Transamidation

Last updated

Transamidation is a chemical reaction in which an amide reacts with an amine to generate a new amide:

RC(O)NR'2 + HNR"2 → RC(O)NR"2 + HNR'2

The reaction is typically very slow, but it can be accelerated with Lewis acid [1] and organometallic catalysts. [2] Primary amides (RC(O)NH2) are more amenable to this reaction.

Ureas

In contrast to the reluctance of amides as substrates, urea is more susceptible to this exchange process. Transamidation is practiced, sometimes even on an industrial scale, to prepare a variety of N-substituted ureas: [3]

(H2N)2CO + R2NH → (R2N)(H2N)CO + NH3
(R2N)(H2N)CO + R2NH → (R2N)2CO + NH3

Methylurea, precursor to theobromine, is produced from methylamine and urea. Phenylurea is produced similarly but from anilinium chloride: [4]

(H2N)2CO + [C6H5NH3]Cl → (C6H5(H)N)(H2N)CO + NH4Cl

Hydrazine derivatives of urea are often produced by transamidation-like reactions. These products include carbohydrazide, semicarbazide, and biurea.

Related Research Articles

In chemistry, amines are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines, trimethylamine, and aniline. Inorganic derivatives of ammonia are also called amines, such as monochloramine.

<span class="mw-page-title-main">Amide</span> Organic compounds of the form RC(=O)NR′R″

In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula R−C(=O)−NR′R″, where R, R', and R″ represent any group, typically organyl groups or hydrogen atoms. The amide group is called a peptide bond when it is part of the main chain of a protein, and an isopeptide bond when it occurs in a side chain, such as in the amino acids asparagine and glutamine. It can be viewed as a derivative of a carboxylic acid with the hydroxyl group replaced by an amine group ; or, equivalently, an acyl (alkanoyl) group joined to an amine group.

Urea, also called carbamide, is an organic compound with chemical formula CO(NH2)2. This amide has two amino groups joined by a carbonyl functional group. It is thus the simplest amide of carbamic acid.

<span class="mw-page-title-main">Ammonium</span> Polyatomic ion (NH₄, charge +1)

The ammonium cation is a positively charged polyatomic ion with the chemical formula NH+4 or [NH4]+. It is formed by the protonation of ammonia. Ammonium is also a general name for positively charged (protonated) substituted amines and quaternary ammonium cations, where one or more hydrogen atoms are replaced by organic or other groups.

<span class="mw-page-title-main">Transamination</span> Chemical reaction that transfers an amino group to a ketoacid

Transamination is a chemical reaction that transfers an amino group to a ketoacid to form new amino acids. This pathway is responsible for the deamination of most amino acids. This is one of the major degradation pathways which convert essential amino acids to non-essential amino acids.

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.

<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.

In chemistry, a trimer is a molecule or polyatomic anion formed by combination or association of three molecules or ions of the same substance. In technical jargon, a trimer is a kind of oligomer derived from three identical precursors often in competition with polymerization.

<span class="mw-page-title-main">Cyanuric acid</span> Chemical compound belonging to the class of triazine

Cyanuric acid or 1,3,5-triazine-2,4,6-triol is a chemical compound with the formula (CNOH)3. Like many industrially useful chemicals, this triazine has many synonyms. This white, odorless solid finds use as a precursor or a component of bleaches, disinfectants, and herbicides. In 1997, worldwide production was 160 000 tonnes.

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

Sulfamic acid, also known as amidosulfonic acid, amidosulfuric acid, aminosulfonic acid, sulphamic acid and sulfamidic acid, is a molecular compound with the formula H3NSO3. This colourless, water-soluble compound finds many applications. Sulfamic acid melts at 205 °C before decomposing at higher temperatures to water, sulfur trioxide, sulfur dioxide and nitrogen.

<span class="mw-page-title-main">Carbodiimide</span> Class of organic compounds with general structure RN=C=NR

In organic chemistry, a carbodiimide is a functional group with the formula RN=C=NR. On Earth they are exclusively synthetic, but in interstellar space the parent compound HN=C=NH has been detected by its maser emissions.

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

Semicarbazide is the chemical compound with the formula OC(NH2)(N2H3). It is a water-soluble white solid. It is a derivative of urea.

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

Lithium amide or lithium azanide is an inorganic compound with the chemical formula LiNH2. It is a white solid with a tetragonal crystal structure. Lithium amide can be made by treating lithium metal with liquid ammonia:

<span class="mw-page-title-main">Thioureas</span> Organosulfur compounds with an >NC(=S)N< structure

In organic chemistry, thioureas are members of a family of organosulfur compounds with the formula S=C(NR2)2 and structure R2N−C(=S)−NR2. The parent member of this class of compounds is thiourea. The thiourea functional group has a planar S=CN2 core.

Carbamic acid, which might also be called aminoformic acid or aminocarboxylic acid, is the chemical compound with the formula H2NCOOH. It can be obtained by the reaction of ammonia NH3 and carbon dioxide CO2 at very low temperatures, which also yields ammonium carbamate [NH4]+[NH2CO2]. The compound is stable only up to about 250 K (−23 °C); at higher temperatures it decomposes into those two gases. The solid apparently consists of dimers, with the two molecules connected by hydrogen bonds between the two carboxyl groups –COOH.

<span class="mw-page-title-main">Metal amides</span>

Metal amides (systematic name metal azanides) are a class of coordination compounds composed of a metal center with amide ligands of the form NR2. Amido complexes of the parent amido ligand NH2 are rare compared to complexes with diorganylamido ligand, such as dimethylamido. Amide ligands have two electron pairs available for bonding.

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

Triuret is an organic compound with the formula (H2NC(O)NH)2CO. It is a product from the pyrolysis of urea. Triuret is a colorless, crystalline, hygroscopic solid, slightly soluble in cold water or ether, and more soluble in hot water. It is a planar molecule. The central carbonyl is hydrogen-bonded to both terminal amino groups.

<span class="mw-page-title-main">Ureas</span>

In chemistry, ureas are a class of organic compounds with the formula (R2N)2CO where R = H, alkyl, aryl, etc. Thus, in addition to describing the specific chemical compound urea ((H2N)2CO), urea is the name of a functional group that is found in many compounds and materials of both practical and theoretical interest. Generally ureas are colorless crystalline solids, which, owing to the presence of fewer hydrogen bonds, exhibit melting points lower than that of urea itself.

In chemistry, ammonolysis (/am·mo·nol·y·sis/) is the process of splitting ammonia into . Ammonolysis reactions can be conducted with organic compounds to produce amines (molecules containing a nitrogen atom with a lone pair, :N), or with inorganic compounds to produce nitrides. This reaction is analogous to hydrolysis in which water molecules are split. Similar to water, liquid ammonia also undergoes auto-ionization, , where the rate constant is k = 1.9 × 10-38.

<span class="mw-page-title-main">Amide (functional group)</span>

In chemistry, the term amide ( or or ) is a compound with the functional group RnE(=O)xNR2, where n and x may be 1 or 2, E is some element, and each R represents an organic group or hydrogen. It is a derivative of an oxoacid RnE(=O)xOH with an hydroxy group –OH replaced by an amine group –NR2.

References

  1. T. A. Dineen; M. A. Zajac; A. G. Myers (2006). "Efficient Transamidation of Primary Carboxamides by in situ Activation with N,N-Dialkylformamide Dimethyl Acetals". J. Am. Chem. Soc. 128 (50): 16406–16409. doi:10.1021/ja066728i. PMID   17165798.
  2. Emma L. Baker; Michael M. Yamano; Yujing Zhou; Sarah M. Anthony; Neil K. Garg (2016). "A two-step approach to achieve secondary amide transamidation enabled by nickel catalysis". Nature Communications. 7: 11554. Bibcode:2016NatCo...711554B. doi:10.1038/ncomms11554. PMC   4876455 . PMID   27199089.
  3. C. Nitschke; G. Scherr (2012). "Urea Derivatives". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.o27_o04.
  4. "Arylureas II. Urea Method p-Ethoxyphenylurea". Org. Synth. 31: 11. 1951. doi:10.15227/orgsyn.031.0011.