邻(对)氯苯甲腈的合成研究

Study on Synthesis of o(p)-Chlorobenzonitrile

以邻(对)氯甲苯为原料,经光氯化、氨化制备邻(对)氯苯甲腈。邻(对)氯甲苯在光照及副反应抑制剂存在下,m〔邻(对)氯甲苯〕∶m(副反应抑制剂)=1000∶1,于120～160℃与氯气反应,邻(对)氯甲苯转化率100%,邻(对)氯三氯甲苯质量分数≥97%,邻氯三氯甲苯、对氯三氯甲苯收率分别为96.1%和98.3%;邻(对)氯三氯甲苯在催化剂作用下,于210℃与氯化铵反应,n〔邻(对)氯三氯甲苯〕∶n(氯化铵)=1∶1.1,m〔邻(对)氯三氯甲苯〕∶m(催化剂)=1000∶5,邻氯苯甲腈、对氯苯甲腈收率分别为92.7%和93.3%,总收率分别为89.1%和91.7%;以邻(对)氯甲苯300kg投入500L氯化釜进行放大实验,邻氯苯甲腈、对氯苯甲腈总收率分别为89.7%和92.5%。用IR、1HNMR对目标产物结构进行了表征。

o （p）-Chlorobenzonitrile were synthesized from o （p）-chlorotoluene by photo-chlorination and ammonolysis. In the presence of visible light and side-reaction inhibitor, o （p） -chlorotoluene reacted with chlorine at 120 - 160 ℃. When the mass ratio of o （p）-ehlorotoluene to side-reaction inhibitor was 1000：1, the conversion of o （p） -chlorotoluene was 100%, the content of o （p） -chlorobenzotrichloride was over 97% , the yields of o-ehlorobenzotrichloride and p-chlorobenzotrichloride were 96. 1% and 98.3 %. In the presence of catalyst, o （p） -chlorobenzotrichloride reacted with ammonium chloride at 210 ℃. When the mole ratio of o（p）-chlorobenzotrichloride to ammonium chloride was 1：1.1, the mass ratio of o （p） -chlorobenzotrichloride to catalyst was 1 000：5, the yields of o-chlorobenzonitrile and p-chlorobenzonitrile were 92. 7% and 93.3%. The total yields were 89. 1% and 91.7%. The scale experiment of 300 kg o （p） -chlorotoluene were carried out in a 500 L chlorinated reactor. The results showed that the total yields of o-chlorobenzonitrile and p-chlorobenzonitrile were 89.7% and 92. 5%. Their structures were characterized by IR and 1HNMR.