Amines polyacetylenes

All three compounds (WF6 and MoF6 are best) will bring about a reaction (not a fluorination) that may have synthetic utility at 0CC in l,l,2-trichloro-l,2,2-trifluoroethane (Freon 113) or chloroform they will cleave N,TV-dimethyl- and N-tosylhydrazones and oximes back to the parent carbonyl compounds12,14 (UF6 converts any first-formed aldehydes into acid fluorides1213). All three hexafluorides will convert1215 tertiary amines into carbonyl compounds and carboxylic acids into acid fluorides.16 They also dope polyacetylene to the metallic regime.17... 

A cast film of 28 also responded to the chirality of liquid and solid chiral amines, and exhibited an ICD in the UV-visible region. The observed Cotton effect patterns were similar to those of 28 induced by the chiral amines in solution [147]. These methods are more convenient and practically feasible to sense the chirality of chiral amines than the solution method, and may be applicable to other dynamic helical polyacetylenes. 

The coupling of a terminal alkyne with a 1-bromoalkyne in the presence of a copper(i) salt and an amine base (B), referred to as the Cadiot-Chodkiewicz coupling , is of particular synthetic importance because of the facile roiite it provides to unsymmetrical polyacetylenes with an even or odd number of triple bonds (equation 10). The reaction has been reviewed and these reviews should be... 

The utility of classical antioxidants such as hindered amines, phenols, and nitrones for the stabilization of pristine polyacetylene (29), poly(methyl acetylene) (30), and poly(l,6-heptadiyne) (31) has been examined. Poly(methyl acetylene), although dopable to only low conductivities (10" S/cm), has similar oxidative behavior to polyacetylene and serves as a good model for other polyenes. In general, the improvement in stability of poly(methyl acetylene) was limited, but combinations of hindered phenols and hydroperoxide scavengers resulted in a factor of 5 decrease in the oxidation rate (30) as monitored by the appearance of IR absorption bands attributable to carbonyl groups. These degradation rates are still too high for the use of these polyenes in an unprotected environment. The compatibility of such stabilizers with the dopants commonly used for polyacetylene was not studied. 

Polypropylene amines, poly(amidoamines) (PAMAM) and silicon dendrimers set records for the number of generations, whereas the polyacetylene dendrimer prepared by Moore et al. [6] with the formula C1398H1278 and a mass of 18079.53 holds the heavyweight championship title of pure hydrocarbons. Mullen et al. have recently published a series of aromatic hydrocarbon dendrimers consisting of phenylene-bridged benzene rings. [7] Interestingly, these species form two-dimensional planes rather than three-dimensionally extended structures. 

Among the classical (summarized in [11]) reactions of cyanoacetylenes (salt and n-complex formation, nucleophilic addition of, inter alia, amines and alcohols, Diels-Alder additions with 2 (see Section 2.22.2), addition of halogens and hydrogen halides, etc.) their polymerization might deserve a second look since the products formed - polyacetylenes - have attracted much attention during the last two decades. Thus 1, several of its derivatives, and 2 have been polymerized with anionic initiators (triethylamine, sodiiun cyanide, butyllithium) to give black, low-molecular-weight polymers claimed to have structures like 33 [38-40], which is obtained from 2 by treatment with butyllithium. 

Fig. 2. Functional modifications of polyacetylene. Where R = H, alkyl, aryl R = alkyl, aryl, ester, ether, amine, thienyl, cyano, vinyl, ethjmyl, alkyl ammonium to = 0, 2.

Copper tends to form more stable organocopper compounds with acetylene compounds than with aryl compounds. The synthetic reaction of acetylenic compounds with copper or copper salt, e.g., the Cadiot-Chodkiewics and Glaser reactions are well known. The Cadiot-Chodkiewics reaction is a reaction where I-bromoalkyne easily reacts with a terminal alkyne in the presence of a catalytic amount of a cuprous salt or amines to afford conjugate diacetylene compounds in high yield [43]. For example, polyacetylene is easily synthesized as shown in eq. (22.19) [43],... 

Christensen LP, Brandt K (2006) Bioactive polyacetylenes in food plants of the Apiaceae family occurrence, bioactivity and analysis. J Pharm Biomed Anal 41 683-693 Chung JG (1998) Inhibitory actions of ellagic acid on growth and aryl amine N-acetyltransferase activity in strains of Helicobacter pylori from peptic ulcer patients. Microbios 93 115-127 Clifford MN (2004) Diet-derived phenols in plasma and tissues and their imphcation for health. Planta Med 70 1103-1114... 

Scheme 7. Synthesis of amine-functionalized polyacetylene (11) by copolymerization of N-propargylethanamlde (14) with tert-butyl propargylcarbamate (15), followed by deprotection.

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