ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
1, 4, 5, 6-Tetrahydro-ν-tetrazin-DerivateThe title compounds 2 and 13 are readily available from α-lithiated N-alkyl-nitrosoamines 1 (see Tables 1 and 2) which decompose at - 73° to yield the N-oxides 2. The ESR. spectra of two derivatives 1 are recorded (Fig. 1), and tentative mechanisms are proposed for the head to head dimerizations (la- 3- 4- 5- 2a and Scheme 1). Coupling of lithionitrosoamines with iodine (-6) and alternative decomposition routes of representatives of this class of organometallics with special substitution [equations (2)-(5)] are reported.The structures of the tetrazines are established by spectroscopic data [ESCA] (Fig. 2), IR., UV., 1H- (cf. Fig. 9) and 13C-NMR., PE. (Scheme 2), by an X-ray analysis of 2a (Fig. 4-8 and Table 3), and by the chemical reactions. The crystal structure of 2a is a twisted boat with non planar terminal nitrogen atoms which reflects the electron repulsion in the 4-atom-6-electron N—N=N≡N-system. Comparisons are made with 2-tetrazenes, the open chain analogues of 13, wherever possible. Raney-Ni reductions of 2 or 13 gives diamines 14 to which is assigned the d, l-configuration through the 1H-NMR. spectra of the aminals 7 and 15. Neither the oxides 2 nor the tetrazines 13 undergo cycloaddition reactions [equation (6) and Section 4].Compound 2a is dimerized to the bis (nitrosoamino)-2-tetrazene 18 by treatment with acid, ZnII, CuI or iodomethane. 2a is oxidized at nitrogen to the ethylene diamine derivative 6a (through 20, with H2O2), or at the CH2-groups of the ring to give oxo-N-oxide 21 (with MnO2 or the ring contracted oxo-tetrazoline-N-oxide 22 (with KMnO4).Pyrolysis or photolysis of the dimethyl tetrahydrotetrazine 13a furnishes the trimer 26 of N-methylimine, but no diazetidine 27. Silver and mercury complexes 29 are obtained from 13a, while Cr(CO)5. THF does not furnish a complex as with azocompounds, but rather replaces N2 in 13a by CO (→ 28). Oxidation with permanganate converts 13a into the oxalic acid derivative 30 with unchanged tetrazine structure.
Additional Material:
10 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19780610512
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