Phenylsodium C
6H
5Na is an
organosodium compound. Solid phenylsodium was first isolated by Nef in 1903. Although the behavior of phenylsodium and
phenyl magnesium bromide are similar, the organosodium compound is very rarely used.
[
]
Synthesis
The existence of phenylsodium was originally proposed by August Kekulé
Friedrich August Kekulé, later Friedrich August Kekule von Stradonitz ( , ; 7 September 1829 – 13 July 1896), was a German organic chemist. From the 1850s until his death, Kekulé was one of the most prominent chemists in Europe, especially ...
after observing the formation of sodium benzoate
Sodium benzoate is the sodium salt of benzoic acid, widely used as a food preservative (with an E number of E211) and a pickling agent. It appears as a white crystalline chemical with the formula C6H5COONa.
Production
Sodium benzoate is commo ...
in the reaction of bromobenzene
Bromobenzene is an aryl halide, C6H5Br. It is a colourless liquid although older samples can appear yellow. It is a reagent in organic synthesis.
Synthesis and reactions
Bromobenzene is prepared by the action of bromine on benzene in the presen ...
with sodium
Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...
under carbon dioxide
Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transpar ...
.
Transmetalation
In the original synthesis, diphenylmercury
Diphenylmercury is the organomercury compound with the formula Hg(C6H5)2. It is a white solid. The compound is of historic interest as a particularly stable organometallic compound but it finds few uses because of its high toxicity.
Preparation
...
and sodium was shown to yield a suspension of phenylsodium:
:(C6H5)2Hg + 3 Na → 2 C6H5Na + NaHg
The Shorigen reaction is also used in the generation of phenylsodium, where an alkyl sodium compound is treated with benzene:
: RNa + C6H6 → RH + C6H5Na
The method can also result in the addition of a second sodium. This dimetallation occurs in the ''meta'' and ''para'' positions. The use of certain alkyl sodium compounds such as n-amyl sodium is known to greatly increase this dimetallation effect.
Metal-halogen exchange
A common route to phenylsodium utilizes powdered sodium with bromobenzene
Bromobenzene is an aryl halide, C6H5Br. It is a colourless liquid although older samples can appear yellow. It is a reagent in organic synthesis.
Synthesis and reactions
Bromobenzene is prepared by the action of bromine on benzene in the presen ...
:
: C6H5Br + 2 Na → C6H5Na + NaBr
The yield of this method is lowered by the formation of diphenyl due to phenylsodium reacting with aryl halide starting material
Lithium exchange
A more modern synthesis involves the reaction of phenyllithium
Phenyllithium or lithobenzene is an organometallic agent with the empirical formula C6H5Li. It is most commonly used as a metalating agent in organic syntheses and a substitute for Grignard reagents for introducing phenyl groups in organic synthes ...
and NaO''t''Bu:
:C6H5Li + NaO''t''Bu → C6H5Na + LiO''t''Bu
Properties and structure
The first syntheses of phenylsodium which employed the organomercury route seemed to yield a light brown powder. It was discovered by Wilhelm Schlenk
Wilhelm may refer to:
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that this product was contaminated by a sodium amalgum. Centrifugation allowed for the isolation of pure phenylsodium which appears as a yellowish-white amorphous powder which readily bursts into flames.[
Like phenyllithium, adducts of the compound with ]PMDTA
PMDTA (''N'',''N'',''N′'',''N′′'',''N′′''-pentamethyldiethylenetriamine) is an organic compound with the formula CH3)2NCH2CH2sub>2NCH3. PMDTA is a basic, bulky, and flexible, tridentate ligand that is a used in orga ...
have been crystallized. While phenyllithium forms a monomeric adduct with PMDTA, phenylsodium exists as a dimer, reflecting the larger radium of sodium.[
Complexes of phenylsodium and magnesium alkoxides, especially magnesium 2-ethoxyethoxide Mg(OCH2CH2OEt)2, are soluble in benzene. The complex is formed by the reaction:
: NaPh + Mg(OCH2CH2OEt)2 → Na2MgPh2(OCH2CH2OEt)2
Although the phenylsodium is complexed, it maintains its phenylation and metalation ability. Additionally, the complex is highly stable in benzene retaining its reactivity after a month of storage.
Phenyllithium can also be used to modify the properties of phenylsodium. Ordinarily, phenylsodium reacts violently with ]diethyl ether
Diethyl ether, or simply ether, is an organic compound in the ether class with the formula , sometimes abbreviated as (see Pseudoelement symbols). It is a colourless, highly volatile, sweet-smelling ("ethereal odour"), extremely flammable liq ...
, but Georg Wittig
Georg Wittig (; 16 June 1897 – 26 August 1987) was a German chemist who reported a method for synthesis of alkenes from aldehydes and ketones using compounds called phosphonium ylides in the Wittig reaction. He shared the Nobel Prize in Che ...
showed that by synthesizing PhNa with PhLi in ether, the complex (C6H5Li)(C6H5Na)n was formed. The phenylsodium component of the complex reacts before the phenyllithium, making it an effective compound to stabilize the highly reactive sodium compound. This complex could be isolated as solid crystals which were soluble in ether and remained stable in solution at room temperature for several days. Phenyllithium is able to stabilize phenylsodium in a ratio as high as 1:24 Li:Na, although this produces an insoluble mass which could be still used for reactions.
Reactions
Reactions involving phenylsodium were employed as early as the mid 19th century, although before 1903. Typically phenylsodium is prepared in situ analogous to methods used for Grignard reagent
A Grignard reagent or Grignard compound is a chemical compound with the general formula , where X is a halogen and R is an organic group, normally an alkyl or aryl. Two typical examples are methylmagnesium chloride and phenylmagnesium bromide ...
s. The work of Acree provides a number of examples of reactions involving the compound.
Cross-coupling
The reaction with ethyl bromide produces ethyl benzene:
:NaPh + BrEt → PhEt + NaBr
An analogous reaction also occurs in the preparation of phenylsodium to produce diphenyl
Biphenyl (also known as diphenyl, phenylbenzene, 1,1′-biphenyl, lemonene or BP) is an organic compound that forms colorless crystals. Particularly in older literature, compounds containing the functional group consisting of biphenyl less one ...
:
:NaPh + PhBr → Ph-Ph + NaBr
Reaction of benzyl chloride
Benzyl chloride, or α-chlorotoluene, is an organic compound with the formula C6H5CH2Cl. This colorless liquid is a reactive organochlorine compound that is a widely used chemical building block.
Preparation
Benzyl chloride is prepared indust ...
and phenylsodium results in diphenylmethane
Diphenylmethane is an organic compound with the formula (C6H5)2CH2 (often abbreviated ). The compound consists of methane wherein two hydrogen atoms are replaced by two phenyl groups. It is a white solid.
Diphenylmethane is a common skeleton in or ...
and (E)-stilbene
(''E'')-Stilbene, commonly known as ''trans''-stilbene, is an organic compound represented by the condensed structural formula CHCH=CHCH. Classified as a diarylethene, it features a central ethylene moiety with one phenyl group substituent on ...
. Diphenylmethane is the expected product from the substitution of chloride. The formation of stilbene is implicates radical intermediates like those proposed in the Wurtz-Fittig reaction mechanism.
The reaction of phenylsodium with benzoyl chloride
Benzoyl chloride, also known as benzenecarbonyl chloride, is an organochlorine compound with the formula . It is a colourless, fuming liquid with an irritating odour, and consists of a benzene ring () with an acyl chloride () substituent. It is ...
yields, after hydrolysis, triphenylcarbinol. Benzophenone
Benzophenone is the organic compound with the formula (C6H5)2CO, generally abbreviated Ph2CO. It is a white solid that is soluble in organic solvents. Benzophenone is a widely used building block in organic chemistry, being the parent diarylket ...
is proposed as an intermediate.
:2NaPh + PhCOCl → Ph3CONa + NaCl
Metallation
Metallation reactions with phenylsodium proceed in the following general form:
: PhNa + RH → C6H6 + RNa
The metallation is confirmed/detected by treatment of the metallated compound with carbon dioxide, affording the corresponding sodium carboxylate which can be acidified to yield the carboxylic acid:
:RNa + CO2 → RCO2Na
Metallation follows a generally predictable order of reactivity. Benzene can be metallated by alkylsodium compounds resulting in phenylsodium. The phenylsodium is then able to metallate other aromatic compounds. The most commonly used reagent for metallation by phenylsodium is toluene, producing benzylsodium. Toluene can be metallated by synthesizing phenylsodium in toluene instead of benzene:
:C6H5Cl + 2Na + C6H5CH3 → C6H6 + NaCl + C6H5CH2Na
The benzylsodium can then be used in a nucleophilic addition. The effectiveness of the metallation can be determined by carbonating and isolating the phenylacetic acid
Phenylacetic acid (PAA; conjugate base phenylacetate), also known by various synonyms, is an organic compound containing a phenyl functional group and a carboxylic acid functional group. It is a white solid with a strong honey-like odor. Endogen ...
product.
See also
*Phenylcopper
Phenylcopper is an organometallic chemical compound of copper. Its chemical formula is .
Synthesis
Phenylcopper was the first known organocopper compound and was first prepared in 1923 from phenylmagnesium iodide and copper(I) iodide and in 1936 ...
References
{{Reflist
Organosodium compounds
Phenyl compounds