Synthèse des monochlorométhyl‐phénanthrènes

Fierens, Paul; Martin, Richard; Rysselberge, J. Van

doi:10.1002/hlca.19550380739

Cited by 9 publications

(7 citation statements)

References 4 publications

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“…The variations noticed in antisymmetric N-H stretching vibrations and intensities are also attributed to steric effects (185) in peri amines. The exceptional behavior of 3-aminopyrene noticed here has been also pointed out in another investigation (199). Krueger (356) has estimated the values of and N-H stretching force constants for a number of substituted 1-and 2-naphthylamines from the data of Bryson (112).…”

Section: XXXVII Xxxviiisupporting

confidence: 80%

“…Another series of reactions which has been employed to study peri effects in polycyclic systems is the SnI solvolysis of arylcarbinyl halides (81,159,160,199,455,458,513,556). The rate of solvolysis is governed by the stability of the carbonium ion intermediate as + ROH ArCRzRsCl -> ArCRiRz + 01" -> ArCRjRzOR R = H, alkyl, or acyl; Ri, Rz = H, alkyl, or aryl well as steric factors.…”

Section: CLXIVmentioning

confidence: 99%

“…Steric inhibition of resonance of the carbonium ion, due to peri-type interactions (e.g., in 1-naphthylmethyl chloride or 9-anthrylmethyl chloride), was believed to lead to diminished carbonium ion stability in 1-naphthalenoid systems (102, 531), although it now appears that the trend may be explained by electron delocalization effects alone (160a). Among the reactions studied are the ethanolysis of triarylmethyl chlorides (445), solvolysis of -arylmethyl chlorides in moist formic acid (159,199) and in aqueous acetone (81,458), acetolysis of naphthylmethyl bromides (513), and the solvolysis of -arylbenzyl chlorides (556). At least in the case of triarylmethyl halides, steric inhibition of resonance may be responsible for the rate trends observed.…”

Section: CLXIVmentioning

confidence: 99%

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peri Interaction in Naphthalene Derivatives

1966

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Section: XXXVII Xxxviiisupporting

confidence: 80%

Section: CLXIVmentioning

confidence: 99%

Section: CLXIVmentioning

confidence: 99%

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peri Interaction in Naphthalene Derivatives

1966

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“…I n the past experimental and theoretical work has been carried out to describe the rates of solvolysis of certain arylmethyl chlorides by Fierens et al [1] and Dewar et al [2]. The results suggested that we are not dealing with a simple type of reaction.…”

Section: Introductionmentioning

confidence: 99%

Elementary addition-substitution reactions. H�ckel approach for the description of aromatic and antiaromatic arylmethyl cations

Buck¹

2000

Int. J. Quant. Chem.

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“…In the case of the ether solvents (SH), NaAlH,(OR), acts as a scavenger for SH'+ and SH(H+) generated through ionization. This scavenging process produces stabilized (Na+, es-) pairs [reactions (13)- ( 17)] which, in turn, reduce aromatic substrates such as 1,ZDPE to their radical anion/sodium cation pairs [reactions (18), (25), (32)]. The prevailing species generated in the radiolysis of solutions in toluene are electronically excited '(TOL) and 3(TOL), which in turn can produce electronically excited substrate molecules '( 1,2-DPE) and 3( 1,ZDPE) via singlet-singlet or triplettriplet energy transfer [reaction (28)].…”

Section: Discussionmentioning

confidence: 99%

Radiation-induced C—C bond cleavage in 1,2-diarylethanes as model compounds of coal. Part 2.—Pulse and steady-state radiolysis of 1,2-di(pyren-1-yl)ethane in tetrahydrofuran, dimethoxyethane and toluene in the presence of sodium dihydridobis(2-methoxyethoxy)aluminate

Solar¹,

Getoff²,

Haenel³

et al. 1993

J. Chem. Soc., Faraday Trans.

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1,2-Di(pyren-l-yl)ethane (1,2-DPE) has been used as a model for coal to study the C-C bond cleavage of the ethano linkage in the radiolysis of solutions containing NaAIH,(OCH,CH20CH,), [NaAIH,(OR),]. Transient species were investigated by pulse radiolysis of solutions of 1,2-DPE, l-methylpyrene (1-MP) and pyrene (P) in THF, DME and toluene in the absence and the presence of NaAIH,(OR),.In the presence of the latter stabilized and long-lived radical anion/sodium cation pairs of 1,2-DPE, 1-MP and P were generated even in the non-polar solvent toluene. The reaction mechanisms differ substantially for the ether solvents (THF or DME) and solutions in toluene. In the case of the ether solvents (SH) NaAIH,(OR), acts as a scavenger for solvent radical cations SH" and solvent cations SH(H+) generated through ionization. This produces stabilized sodium cation/electron pairs (Na+, e ;) which reduce the aromatic substrates to their radical anion/sodium cation pairs. The prevailing species generated in the radiolysis of solutions in toluene are electronically excited molecules of the solvent and the substrate from which the excited triplet molecules are preferentially reduced to radical anions by NaAIH,(OR), in an electron-transfer process. Steady-state radiolysis (60Co prays) of solutions of 1,2-DPE in THF, DME or toluene containing NaAIH,(OR), resulted in the C-C bond cleavage of the ethano linkage. This is attributed to the unstable dianion (1,2-DPE2-, 2Na+) formed in two successive reductions via (1,2-DPE'-, Na+). UV-VIS spectroscopy and product analysis showed that the radiation-induced reduction of 1,2-DPE, 1-MP and P requires lower doses in THF and DME than in toluene. However, reactions of (1,2-DPE'-, Na+) with THF and DME to form substrate-solvent addition products limit C-C bond cleavage (16% in THF and 32% in DME). The inertness of toluene towards such side reactions makes the radiation-induced cleavage process of 1,2-DPE in this solvent (despite of the higher dose required) much more efficient than in THF and DME, yielding after hydrolysis up to 52% 1-MP. Radiation-induced reduction of polycyclic arenes in the NaAIH,(OR),-toluene system is very useful for investigating the radical anions of these arenes by UV-VIS and EPR spectroscopy, since essentially no other interfering species are formed.

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Synthèse des monochlorométhyl‐phénanthrènes

Cited by 9 publications

References 4 publications

peri Interaction in Naphthalene Derivatives

peri Interaction in Naphthalene Derivatives

Elementary addition-substitution reactions. H�ckel approach for the description of aromatic and antiaromatic arylmethyl cations

Radiation-induced C—C bond cleavage in 1,2-diarylethanes as model compounds of coal. Part 2.—Pulse and steady-state radiolysis of 1,2-di(pyren-1-yl)ethane in tetrahydrofuran, dimethoxyethane and toluene in the presence of sodium dihydridobis(2-methoxyethoxy)aluminate

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