion chain mechanism initiated by dissociative electron transfer to a bicyclic endoperoxide: Insight into the fragmentation chemistry of neutral biradicals and distonic radical anions

The electron-transfer (ET) reduction of two diphenyl-substituted bicyclic endoperoxides was studied in N,N-dimethylformamide by heterogeneous electrochemical techniques. The study provides insight into the structural parameters that affect the reduction mechanism of the 0-0 bond and dictate the reactivity of distonic radical anions, in addition to evaluating previously unknown thermochemical parameters. Notably, the standard reduction potentials and the bond dissociation energies (BDEs) were evaluated to be -0.55 ±0.15 V and 20±3 kcal mol-1, respectively, the last representing some of the lowest BDEs ever reported. The endoperoxides react by concerted dissociative electron transfer (DET) reduction of the 0-0 bond yielding a distonic radical-anion intermediate. The reduction of 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]oct-5-ene (1) results in the quantitative formation of 1,4-diphenylcyclohex-2-ene-c/s-1,4-diol by an overall two-electron mechanism. In contrast, ET to 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]octane (2) yields 1,4-diphenylcyclohexane-c/s-1,4-diol as the major product; however, in competition with the second ET from the electrode, the distonic radical anion undergoes a β-scission fragmentation yielding 1,4-diphenyl-1,4-butanedione radical anion and ethylene in a mechanism involving less than one electron. These observations are rationalized by an unprecedented catalytic radical-anion chain mechanism, the first ever reported for a bicyclic endoperoxide. The product ratios and the efficiency of the catalytic mechanism are dependent on the electrode potential and the concentration of weak non-nucleophilic acid. A thermochemical cycle for calculating the driving force for β-scission fragmentation is presented, and provides insight into why the fragmentation chemistry of distonic radical anions is different from analogous neutral biradicals.

The Diastereoselective Formation of 1,2,4-Trioxanes and 1,3-Dioxolanes by the Reaction of Endoperoxides with Chiral Cyclohexanones

1,4-Diphenyl-2,3-dioxabicyclo[2.2.1]hept-5-ene (2), on treatment with a catalytic amount of trimethylsilyl trifluoromethanesulfonate (Me3SiOTf) in CH2Cl2 at -78°, reacts with excess (-)-menthone (10) to give (1S,2S,4′aS,5R,7′aS)-4′a,7′a-dihydro-2-isopropyl-5- methyl-6′,7′-diphenylspiro[cyclohexane-1,3′-[7′H] cyclopenta-[1,2,4]trioxine] (11) and its (1R,2S,4′aS,5R,7′aS)-diastereoisomer 12 in a 1:1 ratio and in 21% yield. Repeating the reaction with 1.1 equiv, of Me3SiOTf with respect to 2 affords 11, 12, and (1S,2S,3′aR,5R,6′aS)-3′a,6′a-dihydro-2-isopropyl-5- methyl-3′a-phenoxy-5′-phenylspiro[cyclohexane-1,2′-[4′H] cyclopenta[1,3]dioxole] (13) together with its (1R,2S,3′aS,5R,6′aR)-diastereoisomer 14 in a ratio of 3:3:3:1 and in 56% yield. (+)-Nopinone (15) in excess reacts with 2 in the presence of 1.1 equiv. of Me3SiOTf to give a pair of 1,2,4-trioxanes (16 and 17) analogous to 11 and 12, and a pair of 1,3-dioxolanes (18 and 19) analogous to 13 and 14, in a ratio of 8:2:3:3 and in 85% yield. (-)-Carvone and racemic 2-(tert-butyl)cyclohexanone under the same conditions behave like 15 and deliver pairs of diastereoisomeric trioxanes and dioxolanes. In general, catalytic amounts of Me3SiOTf give rise to trioxanes, whereas 1.5 equiv. overwhelmingly engender dioxolanes. Adamantan-2-one combines with 2 giving only (4′aRS,7′aRS)-4′a,7′a-dihydro-6′,7′a- diphenylspiro[adamantane-2,3′-[7′H]cyclopenta[1,2,4]trioxine] in 98% yield regardless of the amount of Me3SiOTf used. The reaction of 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]oct-5-ene (32) with 10 and 1.1 equiv. of Me3SiOTf produces only the pair of trioxanes 33 and 34 homologous to 11 and 12. Treatment of the (S,S)-diastereoisomer 33 with Zn and AcOH furnishes (1S,2S)-1,4-diphenylcyclohex-3-ene-1,2-diol. The crystal structures of 11-13 and 16 are obtained by X-ray analysis. The reaction courses of 10 and the other chiral cyclohexanones with prochiral endoperoxides 2 and 32 to give trioxanes are rationalized in terms of the respective enantiomeric silylperoxy cations which are completely differentiated by the si and re faces of the ketone function. The origin of the 1,3-dioxolanes is ascribed to 1,2 rearrangement of the corresponding trioxanes, which occurs with retention of configuration of the angular substituent.

Antimalarially potent, easily prepared, fluorinated endoperoxides

Three or four step chemical synthesis and in vitro antimalarial testing showed crystalline, thermally stable, bicyclic endoperoxides 3c and 4c to be potent antimalarials, having approximately 15% of the antimalarial activity of the clinically used, comple

Deoxygenation of 1,3-Diene 1,4-Endoperoxides by Tin(II) Chloride

The reaction of bicyclic 1,3-diene 1,4-endoperoxides with SnCl2 re-generated the corresponding dienes in 15-70percent yield.The efficiency of the deoxygenation depended on the structure of peroxides.The results were compared with those of Fe(II) as well as Pd(0) assisted reactions.

Model Substances for Electro-optical and Dielectric Studies, Part I. Synthesis and Structure of 1,4-Bis(4'-dimethylamino-3',5'-dicyanophenyl)bicyclooctane

A synthesis for a new 1,2,6-donor-acceptor-substituted chromophoric benzene system is given.This chromophore is incorporated in a bicyclooctane system to build up model compounds for electro-optical and dielectrical studies.Furthermore a preparative convenient route to derivatives of 1,4-bis(diphenyl)bicyclooctane is worked out.The structures of the new compounds are proven by spectroscopical means. - Key words: 1,2,6-Donor-Acceptor-Substituted Benzenes, 1,4-Bis(diphenyl)bicyclooctane Derivatives

Reactions of Cyclic Peroxides with Aldehydes and Ketones catalysed by Trimethylsilyl Trifluoromethanesulphonate. An Efficient Synthesis of 1,2,4-Trioxanes

Trimethylsilyl trifluoromethanesulphonate is found to be an efficient catalyst for the reaction of 1,4-endoperoxides and 1,2-dioxetanes with aldehydes and ketones to give 1,2,4-trioxanes in high yields.