Apparent Acidic Dissociation of Some 5-Aryltetrazoles<sup>1</sup>

Herbst, Robert; Wilson, Kenneth

doi:10.1021/jo01361a002

Cited by 98 publications

(29 citation statements)

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“…The most intense bands in the IR spectrum of 5EPT are associated with modes originated in this group, as well as in the ethoxy group, corresponding to the 3 symmetric, and ωCH 2 vibrational modes (see Table 1 and also Table S2 for definition of coordinates). The νC-O/νNdC vibrational mode, localized within both the C (5)-O (17) and C (5)-N (4) bonds, gives rise to the most intense band of the spectrum and occurs as a triplet at 1567.2/1565.2/ 1552.5 cm -1 (see Figure 3 and Table 1).…”

Section: Synthesis Of 5-ethoxy-1-phenyl-1h-tetrazole (5ept)mentioning

confidence: 99%

“…23 The proposed reaction pathways resulting from irradiation of 5EPT are schematically shown in Scheme 1, and the complete list of bands due to the products of photolysis is presented in Tables 2 and 3. The observed photochemistry of 5EPT shows two major reaction pathways: (1) cleavage of the tetrazole ring through the C (5) -N (1) and N (3) -N (4) bonds, with production of phenylazide and ethylcyanate as primary photoproducts (phenylazide can then undergo further reactions to give 1-aza-1,2,4,6-cycloheptatetraene, ACHT), and (2) cleavage of the N (1) -N (2) and N (3) -N (4) bonds, with molecular nitrogen elimination, leading to formation of the antiaromatic 3-ethoxy-1-phenyl-1H-diazirene (EPD). Both observed photoprocesses imply cleavage of the N (3) -N (4) bond.…”

Section: νC-o/νndc νC-n νNdc/νn-c νN-n δ(T-ring 2) νC-c/νo-c δChmentioning

confidence: 99%

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Photochemistry and Vibrational Spectra of Matrix-Isolated 5-Ethoxy-1-Phenyl-1H-Tetrazole

et al. 2007

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A combined matrix isolation FT-IR and theoretical DFT(B3LYP)/6-311++G(d,p) study of the molecular structure and photochemistry of 5-ethoxy-1-phenyl-1H-tetrazole (5EPT) was performed. A new method of synthesis of the compound is described. Calculations show three minima, very close in energy and separated by low-energy barriers (less than 4 kJ mol -1 ), in the ground-state potential energy profile of the molecule. The method of matrix isolation enabled the reduction of the number of populated conformational states in the experiment at low temperature due to the effect known as conformational cooling. As a result, the spectrum of the as-deposited matrix of 5EPT closely matches that of the most stable conformer predicted theoretically, pointing to the existence of only this conformer in the low-temperature matrixes. In this structure, the dihedral angle between the two rings, phenyl and tetrazole, is ca. 30°, whereas the ethyl group stays nearly in the plane of the tetrazole ring and is as far as possible from the phenyl group. In situ UV irradiation (λ > 235 nm) of the matrix-isolated 5EPT induced unimolecular decomposition, which led mainly to production of ethylcyanate and phenylazide, this later compound further reacting to yield, as final product, 1-aza-1,2,4,6-cycloheptatetraene. Anti-aromatic 3-ethoxy-1-phenyl-1H-diazirene was also observed experimentally as minor photoproduct, resulting from direct extrusion of molecular nitrogen from 5EPT. This species has not been described before and is now characterized by infrared spectroscopy for the first time.

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Section: Synthesis Of 5-ethoxy-1-phenyl-1h-tetrazole (5ept)mentioning

confidence: 99%

Section: νC-o/νndc νC-n νNdc/νn-c νN-n δ(T-ring 2) νC-c/νo-c δChmentioning

confidence: 99%

Photochemistry and Vibrational Spectra of Matrix-Isolated 5-Ethoxy-1-Phenyl-1H-Tetrazole

et al. 2007

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“…1; cf. also the data reported for ilitrobenzenes (7), acetanilides (S), N,N-dimethylanilines (12), and 5-phenyltetrazoles (13), which show that the maximal extinction coefficient +Atz example of a n exception i s tlze B-band of o-bromobenzaldelzyde (see Table 1 of the B-band of the o-bromo derivative is less than the correspondi~~g maximal extinction coefficient of the o-chloro derivative.) lMoreover, in examples like o-bromoacetopheno~~e, where the non-bromo substituent is large, the absorption intensity is also smaller than the intensity of the corresponding m-isomer (see Table 11).…”

Section: Tiie Spectra O F Ortiio-substituted Bromobenzenesmentioning

confidence: 52%

Light Absorption Studies: Part Xviii. The Ultraviolet Absorption Spectra of Bromobenzenes

Forbes¹

1961

Can. J. Chem.

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The ultraviolet absorption spectra of bromobenzene in various solvents, and the spectra of a series of substituted bromobenzenes in cyclohexane solution, are reported. The B-band spectral data confirm the hypotheses postulated for the B-band spectra of chlorobenzenes in the previous part of this series of papers. That is, the bromine atom usually gives rise to greater steric effects than the chlorine atom and the apparent mesomeric interaction as judged from these spectra increases with the size of the halogen substituent.Both bromobenzene and chlorobenzene C-band intensities are unusually small, and this is assumed to account for the frequent C-band similarity between the spectrum of a mono-substituted benzene derivative PhX, where X = OH, OCH3, NH2, and the spectrum of the corresponding chloro- or bromo-substituted PhX derivative.

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“…), yield 48%. The latter proved to be 5-phenyltetrazole by melting point and mixture melting point with an authentic specimen (10). Similarly isopropylidene anisuric diazide 2c gave 5-anisyltetrazole 6c, m.p.…”

Section: Pyrolysis Of Monoazides and Diazidesmentioning

confidence: 82%

Studies on the azidolysis of 4-arylidene and 4-alkylidene 5(4)-oxazolones. Part II

Awad¹,

Fahmy²

1968

Can. J. Chem.

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4-Alkylidene-5(4)-oxazolones (1) react with sodium azide in acetic acid in 5 min, or with hydrazoic acid m benzene to give the diazide 2. The latter gives by thermolysis the oxadiazine (4), which forms on hydrolysis the diamide (5). The corresponding monoazides (3) react with sodium azide – acetic acid mixture to give the corresponding diazides.4-Arylidene-5(4)-oxazolones (8) react under the same conditions to give α-[tetrazolyl-(1)]-acryhc acid derivatives (9).The work of Deorha and Gupta (6) is reinvestigated. The constitution of the products is discussed chemically and spectroscopically.

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Apparent Acidic Dissociation of Some 5-Aryltetrazoles¹

Cited by 98 publications

References 1 publication

Photochemistry and Vibrational Spectra of Matrix-Isolated 5-Ethoxy-1-Phenyl-1H-Tetrazole

Photochemistry and Vibrational Spectra of Matrix-Isolated 5-Ethoxy-1-Phenyl-1H-Tetrazole

Light Absorption Studies: Part Xviii. The Ultraviolet Absorption Spectra of Bromobenzenes

Studies on the azidolysis of 4-arylidene and 4-alkylidene 5(4)-oxazolones. Part II

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Apparent Acidic Dissociation of Some 5-Aryltetrazoles1

Cited by 98 publications

References 1 publication

Photochemistry and Vibrational Spectra of Matrix-Isolated 5-Ethoxy-1-Phenyl-1H-Tetrazole

Photochemistry and Vibrational Spectra of Matrix-Isolated 5-Ethoxy-1-Phenyl-1H-Tetrazole

Light Absorption Studies: Part Xviii. The Ultraviolet Absorption Spectra of Bromobenzenes

Studies on the azidolysis of 4-arylidene and 4-alkylidene 5(4)-oxazolones. Part II

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Apparent Acidic Dissociation of Some 5-Aryltetrazoles¹