• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.881-884
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• 2012

We report a quantum chemical study of an extremely efficient nucleophilic aromatic fluorination in molten salts. We describe that the mechanism involves solvent anion interacting with the ion pair nucleophile $M^+F^-$(M = Na, K, Rb, Cs) to accelerate the reaction. We show that our proposed mechanism may well explain the excellent efficiency of molten salts for SNAr reactions, the relative efficacy of the metal cations, and also the observed large difference in rate constants in two molten salts $(n-C_4H_9)_4N^+\;CX_3SO_3^-$, (X=H, F) with slightly different sidechain ($-CH_3$ vs. $-CF_3$).

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.2135-2138
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• 2014

A kinetic study is reported for the SNAr reaction of 1-Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1h) with OH- in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The second-order rate constant ($k_{OH^-}$) increases as the substituent Y in the leaving group changes from an electron-donating group (EDG) to an electronwithdrawing group (EWG). The Br${\o}$nsted-type plot for the reactions of 1a-1h is linear with ${\beta}_{lg}$ = -0.16, indicating that the reactivity of substrates 1a-1h is little affected by the leaving-group basicity. A linear Br${\o}$nsted-type plot with ${\beta}_{lg}=-0.3{\pm}0.1$ is typical for reactions reported previously to proceed through a stepwise mechanism in which formation of a Meisenheimer complex is the rate-determining step (RDS). The Hammett plot correlated with ${\sigma}_Y{^{\circ}}$ constants results in a much better correlation than that correlated with ${\sigma}_Y{^-}$constants, implyng that no negative charge is developing on the O atom of the leaving group (or expulsion of the leaving group is not advanced at all in the TS). This excludes a possibility that the $S_NAr$ reaction of 1a-1h with $OH^-$ proceeds through a concerted mechanism or via a stepwise pathway with expulsion of the leaving group being the RDS. Thus, the current reactions have been concluded to proceed through a stepwise mechanism in which expulsion of the leaving group occurs rapidly after the RDS.

• Bulletin of the Korean Chemical Society
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• 제27권8호
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• pp.1203-1205
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• 2006

During the synthesis of 4-fluorobenzaldehyde via the SNAr reaction of 4-nitrobenzaldehyde with TBAF, it was found that an equivalent amount of TBAF could oxidize benzaldehyde to benzoic acid. The reaction of 4-nitrobenzaldehyde with tetrabutylammonium fluoride (TBAF) gave 4-nitrobenzoic acid in high yield. Depending on the reaction conditions, other aromatic aldehydes produced acids with fewer amounts of alcohols. However, this type of oxidation has limited practical applications. Nevertheless, the mechanism is quite different from the Cannizzaro reaction because the amounts of the acid salt and alcohol formed were different.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2571-2574
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• 2010

We investigate the mechanism of $S_NAr$ fluorination reactions under the influence of protic solvents and ions. We find that counterion or protic solvent alone retards the $S_NAr$ reactions, but together they may promote the reaction. In this mechanism, the protic solvent acts on the counterion as a Lewis base, and the nucleophile reacts as an ion pair. We also show that an anion (mesylate) may exhibit catalytic effects, suggesting the role of ionic liquids for accelerating the $S_NAr$ reactions.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2801-2805
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• 2010

A nucleophilic substitution reaction of 4-chloro-7-nitrobenzofurazan (NBF-Cl) with anilines in MeOH-MeCN mixtures was conducted at 25, 35, and $45^{\circ}C$. Based on the higher $\beta_{nuc}$ values (1.0 - 1.6) of the reaction and a good correlation of the rate constants with the reduction potentials of the aniline nucleophiles, the present reaction was initiated by a single electron transfer (SET). After this step, the reaction proceeds through a transition state similar to the normal $S_NAr$-Ad.E pathway.

• Bulletin of the Korean Chemical Society
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• 제5권3호
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• pp.126-129
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• 1984

The reaction of aryl halides with phenoxides and alkoxides were investigated under phase transfer catalytic conditions. 2,4-Dinitro- and 4-nitrohalobenzenes reacted readily with phenoxides in NaOH(aq)-benzene in the presence of Bu4N+Br, affording the products quantitatively. Although the aryl halides did not react with alkoxides under the same condition, the reactions were completed within 2 hours at room temperature when conducted under solid-liquid phase transfenr catalytic condition. The reactivity of aryl halides was in the order, Ar = 2,4-dinitrophenyl > 4-nitrophenyl, and X = F > Cl, consistent with the SNAr mechanism. The reactivity of oxyanions increased with the change of reaction condition from liquid-liquid to solid-liquid phase transfer catalysis. The results were explained with the concentration and the degree of hydration of the anion in benzene.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2371-2374
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• 2014

A kinetic study is reported on SNAr reaction of 1-fluoro-2,4-dinitrobenzene with a series of primary amines including hydrazine in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{obsd}$ vs. [amine] are linear and pass through the origin, indicating that general-base catalysis by a second amine molecule is absent. The Br${\o}$nsted-type plot exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.46 when hydrazine is excluded from the correlation. The reaction has been suggested to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs after the rate-determining step (RDS). Hydrazine is ca. 10 times more reactive than similarly basic glycylglycine (i.e., the ${\alpha}$-effect). A five-membered cyclic intermediate has been suggested for the reaction with hydrazine, in which intramolecular H-bonding interactions would facilitate expulsion of the leaving group. However, the enhanced leaving-group ability is not responsible for the ${\alpha}$-effect shown by hydrazine because expulsion of the leaving group occurs after RDS. Destabilization of the ground-state of hydrazine through the electronic repulsion between the nonbonding electron pairs is responsible for the ${\alpha}$-effect found in the current $S_NAr$ reaction.

• 공업화학
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• 제9권3호
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• pp.440-444
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• 1998

p-Dichlobenzene(DCB), p-dibromobenzene(DBB), p-diiodobenzene(DIB) 및 4-chlorophenyl sulfone(CPS)을 공단량체로, 그리고 N-methyl-2-pyrrolidinone(NMP)를 용매로 사용하여 고온, 고압하에서 poly(phenylene sulfide-co-phenylene sulfide sulfone), PPS/PPSS 공중합체를 합성하고 공중합 반응 특성과 합성된 공중합체들의 구조 및 열적성질에 대해 조사하였다. PPS/PPSS 공중합체의 수율은 [DBB]/[CPS] 및 [DIB]/[CPS] 공단량체 조합의 경우 [DCB]/[CPS] 공단량체 조합보다 낮은 온도인 $190^{\circ}C$에서 최고 수율을 나타내었으며 [DCB]/[CPS] 공단량체 조합의 경우는 이보다 높은 온도인 $230^{\circ}C$에서 최고 수율을 나타내어 leaving group이 I>Br>Cl의 순서로 공중합 반응이 잘 진행되었으며 이것으로부터 공중합 반응은 nucleophilic aromatic substitution(SNAr) 기구에 적합함을 알 수 있었다. [DBB]/[CPS] 공단량체 조합중에서 CPS의 공급비가 10 mol%일 때 생성된 PPS/PPSS 공중합체의 분자량은 8,330g/mol로 가장 높게 나타났다. CPS 단량체의 공급비가 30 mol% 이상일 경우 생성되는 PPS/PPSS 공중합체는 $T_m$을 나타내지 않았으나, CPS의 공급비가 10 mol%인 PPS/PPSS 공중합체 시료의 경우 $T_g$는 약 $15^{\circ}C$ 증가하였고 $T_m$은 약 $15^{\circ}C$ 감소하여 열적 성질이 향상되는 것을 볼 수 있었다. 또 중합 온도를 $240^{\circ}C$로 고정하고 [DBB]/[CPS]의 공급비를 95/5 mol%로 하여 얻어진 PPS/PPSS 공중합체는 PPS 단독 중합체보다 분자량이 높게 나타나 PPS 단독 중합체의 고결정성 및 내열성을 유지한채 PPS 단독 중합체의 결점의 하나인 중합도를 향상시킬 수 있는 방법으로 이용될 수 있다고 생각되었다.