Study on one-step catalytic amination of oleyl alcohol to unsaturated tertiary amine

The synthesis of unsaturated tertiary amine by the amination of oleyl alcohol and dimethylamine under atmospheric pressure over Cu–Ni catalysts supported on CaCO₃ was studied. The yield of tertiary amine and the retention rate of the unsaturated bond can reach 95.4 and 93.3 %, respectively. The yields of tertiary amine over different Cu/Ni ratios catalysts were close to each other, which meant that Cu/Ni ratios had no obvious influence on the production of tertiary amine, while the retention rate of the unsaturated bond over the catalyst containing only Cu was higher than the catalysts containing Cu–Ni. The major effect of the Cu element was dehydrogenation, and the ability of the hydrogenation was weak. The ability of the Ni element to break the carbon–carbon bonds and hydrogenation was strong. Therefore, the performance of the Cu catalyst was better than the conventional Cu–Ni-based catalyst for the retention of the unsaturated bond in long-chain R of the tertiary amine.     

β-Lactone as intermediate in the perkin reaction catalyzed by tertiary amines

The Perkin reaction catalyzed by tertiary amines is found to run not according to the aldol-type condensation mechanism but according to the mechanism in which the first stage is the formation and cycloaddition of ketene, yielding a β-lactone, which cleaves to the unsaturated acid.     

Acetylene derivatives Communication 191. Preparation of acids from tertiary acetylenic alcohols

Summary A method was developed for the conversion of tertiary acetylenic alcohols to unsaturated acids.     

Oxidation of unsaturated tertiary amines,amides, and imides by molecular oxygen catalyzed by palladium complexes

Conclusions Oxidation of higher unsaturated tertiary amines, amides, and imides has been carried out using PdCl₂-CuCl-CF₃COOH catalyst system and molecular oxygen, the products being the corresponding amino-, amido-, and imidoketones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimieheskaya, No. 9, pp. 2148–2151, September, 1988.     

Reaction of tertiary allylic amines with butadiene catalyzed by palladium

Tertiary allylic amines react with butadiene in the presence of palladium(O) with cleavage of the carbon-nitrogen bond of the allylic amine and formation of the unsaturated tertiary amine $\text{4}$.     

Carboxylate phosphabetaines based on tertiary phosphines and unsaturated dicarboxylic acids

By reaction of triorganylphosphines with unsaturated dicarboxylic acids adducts of betaine structure were synthesized whose stability depended on the character of substituents at phosphorus and on the structure of acid. The betaine obtained from phosphines and maleic and fumaric acids redily underwent decarboxylation into the corresponding monoacyl phosphonium derivatives. The structure of the latter was established by means of X-ray crystallography. The adduct prepared from phosphines and itaconic acid was stabilized by intramolecular hydrogen bond between the acylate anionic center and the “second” carboxy group.     

A long-range chiral relay via tertiary amide group in asymmetric catalysis: new amino acid-derived N,P-ligands for copper-catalysed conjugate addition

New N,P-ligands 4-6, derived from valinol and prolinol, respectively, have been developed for the asymmetric, copper(I)-catalysed conjugate addition of diethylzinc to unsaturated ketones; the tertiary amide group has been shown to effectively relay the chiral information from the ligand backbone to the active centre.     

Versatile, fragrant, convertible isonitriles

The metalation of oxazoles leads to ring opening to the isocyanoenolate that can be O-acylated to give the unsaturated isonitriles. These substances undergo conventional multicomponent reactions. The products of their reactions are readily converted to acyl substitution products by treatment with acid and a nucleophile. These unsaturated isonitriles are notable by their simple preparations and, unusually, their nonoffensive odors.     

Synthesis of glycidyl ethers of tertiary 1-alkoxy-1-en-3-ynols

Conclusions New unsaturated glycidyl ethers have been prepared by reaction of tert-1-alkoxy-1-en-3-ynols with epichlorohydrin in alkaline solution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2792–2795, December, 1975.     

Transition-metal-catalyzed reaction of diazocompounds,efficient synthesis of functionalized ethers by carbene insertion into the hydroxylic bond of alcohols

An Efficient catalytic synthesis of unsaturated ethers by carbene insertion (with diazoesters as carbene precursors) into the OH bond of unsaturated alcohols is reported. The regioselectivity for the OH insertion is high. However, depending on the catalyst counter-ions and the diazoester alkoxy group, addition to the unsaturated centre can be promoted to some extent, yielding then cyclopropyl and cyclopropenyl carbinols. The mechanistic aspects of the reactions are discussed.     

The lead tetraacetate oxidation of Δ6-unsaturated tertiary alcohols. Eight-membered cyclic ether formation

In the lead tetraacetate oxidation of the unsaturated tertiary cyclic alcohols 1a and 1b, and the acyclic alcohol 15a, all possessing a Δ⁶-olefinic bond (with respect to the hydroxyl group), the α-acetoxylated eight-membered cyclic ethers 6a, 6b and 16a, respectively, were obtained. With these substrates lead tetraaeetate reacts at the double bond and, if at all, only by weak association with the hydroxyl group, so that fragmentation products derived from alkoxy radical intermediates (such as 2) were not formed. The mechanism of this cyclisation reaction is discussed.     

Synthesis of unsaturated tertiary amines and α-allyl substituted ketones from azomethines using metal complex catalysts

A method has been developed for the regioselective synthesis of unsaturated tertiary amines via the reaction of magnesium amides, derived from Schiff bases, with allylic electrophiles in the presence of Pd and Cu complexes. The reaction of ketimines which have been metallated using magnesium amide with functionalized allylic compounds is catalyzed by Pd complexes and leads to the formation of -allyl substituted ketones with high regioselectivity.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 155–160, January, 1990.     

The O-nitration of tertiary unsaturated alcohols andα-epoxyalcohols

Conclusions The method for O-nitrating unsaturated alcohols and-epoxyalcohols has been extended to tertiary alcohols;, -dimethylallyl and, ;-dimethylglycidyl nitrates have been synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1354–1355, June, 1967.     

Quantum chemical investigation on the reaction mechanism of tertiary phosphines with unsaturated carboxylic acids: An insight into kinetic data

The structures of intermediates and transition states in the reaction of tertiary phosphines with unsaturated carboxylic acids have been calculated at the B3LYP level of theory using the 6‐31+G(d,p) basis set. Analysis of the results shows that [1,3]‐intramolecular migration of carboxylic proton to carbanionic center of generated zwitterionic intermediate is strongly kinetically unfavorable, and external proton‐donor source is essential to complete quaternization. A molecular cluster of the intermediate with one molecule of water has been modeled for intermolecular reaction pathway, but even in this case, the proton transfer remains to be the rate‐determining step that is in a good agreement with previous kinetic investigations on this reaction. The data obtained for this reaction have much in common with recent studies on the mechanisms of the Morita–Baylis–Hillman reaction and phosphine‐catalyzed [3+2] cycloaddition, which revealed paramount importance of proton‐transfer steps. © 2013 Wiley Periodicals, Inc.     

Structural Effects on the Intrinsic Basicities of alpha,beta-Unsaturated Lactones and Ketones

The proton affinities of 2(5H)-furanone, 1 (836 kJ/mol), 5,6-dihydro-2H-pyran-2-one, 2 (862 kJ/mol), cyclopentenone, 3 (857 kJ/mol), and cyclohexenone, 4 (863 kJ/mol), have been measured by Fourier transform ion cyclotron resonance techniques. A comparison is made with (reexamined) data concerning saturated cyclic and unsaturated aliphatic analogs. Three general observations are made. First, the basicity is found to increase with the size of the ring. Second, unsaturated lactones are more basic than their corresponding aliphatic unsaturated esters. Third, unsaturated and saturated lactones have almost identical gas-phase basicities, while unsaturated and saturated lactones have almost identical gas-phase basicities, while unsaturated cyclic ketones are more basic than their saturated analogs. All these experimental findings have been rationalized by means of ab initio calculations up to the G2(MP2,SVP) level. The basicity trends along the series are the result of two main factors: the different hybridization pattern of the carbonyl carbon as the size of the ring changes and, in the case of lactones, the nonbonding interaction between the proton attached to the carbonyl group and the ether-like oxygen which contributes to the enhanced stability of the protonated form. For unsaturated ketones the C=C double bond participates fully in the change in charge distribution induced by the protonation, while for unsaturated lactones the existence of an oxygen atom within the ring impedes this shift of the electron density.     

Kinetics and mechanism of quaternization of tertiary phosphines with unsaturated carboxylic acids. Kinetic studies of the reactions in aprotic solvents

Data obtained while studying the kinetics of quaternization of tertiary phosphines with the unsaturated carboxylic acids in the series of aprotic solvents indicate the participation of a second molecule of acid playing the part of the external proton donor in this process. Quantitative analysis of the effect of solvent within the frames of the Koppel-Palm equation showed that the main contribution in the reaction rate belongs to the nucleophilicity of medium while the effects of polarity and electrophilicity are smaller. The results obtained suggest the step-by-step mechanism of interaction including the formation of the zwitterionic intermediate on the reaction pathway common for the solvents with different proton activity.     

An Improved Method for the Efficient Conversion of Unstaurated Alcohols,Ethers and Esters to Their Corresponding Aldehydes,Ketones, Enol Ethers and Enol Esters

Catalytic conversion of unsaturated alcohols to their corresponding aldehydes and ketones with nonacarbonyl diiron in benzene at 40–50 C are performed efficiently in high yields. The efficient preparation of some enol ethers and also preperation of a few esters from their corresponding unsaturated ethers and esters are also performed by this method.     

1,2-Nucleophilic addition of 2-(picolyl)organoboranes to nitrile, aldehyde, ketone, and amide

A series of 2-(picolyl)borane molecules were synthesized as products of the reaction between 2-(picolyl)lithium and R(2)BOMe (R = ethyl, 9-BBN, phenyl, 9-borafluorenyl). The 2-(picolyl)boranes were dimeric; whereas, monomers coordinated to LiOMe could be isolated when the synthesis was carried out in the presence of TMEDA and THF. The 2-(picolyl)boranes undergo reaction with nitriles, ketones, aldehydes, and amides with apparent 1,2-addition of the B-C(picolyl) bond to the unsaturated bond. Theoretical models reveal the presence of a donor orbital on the 2-(picolyl)borane with significant electron density at the benzylic carbon that we conclude was involved in nucleophilic attack on the electrophilic center of unsaturated organic functional groups.     

A 13C-NMR investigation of plasma polymerized ethane,ethylene, and acetylene

Solid-state ¹³C-NMR spectra were obtained by cross-polarization and magic angle spinning of polymers prepared by injecting ethane, ethylene, and acetylene into a radiofrequency plasma. By use of the delayed decoupling technique to suppress protonated carbon peaks and difference spectroscopy five resolved spectral bands can be distinguished. These bands are assigned to (I) unsaturated nonprotonated, (II) unsaturated CH and CH₂, (III) quaternary, (IV) methine and methylene, and (V) methyl carbons by comparison with standard ¹³C shifts compiled for organic materials. The relative amounts of these structural features in the polymers were determined quantitatively and the possible sources of errors considered.     

Syntheses of functional condensation polymer. I. Polyesters having pendant functional groups such as hydroxyl,formyl, aldoxime,aminomethyl and hydroxymethyl

Unsaturated polyesters having pendant functional groups such as hydroxyl, formyl, aldoxime, aminomethyl and hydroxymethyl, have been prepared and characterized, and some of their properties were investigated. Reaction conditions for the epoxidation of unsaturated polyesters and hydrolysis of the epoxy groups in the polyesters were established to control the amount of pendant diol groups. It was possible to incorporate up to 90 mole-% of formyl side groups into the unsaturated polyester by the hydroformylation with the rhodium catalyst. In addition, the formyl side groups of the modified polyester were converted into hydroxymethyl or aldoxime groups and were then converted to amino groups. The melting points of the modified polyesters decreased with increasing the pendant group content of the polyesters, as expected. Aliphatic polyesters having pendant hydroxyl or amino groups had a high affinity for moisture, which might be ascribed to the participation of the hydrophilic pendant groups in the modified polyesters.