申请人:The University of Wales Swansea
公开号:EP0866049A2
公开(公告)日:1998-09-23
A process for the chlorination of an aromatic compound of the following formula (A) :
wherein RA is H or C1 to C12 alkyl, cycloalkyl, aryl, alkaryl, aralkyl or carboxyalkyl, the or each RB independently is selected from H, C1-C4 alkyl (especially methyl), C1-C4 haloalkyl or polyhaloalkyl, e.g. C1-C4 perfluoroalkyl, C1-C4 alkoxy, C5-C12 aryl (e.g. phenyl), alkaryl or aralkyl, or halogen, n is an integer which is 0, 1 or 2, and the or each RB, if present, may independently be attached at the ortho or the meta position (preferably at the meta-position), which process comprises reacting (preferably in homogeneous liquid phase below 35°C) the aromatic compound (which is preferably phenol) with a chlorinating agent (preferably sulphuryl chloride) in the presence of a sulphur-containing catalyst, optionally also in the presence of a Lewis acid co-catalyst, characterised in that the sulphur-containing catalyst is a compound according to the following formula (I) or formula (II) :
in which:
each of X1, X2, and X3 is independently selected from the group consisting of: S, SO, SO2 ;
R1 is selected from the group consisting of:
optionally substituted straight or branched chain alkyl or alkanediyl having from 2 to 20 carbon atoms, optionally substituted straight or branched chain alkaryl or aralkyl having from 5 to 20 carbon atoms, and optionally substituted aryl having from 5 to 20 carbon atoms;
R2 is an optionally substituted straight or branched chain alkyl or alkanediyl group having from 1 to 20 carbon atoms;
R3 and R4 are each independently selected from the group consisting of: H, optionally substituted straight or branched chain alkyl or alkanediyl having from 1 to 20 carbon atoms, optionally substituted straight or branched chain alkaryl or aralkyl having from 5 to 20 carbon atoms, and optionally substituted aryl having from 5 to 20 carbon atoms;
R5 is an optionally substituted straight or branched chain alkylene, arylene, alkarylene or arylalkylene group having from 1 to 20 carbon atoms;
wherein in the above definitions of R1, R2, R3, R4 and R5 the optional substituents may be independently selected from the following: halogen (e.g. F, Cl), hydroxy, amino, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl e.g. C1-C4 perfluoroalkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl.
一种下式(A)芳香化合物的氯化工艺:
其中 RA 为 H 或 C1 至 C12 烷基、环烷基、芳基、烷芳基、芳烷基或羧烷基,RB 或每个 RB 独立选自 H、C1-C4 烷基(尤其是甲基)、C1-C4 卤代烷基或多卤代烷基(如 C1-C4 全氟烷基)、C1-C4 烷氧基、C5-C12 芳基(如苯基)、烷芳基或芳烷基,或卤素,n 为 0、1 或 2 的整数,以及 n 为 0、1 或 2 的整数。或卤素,n 为 0、1 或 2 的整数,RB 或每个 RB(如有)可独立地连接在正位或偏位(最好是偏位)、该工艺包括在含硫催化剂存在下,也可选择在路易斯酸助催化剂存在下,使芳香族化合物 (最好是苯酚)与氯化剂(最好是硫酰氯)反应(最好在低于 35℃的均相液相中进行), 其特征在于含硫催化剂是符合下式(I)或式(II)的化合物:
其中
X1、X2 和 X3 各自独立地选自由以下组成的组:S、SO、SO2 ;
R1 选自以下组成的组
任选取代的具有 2 至 20 个碳原子的直链或支链烷基或烷二基,任选取代的具有 5 至 20 个碳原子的直链或支链烷芳基或芳烷基,以及任选取代的具有 5 至 20 个碳原子的芳基;
R2 是任选取代的直链或支链烷基或烷二基,具有 1 至 20 个碳原子;
R3 和 R4 各自独立地选自由以下组成的组H、任选取代的具有 1 至 20 个碳原子的直链或支链烷基或烷二基、任选取代的具有 5 至 20 个碳原子的直链或支链烷芳基或芳烷基以及任选取代的具有 5 至 20 个碳原子的芳基;
R5 是任选取代的具有 1 至 20 个碳原子的直链或支链亚烷基、芳基、芳烷基或芳烷基;
其中,在 R1、R2、R3、R4 和 R5 的上述定义中,任选取代基可独立选自以下基团:卤素(如 F、Cl)、羟基、氨基、氰基、硝基、C1-C4 烷基、C1-C4 卤代烷基(如 C1-C4 全氟烷基)、C1-C4 烷氧基、C1-C4 烷氧羰基。