Room temperature metathesis of aryl isocyanates and aromatic aldehydes catalyzed by group(IV) metal alkoxides: An experimental and computational study

Aromatic aldehydes and aryl isocyanates do not react at room temperature. However, we have shown for the first time that in the presence of catalytic amounts of group(IV) n-butoxide, they undergo metathesis at room temperature to produce imines with the extrusion of carbon dioxide. The mechanism of action has been investigated by a study of stoichiometric reactions. The insertion of aryl isocyanates into the metal n-butoxide occurs very rapidly. Reaction of the insertion product with the aldehyde is responsible for the metathesis. Among the n-butoxides of group(IV) metals, Ti((OBu)-Bu-n)(4) (8aTi) was found to be more efficient than Zr((OBu)-Bu-n)(4) (8aZr) and Hf((OBu)-Bu-n)(4) (8aHf) in carrying out metathesis. The surprisingly large difference in the metathetic activity of these alkoxides has been probed computationally using model complexes Ti(OMe)(4) (8bTi), Zr(OMe)(4) (8bZr) and Hf(OMe)(4) (8bHf) at the B3LYP/LANL2DZ level of theory. These studies indicate that the insertion product formed by Zr and Hf are extremely stable compared to that formed by Ti. This makes subsequent reaction of Zr and Hf complexes unfavorable.

Efficient reductive selenation of aromatic aldehydes to symmetrical diselenides with Se/CO/H2O under atmospheric pressure

An efficient method for the synthesis of symmetrical diselenides is described. Reductive selenation of aromatic and heterocyclic aromatic aldehydes (ArCHO) with Se/CO/H2O in DMF afforded diselenides (ArCH2SeSeCH2Ar) in yields up to 94% under atmospheric pressure without use of a base.

Chemoselective condensation of β-naphthol, dimethyl malonate, and aromatic aldehydes promoted by niobium pentachloride

A multicomponent reaction of β-naphthol, dimethyl malonate, and aromatic aldehydes in the presence of NbCl5 as promoter is described. Under similar conditions, aromatic aldehydes with different substituents exhibited different behaviors than β-naphthol and dimethyl malonate. In these MCRs, 4-aryl-3,4-dihydrobenzo[f]coumarins are obtained as the major products (41–93%) and 14-aryl-14H-dibenzo[a,j]xanthenes as the minor products (1–38%).

Organic reactions in ionic liquids:ionic liquids ethylammonium nitrate promoted Knoevenagel condensation of aromatic aldehydes with active methylene compounds

The Knoevenagel condensation of aromatic aldehydes with active methylene compounds proceeded efficiently in a reusable ionic liquid, ethylammonium nitrate, at room temperature in the absence of any catalyst with high yields.

Organic reactions in ionic liquids:Ionic liquid promoted Knoevenagel condensation of aromatic aldehydes with (2-thio)barbituric acid

The Knoevenagel condensation of aromatic aldehydes with (2-thio)barbituric acid proceeded efficiently in reusable ionic liquids, EAN, BmimBF4, and BmimPF6 at room temperature in the absence of any catalyst with high yields.

Recognition of Polycyclic Aromatic Hydrocarbons and Their Derivatives by the 1,3-Dinaphthalimide Conjugate of Calix4]arene: Emission, Absorption, Crystal Structures, and Computational Studies

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants as well as well-known carcinogens. Therefore, it is important to develop an effective receptor for the detection and quantification of such molecules in solution. In view of this, a 1,3-dinaphthalimide derivative of calix4]arene (L) has been synthesized and characterized, and the structure has been established by single crystal XRD. In the crystal lattice, intermolecular arm-to-arm pi center dot center dot center dot pi overlap dominates and thus L becomes a promising receptor for providing interactions with the aromatic species in solution, which can be monitored by following the changes that occur in its fluorescence and absorption spectra. On the basis of the solution studies carried out with about 17 derivatives of the aromatic guest molecular systems, it may be concluded that the changes that occur in the fluorescence intensity seem to be proportional to the number of aromatic rings present and thus proportional to the extent of pi center dot center dot center dot pi interaction present between the naphthalimide moieties and the aromatic portion of the guest molecule. Though the nonaromatic portion of the guest species affects the fluorescence quenching, the trend is still based on the number of rings present in these. Four guest aldehydes are bound to L with K-ass of 2000-6000 M-1 and their minimum detection limit is in the range of 8-35 mu M. The crystal structure of a naphthaldehyde complex, L.2b, exhibits intermolecular arm-to-arm as well as arm-to-naphthaldehyde pi center dot center dot center dot pi interactions. Molecular dynamics studies of L carried out in the presence of aromatic aldehydes under vacuum as well as in acetonitrile resulted in exhibiting interactions observed in the solid state and hence the changes observed in the fluorescence and absorption spectra are attributable for such interactions. Complex formation has also been delineated through ESI MS studies. Thus L is a promising receptor that can recognize PAHs by providing spectral changes proportional to the aromatic conjugation of the guest and the extent of aromatic pi center dot center dot center dot pi interactions present between L and the guest.

Complexity and Uniqueness of the Aromatic Profile of Smoked and Unsmoked Herreno Cheese

In this work, the volatile fraction of unsmoked and smoked Herreno cheese, a type of soft cheese from the Canary Islands, has been characterized for the first time. In order to evaluate if the position in the smokehouse could influence the volatile profile of the smoked variety, cheeses smoked at two different heights were studied. The volatile components were extracted by Solid Phase Microextraction using a divinylbenzene/carboxen/polydimethylsiloxane fiber, followed by Gas Chromatography/Mass Spectrometry. In total, 228 components were detected. The most numerous groups of components in the unsmoked Herreno cheese were hydrocarbons, followed by terpenes and sesquiterpenes, whereas acids and ketones were the most abundant. It is worth noticing the high number of aldehydes and ketones, and the low number of alcohols and esters in this cheese in relation to others, as well as the presence of some specific unsaturated hydrocarbons, terpenes, sesquiterpenes and nitrogenated derivatives. The smoking process enriches the volatile profile of Herreno cheese with ketones and diketones, methyl esters, aliphatic and aromatic aldehydes, hydrocarbons, terpenes, nitrogenated compounds, and especially with ethers and phenolic derivatives. Among these, methylindanones or certain terpenes like a-terpinolene, have not been detected previously in other types of smoked cheese. Lastly, the results obtained suggest a slightly higher smoking degree in the cheeses smoked at a greater height.

Chemoenzymatic synthesis of a mixed phosphine-phosphine oxide catalyst and its application to asymmetric allylation of aldehydes and hydrogenation of alkenes

The chemoenzymatic synthesis of a Lewis basic phosphine-phosphine oxide organocatalyst from a cis-dihydrodiol metabolite of bromobenzene proceeds via a palladium-catalysed carbon-phosphorus bond coupling and a novel room temperature Arbuzov [2,3]-sigmatropic rearrangement of an allylic diphenylphosphinite. Allylation of aromatic aldehydes were catalysed by the Lewis basic organocatalyst giving homoallylic alcohols in up to 57% ee. This compound also functioned as a ligand for rhodium-catalysed asymmetric hydrogenation of acetamidoacrylate giving reduction products with ee values of up to 84%.

Chemoselective condensationof beta-naphthol, dimethyl malonate, andaromatic aldehydes promoted by niobium pentachloride

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structural assignment of monothiocarbonohydrazones by 1H NMR spectroscopy

Analysis of the 1H NMR spectra of several monothiocarbonohydrazones, some of them synthesized for the first time, shows that they exist as two structural isomers. Whereas, in general, the derivatives of aromatic aldehydes conform to a linear structure, the aliphatic carbonyl derivatives conform to heterocyclic or linear structures, depending on the size of the substituent groups. This dual behaviour is explained in terms of extended conjugation and steric hindrance.

The Erlenmeyer synthesis with a thioazlactone

2-Phenylthiazolin-5-one (2b) was generated in situ and condensed with various aldehydes in CH2Cl2 (r.t./20 min.), to obtain the corresponding 4-alkylidene or arylidene products in good yields (68-81%). The reaction is catalyzed by basic lead acetate, and is equally successful with both aliphatic and aromatic aldehydes. This mild version of the classical Erlenmeyer azlactone synthesis is apparently enabled by the enhanced aromaticity of the thioazlactone anion intermediate.

A bifunctional approach towards the mild oxidation of organic halides: 2-dimethylamino-N,N-dimethylaniline N-oxide

The titled reagent incorporates an oxygen-centred nucleophile and a basic moiety�in a suitably mutual orientation�in the same molecule. It oxidises various primary benzylic bromides to the corresponding aromatic aldehydes under relatively mild conditions (MeCN/rt�50°C/6�24 h) in high yields (83�97%), and is thus a useful alternative to the Kornblum procedure.

Multicomponent self-sorting of a Pd-7 molecular boat and its use in catalytic Knoevenagel condensation

Unique three-component self-assembly of a cis-blocked 90 degrees Pd(II) acceptor with amixture of tri- and tetra-imidazole donors led to the self-sorting of a Pd-7 molecular boat with an internal nanocavity, which catalyses the Knoevenagel condensation of a series of aromatic aldehydes with 1,3-dimethylbarbituric acid and Meldrum's acid in aqueous media.

Improved Erlenmeyer Synthesis with 5-Thiazolone and Catalytic Mn(II) Acetate. Crystal Structure Confirmation of the Reaction Stereochemistry

2-Phenylthiazolin-5-one (5, a thioazlactone) condenses with various aldehydes in the presence of the mild base Mn(II) acetate as catalyst in CH2Cl2 solution. This leads to the corresponding Erlenmeyer reaction products (6) in excellent yields in the case of aromatic aldehydes and moderate yields in others. The mildness of the reaction conditions is apparently enabled by the aromaticity of the (putative) intermediate thiazolone anion. The structure and stereochemistry (Z) of the product derived from i-BuCHO was confirmed by single crystal X-ray diffraction. This study overcomes key limitations of the classical Erlenmeyer synthesis and also introduces the relatively nontoxic Mn(II) acetate as a reagent in heterocyclic chemistry.