5-Aminotetrazole

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5-Aminotetrazole
Aminotetrazole.png
5-amino-1H-tetrazole.jpg
Names
Preferred IUPAC name
1H-1,2,3,4-Tetrazol-5-amine
Other names
5-ATZ
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.022.348 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/CH3N5/c2-1-3-5-6-4-1/h(H3,2,3,4,5,6)
    Key: ULRPISSMEBPJLN-UHFFFAOYSA-N
  • InChI=1/CH3N5/c2-1-3-5-6-4-1/h(H3,2,3,4,5,6)
    Key: ULRPISSMEBPJLN-UHFFFAOYAD
  • c1([nH]nnn1)N
Properties
CH3N5
Molar mass 85.070 g·mol−1
AppearanceWhite solid
Density 1.502 g/cm3
Melting point 201–205 °C (394–401 °F; 474–478 K)
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-acid.svg
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

5-Aminotetrazole is an organic compound with the formula HN4CNH2. It is a white solid that can be obtained both in anhydrous and hydrated forms.

Contents

The molecule is planar. [1] The hydrogen bonding pattern in the hydrate supports the assignment of NH being adjacent to carbon in the ring. [2]

Preparation

A synthesis of 5-aminotetrazole through the action of nitrous acid on aminoguanidine was reported by Johannes Thiele in 1892. [3]

5-Aminotetrazole synthesis01.svg

The exact structure of the compound was not known at the time, although it was known to crystallize as a monohydrate. The correct structural formula was published in 1901 by Arthur Hantzsch, who obtained it from the reaction between cyanamide and hydrazoic acid. [4]

5-Aminotetrazol Synthese aus Cyanamid.svg

To avoid direct handling of the problematic hydrazoic acid, a mixture of sodium azide and hydrochloric acid has been used to give the monohydrate at 73% yield. [5]

5-Aminotetrazol Synthese aus Dicyandiamid.svg

In a more efficient and controllable one-pot synthesis, cyanamide is treated with hydrazine hydrochloride to give aminoguanidine hydrochloride, which is then diazotized as in Thiele's original process. Addition of ammonia or sodium hydroxide followed by heat-induced cyclization gives the anhydrous product in 74% yield. [6] [7]

Structure

The structure of 5-aminotetrazole has been determined several times by X-ray crystallography, both as the anhydrous [8] and monohydrated forms. [9] The structures are very similar, consisting of a planar molecule, including the amino group.

Uses

5-Aminotetrazole has found applications in heterocyclic chemistry, particularly as a synthon for some multicomponent reactions. [10]

The N-4 is basic as indicated by its binding to metal halides, such as the coordination complex [CoCl2(aminotetrazole)4. [11]

The compound has a particularly high nitrogen content of 80%. Partly for this reason, the compound is prone to decomposition to nitrogen gas (N2). It has been widely investigated for gas-generating systems, such as airbags and blowing agents. [12]

Related Research Articles

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<span class="mw-page-title-main">Cadmium sulfate</span> Chemical compound

Cadmium sulfate is the name of a series of related inorganic compounds with the formula CdSO4·xH2O. The most common form is the monohydrate CdSO4·H2O, but two other forms are known CdSO4·8⁄3H2O and the anhydrous salt (CdSO4). All salts are colourless and highly soluble in water.

<span class="mw-page-title-main">Hydrazoic acid</span> Unstable and toxic chemical compound

Hydrazoic acid, also known as hydrogen azide, azic acid or azoimide, is a compound with the chemical formula HN3. It is a colorless, volatile, and explosive liquid at room temperature and pressure. It is a compound of nitrogen and hydrogen, and is therefore a pnictogen hydride. The oxidation state of the nitrogen atoms in hydrazoic acid is fractional and is -1/3. It was first isolated in 1890 by Theodor Curtius. The acid has few applications, but its conjugate base, the azide ion, is useful in specialized processes.

A multi-component reaction, sometimes referred to as a "Multi-component Assembly Process", is a chemical reaction where three or more compounds react to form a single product. By definition, multicomponent reactions are those reactions whereby more than two reactants combine in a sequential manner to give highly selective products that retain majority of the atoms of the starting material.

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<span class="mw-page-title-main">Gold(III) chloride</span> Chemical compound

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<span class="mw-page-title-main">Cyanamide</span> Chemical compound featuring a nitrile group attached to an amino group

Cyanamide is an organic compound with the formula CN2H2. This white solid is widely used in agriculture and the production of pharmaceuticals and other organic compounds. It is also used as an alcohol-deterrent drug. The molecule features a nitrile group attached to an amino group. Derivatives of this compound are also referred to as cyanamides, the most common being calcium cyanamide (CaCN2).

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<span class="mw-page-title-main">Aluminium fluoride</span> Chemical compound

Aluminium fluoride is an inorganic compound with the formula AlF3. It forms hydrates AlF3·xH2O. Anhydrous AlF3 and its hydrates are all colorless solids. Anhydrous AlF3 is used in the production of aluminium metal. Several occur as minerals.

<span class="mw-page-title-main">Cobalt(II) nitrate</span> Chemical compound

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<span class="mw-page-title-main">Chromium(II) sulfate</span> Chemical compound

Chromium(II) sulfate is an inorganic compound with the chemical formula CrSO4. It often comes as hydrates CrSO4·nH2O. Several hydrated salts are known. The pentahydrate CrSO4·5H2O is a blue solid that dissolves readily in water. Solutions of chromium(II) are easily oxidized by air to Cr(III) species. Solutions of Cr(II) are used as specialized reducing agents of value in organic synthesis.

<span class="mw-page-title-main">Titanyl sulfate</span> Chemical compound

Titanyl sulfate is the inorganic compound with the formula TiOSO4. It is a white solid that forms by treatment of titanium dioxide with fuming sulfuric acid. It hydrolyzes to a gel of hydrated titanium dioxide. The structure consists of dense polymeric network with tetrahedral sulfur and octahedral titanium centers. The six ligands attached to titanium are derived from four different sulfate moieties and a bridging oxide. A monohydrate is also known, being prepared similarly to the anhydrous material. In the hydrate, one Ti–OS bond is replaced by Ti–OH2.

<span class="mw-page-title-main">Rhodium(III) iodide</span> Chemical compound

Rhodium(III) iodide is an inorganic compound with the formula RhI3. It is a black solid.

Lithium thiocyanate is a chemical compound with the formula LiSCN. It is an extremely hygroscopic white solid that forms the monohydrate and the dihydrate. It is the least stable of the alkali metal thiocyanates due to the large electrostatic deforming field of the lithium cation.

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References

  1. ↑ Hiroshi Fujihisa, Kazumasa Honda, Shigeaki Obata, Hiroshi Yamawaki, Satoshi Takeya, Yoshito Gotoha, Takehiro Matsunaga "Crystal structure of anhydrous 5-aminotetrazole and its high-pressure behavior" CrystEngComm, 2011, volume 13, pp. 99-102. doi : 10.1039/C0CE00278J
  2. ↑ D. D. Bray and J. G. White "Refinement of the structure of 5-aminotetrazole monohydrate" Acta Crystallogr. (1979). B35, pp. 3089-3091. doi : 10.1107/S0567740879011493
  3. ↑ Thiele, Johannes (1892-01-01). "Ueber Nitro- und Amidoguanidin". Justus Liebigs Annalen der Chemie. 270 (1–2): 1–63. doi:10.1002/jlac.18922700102. ISSN   0075-4617.
  4. ↑ Hantzsch, A.; Vagt, A. (1901-01-01). "Ueber das sogenannte Diazoguanidin". Justus Liebigs Annalen der Chemie. 314 (3): 339–369. doi:10.1002/jlac.19013140307. ISSN   0075-4617.
  5. ↑ MIHINA, JOSEPH S.; HERBST, ROBERT M. (1950-09-01). "The Reaction of Nitriles with Hydrazoic Acid: Synthesis of Monosubstituted Tetrazoles". The Journal of Organic Chemistry. 15 (5): 1082–1092. doi:10.1021/jo01151a027. ISSN   0022-3263.
  6. ↑ US 5424449,Rothgery, Eugene F.&Knollmueller, Karl O.,"Process for the preparation of 5-aminotetrazole",published 1995-06-13,issued 1995-06-13
  7. ↑ US 5594146,Murotani, Masahiro; Mura, Hajime& Takeda, Makotoet al.,"Process for producing 5-aminotetrazole",published 1997-01-14,issued 1997-01-14
  8. ↑ Fujihisa, Hiroshi; Honda, Kazumasa; Obata, Shigeaki; Yamawaki, Hiroshi; Takeya, Satoshi; Gotoh, Yoshito; Matsunaga, Takehiro (2011). "Crystal structure of anhydrous 5-aminotetrazole and its high-pressure behavior". CrystEngComm. 13: 99–102. doi:10.1039/c0ce00278j.
  9. ↑ Bray, D. D.; White, J. G. (1979). "Refinement of the structure of 5-aminotetrazole monohydrate". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 35 (12): 3089–3091. doi:10.1107/S0567740879011493.
  10. ↑ Dolzhenko, A. V. (2017). "5-Aminotetrazole as a Building Block for Multicomponent Reactions (Review)". Heterocycles. 94 (10): 1819–1846. doi:10.3987/rev-17-867 (inactive 31 January 2024).{{cite journal}}: CS1 maint: DOI inactive as of January 2024 (link)
  11. ↑ Zhao, Fang-Hua; Che, Yun-Xia; Zheng, Ji-Min; Grandjean, Fernande; Long, Gary J. (2012). "Two Acentric Mononuclear Molecular Complexes with Unusual Magnetic and Ferroelectric Properties". Inorganic Chemistry. 51 (8): 4862–4868. doi:10.1021/ic300394c. PMID   22480292.
  12. ↑ Lesnikovich, A. I.; Ivashkevich, O. A.; Levchik, S. V.; Balabanovich, A. I.; Gaponik, P. N.; Kulak, A. A. "Thermal decomposition of aminotetrazoles" Thermochimica Acta 2002, vol. 388, pp. 233-251. doi : 10.1016/S0040-6031(02)00027-8
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