Sonolysis of actinide(IV) β-diketonates in alkanes

Ultrasonic irradiation with the frequency of 20–22 kHz and absorbed acoustic power about 0.4 W ml^–1 causes degradation of An(IV) tetrakis-β-diketonates, AnL₄, where An(IV) is Th(IV), Np(IV), and Pu(IV), and HL is hexafluoroacetylacetone (HFAA) and dibenzoylmethane (HDBM), in hexadecane solutions in the presence of argon. The rate of the sonochemical process corresponds to a first-order kinetic law with respect to metal β-diketonate concentrations. The first-order rate constant of sonolysis increases with the increase in the volatility of the metal complexes. Solid sonication products consisted of a mixture of actinide carbides and partial degradation products, PDP, of initial metal β-diketonates. It is assumed that metal carbides are formed within the cavitating bubbles as a result of high-temperature process with participation of actinide(IV) β-diketonates and solvent vapours. PDP formation is attributed to the thermolysis of the complexes in a liquid reaction zone surrounding the cavitating bubble. To cite this article: S.I. Nikitenko et al., C. R. Chimie 7 (2004).

Résumé

L’irradiation ultrasonore avec une fréquence de 20–22 kHz et une intensité acoustique de 0,4 W ml^–1 conduit à la décomposition de An(IV) tétrakis-β-dicétones, AnL₄, où An(IV) est Th(IV), Np(IV) et Pu(IV), et HL est l’hexafluoroacétylacétone (HFAA) et le dibenzoylméthane (HDBM) en milieu hexadécane sous argon. La cinétique de décomposition sonochimique est d’ordre 1 par rapport à la concentration du complexe et la cinétique augmente avec la volatilité du complexe métallique. Les produits solides de décomposition sont un mélange de carbure d’actinides et de produits de décomposition partielle PDP. Il a été observé que les carbures d’actinide sont formés dans la bulle de cavitation compte tenu des fortes températures et de la présence simultanée du complexe métallique volatil et du solvant (hexadécane). La formation des PDP est attribuée à la thermolyse du complexe à l’interface de la bulle de cavitation. Pour citer cet article : S.I. Nikitenko et al., C. R. Chimie 7 (2004).     

Synthesis of 1,3-diketones through ring-opening of ketoketene dimer β-lactones

The reaction of ketoketene dimers with organolithium reagents afforded 1,3-diketones in good to excellent yields, and with good diastereoselectivity in some cases.     

Synthesis of β‐Haloketones by β‐Addition Reactions of α,β‐Unsaturated Ketones with BX3 (X = Br,Cl) as Halide Source

A series of β‐bromoketones and β‐chloroketones were synthesized by the addition reactions of α,β‐unsaturated ketones under BX₃ (X = Br, Cl) and ethylene glycol reaction system. The α,β‐unsaturated ester also was successfully converted to its corresponding β‐bromoester under the reaction condition.     

Synthesis of new optically active α,α′,β‐trisubstituted‐β‐lactones as monomers for stereoregular biopolyesters

Various optically active (4R)‐alkyloxycarbonyl‐3,3‐dialkyl‐2‐oxetanones as monomers were synthesized from L‐(S)‐malic acid in six steps to prepare a new family of stereopolyesters for biomedical applications. The synthesis began with an esterification followed of a dialkylation in the aim to introduce hydrophobic groups as methyl or reactive group as allyl. Then, a saponification has permitted to obtain the corresponding diacids that reacted with appropriate alcohols to furnish different monoesters. The last and most important step was activation of hydroxyl group of monoesters with the asymmetric carbon configuration inversion according to the Mitsunobu reaction. Thus, this reaction has provided lactones from monoesters with 100% enantiomeric excess which was confirmed by ¹H NMR and by the synthesis of corresponding isotactic and semicrystalline homopolyesters. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2586–2597     

Synthesis of α,β-unsaturated ketone from α-iodo ketone using photoirradiation

Irradiation of α-iodo ketone in hexane under a nitrogen atmosphere with a high-pressure mercury lamp (λ>300nm) at room temperature afforded the corresponding α,β-unsaturated ketones in good yield. This reaction affords a new, clean and convenient synthetic method for the α,β-unsaturated ketone.     

Synthesis of Phenanthrene Derivatives through the Reaction of an α,α‐Dicyanoolefin with α,β‐Unsaturated Carbonyl Compounds

Phenanthrene derivatives were prepared by reacting an α,α‐dicyanoolefin with different α,β‐unsaturated carbonyl compounds resulting from Wittig reaction of ninhydrin and phosphanylidene or condensation of barbituric acid and an aldehyde. The easy procedure, mild and metal‐catalyst free, reaction conditions, good yields, and no need for chromatographic purifications are important features of this protocol. The structures of the product of type 3 and 5 were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS). A plausible mechanism for this type of reaction is proposed (Scheme 1).     

A Novel Method for the Synthesis of α,β‐Unsaturated Amides Mediated by Samarium Diiodide

Promoted by Samarium diiodide (SmI₂), α,β‐unsaturated amides were formed from nitrogen anions (formed in situ by the reduction of nitro compounds) and α,β‐unsaturated esters. This reaction contrasts with the conjugate addition between amines and α,β‐unsaturated esters promoted by samarium triiodide (SmI₃) and provides an alternative attractive way to obtain α,β‐unsaturated amides using SmI₂.     

Synthesis of novel α,α′,β-trisubstituted β-lactones

A concise and efficient synthesis of α,α′,β-trisubstituted β-lactones is presented. These novel lactones are easily obtained in five steps and will be dedicated to anionic ring opening polymerization.     

Photoinduced transformation of α,β-epoxyketones to β-hydroxyketones by Hantzsch 1,4-dihydropyridine

Irradiation (λ >300 nm) of Hantzsch 1,4-dihydropyridine with aromatic α,β-epoxyketones in acetonitrile selectively breaks the Cα---O bond of the epoxides giving the corresponding β-hydroxyketones in excellent yields.     

Preparation,characterization and properties of β-chitin and N-acetylated β-chitin

Free amino groups in β-chitin from squid pen were acetylated to obtain N-acetylated β-chitin. After careful control of degree of acetylation, thermal and mechanical properties of β-chitin and N-acetylated β-chitin were compared. The structural differences of β-chitin and N-acetylated β-chitin were characterized by Fourier transform infrared (FTIR) and wide-angle x-ray diffraction (WAXD) analysis. The results indicated that the crystallinity of N-acetylated β-chitin was higher than that of β-chitin and N-acetylated β-chitin exhibited characteristics similar to α-chitin. Equilibrium water content (EWC) of β-chitin reached to about 50% and this hydrophilic nature was assumed to be caused by a relatively weak hydrogen bonding force of β-chitin with parallel main chains. On the other hand, EWC of N-acetylated β-chitin was 40% due to the introduction of ordered structure. β-chitin and N-acetylated β-chitin have the tensile strength of 0.4 and 0.7 Mpa in the swollen state, respectively. Viscoelastic properties and thermal relaxation behaviors were investigated by dynamic mechanical thermal analysis (DMTA). DMTA spectra of these samples showed that α-transition peaks of β-chitin and N-acetylated β-chitin were observed at 170 and 190°C, respectively. These relaxation peak maxima were assigned to be their glass transition temperature. In addition, a second relaxation peak of β-chitin resulting from acetamide groups was found at 112°C and a broad relaxation peak of N-acetylated β-chitin at around 81–100°C. As a result of thermogravimetric analysis, 10% weight loss temperatures of β-chitin and N-acetylated β-chitin were 270 and 285°C, respectively. © 1996 John Wiley & Sons, Inc.     

The Preparation of β-Cycloalkyl-L-Aspartate and γ-Cycloalkyl-L-Glutamate by Enzymatic Hydrolyses

The simple method to prepare the β-cycloalkyl aspartate and γ-cycloalkyl glutamate by enzymatic reactions has been developed. Compared with conventional chemical methods, the enzymatic method is more facile.     

Synthesis of β,γ‐Unsaturated Acids from Allenes and Carbon Dioxide

Hidden talent : Often perceived to be too thermodynamically and kinetically inert to be a useful chemical feedstock, carbon dioxide adds to allenes under exceptionally mild reductive conditions in the presence of a palladium pincer complex to give β,γ‐unsaturated carboxylic acids (see scheme). This transformation is discussed in the context of the requirements for CO₂ fixation. DMF=N,N‐dimethylformamide, Tf=trifluoromethanesulfonyl.

     

Ketenimines from Isocyanides and Allyl Carbonates: Palladium‐Catalyzed Synthesis of β,γ‐Unsaturated Amides and Tetrazoles

The reaction of allyl ethyl carbonates with isocyanides in the presence of a catalytic amount of Pd(OAc)₂ provided ketenimines through β‐hydride elimination of the allyl imidoylpalladium intermediates. The insertion of the isocyanide into the π‐allyl Pd complex proceeded via an unusual η¹‐allyl Pd species. The resulting ketenimines were hydrolyzed to β,γ‐unsaturated carboxamides during purification by flash column chromatography on silica gel or converted in situ into 1,5‐disubstituted tetrazoles by [3+2] cycloaddition with hydrazoic acid or trimethylsilyl azide.     

Microwave‐Assisted Synthesis of β‐Lactams and Cyclo‐β‐dipeptides

Different cyclo‐β‐dipeptides were prepared from corresponding N‐substituted β‐alanine derivatives under mild conditions using PhPOCl₂ as activating agent in benzene and Et₃N as base. To evaluate β³‐substituent influence, the amino acids 7 – 26 were synthesized, and a β‐lactam formation reaction was carried out instead of cyclo‐β‐dipeptide formation. The crystal structures of three derivatives of cyclo‐β‐peptides and one β‐lactam are presented.     

Studies on the Mass Spectra of N‐Aryl α,β‐Unsaturated γ‐Lactams

The mass spectra of a series of N‐aryl α,β‐unsaturated γ‐lactams were studied. Besides the molecular ion, the three characteristic fragments such as [M⁺‐29], [M⁺‐55], and [M⁺‐82] were commonly found in a series of N‐Aryl α,β‐unsaturated γ‐lactams in EI/MS. Further more the mechanism for the interpretation of these fragments is also de scribed.     

Photolysis of α,β‐Epoxyketones: A Green Synthesis of β‐Hydroxyenones through Tandem H‐Abstraction,Ring Cleavage and Isomerisation

The photochemical behavior of various substituted epoxycarbonyl compounds consisting of more than one possible photo‐labile site (i.e. δ‐hydrogen, β‐hydrogen and epoxide ring) has been investigated. These compounds on photo‐irradiation produced the β‐hydroxyenones in an eco‐friendly green approach. Mechanistically, these photo‐transformations have been envisaged to occur via an intramolecular β‐hydrogen abstraction by the carbonyl group of benzoyl moiety to generate the 1,3‐biradical followed by epoxide ring opening that isomerizes into the photoproducts. The photolysis of the probed epoxy ketones didn’t furnish any photoproduct through δ‐hydrogen abstraction, whatsoever. This exclusive preference for β‐H abstraction over δ‐H abstraction by carbonyl group has been vindicated by the MM2 energy mini‐ mized program for the investigated photochemical substrates. The structures of these photoproducts were established from the analysis of their spectral parameters (IR, ¹H/¹³C NMR and Mass) and single crystal X‐ray crystallography data.     

Toward the Synthesis of Modified Carbohydrates by Conjugate Addition of Propane‐1,3‐dithiol to α,β‐Unsaturated Ketones

Selected 5‐substituted derivatives 4 of 1,1‐diethoxy‐5‐hydroxypent‐3‐yn‐2‐one were treated with propane‐1,3‐dithiol under various conditions. The unprotected hydroxy ketones underwent cyclization during the dithiol addition and gave the corresponding 3‐(diethoxymethyl)‐2‐oxa‐6,10‐dithiaspiro[4.5]decan‐3‐ols 5 in 80–90% yield as the only products (Scheme 3 and Table 1). These products can be regarded as partly modified carbohydrates in the furanose form. When the benzyl‐protected analogues 10‐Bn of the 1,1‐diethoxy‐5‐hydroxypent‐3‐yn‐2‐one derivatives were treated with the same dithiol, however, no cyclization occurred; instead the corresponding 3‐{2‐[(benzyloxy)methyl]‐1,3‐dithian‐2‐yl}‐1,1‐diethoxypropan‐2‐one derivatives 11‐Bn were formed in good yield (up to 99%; Table 4). These 1,3‐dithianes were and are in the process of being converted to a number of new carbohydrate analogues, and here are reported high‐yield syntheses of functionalized molecules 17 belonging to the 5,5‐diethoxy‐1,4‐dihydroxypentan‐2‐one family of compounds (Table 7), via 15‐Bn (Table 5) and 16‐Bn (Table 6 and Scheme 8).     

Polymer-Attached Thiazolium Salts-Catalyzed Addition of Aldehydes to α, β-Unsaturated Carbonyl Compounds

A homogeneous catalyst, 3-benzyl-5-(2-hydroxyethyl)-4-methyl-1,3-thiazolium chloride, for addition of aldehydes to activated double bond, was attached to 20% cross-linked polystyrene-divinylbenzene copolymer. The attached catalysts could be easily removed from the reaction mixture. Polymer-attached thiazolium salts in the presence of triethylamine are active catalysts for addition of aromatic and aliphatic aldehydes to α,β-unsaturated ketones to yield γ-diketones.