Acetamidine hydrochloride

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Acetamidine hydrochloride
Acetamidine hydrochloride.png
Names
IUPAC name
Ethanimidamide;hydrochloride
Other names
Acetamidinium chloride
Ethanimidamide monohydrochloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.004.274 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 204-700-9
PubChem CID
UNII
  • InChI=1S/C2H6N2.ClH/c1-2(3)4;/h1H3,(H3,3,4);1H
    Key: WCQOBLXWLRDEQA-UHFFFAOYSA-N
  • Cl.N=C(N)C
Properties
C2H7ClN2
Molar mass 94.54 g·mol−1
Structure
Monoclinic
C2/c
a = 11.673, b = 9.862, c = 9.601
α = 90°, β = 111.71°, γ = 90° [1]
Hazards [2]
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P362+P364, P403+P233, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
0
0
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Acetamidine hydrochloride is an organic compound with the formula CH3C(NH)NH2·HCl, used in the synthesis of many nitrogen-bearing compounds. It is the hydrochloride of acetamidine, one of the simplest amidines.

Contents

Properties

Acetamidine hydrochloride is a hygroscopic solid which forms colourless monoclinic crystals. [1] It is soluble in water and alcohol.

It releases ammonium chloride upon heating. Dry acetamidine hydrochloride releases acetonitrile, while in aqueous solution, it instead undergoes hydrolysis to acetic acid and ammonia. [3]

CH3C(NH)NH2·HCl → CH3CN + NH4Cl
CH3C(NH)NH2·HCl + 2 H2O → CH3COOH + NH3 + NH4Cl

As free base amidines are strong Lewis bases, acetamidine hydrochloride is a weak Lewis acid. Treatment with strong base gives free base acetamidine:

CH3C(NH)NH2·HCl + KOH → CH3C(NH)NH2 + KCl + H2O

Synthesis

Acetamidine hydrochloride is synthesised in a two-step process that begins with a solution of acetonitrile in ethanol at close to 0 °C. [4] First, the mixture is treated with anhydrous hydrogen chloride in a Pinner reaction, producing crystals of acetimido ethyl ether hydrochloride:

H3C−C≡N + C2H5OH + HCl → H3C−C(=NH·HCl)−OC2H5

The imino ether salt is then treated with an excess of ammonia in dry ethanol, converting the ether to the amidine:

H3C−C(=NH·HCl)−OC2H5 + NH3 → H3C−C(=NH)−NH2·HCl + C2H5OH

All reagents must be thoroughly dried using a strong desiccant such as phosphorus pentoxide, as the intermediate imido ether is susceptible to hydrolysis, yielding ammonium chloride and ethyl formate. Layers of ammonium chloride can form on the imido ether salt, limiting the formation of amidine. [4]

Applications

As a source of amidine, acetamidine hydrochloride is a precursor to the industrial and laboratory synthesis of many nitrogen compounds. It reacts with β-dicarbonyls to produce substituted pyrimidines, [5] with acetaldehydes to form substituted imidazoles, [6] and with imidates to form substituted triazines. [7]

In particular, its reaction with a dicarbonyl intermediate is an early step in the synthesis of thyamine (vitamin B1) and many of its derivatives. [8]

Related Research Articles

Pyrimidine is an aromatic, heterocyclic, organic compound similar to pyridine. One of the three diazines, it has nitrogen atoms at positions 1 and 3 in the ring. The other diazines are pyrazine and pyridazine.

<span class="mw-page-title-main">Hydroxylamine</span> Inorganic compound

Hydroxylamine is an inorganic compound with the chemical formula NH2OH. The compound is in a form of a white hygroscopic crystals. Hydroxylamine is almost always provided and used as an aqueous solution. It is consumed almost exclusively to produce Nylon-6. The oxidation of NH3 to hydroxylamine is a step in biological nitrification.

In organic chemistry, a nitrile is any organic compound that has a −C≡N functional group. The name of the compound is composed of a base, which includes the carbon of the −C≡N, suffixed with "nitrile", so for example CH3CH2C≡N is called "propionitrile". The prefix cyano- is used interchangeably with the term nitrile in industrial literature. Nitriles are found in many useful compounds, including methyl cyanoacrylate, used in super glue, and nitrile rubber, a nitrile-containing polymer used in latex-free laboratory and medical gloves. Nitrile rubber is also widely used as automotive and other seals since it is resistant to fuels and oils. Organic compounds containing multiple nitrile groups are known as cyanocarbons.

Acetamide (systematic name: ethanamide) is an organic compound with the formula CH3CONH2. It is an amide derived from ammonia and acetic acid. It finds some use as a plasticizer and as an industrial solvent. The related compound N,N-dimethylacetamide (DMA) is more widely used, but it is not prepared from acetamide. Acetamide can be considered an intermediate between acetone, which has two methyl (CH3) groups either side of the carbonyl (CO), and urea which has two amide (NH2) groups in those locations. Acetamide is also a naturally occurring mineral with the IMA symbol: Ace.

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

Samarium(III) chloride, also known as samarium trichloride, is an inorganic compound of samarium and chloride. It is a pale yellow salt that rapidly absorbs water to form a hexahydrate, SmCl3.6H2O. The compound has few practical applications but is used in laboratories for research on new compounds of samarium.

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

Acetylacetone is an organic compound with the chemical formula CH3−C(=O)−CH2−C(=O)−CH3. It is classified as a 1,3-diketone. It exists in equilibrium with a tautomer CH3−C(=O)−CH=C(−OH)−CH3. The mixture is a colorless liquid. These tautomers interconvert so rapidly under most conditions that they are treated as a single compound in most applications. Acetylacetone is a building block for the synthesis of many coordination complexes as well as heterocyclic compounds.

<span class="mw-page-title-main">Thiourea</span> Organosulfur compound (S=C(NH2)2)

Thiourea is an organosulfur compound with the formula SC(NH2)2 and the structure H2N−C(=S)−NH2. It is structurally similar to urea, except that the oxygen atom is replaced by a sulfur atom ; however, the properties of urea and thiourea differ significantly. Thiourea is a reagent in organic synthesis. Thioureas are a broad class of compounds with the general structure R2N−C(=S)−NR2.

Triethylamine is the chemical compound with the formula N(CH2CH3)3, commonly abbreviated Et3N. It is also abbreviated TEA, yet this abbreviation must be used carefully to avoid confusion with triethanolamine or tetraethylammonium, for which TEA is also a common abbreviation. It is a colourless volatile liquid with a strong fishy odor reminiscent of ammonia. Like diisopropylethylamine (Hünig's base), triethylamine is commonly employed in organic synthesis, usually as a base.

<span class="mw-page-title-main">Pyridinium chloride</span> Chemical compound

Pyridinium chloride is an organic chemical compound with a formula of C5H5NHCl.

Guanidine is the compound with the formula HNC(NH2)2. It is a colourless solid that dissolves in polar solvents. It is a strong base that is used in the production of plastics and explosives. It is found in urine predominantly in patients experiencing renal failure. A guanidine moiety also appears in larger organic molecules, including on the side chain of arginine.

1,3,5-Triazine, also called s-triazine, is an organic chemical compound with the formula (HCN)3. It is a six-membered heterocyclic aromatic ring, one of several isomeric triazines. s-Triazine —the "symmetric" isomer—and its derivatives are useful in a variety of applications.

<span class="mw-page-title-main">Triflic acid</span> Chemical compound

Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for esterification. It is a hygroscopic, colorless, slightly viscous liquid and is soluble in polar solvents.

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

Benzamidine is an organic compound with the formula C6H5C(NH)NH2. It is the simplest aryl amidine. The compound is a white solid that is slightly soluble in water. It is usually handled as the hydrochloride salt, a white, water-soluble solid.

Monochloramine, often called chloramine, is the chemical compound with the formula NH2Cl. Together with dichloramine (NHCl2) and nitrogen trichloride (NCl3), it is one of the three chloramines of ammonia. It is a colorless liquid at its melting point of −66 °C (−87 °F), but it is usually handled as a dilute aqueous solution, in which form it is sometimes used as a disinfectant. Chloramine is too unstable to have its boiling point measured.

<span class="mw-page-title-main">Ortho ester</span> Chemical group with the structure RC(OR)3

In organic chemistry, an ortho ester is a functional group containing three alkoxy groups attached to one carbon atom, i.e. with the general formula RC(OR')3. Orthoesters may be considered as products of exhaustive alkylation of unstable orthocarboxylic acids and it is from these that the name 'ortho ester' is derived. An example is ethyl orthoacetate, CH3C(OCH2CH3)3, more correctly known as 1,1,1-triethoxyethane.

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

Lanthanum chloride is the inorganic compound with the formula LaCl3. It is a common salt of lanthanum which is mainly used in research. It is a white solid that is highly soluble in water and alcohols.

<span class="mw-page-title-main">1-Methylimidazole</span> Chemical compound

1-Methylimidazole or N-methylimidazole is an aromatic heterocyclic organic compound with the formula CH3C3H3N2. It is a colourless liquid that is used as a specialty solvent, a base, and as a precursor to some ionic liquids. It is a fundamental nitrogen heterocycle and as such mimics for various nucleoside bases as well as histidine and histamine.

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

Amprolium is the organic compound sold as a coccidiostat used in poultry. It has many International Nonproprietary Names.

Fulminating gold is a light- and shock-sensitive yellow to yellow-orange amorphous heterogeneous mixture of different polymeric compounds of predominantly gold(III), ammonia, and chlorine that cannot be described by a chemical formula. Here, "fulminating" has its oldest meaning, "explosive" ; the material contains no fulminate ions. The best approximate description is that it is the product of partial hydrolysis of . Upon combustion, it produces a purple vapor. The complex has a square planar molecular geometry with a low spin state.

<span class="mw-page-title-main">3-Dimethylaminoacrolein</span> Chemical compound

3-Dimethylaminoacrolein is an organic compound with the formula Me2NC(H)=CHCHO. It is a pale yellow water-soluble liquid. The compound has a number of useful and unusual properties, e.g. it "causes a reversal of the hypnotic effect of morphine in mice" and has a "stimulating effect in humans".

References

  1. 1 2 Cannon, Jack R.; White, Allan H.; Willis, Anthony C. (1976). "Crystal structure of acetamidinium chloride". Journal of the Chemical Society, Perkin Transactions 2 (3): 271. doi:10.1039/P29760000271.
  2. ↑ Fisher Scientific, acetamidine hydrochloride 98+%
  3. ↑ Shriner, R. L.; Neumann, Fred W. (1944). "The Chemistry of the Amidines". Chemical Reviews. 35 (3): 351–425. doi:10.1021/cr60112a002.
  4. 1 2 Dox, A. W. (1928). "Acetamidine hydrochloride". Organic Syntheses . doi:10.15227/orgsyn.008.0001 .
  5. ↑ Chu, Xue-Qiang; Cao, Wen-Bin; Xu, Xiao-Ping; Ji, Shun-Jun (2017). "Iron Catalysis for Modular Pyrimidine Synthesis through β-Ammoniation/Cyclization of Saturated Carbonyl Compounds with Amidines". The Journal of Organic Chemistry. 82 (2): 1145–1154. doi:10.1021/acs.joc.6b02767.
  6. ↑ Wang, Jing; Zhang, Fang-Dong; Tang, Dong; Wu, Ping; Zhang, Xue-Guo; Chen, Bao-Hua (2017). "I2/TBPB mediated oxidative reaction of aryl acetaldehydes with amidines: Synthesis of 1,2,5-triaryl-1H-imidazoles". RSC Advances. 7 (40): 24594–24597. Bibcode:2017RSCAd...724594W. doi: 10.1039/C7RA01966A .
  7. ↑ USpatent 3203550A,Frederic Charles Schaefer,"Method for the preparation of substituted s-triazine compounds",issued 1965-08-31, assigned to American Cyanamid Company
  8. ↑ Tylicki, Adam; Łotowski, Zenon; Siemieniuk, Magdalena; Ratkiewicz, Artur (2018). "Thiamine and selected thiamine antivitamins — biological activity and methods of synthesis". Bioscience Reports. 38. doi:10.1042/BSR20171148. PMID   29208764.
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