591-51-5 Usage
Description
Phenyllithium is an organometallic compound that is used as a nucleophile for substitution and addition reactions, and in the synthesis of organolithium building blocks through lithium-metalloid and metalation exchange reactions.
Properties
Phenyllithium has a molecular weight of 84.046 g/mol, a monoisotopic mass of 84.055 g/mol and an exact mass of 84.055 g/mol. It has a heavy atom count of 7 and a complexity of 95.8.
Phenyllithium is soluble in ether solvents; it is soluble in hydrocarbon solvents especially through the addition of donor additives/solvents.
Uses
Different sources of media describe the Uses of 591-51-5 differently. You can refer to the following data:
1. Phenyllithium is used for synthetic purposes to introduce a phenyl group into a compound or for metalation reactions. It undergoes typical Grignard type reactions.
2. Phenyllithium Solution (1.9M in Dibutyl Ether) is used as catalyst in the synthesis of pharmaceuticals. Used in the preparation of sulfonamides as well as in the preparation of orally bioavailable inhibitors of lipoprotein-associated phospholipase A2.
Preparation
Different sources of media describe the Preparation of 591-51-5 differently. You can refer to the following data:
1. Phenyllithium is synthesized by reacting elemental lithium with bromobenzene and dissolving the resulting products in ether. 18g[2.57 mol] of lithium that contains about 1-3% of sodium is flattened out using a hammer to attain a thickness of about 1.5 mm and then it is cut into chips of about 2x10x1.5 mm. The chips are placed into a flask holding 800 ml of anhydrous diethyl ether. The air is purged with dry argon or dry nitrogen and the ether is condensed to -250 C in the first two minutes of the reaction.
150.7 g of bromobenzene is placed into the flask through the dropping funnel, where one portion contains only 10 g of bromobenzene. After a few minutes of the reaction, there is a significant rise in temperature and the contents of the flask appear turbid. When the reaction starts to subside, after about 10 minutes, the remaining bromobenzene is added gradually to the flask using a dropper over a period of 1 hour, while maintaining the temperature of the contents between -150 C and -200 C. The dark coating on the lithium metal subsides almost entirely leaving behind a silver-like appearance.
Once all the bromobenzene is added to the flask, the contents are stirred and the temperature is maintained at -150 C for 1 hour. The temperature should then be allowed to increase up to 00, which will also be indicated a gradually fading glow of the reacting metal.
The resulting solution is emptied into a storage flask that has been filled with an inert gas. The filtration of the solution should take place in an inert atmosphere where a steady stream of argon or nitrogen[2-3 l/min] is passed through the reaction contents to prevent the solution from oxidation. Diethyl ether is then added to increase the Volume of the solution to 1 litre. The contents of the flask are then swirled gently[homogenization] to allow for the final step of the reaction, where the concentration is determined.
Solutions containing Phenyllithium are unstable at room temperature when left for long periods of time. The gradual attack of Phenyllithium on ethyl ether makes the commercial preparation of the compound undesirable. The incorporation of small quantities of ethyl ether to attain solutions of 1:1 phenyllithiumzethyl etherate complex in the presence of benzene reduces the average titer of the ethyl ether hence it makes the solution more stable.
The average titer should be about 1 molar, which corresponds to a high yield[90%] and purity. Amounts that are significantly higher or lower than the mol ratio often yield lesser amounts of Phenyllithium. The resulting 1:1 phenyllithiumzethyl etherate complex could be a tetramer or a dimer but it does not affect the ethyl ether to Phenyllithium ratio, which remains 1:1.
2. Phenyllithium is usually prepared in the laboratory from bromobenzene and lithium metal in diethyl ether. Since phenyllithium cleaves ether, the solution must be used within a day or refrigerated. Industrially, it is produced from chlorobenzene and lithium metal dispersion in a benzene-ether mixture. A potentially useful and inexpensive process is one in which benzene is metalated by n-butyllithium in the presence of di-tertiary amines.
Application
Phenyllithium can be used in the preparation of 1-Acetyl-1′-diphenylphosphinoferrocene from ferrocenophane
Hazard Statements
Phenyllithium is a flammable liquid/vapour and it may catch fire when exposed to air. When it comes into contact with water it emits flammable gases. Phenyllithium may result in acute toxicity upon ingestion and inhalation, or when it comes into contact with one’s eyes and skin.
Chemical Properties
Phenyllithium is a colorless crystalline solid or dark brown to black solution, It is soluble in polar solvents such as ethers and tertiary amines but insoluble in hydrocarbons. Concentrated solutions in volatile solvents are pyrophoric but can be safely handled under inert atmosphere.
Check Digit Verification of cas no
The CAS Registry Mumber 591-51-5 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 5,9 and 1 respectively; the second part has 2 digits, 5 and 1 respectively.
Calculate Digit Verification of CAS Registry Number 591-51:
(5*5)+(4*9)+(3*1)+(2*5)+(1*1)=75
75 % 10 = 5
So 591-51-5 is a valid CAS Registry Number.
InChI:InChI=1/C6H5.Li/c1-2-4-6-5-3-1;/h1-5H;/rC6H5Li/c7-6-4-2-1-3-5-6/h1-5H
591-51-5Relevant articles and documents
Lithium Hexaphenylrhodate(III) and-Iridate(III): Structure in the Solid State and in Solution
Iwasaki, Takanori,Hirooka, Yuko,Takaya, Hikaru,Honma, Tetsuo,Nozaki, Kyoko
, p. 2489 - 2495 (2021)
Anionic homoleptic organo-Transition metal complexes can be prepared from organolithium reagents and transition metal salts and are key reactive intermediates in C-C bond formation. However, the interaction between the anionic component and cationic counterparts of multianionic homoleptic organo-Transition metal complexes in solution remains unclear, unlike well-studied monoanionic complexes such as organocuprates. Here we have prepared and structurally characterized lithium hexaphenylrhodate(III) and-iridate(III) complexes, [Li(12-crown-4)2][MPh6{Li(thf)}2] (M = Rh and Ir), as the first examples of hexaaryl complexes of d6 metals. In the crystals, two Li cations contact the trianionic MPh6 moiety, while the other exists as a solvent-separated ion pair. In THF, hexaphenylrhodate decomposed within 1 h. In contrast, the Ir analog was stable. 7Li NMR and X-ray absorption fine structure analysis revealed the solution-phase structure of hexaphenyliridate, which maintained a partially contacted ion pair structure even in THF, a coordinating solvent.
CETONES PYRIDINIQUES. VIII. METALLATION REGIOSELECTIVE DE LA s-COLLIDINE: EFFETS DE METAUX ET DE SOLVANTS
Compagnon, P.-L.,Kimny, Tan
, p. 297 - 308 (1980)
The regioselective metalation of s-collidine yielding two anions, trapped by PhCN, was found to be essentially determined by the solvent and the size of the cation: twelve solvents and three cations (Li+, Na+, K+) were examined.The effect of various bases (alkali metals, phenyllithium, amides, "complex bases", amines) and of some metallic cations (Li+, Ag+, Pd2+) was studied.The solvent basicity was not responsible for the regioselectivity.
Phenylchromium(III) Chemistry Revisited 100 Years after Franz Hein (Part II): From LinCrPh3+ n(thf)x(n = 1, 2, 3) to Dimeric Triphenylchromate(II) Complexes
Fischer, Reinald,G?rls, Helmar,Suxdorf, Regina,Westerhausen, Matthias
, p. 3892 - 3905 (2020/11/13)
Polyphenylchromium(III) organometallics with various phenylation degrees and stabilized by diverse Lewis bases with various donor strengths and denticity were investigated in order to better understand the formation of (η6-arene)chromium complexes according to the procedure of Franz Hein (1892-1976) [ Organometallics 2019, 38, 498-511, DOI: 10.1021/acs.organomet.8b00811]. Part II focuses on hexa-, penta-, and tetraphenylchromates(III). Chromium(III) compounds with a lower phenylation degree will be discussed in a future part III. The numbering scheme of the complexes relates to the number of Cr-bound phenyl substituents. Hexaphenylchromate(III): The reaction of Ph3Cr(thf)3·0.25dx (3) (dx = 1,4-dioxane) with an ethereal solution of phenyllithium yields yellow-orange [Li3CrPh6(thf)2.3(OEt2)0.7] (6-thf-OEt2) which slowly degrades in contact with the reaction solution leading to emerald-green crystals of [{(Et2O)Li}2Ph3Cr(μ-O)]2 (3-Li2O). Pentaphenylchromate(III): Compound 6-thf-OEt2 reacts with 1 equiv of HCl-OEt2 solution to turquoise [{(thf)2Li}{(Et2O)Li}CrPh5] (5-thf-OEt2) that reacts with THF to the green contact ion pair [{(thf)2Li}2CrPh5] (5-thf) and with 12-crown-4 (12C4) to the light green solvent-separated ion pair [(12C4)Li(thf)]2 [CrPh5] (5-thf-12C4). Refluxing of 5-thf-OEt2 in diethyl ether leads to ether degradation and formation of 3-Li2O, whereas 5-thf-12C4 liberates biphenyl under similar reaction conditions. Tetraphenylchromate(III): The reaction of 3 with 1 equiv of phenyllithium in THF leads to a green reaction mixture. At -50 °C, red [(thf)4Li] [cis-(thf)2CrPh4]·2THF (4-thf) crystallizes which reversibly transforms into a green oil above -50 °C. Upon acidolysis of 5-thf-OEt2 with 1 equiv of HCl-OEt2 at -20 °C, the intermediately formed red complex is reduced to the dinuclear chromate(II) [{(thf)Li}CrPh3]2 (3-CrII-thf) (Cr-Cr 187.66(8) pm). Recrystallization of this product from THF yields solvent-separated [(thf)4Li]2 [(CrPh3)2] (3-CrII-thf4) with a Cr-Cr quadruple bond (Cr-Cr 183.7(2) pm) without contacts between the lithium ions and Cr-bound phenyl groups. Complex 3-CrII-thf reacts at room temperature in diethyl ether to the sandwich complexes bis(biphenyl)chromium(0) [(η6-Ph2)2Cr0] (π-4) and benzene-biphenylchromium(0) [(η6-C6H6)(η6-Ph2)Cr0] (π-3). Compounds in bold letters are authenticated by X-ray structure determinations.
Generation of Phosphonium Sites on Sulfated Zirconium Oxide: Relationship to Br?nsted Acid Strength of Surface -OH Sites
Rodriguez, Jessica,Culver, Damien B.,Conley, Matthew P.
supporting information, p. 1484 - 1488 (2019/01/25)
The reaction of (tBu)2ArP (1a-h), where the para position of the Ar group contains electron-donating or electron-withdrawing groups, with sulfated zirconium oxide partially dehydroxylated at 300 °C (SZO300) forms [(tBu)2ArPH][SZO300] (2a-h). The equilibrium binding constants of 1a-h to SZO300 are related to the pKa of [(tBu)2ArPH]; R3P that form less acidic phosphoniums (high pKa values) bind stronger to SZO300 than R3P that form more acidic phosphoniums (low pKa values). These studies show that Br?nsted acid sites on the surface of SZO300 are not superacidic.
