Kolbe-Schmitt reaction of sodium 2-naphthoxide

Marković, Zoran; Marković, Svetlana; Đurović, Igor

doi:10.1007/s00706-007-0771-6

Cited by 7 publications

(13 citation statements)

References 19 publications

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“…However, the direct CO2 substitution on to C6 position was not possible. Similar results were reported for the CO2 substitution on Na-2-naphthoxide [2][3][4][5]12], where the direct CO2 substitution on Na-2-naphthoxide could not proceed at the C6 position. These results may be due to a longer distance between C6 and C2 positions [1,3].…”

Section: Structure Of the K-2-naphthoxide-co2 Complexsupporting

confidence: 86%

“…Alkali metal naphthoxides are another important reactant in the Kolbe-Schmitt reaction, as the resulting product of 2,6-HNA is used as an intermediate for polyesters and polymeric liquid crystals. Hence, the carboxylation reaction of alkali metal naphthoxides has drawn much interest in experimental and theoretical investigations [7][8][9][10][11][12][13]. Scheme 1 depicts the structure of K-2-naphthoxide and HNA isomers.…”

Section: Introductionmentioning

confidence: 99%

“…Scheme 1 depicts the structure of K-2-naphthoxide and HNA isomers. Marcovic et al theoretically examined the reaction mechanism for the carboxylation of sodium naphthoxide using DFT calculations and revealed that the carboxylation is initiated by the complexation between Na-naphthoxide and CO2, followed by the substitution of the electrophilic CO2 at the 1-and 3-positions of the naphthalene ring [12]. They also found that the direct substitution on the 6-position is difficult due to a small ionic radius of sodium, and instead the substitution on the 8-position is possible, which is followed by the transfer of CO2 to the 6-position to give sodium 2-hydroxy-6-naphthoate [13].…”

Section: Introductionmentioning

confidence: 99%

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Formation of Potassium 2-Hydroxy-6-naphthoate by Kolbe-Schmitt Carboxylation: A Joint Experimental and Theoretical Study

Kim¹,

D²,

Kim³

et al. 2019

Preprint

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The reaction mechanism of the carboxylation of K-2-naphthoxide was investigated by density functional theory calculations and spectroscopic studies. The reaction intermediates and products were confirmed by CO2 adsorbed-FTIR and 1H-NMR measurements. Four steps of the reaction pathway were identified: CO2 activation, electrophilic substitution, CO2-K complex rearrangement, and H-shift, producing 2-hydroxy-1-naphthoic acid (2,1-HNA), 2-hydroxy-3-naphthoic acid (2,3-HNA), and 2-hydroxy-6-naphthoic acid (2,6-HNA). The occurrence of CO2-K complex rearrangement was also confirmed. These energy profiles of reaction pathways for the reaction intermediates were well consistent the experimental results on the carboxylation of K-2-naphthoxide.

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Section: Structure Of the K-2-naphthoxide-co2 Complexsupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Formation of Potassium 2-Hydroxy-6-naphthoate by Kolbe-Schmitt Carboxylation: A Joint Experimental and Theoretical Study

Kim¹,

D²,

Kim³

et al. 2019

Preprint

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“…Kolbe-Schmitt reakcija je reakcija karboksilacije fenoksida i naftoksida alkalnih i zemnoalkalnih metala, u kojoj nastaju aromatične hidroksi kiseline [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Proizvodi Kolbe-Schmitt reakcije imaju značajnu industrijsku ulogu u sintezi brojnih jedinjenja kao što su farmaceutski preparati i akivne supstance, antiseptici, fungicidi, insekticidi i razvijači boja, zatim u tekstilnoj industriji, proizvodnji poliestara i visoko polimerizovanih tečnih kristala, itd.…”

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“…Pokazalo se da je NaONaph potrebno zagrejati iznad 200 °C, pri čemu nastaje smesa 2-hidroksi-1-naftoeve kiseline, kao i 3-i 6-hidroksi-2-naftoevih kiselina (slika 1). Nedavna teorijska istraživanja reakcionog mehanizma karboksilacije NaONaph u položajima 1, 3 i 6 ponovo su potvrdila da reakcija teče preko imtermedijernog NaONaph-CO 2 kompleksa [18,19]. Prema ovim istraživanjima ugljenik iz CO 2 vrši elektrofilni napad na naftalenski prsten u položaju 1, što vodi do obrazovanja natrijum-2-hidroksi-1-naftoata (E1).…”

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Carboxylation of sodium 2-naphthoxide. Reinvestigation of the mechanism by means of a hybrid meta density functional theory method

Djurovic

Marković

Markovic

2015

Hem Ind

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Aromatic hydroxy acids, the compounds of large industrial importance, can be prepared in the Kolbe-Schmitt reaction, i.e. a carboxylation reaction of alkali metal phenoxides (MOPh) and naphthoxides (MONaph). On the basis of the experimental results two contradictory reaction mechanisms have been proposed: the one of direct carboxylation, and the other involving initial formation of the MOPh-CO2 or MONaph-CO2 complex. Previous theoretical investigations of the carboxylation reaction of sodium 2-naphthoxide, performed by means of the B3LYP method, confirmed the initial formation of the NaONaph-CO2 complex, and showed that the carbon of the CO2 moiety performs an electrophilic attack at C1 of the ring, leading to the formation of sodium 2-hydroxy-1-naphthoate (E1). Surprisingly, transition states for possible electrophilic attacks at C3 and C6 were not revealed, and the formation of other two products (E3 and E6) was explained by a number of consecutive rearrangements. In addition, this mechanism includes a reaction step with rather high activation energy. Since more sophisticated functionals are today available, the aim of this work is to reinvestigate the mechanism of the Kolbe-Schmitt reaction of NaONaph in all three positions (1, 3, and 6). Our investigations with the M062X method demonstrated that CO2 and NaONaph can spontaneously build two complexes: B (the one previously reported) and C. While B cannot be further transformed to yield the reaction products, the CO2 moiety in C takes perfect position for electrophilic attacks at all three sites of the ring. These attacks are realized via the transition states TS1, which lead to the formation of the new C-C bonds, and corresponding intermediates D. In the next, bimolecular reaction step two D intermediates exchange the protons adjacent to the CO2 groups. These intermolecular reaction steps require significantly lower activation energies in comparison to the intramolecular proton shift from C to O. The carboxylation reaction in the position 6 is both kinetically and thermodynamically unfavourable, whereas the pathways in the positions 1 and 3 are competitive. Pathway 1 requires the lowest activation energies, but E3 is significantly more stable than other two products. In accord with these findings are the experimental results which show that, at very low temperature (293 K) only E1 is formed at low yield, whereas the yields of E3 and E6 increase with the increasing temperature. Since the Kolbe-Schmitt reaction is experimentally performed at relatively high temperatures (around 500 K), the main product is thermodynamically most stable E6.

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Transformations of Carbocycles

2010

Name Reactions for Carbocyclic Ring Formations

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Kolbe-Schmitt reaction of sodium 2-naphthoxide

Cited by 7 publications

References 19 publications

Formation of Potassium 2-Hydroxy-6-naphthoate by Kolbe-Schmitt Carboxylation: A Joint Experimental and Theoretical Study

Formation of Potassium 2-Hydroxy-6-naphthoate by Kolbe-Schmitt Carboxylation: A Joint Experimental and Theoretical Study

Carboxylation of sodium 2-naphthoxide. Reinvestigation of the mechanism by means of a hybrid meta density functional theory method

Transformations of Carbocycles

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