Loeppky R N, Tomasik W, Millard T G
IARC Sci Publ. 1984(57):353-63.
N-Nitrosamines are formed from the heating of either a secondary or a tertiary amine with sodium nitrite in the presence of a high-boiling ester such as 2-acetoxyethanol in ethylene glycol. The four secondary and six tertiary amines examined were found to produce N-nitrosamines in yields ranging from 4% to 80% when equimolar amounts of amine and ester were heated at 120 degrees C with one- to ten-fold equivalents of sodium nitrite in ethylene glycol. Secondary amines competitively produced acetamides at a rate slightly greater than N-nitrosamine formation. Preincubation of a large excess of sodium nitrite and ester led to the rapid formation of N-nitrosamines in high yield. The reaction of tribenzylamine resulted in the formation of both benzaldehyde and dibenzylnitrosamine. N,N-Dimethylbenzylamine reacted to give nearly equimolar amounts of N-nitrosodimethylamine and N-nitroso-N-methylbenzylamine. It is proposed that the nitrosating agent is a nitrous ester, and it is shown that 2-benzoxyethyl nitrite rapidly nitrosates secondary and tertiary amines under these reaction conditions. It is also proposed that these transformations are good models for the environmental formation of N-nitrosamines in foods and commercial products.
N-亚硝胺是由仲胺或叔胺与亚硝酸钠在高沸点酯（如乙二醇中的2-乙酰氧基乙醇）存在下加热形成的。当等摩尔量的胺和酯在120℃下与一至十倍当量的亚硝酸钠在乙二醇中加热时，所检测的四种仲胺和六种叔胺被发现能产生产率在4%至80%之间的N-亚硝胺。仲胺竞争性地生成乙酰胺，其速率略高于N-亚硝胺的形成速率。大量过量的亚硝酸钠和酯预孵育导致高产率地快速形成N-亚硝胺。三苄基胺的反应导致苯甲醛和二苄基亚硝胺的形成。N,N-二甲基苄胺反应生成几乎等摩尔量的N-亚硝基二甲胺和N-亚硝基-N-甲基苄胺。有人提出亚硝化剂是亚硝酸酯，并且表明在这些反应条件下，2-苄氧基乙基亚硝酸酯能迅速使仲胺和叔胺亚硝化。还提出这些转化是食品和商业产品中N-亚硝胺环境形成的良好模型。
