Synthesis and Characterization of Sodium 5‐Chlorotetrazolate Dihydrate by Chlorination of 1H‐Tetrazole

Abstract

A convenient, simple work-up procedure and low-cost chlorination method was developed to prepare sodium 5-chlorotetrazolate dihydrate by chlorination of self-prepared 1H-tetrazole with sodium hypochlorite solution. Several organic extracting solvents and factors (raw material ratio, reaction temperature, and reaction time) were investigated to optimize the operating conditions of the chlorination procedure. These products were characterized by 1 H and 13 C NMR spectroscopy, vibrational spectroscopy (IR), mass spectroscopy (MS), and single-crystal X-ray diffraction. In addition, the thermal behaviors of the resulting sodium 5-chlorotetrazolate dihydrate and sodium tetrazolate monohydrate were investigated and compared by differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). The results indicated that the optimum chlorination conditions were a stoi-* Prof. J. Liu

Functionalization of Tetrazoles Bearing the Electrochemically Cleavable 1N-(6-Methylpyridyl-2-methyl) Protecting Group

“…4 (11.4 g, 73%) was synthesized according to a literature procedure. 17 2-(Bromomethyl)-6-methylpyridine (3). 3 (13.1 g, 68%) was synthesized according to a known method.…”

Tetraorganopnictonium and Alkali Metal Salts of Pyridine‐2,6‐di‐tetrazolate

“…Only one Na + cation showing a trans N,N tetrazole coordination is observed in the structure of Na 2 (BTT) · 6H 2 O [H 2 BTT = 3,6‐bis(tetrazol‐5‐yl)‐1,2,4,5‐tetrazine] [ d (Na–N) = 2.523(1) Å] . A trans ‐[Na(N tet ) 2 (H 2 O) 4 ] coordination motive is also observed in sodium 5‐chlorotetrazolate dihydrate . The Na–N distance is 2.549(1) Å. Interestingly, the sodium tetrazolate shows a trans ‐[Na(N tet ) 4 (H 2 O) 2 ] coordination with similar Na–N distances of 2.536(6) and 2.544(6) Å, respectively.…”

“…[49] One Na + cation is trans coordinated by two N atoms of two BT 2- [50] A trans-[Na(N tet ) 2 (H 2 O) 4 ] coordination motive is also observed in sodium 5-chlorotetrazolate dihydrate. [47] The Na-N distance is 2.549(1) Å. Interestingly, the sodium tetrazolate shows a trans-[Na(N tet ) 4 (H 2 O) 2 ] coordination with similar Na-N distances of 2.536(6) and 2.544(6) Å, respectively. Furthermore, a trans-[Na(N tet ) 2 (H 2 O) 4 ] coordination motive is found in sodium tetrazolate monohydrate, the Na-N distance is 2.541(1) Å.…”

“…Compounds of alkali or alkaline earth metals containing tetrazolate anions have been long reported as largely insoluble and described as salt-like. [41][42][43][44][45][46][47][48][49][50][51] A salt-like description is basically correct in view of the presumably weak coordination forces of mono-or bidentate tetrazolate ligands but very probably the assignment of salt-like is largely based on the versatile application of salt metathesis reactions such as Mn(BT) + BaS i Ba(BT) + MnSȇ (BT 2-= 5,5Јbitetrazolate) [45] and a lack of crystal structures. However, in the last few years a number of such tetrazolates has been structurally characterized and interesting insight was obtained regarding salt-like behavior vs. coordination of tetrazolates.…”

“…Compounds of alkali or alkaline earth metals containing tetrazolate anions have been long reported as largely insoluble and described as salt‐like . A salt‐like description is basically correct in view of the presumably weak coordination forces of mono‐ or bidentate tetrazolate ligands but very probably the assignment of salt‐like is largely based on the versatile application of salt metathesis reactions such as Mn(BT) + BaS [rlarr2] Ba(BT) + MnS↓ (BT 2– = 5,5′‐bitetrazolate) and a lack of crystal structures.…”