Unsaturated Tertiary Amines Research Articles

Copolymerization of unsaturated carboxylic acids with styrene and an unsaturated tertiary amine in dimethyl sulfoxide

AbstractThe copolymerization parameters of N‐methyl‐N‐phenyl‐2‐aminoethyl methacrylate (MPAM) and 2‐acryloyloxybenzoic (AOB), 2‐methacryloyloxybenzoic (MOB), and methacrylic acid (MAA) with styrene in DMSO solution at 50°C were determined and used in the calculation of the Alfrey‐Price copolymerization constants e and Q for MPAM, AOB, MOB, and MAA. From the e and Q constants of the monomers thus determined, the copolymerization parameters of the pairs MPAM‐AOB, MPAM‐MOB, MPAM‐MAA were calculated and compared with those determined by the copolymerization of the corresponding pairs in DMSO.

Additions of organolithium compounds to unsaturated tertiary amines

Etude de l'addition du butyl et t-butyl-lithium sur des amines tertiaires allyliques et propargyliques

Epoxidation of an unsaturated tertiary amine. Application to the synthesis of two pirprofen metabolites

Epoxidation of an unsaturated tertiary amine. Application to the synthesis of two pirprofen metabolites

The copolymerization of unsaturated carboxylic acids with styrene and an unsaturated tertiary amine in benzene

AbstractThe copolymerization parameters of 2‐acryloyoxybenzoic (AOB) and 2‐methacryloyloxybenzoic (MOB) acids, methyl 2‐methacryloyloxybenzoate (MMOB), and N‐methyl‐N‐phenyl‐2‐aminoethyl methacrylate (MPAM) with styrene in benzene solution were determined and used in the calculation of the Alfrey‐Price copolymerization constants e and Q for AOB, MOB, MMOB, and MPAM. Using e Q thus determined and the corresponding tabulated values for methacrylic acid (MAA), the copolymerization parameters of pairs AOB‐MPAM, MOB‐MPAM, MMOB‐MPAM, and MAA‐MPAM were calculated. They are compared with those determined by the copolymerization of these pairs in which the interaction of functional groups on comonomers plays a role.

The initiation of polymerization of unsaturated tertiary amines with carboxylic acids

AbstractThe polymerization rate (Rp) of N‐methyl‐N‐phenyl‐2‐aminoethyl methacrylate (MPAEMA) initiated with 2,2' ‐azodiisobutyronitrile (AIBN) at 50°C increased considerably after the addition of CCI3COOH, and distinctly after the addition of CH3COOH. Rp in a benzene solution of 2 mol. dm−3 MPAEMA and 5 · 10−2 mol. dm−3 CCl3COOH (without AIBN) was 13% · h−1. [η] of the obtained polymer corresponded to 64 cm3 · g−1. The polymerization order of MPAEMA initiated with CCl3COOH is 0,93 with respect to monomer and 0,51 with respect to CCl3COOH. The overall activation energy of polymerization of MPAEMA calculated from the temperature dependence of Rp between 20 and 50°C is 43 ± 1,2 kJ · mol−1. In a benzene solution of 2 mol.dm−3 MPAEMA, 5 · 10−2 mol · dm−3CCl3COOH and 5 · 10−3 mol · dm−3 1,4‐benzoquinone at 50°C the polymerization does not proceed for 6 h. In a benzene solution of 2 mol · dm−3 4‐dimethylaminostyrene (4‐DMAS) and 2 mol · dm−3 CH3COOH (without AIBN), 40% of monomer polymerized within one hour. [η] of the polymer was 4 cm3 · g−1. The overall activation energy of polymerization of 4‐DMAS in the presence of CH3COOH is ca · 54 kJ · mol−1. The addition of 5 · 10−3 1,4‐benzoquinone slows down the polymerization rate only slightly. The effect of acids on the elementary polymerization reactions is characterized.

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 4 .

Catalytic synthesis of unsaturated tertiary amines

1. The possibility of synthesizing unsaturated mono- and bisamines by the telomerization of butadiene with N-hydroxymethylpiperidine and N-hydroxymethyldiethylamine in the presence of homogeneous Pd catalysts has been demonstrated. Under the conditions of this reaction the N-hydroxymethylamines indicated decompose into formaldehyde, methylenebisamine, and a secondary amine. 2. The mixed telomerization of butadiene with formaldehyde and secondary amines in the presence of Pd catalysts results in the synthesis of 2,5-divinyltetrahydropyran, the corresponding N-2,7-octadienylamines, and homodimers of butadiene (vinylcyclohexene and 1,3,7-octatriene). 3. The telomerization of tetramethylmethylenediamine with butadiene, which results in the synthesis of unsaturated 1,1-dimethylamino-3,8-nonadiene, 1,1-dimethylamino-2-pentene, and 1,2-dimethylamino-3-methyl-1-butene, has been studied for the first time.

Polymerizable amines as promoters of cold-curing resins and composites.

The accelerating activity of N,N-substituted aminoethyl methacrylates on the curing of methyl methacrylate and composite resins with benzoyl peroxide is somewhat smaller than that of dimethyl-p-toluidine. Tesins cured with aminoethyl methacrylates containing a p-tolyl and 3,5-xylyl substituent on the nitrogen atom turned approximately the same color in ultraviolet light as resins cured with dimethyl-p-toluidinemthe incorporation of the predominant part of an unsaturated tertiary amine into polymer chains reduces to a minimum the possibility of its diffusion from the resin into the surrounding tissue.

New completely aliphatic anionic membranes from polymers of unsaturated tertiary amines. Part I. Preparation and properties

AbstractNew anionic membranes of completely aliphatic structure have been prepared starting from homopolymers and copolymers of unsaturated aliphatic tertiary amines.These membranes have an exchange capacity ranging from 0.5 to 4.0 meq/g dry substance and a permoselectivity exceeding 90%.Using reversible Ag/AgCl electrodes, the membrane potential for these membranes has been measured in various NaCl solutions, in order to determine the transport number. Moreover, the membrane conductivity has been determined as function of the concentration of the electrolyte in the external solution.These membranes, since they do not contain the arylalkyl‐trimethylammonium group, offer greater resistance to alkaline conditions than conventional ones.

γ-Ray induced copolymerization of enamines

Attempts were made to obtain copolymers of α- β unsaturated tertiary aliphatic amines (enamines) by using γ-radiations from 60Co to initiate. Copolymerization takes place readily in the liquid state at 35°, with the following monomeric mixtures: 1-morpholinebutene-benzovinyltriazole, 1-morpholinebutene-acrylamide, 1-morpholinebutene-acrylonitrile, 1-piperidine isobutene-acrylonitrile. No copolymers were obtained from 1-morpholine propene, presumably because this enamine cannot exist in a sufficiently pure state. In the system 1-morpholinebutene-acrylonitrile, copolymerization takes place also at −78°, with the monomers mostly in a crystalline state and at −196° with the monomers in a crystalline or glassy state. Experiments with scavengers suggest that the mechanism of copolymerization at −78° is similar to that operating in the liquid state at 35° and involves radical intermediates.

Polymerization of nitrogen‐containing and oxygen‐containing monomers by Ziegler‐Natta catalysts

AbstractThe polymerization of oxygen‐ and nitrogen‐containing monomers by Ziegler‐Natta catalysts is described. In particular, the results obtained in the polymerization of unsaturated tertiary amines are reported. The polymerization is possible when both the nitrogen atom of the monomer and the aluminum atom of the organometallic compound used in the catalysis are shielded by branched alkyl groups. The influence of the distance of the nitrogen atom from the double bond is also studied. The polymerization of monomers containing siloxanic or silazanic groups are described. By hydrolysis of the polymers in an acid medium crystalline polymers of primary alcohols and an amorphous polymer of a secondary amine have been isolated.

Δ5‐steroids and provitamins D with branched side chains, III. Preparation and reduction of some Δ5‐steroid‐ω‐amides

AbstractThis paper deals with the dimethyl and diethyl amides of Δ5‐cholenic acid and Δ5‐bisnorcholenic acid. These amides could be converted into the corresponding unsaturated tertiary amines by reduction with LiAlH4.