双环[2,2,1]庚-5-烯-1,4,5,6,7,7-六氯-2,3-二酰亚胺的N-曼尼希碱的制备

The Preparation of Some N-Mannich Bases of Bicyclo(2,2,1)Hept-5-ene-1,4,5,6,7,7-Hexachloro-2,3-Dicarboximide

用双环[2,2,1]庚-5-烯-1,4,5,6,7,7-六氯-2,3-二酸酐与尿素共熔制备双环[2,2,1]庚-5-烯-1,4,5,6,7,7-六氯-2,3-二酰亚胺.此酰亚胺与甲醛和胺(芳香及脂肪胺)在乙醇中反应,可生成N-曼尼希碱,且产率较高.用此法共制备了二十四个N-曼尼希碱,其中二十二个是新化合物.除了11及13号外(见表)都是在室温下获得的.硝基(对、邻)苯胺与甲醛及该酰亚胺的反应,在室温得到双(对、邻硝基苯胺基)甲烷,回馏一小时后亦可获得预期的N-曼尼希碱.先把该酰亚胺转变成N-羟甲基的衍生物,然后再与胺反应也可得到N-曼尼希碱.该酰亚胺与胺-甲醛缩合物反应,不需另加酸同样也生成N-曼尼希碱.

Bicyclo(2, 2, 1)hept-5-ene-1, 4,5,6,7, 7-hexachloro-2, 3-dicarboximide has been prepared by fusing bicyclo(2, 2, 1)-hept-5-ene-1, 4, 5, 6, 7, 7-hexachloro-2, 3-dicarboxylic anhydride with urea. This imide reacts with formaldehyde and arnine(aromatic as well as aliphatic) in ethyl alcohol at room temperature to give N-Mannich bases in good yields. Twenty-four such bases, of which twenty-two are new compounds, were prepared by this method except No. 11 and 13 (see table). At room temperature, p-nitroariline or o-nitroaniline reads with this imide and formaldehyde yielding the bis(p-nitrophenylamino)methane or bis(o-nitrophenylamino) methane. When they are refluxtd for one hour, the expected N-Mannich bases were also obtained.These N-mannich bases can also be obtained by first converting the imide to the N-hydroxymethyl derivative followed by treatment with amine.It was found that the imide can also react with the amine-formaldehyde condensation product to yield N-Mannich bases without the aid ofexternally added acid.