Kirsanov reaction

Last updated April 15, 2019

The Kirsanov reaction is a method for the synthesis of certain organophosphorus compounds. In this reaction a tertiary phosphine is combined with a halogen and then an amine to give the iminophosphines, which are useful ligands and useful reagents.^[1] A typical reaction involves triphenylphosphine with bromine to give bromotriphenylphosphonium bromide:

Organophosphorus compounds are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective insecticides, although some are extremely toxic to man, including sarin and VX nerve agents.

Ligand molecule or functional group that binds or can bind to the central atom in a coordination complex

In coordination chemistry, a ligand is an ion or molecule that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands".

Reagent substance or compound that is added to a system in order to bring about a chemical reaction, or added to see if a reaction occurs

A reagent is a substance or compound added to a system to cause a chemical reaction, or added to test if a reaction occurs. The terms reactant and reagent are often used interchangeably—however, a reactant is more specifically a substance consumed in the course of a chemical reaction. Solvents, though involved in the reaction, are usually not called reactants. Similarly, catalysts are not consumed by the reaction, so they are not reactants. In biochemistry, especially in connection with enzyme-catalyzed reactions, the reactants are commonly called substrates.

Ph₃P + Br₂ → Ph₃PBr⁺Br⁻

This salt is treated in situ with alkylamines to give the iminophosphorane:

Ph₃PBr⁺Br⁻ + 3 RNH₂ → Ph₃PNR + 2 RNH₃⁺Br⁻

The method is used when the conventional Staudinger reaction is not applicable, i.e. when the organic azide is not available to generate the iminophosphorane. Thus, it is used to make iminophosphoranes from alkyl amines.^[2]

The Staudinger reaction is a chemical reaction of an azide with a phosphine or phosphite produces an iminophosphorane. The reaction was discovered by and named after Hermann Staudinger. The reaction follows this stoichiometry:

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In organic chemistry, amines (, UK also ) 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 (these may respectively be called alkylamines and arylamines; amines in which both types of substituent are attached to one nitrogen atom may be called alkylarylamines). Important amines include amino acids, biogenic amines, trimethylamine, and aniline; see Category:Amines for a list of amines. Inorganic derivatives of ammonia are also called amines, such as chloramine (NClH₂); see Category:Inorganic amines.

The haloalkanes are a group of chemical compounds derived from alkanes containing one or more halogens. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially and, consequently, are known under many chemical and commercial names. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes which contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

Azide is the anion with the formula N⁻
₃. It is the conjugate base of hydrazoic acid (HN₃). N⁻
₃ is a linear anion that is isoelectronic with CO₂, NCO⁻, N₂O, NO⁺
₂ and NCF. Per valence bond theory, azide can be described by several resonance structures; an important one being $. Azide is also a functional group in organic chemistry, RN 3 . The dominant application of azides is as a propellant in air bags.$

Diphosgene is a chemical compound with the formula ClCO₂CCl₃. This colorless liquid is a valuable reagent in the synthesis of organic compounds. Diphosgene is related to phosgene and has comparable toxicity, but is more conveniently handled because it is a liquid, whereas phosgene is a gas.

An imine is a functional group or chemical compound containing a carbon–nitrogen double bond. The nitrogen atom can be attached to a hydrogen (H) or an organic group (R). If this group is not a hydrogen atom, then the compound can sometimes be referred to as a Schiff base. The carbon atom has two additional single bonds. The term "imine" was coined in 1883 by the German chemist Albert Ladenburg.

Acyl chloride any chemical compound having a chlorine atom bonded to a carboacyl group

In organic chemistry, an acyl chloride (or acid chloride) is an organic compound with the functional group -COCl. Their formula is usually written RCOCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH₃COCl. Acyl chlorides are the most important subset of acyl halides.

In organic chemistry, an imide is a functional group consisting of two acyl groups bound to nitrogen. The compounds are structurally related to acid anhydrides, although imides are more resistant toward hydrolysis. In terms of commercial applications, imides are best known as components of high-strength polymers, called polyimides.

The Sonogashira reaction is a cross-coupling reaction used in organic synthesis to form carbon–carbon bonds. It employs a palladium catalyst as well as copper co-catalyst to form a carbon–carbon bond between a terminal alkyne and an aryl or vinyl halide.

Phosphorus trichloride chemical compound

Phosphorus trichloride is a chemical compound of phosphorus and chlorine, having the chemical formula PCl₃. It has a trigonal pyramidal shape. It is the most important of the three phosphorus chlorides. It is an important industrial chemical, being used for the manufacture of organophosphorus compounds for a wide variety of applications. It has a ³¹P NMR signal at around +220 ppm with reference to a phosphoric acid standard.

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C₆H₅)₃ - often abbreviated to PPh₃ or Ph₃P. It is widely used in the synthesis of organic and organometallic compounds. PPh₃ exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

Cyanuric chloride is an organic compound with the formula (NCCl)₃. This white solid is the chlorinated derivative of 1,3,5-triazine. It is the trimer of cyanogen chloride. Cyanuric chloride is the main precursor to the popular but controversial herbicide atrazine.

Sodium bis(trimethylsilyl)amide is the organosilicon compound with the formula ((CH₃)₃Si)₂NNa. This species, usually called NaHMDS (sodium hexamethyldisilazide), is a strong base used for deprotonation reactions or base-catalyzed reactions. Its advantages are that it is commercially available as a solid and it is soluble not only in ethers, such as THF or diethyl ether, but also in aromatic solvents, like benzene and toluene by virtue of the lipophilic TMS groups.

Cyanogen bromide is the inorganic compound with the formula (CN)Br or BrCN. It is a colorless solid that is widely used to modify biopolymers, fragment proteins and peptides, and synthesize other compounds. The compound is classified as a pseudohalogen.

Organozinc compounds in organic chemistry contain carbon to zinc chemical bonds. Organozinc chemistry is the science of organozinc compounds describing their physical properties, synthesis and reactions.

Diphenyl diselenide is the chemical compound with the formula (C₆H₅)₂Se₂, abbreviated Ph₂Se₂ This orange-coloured solid is the oxidized derivative of benzeneselenol. It is used as a source of the PhSe unit in organic synthesis.

Chlorodiphenylphosphine chemical compound

Chlorodiphenylphosphine is an organophosphorus compound with the formula (C₆H₅)₂PCl, abbreviated Ph₂PCl. It is a colourless oily liquid with a pungent odor that is often described as being garlic-like and detectable even in the ppb range. It is useful reagent for introducing the Ph₂P group into molecules, which includes many ligands. Like other halophosphines, Ph₂PCl is reactive with many nucleophiles such as water and easily oxidized even by air.

A cyclodiphosphazane is a type of chemical compound and a saturated four membered P₂N₂ ring and one of the major classes of cyclic phosphazene compounds. Bis(chloro)cyclodiphosphazanes, (cis-[ClP(μ-NR)]₂) are important starting compounds for synthesizing a variety of cyclodiphosphazane derivatives by nucleophilic substitution reactions; are prepared by reaction of phosphorus trichloride (PCl₃) with a primary amine (RNH₂) or amine hydrochlorides (RNH₃Cl).

Organosilver chemistry in chemistry is the study of organometallic compounds containing a carbon to silver chemical bond and the study of silver as catalyst in organic reactions. In the group 11 elements silver is the element below copper. The chemistries have much in common but organosilver catalysis is much less common (mostly academic study) than organocopper chemistry due both to the relatively high price of silver and to the poor thermal stability of organosilver compounds. The oxidation state for silver in organosilver compounds in exclusively +1 with the notable exception of Ag(III) in the trifluoromethyl silver anion Ag(CF₃)₄⁻ because of the electron-withdrawing effect of the trifluoromethyl groups. Poor thermal stability is reflected in decomposition temperatures of AgMe (-50 °C) versus CuMe (-15 °C) and PhAg (74 °C) vs PhCu (100 °C).

References

↑ Eguchi, Shoji; Matsushita, Yuji; Yamashita, Keizo (April 1992). "THE AZA-WITTIC REACTION IN HETEROCYCLIC SYNTHESIS. A REVIEW". Organic Preparations and Procedures International. 24 (2): 209–243. doi:10.1080/00304949209355702.
↑ Buchard, Antoine; Heuclin, Hadrien; Auffrant, Audrey; Le Goff, Xavier F.; Le Floch, Pascal (2009). "Coordination of tetradentate X2N2 (X = P, S, O) ligands to iron(ii) metal center and catalytic application in the transfer hydrogenation of ketones". Dalton Transactions (9): 1659. doi:10.1039/b816439h.

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[1] Eguchi, Shoji; Matsushita, Yuji; Yamashita, Keizo (April 1992). "THE AZA-WITTIC REACTION IN HETEROCYCLIC SYNTHESIS. A REVIEW". Organic Preparations and Procedures International. 24 (2): 209–243. doi:10.1080/00304949209355702.

[2] Buchard, Antoine; Heuclin, Hadrien; Auffrant, Audrey; Le Goff, Xavier F.; Le Floch, Pascal (2009). "Coordination of tetradentate X2N2 (X = P, S, O) ligands to iron(ii) metal center and catalytic application in the transfer hydrogenation of ketones". Dalton Transactions (9): 1659. doi:10.1039/b816439h.