公开(公告)号：US4943358A

公开(公告)日：1990-07-24

申请号：US323976

申请日：1989-03-15

申请人： Kenneth M. Dear ,  Philip J. Turner

发明人： Kenneth M. Dear ,  Philip J. Turner

IPC分类号： B01J19/12 ,  C07C45/00 ,  C07C45/30 ,  C07C49/784 ,  C07C49/786 ,  C07C49/813 ,  C07C67/00 ,  C07C201/00 ,  C07C201/12 ,  C07C205/46 ,  C07C309/44

CPC分类号： C07C49/813 ,  C07C45/30 ,  C07C49/784

摘要： It is desired to find an alternative way to produce benzophenones or substituted benzophenones which does so selectively and avoids the problems of previous methods that use, for example, large amounts of an aluminium chloride catalyst or nitric acid.In the invention process, a diphenyl methane starting material (DPM) in a hydrophobic phase is oxidized in a photolytic process by contact with an aqueous phase containing greater than 1 mole of HBr and at least 1.5 moles of H.sub.2 O.sub.2, both per mole of DPM, the radiation being capable of dissociating bromine to its radicals, and especially using light of wavelength 600 to 250 nm. Preferably, a reaction temperature of around 50.degree. to 65.degree. C., is used, the organic solvent comprising a suitably boiling chlorinated carbon or hydrocarbon. The H.sub.2 O.sub.2 is introduced progressively into the reaction mixture. The benzophenone product is recovered substantially in the organic phase, whereas most of the bromine/bromide is retained in the aqueous phase which can be re-employed in a subsequent oxidation of DPM, possibly after restoration of the bromide to its initial concentration.In a modification to the process, by suitably controlling the mole ratios of bromide and H.sub.2 O.sub.2 to DPM at about 1:1:1, and preferably using a reaction temperature of about ambient to 35.degree. C., the DPM can be substituted by a single bromine atom on the methane carbon also with good selectively, instead of being oxidized to the benzophenone.

公开(公告)号：US5139628A

公开(公告)日：1992-08-18

申请号：US674380

申请日：1991-04-11

申请人： Kenneth M. Dear ,  Kevan M. Reeve ,  Philip J. Turner

发明人： Kenneth M. Dear ,  Kevan M. Reeve ,  Philip J. Turner

IPC分类号： C07C51/265 ,  C07C309/58 ,  C07F9/6547

CPC分类号： C07C309/58

摘要： A multi stage process for the conversion of 2-chloro-4-sulphotoluene (SCT) to 2-chloro-4-sulphobenzoic acid (SCUBA). Stage (a) comprises a process S1 for the selective side chain bromination of SCT to 2-chloro-4-sulpho-dibromotoluene (SCDBT) or 2-chloro-4-sulpho-bromotoluene (SCMBT) by contacting the starting material with bromine in chloroform or trichloroethane and irradiating the mixture with light that dissociates bromine. Subsequently, in stage (b), process S2, the product of S1 can be hydrolysed at elevated temperature after separation from the organic solvent to the corresponding alcohol (SCOL) or aldehyde (SCAB). In stage (c), the product of S2 can be oxidized to SCUBA either by oxidation with a peroxyacid, optionally generated in situ, provided that the aqueous solution has previously been stripped of bromide/bromine in process S3. The oxidation can also be carried out using bromine, preferably generated in situ in process S5 by oxidation of residual bromide with hydrogen peroxide, which can then be followed by process S3 to strip out the bromine/bromide. A combination of processes S1, S2, S5 and S3 in that order provides a closed loop process cycle which recycles the environmentally harmful reagent, bromine.

摘要翻译： PCT No.PCT / GB89 / 01068 Sec。 371日期1991年4月11日 102（e）日期1991年4月11日PCT提交1989年9月12日PCT公布。 出版物WO90 / 02731 1990年3月22日。用于将2-氯-4-磺基丙烯（SCT）转化为2-氯-4-磺基苯甲酸（SCUBA）的多阶段方法。 阶段（a）包括通过使原料与溴接触，将SCT的选择性侧链溴化为2-氯-4-磺基 - 二溴甲苯（SCDBT）或2-氯-4-磺基 - 溴甲苯（SCMBT）的方法S1 氯仿或三氯乙烷，并用分解溴的光照射混合物。 随后，在步骤（b）中，方法S2中，S1的产物可以在从有机溶剂分离到相应的醇（SCOL）或醛（SCAB）之后在升高的温度下水解。 在阶段（c）中，S2的产物可以通过过氧酸的氧化被氧化成SCUBA，任选地原位生成，条件是在方法S3中先前已经将水溶液除去了溴化物/溴。 氧化还可以使用溴进行，优选在方法S5中原位通过用过氧化氢氧化残余溴化物，然后可以通过方法S3除去溴/溴。 过程S1，S2，S5和S3的组合按照该顺序提供闭环处理循环，其循环利用环境有害的试剂溴。