A Simple Nitrovinylation Reaction

Abstract

formula [(CH3)2N]2Se. The solid is thermolabile, being converted with loss of oxygen into the liquid [(CH3)2N]2Se. We have also prepared the solid [(CH3)2N]2SeO from SeOCI2 and dimethylamine [5].[(CH3)2N]zSeO and [(CH&NH212Se205 (1) are always formed together in a 1 : 1 molar ratio. Thus, the following equation can be written for the aminolysis of selenium dioxide:It therefore appears that not every Se-0-Se bridge in the selenium dioxide undergoes aminolysis. Terminal anionic groups apparently increase the stability of adjacent Se-0-Se bridges towards solvolysis. This interpretation is supported by the fact that the diselenites (NH4)2Se205 and K2Se205 are resistant to liquid dimethylamine at room temperature and even to liquid ammonia. Received, October 23rd, 1964 [Z 8491675 IE] German version: Angew. Chem. 76. 992 (1964) [ I ] Investigations of Selenium-Oxygen Compounds, Part 29. ~ The reaction of 2-chloropyridine N-oxide with KNH2 in liq. ammonia leads mainly to undefined products plus 5 % 2aminopyridine N-oxide and 1 % 3-aminopyridine N-oxide; the latter two products are suggestive of the intermediate occurrence of 3,4-dehydropyridine N-oxide ( I ) . In contrast, 3chloropyridine N-oxide yields only the 3-amino compound [l]. We heated 3-chloropyridine N-oxide for 8 days with piperidine in anhydrous benzene at 100 "C and obtained ca. 80 % of the starting material, non-identified products, and 3piperidinopyridine N-oxide (82 % [2] ; picrate has m. p. 189 "C), plus 4 % [2] 4-piperidinopyridine N-oxide (m.p. of picrate 153-154OC), but could not detect the 2-piperidino isomer. Analogously, when 3-bromoquinoline N-oxide was heated with piperidine at 115 "C for three days, 22 % [2] 4piperidinoquinoline N-oxide [3] (m. p. of picrate 132-1 33 "C) was isolated in addition to a small amount of starting material, non-identified products, and 3-piperidinoquinoline N-oxide (20 % [2]; m.p. of picrate 165--166'C), but again no 2-piperidino isomer was found.The formation of the 4-piperidino compounds indicates an elimination/addition mechanism for the substitution proceeding via the heterocyclic N-oxides (2) and (3) t41.In contrast to the 3-halogeno compounds, 2-and 4-chloropyridine N-oxides and 4-chloroquinoline N-oxide appear to react completely according to the normal addition/elimina-tion mechanism [5] when heated in piperidine t o about 100 'C, for only the "non-rearranged" substitution products, viz. 2-piperidinopyridine N-oxide (m.p. 124.5-125.5 "C), 4-piperidinopyridine N-oxide, and 4-piperidinoquinoline N-oxide are formed in almost quantitative yield. Received, October 26th, 1964 [ Z 852/678 I€] German version: Angew. Chem. 76, 993 (1964) [I] R . 1. Martens and H .

Improving interfacial adhesion between thermoplastic polyurethane and copper foil using amino carboxylic acids

“…The SEM photomicrographs also reveal very strong interfacial adhesion between chemically treated Cu and TPU matrix. It is assumed from the literature 22,23,[33][34][35][36][37][38][39][40] and the ATR-IR spectra presented herein that the free amino groups of the TPU are H-bonded to free carbonyl group of the chelated copper carboxylate of 6-aminohexanoic acid; there is another possibility that the acid group of amino carboxylic acids coordinate with Cu and amino ends are hydrogen-bonded to polyurethane. Finally, it may be concluded that 6-aminohexanoic acid has the potential to replace the conventional silane coupling agent for improving interfacial adhesion between copper and TPU matrices.…”

“…Many researchers in the field of biochemistry have reported that the strong coordination bonding of amino acids to transition metals occurring via a chelate binding mode involving both carboxylate and amine groups. [33][34][35][36] Thus, there exists a possibility that the free carbonyl group of the chelated carboxylate of 6-aminohexanoic acid may be assigned to bond TPU through H-bonding with free ANH group of polyurethane. There are some reports about interfacial activity of a nitrogen-or oxygencontaining functionality onto metal surfaces [37][38][39][40] and it was reported that OH groups are more effective than NH 2 groups in enhancing the adhesion strength between polystyrene and copper.…”