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At 250–300 °C and 30–50 bar, a continuous-flow (CF) transesterification of different dialkyl and alkylene carbonates (dimethyl-, diethyl-, dibenzyl-, and propylene carbonate, respectively) with two glycerol derived acetals (glycerol formal and solketal) was investigated without any catalyst. An unprecedented result was obtained; not only the desired process occurred, but also the formation of the corresponding mono-transesterification products took place with an excellent selectivity (up to 98%) in all cases. Under isothermal conditions, a study on the effect of pressure allowed us to optimize the conversion of acetals (up to 95%) for the reactions of dimethyl- and diethyl-carbonate (DMC and DEC, respectively). This proved that an abrupt progress of the reaction occurred for very small increments of pressure. For example, at 250 °C, the thermal transesterification of DMC with glycerol formal showed a sharp increase of the conversion from 1–2% at 30 bar to ∼85% at 37 bar. The lower the temperature, the lower the pressure interval at which the onset of the reaction is achieved. The absence of catalysts allowed us to run CF-reactions virtually indefinitely and with a very high productivity (up to 68 mg min−1) compared to the capacity (1 mL) of the used CF-reactor. Products of the transesterification of DMC and DEC were isolated in good-to-almost quantitative yields. In the case of heavier carbonates, steric reasons were responsible for the considerably lower reactivity of propylene carbonate (PC) with respect to DMC and DEC, while the transesterification of dibenzyl carbonate (DBnC, solid at room temperature) with glycerol formal required the presence of acetone as an additional solvent/carrier. Although the reactions of both PC and DBnC were not optimized, results offered a proof-of-concept on the extension of thermal transesterification processes to higher homologues of linear and alkylene carbonates.

Carbonate and carboxylate methyltrioctylphosphonium ionic liquids [P8881][A], made by a totally halide- and metal-free procedure, have been used as new organocatalysts for the cycloaddition of CO2 to styrene oxide. At 100 °C and ambient pressure, the performance of such compounds, particularly the acetate salts, was quite satisfactory. Even in the presence of catalyst amounts as low as 1–5 mol %, reaction conversions of 35–75 % were achieved with 100 % selectivity towards the expected cyclic carbonate. An analysis on the effect of the catalyst structure and loading, as well as operative parameters including temperature and pressure, demonstrated that anions played a major role on the activity and the stability of the ionic liquids. A parallel transformation of the phosphonium cation into its phosphine oxide was also identified as a consequence of the combined action of epoxide reagents and weakly nucleophilic carbonate and carboxylate species. Accordingly, a reaction mechanism was formulated.

At 90-120 °C, in the presence of methylcarbonate and bicarbonate methyltrioctylphosphonium salts as catalysts ([P8881][A]; [A] = MeOCO2 and HOCO2), the transesterification of non-toxic dimethyl- and diethyl-carbonate (DMC and DEC, respectively) with 1,X-diols (2 ≤ X ≤ 6) proceeds towards the formation of cyclic and linear products. In particular, 1,2-propanediol and ethylene glycol afford propylene- and ethylene-carbonate with selectivity and yields up to 95 and 90%, respectively; while, the reaction of DMC with higher diols such 1,3-butanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol produce linear C8-C10 dicarbonates of general formula MeOC(O)O∼∼∼OC(O)OMe as the almost exclusive products. Of note, these dicarbonate derivatives are not otherwise accessible in good yields by other conventional base catalyzed methods. Among 1,3-diols, the only exception was 2-methyl 2,4-pentandiol that yields the corresponding cyclic carbonate, i.e. 4,4,6-trimethyl-1,3-dioxan-2-one. In no one case, polycarbonates are observed. Such remarkable differences of product distributions are ascribed to the structure (branching and relative position of OH groups) of diols and to the role of cooperative (nucleophilic and electrophilic) catalysis which has been proved for onium salts. The investigated carbonate salts are not only effective in amounts as low as 0.5 mol%, but they are highly stable and recyclable.

The acetalization of six different types of glycerol including pure, wet, and crude-like grade compounds of compositions simulating those of crude glycerols produced by the biodiesel manufacture, was carried out with two model ketones such as acetone and 2-butanone. The reaction was investigated under continuous-flow (CF) conditions through a comparative analysis of an already known acetalization catalyst such as Amberlyst 36 (A36), and aluminum fluoride three hydrate (AlF3·3H2O, AF) whose use was never previously reported for the synthesis of acetals. At 10 bar and 25 °C, A36 was a highly active catalyst allowing good-to-excellent conversion (85%–97%) and selectivity (99%) when either pure or wet glycerol was used as a reagent. This catalyst however, proved unsuitable for the CF acetalization of crude-like glycerol (CG) since it severely and irreversibly deactivated in a few hours by the presence of low amounts of NaCl (2.5 wt %) which is a typical inorganic impurity of raw glycerol from the biorefinery. Higher temperature and pressure (up to 100 °C and 30 bar) were not successful to improve the outcome. By contrast, at 10 bar and 100 °C, AF catalyzed the acetalization of CG with both acetone and 2-butanone, yielding stable conversion and productivity up to 78% and 5.6 h−1, respectively. A XRD analysis of fresh and used catalysts proved that the active phase was a solid solution (SS) of formula Al2[F1-x(OH)x]6(H2O)y present as a component of the investigated commercial AF sample. A hypothesis to explain the role of such SS phase was then formulated based on the Bronsted acidity of OH groups of the solid framework. Overall, the AF catalyst allowed not only a straightforward upgrading of CG to acetals, but also a more cost-efficient protocol avoiding the expensive refining of raw glycerol itself.

An innovative thermal transesterification protocol for the synthesis of linear and alkylene carbonates was investigated under both batch and continuous-flow (CF) conditions. Accordingly, model 1,n-diols (n = 2–4) and glycerol were set to react with dimethyl carbonate (DMC) at T and p of 150–260 °C and 1–50 bar, respectively, in the absence of any catalyst. 1,2-diols afforded the corresponding five-membered ring carbonates as the main products with a quantitative conversion and a selectivity up to 94%, whereas 1,3-diols gave the six-membered ring products along with linear mono- and dicarbonate derivatives. A complete conversion was attained also for glycerol, but the products distribution depended on reaction conditions: the CF mode allowed the synthesis of glycerol carbonate, whereas batch reactions yielded either glycerol carbonate or its derivative from a further transesterification reaction, i.e., methyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate. The selectivity toward these two compounds was in the r...

The methyltriphenylphosphonium methylcarbonate salt [Ph3PCH3][CH3OCO2], obtained directly by quaternarization of triphenylphosphine with dimethylcarbonate, is a latent ylide that promotes Wittig vinylation of aldehydes and ketones. Alkenes are obtained simply by mixing [Ph3PCH3][CH3OCO2] and the carbonyl and heating in a solvent (no base, no halides, and no inorganic byproducts). Deuterium exchange experiments and the particularly short anion-cation distance measured by XRD in [Ph3PCH3][CH3OCO2] allowed to explain the nature and reactivity of this species. Green chemistry metrics (atom economy, mass index, environmental factor) indicate that this vinylation procedure is more efficient than comparable ones. Deuterated [Ph3PCD3][CH3OCO2] promoted the synthesis of deuterated olefins.

Phosphonium ionic liquids exchanged with bicarbonate and methylcarbonate anions (CILs) exhibit catalytic performances comparable to those of sterically hindered (non nucleophilic) organosuperbases such as DBU. At 25-50 °C, under solventless conditions, CILs efficiently catalyze the Henry addition of different aldehydes and ketones to nitroalkanes: not only they allow the selective formation of nitroaldols but they unlock a novel high-yielding access to dinitromethyl derivatives of ketones.

The kinetics of solvent-free reactions can be followed in situ by 13C nuclear magnetic resonance (NMR) spectroscopy, provided that the reaction mixture can be maintained liquid at the monitoring temperature. The pros and cons of the technique and the correct translation of the signal intensities into concentrations are discussed. A good model for this investigation is the reaction of ethylene carbonate (1) with aniline (2) at 140°C, two alkylation products of N-mono- and N, N-bis-(2-hydroxy)ethylation of aniline form (compounds 3 and 4, respectively). The overall reaction occurs with heavy volume shrinking, so that the physical as well as the chemical features evolve during the course of the process. The chemical evolution is described by the kinetic constants k1 and k2 of the two N-alkylation steps, the physical evolution by the time-dependent activity coefficients α(t). Two complementary procedures are utilized for the determination of these parameters. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 154–160, 2011

This article describes 1) a methodology for the green synthesis of a class of methylammonium and methylphosphonium ionic liquids (ILs), 2) how to tune their acid-base properties by anion exchange, 3) complete neat-phase NMR spectroscopic characterisation of these materials and 4) their application as active organocatalysts for base-promoted carbon-carbon bond-forming reactions. Methylation of tertiary amines or phosphines with dimethyl carbonate leads to the formation of the halogen-free methyl-onium methyl carbonate salts, and these can be easily anion-exchanged to yield a range of derivatives with different melting points, solubility, acid-base properties, stability and viscosity. Treatment with water, in particular, yields bicarbonate-exchanged liquid onium salts. These proved strongly basic, enough to efficiently catalyse the Michael reaction; experiments suggest that in these systems the bicarbonate basicity is boosted by two orders of magnitude with respect to inorganic bicarbonate salts. These basic ionic liquids used in catalytic amounts are better even than traditional strong organic bases. The present work also introduces neat NMR spectroscopy of the ionic liquids as a probe for solute-solvent interactions as well as a tool for characterisation. Our studies show that high catalytic efficacy of functional ionic liquids can be achieved by integrating their green synthesis, along with a fine-tuning of their structure. Demonstrating that ionic liquid solvents can be made by a truly green procedure, and that their properties and reactivity can be tailored to the point of bridging the gap between their use as solvents and as catalysts.

The methyltriphenylphosphonium methylcarbonate salt [Ph3 PCH3 ][CH3 OCO2 ], obtained directly by quaternarization of triphenylphosphine with dimethylcarbonate, is a latent ylide that promotes Wittig vinylation of aldehydes and ketones. Alkenes are obtained simply by mixing [Ph3 PCH3 ][CH3 OCO2 ] and the carbonyl and heating in a solvent (no base, no halides, and no inorganic byproducts). Deuterium exchange experiments and the particularly short anion-cation distance measured by XRD in [Ph3 PCH3 ][CH3 OCO2 ] allowed to explain the nature and reactivity of this species. Green chemistry metrics (atom economy, mass index, environmental factor) indicate that this vinylation procedure is more efficient than comparable ones. Deuterated [Ph3 PCD3 ][CH3 OCO2 ] promoted the synthesis of deuterated olefins.

The present chapter is aimed at describing the state-of-the-art, for the period January–December 2013, of two pillar classes of phosphorus-containing compounds, the phosphonium salts and ylides. Topics are organized to offer an introductory survey on the methods of preparation and characterisation of both types of compounds, followed by an analysis of the most remarkable but also curiosity driven researches for their applications. A special section is devoted to phosphonium-based ionic liquids (PILs) due to the exceptional importance of this subject.

Four renewable lactones, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and e-caprolactone (GBL, GVL, DVL, ECL, respectively) were shown to react with dimethyl-, diethyl-, and dibenzyl-carbonate (DMC, DEC, DBnC, respectively) in the presence of K2CO3 as basic catalyst, to yield selectively either the α-alkyl derivatives 1c–6c in the case of the five-membered ring GBL and GVL or the highly oxygenated acyclic monomeric derivatives 7a, 8a, and 9a in the case of the six- and seven-membered rings DVL and ECL. Selectivity and reaction conditions are investigated and a reaction mechanism is proposed. The organic carbonates act both as reagent and as reaction solvents, and the catalyst can be recovered by filtration and recycled.

The review collects and describes the literature on the preparation, characterisation and applications of phosphonium salts and ylides for the period January–December 2018. For the Reader's convenience, topics are organized to offer an introductory survey on the methods of preparation and characterisation of both types of compounds, followed by an analysis of applicative and curiosity driven research. A special section is devoted to phosphonium-based ionic liquids (PILs).

The present review was aimed at describing the state-of-the-art, for the period January 2011–December 2012, of two pillar classes of phosphorus-containing compounds, the phosphonium salts and ylides. For the Reader’s convenience, topics are organized to offer an introductory survey on the methods of preparation and characterisation of both types of compounds, followed by an analysis of the most remarkable but also curiosity driven researches for their applications. A special section is devoted to phosphonium-based ionic liquids (PIls) due to the exceptional importance of this topic.

An improved synthesis of tadalafil, a drug for the treatment of male erectile dysfunction, involves the use of safer solvents and reagents as well as a reduced number of steps.

In the absence of additional solvents, a novel procedure was implemented for the synthesis of trimethylorthoesters through the Pinner reaction. At 5 °C, the reaction of both aliphatic and aromatic nitriles (RCN; R = Et, Bu, Ph) with a moderate excess of MeOH and gaseous HCl gave the corresponding imidate hydrochlorides [RC(NH)OR′·HCl] in excellent yields (>90%). At 25–65 °C, the methanolysis of alkyl imidate salts provided trimethylortho-propionate and valerate, while only traces of trimethylorthobenzoate (TMOB) were observed. However, the aromatic hydrochloride could be readily converted into the hydrogenphosphate salt [PhC(NH)OR′·H3PO4] which, in turn, underwent a selective (>80%) reaction with MeOH to produce TMOB in a 62% isolated yield. This allowed for an unprecedented Pinner-type synthesis of TMOB starting from benzonitrile, rather than from the highly toxic trichloromethylbenzene. Overall, remarkable improvements in safety and process intensification were achieved.

The phosphonium salt CPS and its bicarbonate analogue efficiently promote the addition of aldehydes and ketones to nitroalkanes.

The anionic and the cationic partners of ionic liquids may act cooperatively and independently as nucleophilic and electrophilic catalysts. This ambiphilic propensity was demonstrated by kinetically discriminating the contributions of the anion (nucleophilic catalyst) and of the cation (electrophilic catalyst) to the solvent-free Baylis–Hillman dimerization of cyclohexenone catalysed by ionic liquids.

Trioctyl(methyl)phosphonium nitrate effectively catalyzes electrophilic aromatic chlorination of arenes with HCl in the absence of any additive using atmospheric oxygen as oxidant.

At T≥ 140 °C, different primary aromatic amines (pX-C(6)H(4)NH(2); X = H, OCH(3), CH(3), Cl) react with both ethylene- and propylene-carbonates to yield a chemoselective N-alkylation process: bis-N-(2-hydroxyalkyl)anilines [pX-C(6)H(4)N(CH(2)CH(R)OH)(2); R = H, CH(3)] are the major products and the competitive formation of carbamates is substantially ruled out. At 140 °C, under solventless conditions, the model reaction of aniline with ethylene carbonate goes to completion by simply mixing stoichiometric amounts of the reagents. However, a class of phosphonium ionic liquids (PILs) such as tetraalkylphosphonium halides and tosylates turn out to be active organocatalysts for both aniline and other primary aromatic amines. A kinetic analysis monitored by (13)C NMR spectroscopy, shows that bromide exchanged PILs are the most efficient systems, able to impart a more than 8-fold acceleration to the reaction. The reactions of propylene carbonate take place at a higher temperature than those of ethylene carbonate, and only in the presence of PIL catalysts. A mechanism based on the Lewis acidity of tetraalkylphosphonium cations and the nucleophilicity of halide anions has been proposed to account for both the reaction chemoselectivity and the function of the catalysts.

At 40-60 degrees C, in the presence of heterogeneous catalysts based on Al2O3, supercritical carbon dioxide not only acts as a good solvent for the reaction of aromatic and aliphatic aldehydes with 1-nitroalkanes but, most importantly, it also allows the selectivity to be tuned between the competitive formation of beta-nitroalcohols and nitroalkenes (from the Henry reaction and the nitroaldol condensation, respectively). In particular, when the pressure (and the density) of the supercritical phase is enhanced from 80 to 140 bar, the nitroalkene's selectivity increases, on average, from approximately 60 to90%. Experiments show that, in the same pressure range, a steep increase of the concentration profiles of reactant aldehydes takes place. By contrast, under solvent-free conditions, the reaction usually proceeds with a higher conversion, but nitroalkanols are the major products.

Hydroxylamine and O-methylhydroxylamine complexes [M(NH 2 OH)(CO) n P 5-n ]BPh 4 and [M(NH 2 OCH 3 )(CO) n P 5-n ]-BPh 4 [M = Mn, Re; n = 1, 2, 3; P = P(OEt) 3 , PPh(OEt) 2 , PPh 2 OEt] were prepared by allowing hydrides MH(CO) n -P 5-n to react first with triflic acid and then with an excess of hydroxylamine. Bidentate phosphane and phosphite can also be used to prepare both NH 2 OH and NH 2 OCH 3 complexes of manganese and rhenium of the [M(NH 2 OR)(CO) 2 (P-P)-{P(OEt) 3 }]BPh 4 and [M(NH 2 OR)(CO) 3 (P-P)]BPh 4 [R = H, CH 3 ; P-P = Ph 2 POCH 2 CH 2 OPPh 2 , Ph 2 PO(CH 2 ) 3 OPPh 2 , Ph 2 PN-(CH 3 )CH 2 CH 2 N(CH 3 )PPh 2 ] types with the use of MH(CO) 2 -(P-P)(P(OEt) 3 } and MH(CO) 3 (P-P) as precursors. The complexes were characterized spectroscopically and by the X-ray crystal-structure determination of [Re(NH 2 OCH 3 )(CO) 2 -{PPh(OEt) 2 } 3 ]BPh 4 and [Re(NH 2 OCH 3 )(CO) 3 {Ph 2 PO(CH 2 ) 3 -OPPh 2 }]BPh 4 . Oxidation of the hydroxylamine complexes with Pb(OAc) 4 was studied at -40 °C and led to an unstable compound tentatively characterized as a nitroxyl [M]- N(H)=O derivative.

Methyl trioctylphosphonium methyl carbonate [P(8881)](+)[MeOCO(2)](-) was prepared by the alkylation of trioctyl phosphine with the non-toxic dimethyl carbonate. This salt was a convenient source to synthesize different ionic liquids where the methyl trioctylphosphonium cation was coupled to weakly basic anions such as bicarbonate, acetate, and phenolate. At 90-220 °C, all these compounds [P(8881)](+)X(-); X = MeOCO(2); HOCO(2); AcO; PhO were excellent organocatalysts for the transesterification of dimethyl and diethyl carbonate with primary and secondary alcohols, including benzyl alcohol, cyclopentanol, cyclohexanol, and the rather sterically hindered menthol. Conditions were optimized to operate with very low catalyst loadings up to 1 mol% and to obtain non-symmetric dialkyl carbonates (ROCO(2)R'; R = Me, Et) with selectivity up to 99% and isolated yields90%. The catalytic performance of the investigated ionic liquids was discussed through a cooperative mechanism of simultaneous activation of both electrophilic and nucleophilic reactants.

Trioctylmethylphosphonium nitrate (P8,8,8,1NO3), an ionic liquid made via a green synthesis, catalyses electrophilic aromatic chlorination of arenes with HCl and air at 80 °C. The aromatic oxychlorination is truly catalytic in nitrate, proceeds without added solvents, and uses atmospheric oxygen as oxidant. The extent of chlorination can be controlled to yield selectively mono or dichlorinated products, and the ionic liquid catalyst can be recycled. Dependence of the chlorination rate on HCl and nitrate concentrations as well as on the rate of re-oxidation of the nitrogen intermediates by air, allowed us to propose a reaction mechanism.

Trichlorostannyl complexes [M(SnCl3)(bpy)2P]BPh4 [M = Ru, P = P(OEt)(3), 1a PPh(OEt)2 1b; M = Os, P = P(OEt)3 2; bpy = 2,2'-bipyridine] were prepared by allowing chloro complexes [MCl(bpy)2P]BPh4 to react with SnCl2 in 1,2-dichloroethane. Bis(trichlorostannyl) compounds Ru(SnCl3)2(N-N)P2 [N-N = bpy, P = P(OEt)3 3a, PPh(OEt)2 3b; N-N = 1,10-phenanthroline (phen), P = P(OEt)3 4] were also prepared by reacting [RuCl(N-N)P3]BPh4 precursors with SnCl2.2H2O in ethanol. Treatment of both mono- 1a, 2 and bis 3a trichlorostannyl complexes with NaBH4 afforded mono- and bis(trihydridestannyl) derivatives [M(SnH3)(bpy)2P]BPh4 5, 6 and Ru(SnH3)2(bpy)P2 7[P = P(OEt)3], respectively. Treatment of 1a, 2 with MgBrMe gave the trimethylstannyl complexes [M(SnMe3)(bpy)2P]BPh4 8, 9 and treatment of 3a afforded the bis(stannyl) Ru(SnClMe2)2(bpy)P2 10 derivative. Alkynylstannyl complexes [M{Sn(C triple bond CR)3}(bpy)2P]BPh4 11-13 and Ru[Sn(C triple bond CR)3]2(N-N)P2 14-17(R = p-tolyl, Bu t; N-N = bpy, phen) were also prepared by allowing trichlorostannyl compounds 1-4 to react with Li+[RC triple bond C]* in thf. The complexes were characterised spectroscopically and by the X-ray crystal structure determination of [Ru(SnMe3)(bpy)2{P(OEt)3}]BPh4 derivative.