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。

公开(公告)号：US4923580A

公开(公告)日：1990-05-08

申请号：US326065

申请日：1989-03-20

申请人： Philip J. Turner ,  Martin Jeff ,  Kevan M. Reeve

发明人： Philip J. Turner ,  Martin Jeff ,  Kevan M. Reeve

IPC分类号： B01J19/12 ,  C07B39/00 ,  C07C17/00 ,  C07C17/14 ,  C07C22/04 ,  C07C25/02 ,  C07C25/13 ,  C07C45/43 ,  C07C67/00 ,  C07C201/00 ,  C07C201/12 ,  C07C201/14 ,  C07C205/11 ,  C07C205/12 ,  C07C303/22 ,  C07C309/30

CPC分类号： C07B39/00 ,  C07C201/12

摘要： Selective bromination of alkylarenes to the alpha dibrominated derivative is desirable as a precursor for the selective production of, for example, the corresponding aromatic aldehyde.Improvements in the extent of selectivity of the product and/or its rate of production can be obtained by employing a photolytic reaction between the substrate, hydrogen peroxide and hydrogen bromide using mole ratios of H.sub.2 O.sub.2 : substrate of about 2.8:1 or higher, preferably 3,2: to 3.5:1 and of bromide:substrate of over 2.5:1, preferably about 2.8:1 to 3.2:1 and progressive controlled introduction of the H.sub.2 O.sub.2, the reaction being carried out in the presence of a substantial amount of an organic solvent, and preferably more than 5.5 volumes per volume of substrate, whilst irradiating with light preferably having principal emissions in the range of 250 to 600 nm. The reaction mixture is preferably maintained at 50.degree. to 60.degree. C. The reaction often takes from 5 to 12 hours, of which period hydrogen peroxide is introduced progressively into the reaction mixture during preferably the first 3 to 5 hours. The process is especially suitable for deactivated alkylarenes, such as o-nitrotoluene.

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：US5092971A

公开(公告)日：1992-03-03

申请号：US326109

申请日：1989-03-20

申请人： Philip J. Turner ,  Martin Jeff

发明人： Philip J. Turner ,  Martin Jeff

IPC分类号： B01J19/12 ,  C07B39/00 ,  C07C17/00 ,  C07C17/14 ,  C07C22/04 ,  C07C25/02 ,  C07C25/13 ,  C07C67/00 ,  C07C201/00 ,  C07C201/12 ,  C07C201/14 ,  C07C205/11 ,  C07C205/12 ,  C07C303/22 ,  C07C309/30

CPC分类号： C07B39/00 ,  C07C201/12

摘要： Selective bromination of alkylarenes to the alpha monobrominated derivative is desirable as a precursor for the selective production of, for example, the corresponding alcohols. The product can be obtained by a photolytic reaction between the substrate, hydrogen peroxide and hydrogen bromide in approximately equimolar ratios in an organic solvent, but improvement in the yield of the product coupled with similar or improved selectivity in its production was either not achieved or was actually impaired by a range of variations in the ratios and by omitting the solvent.The invention employs mole ratios of H.sub.2 O.sub.2 :substrate of 0.1:1 to 0.4:1, preferably 0.2:1 to 0.33:1 and of H.sub.2 O.sub.2 :bromide of 1:1.2 to 1:2, preferably about 1:1.3 to 1:1.8 and progressive introduction of the H.sub.2 O.sub.2, either in the presence or absence of the solvent, while irradiating with light preferably having principal emissions in the range of 250 to 600 nm, and the process thereby achieves either or both of improved yield and improved selectivity of the alpha monobrominated product. The reaction mixture is preferably maintained at 50.degree. to 70.degree. C. The process is especially suitable for deactivated alkylarenes, such as o-nitrotoluene.

公开(公告)号：US4846945A

公开(公告)日：1989-07-11

申请号：US92362

申请日：1987-09-02

申请人： Philip J. Turner ,  Vincent I. Routledge ,  Martin Jeff

发明人： Philip J. Turner ,  Vincent I. Routledge ,  Martin Jeff

IPC分类号： C07C45/00 ,  C07C45/30 ,  C07C49/16 ,  C07C49/463 ,  C07C67/00

CPC分类号： C07C45/30

摘要： Oxidation of alcohols to ketones using bromine suffers from a side reaction of comparable speed in which a bromide substituted product is formed. Additionally, the use of bromine as reagent is relatively unpleasant and it creates a major waste disposal problem.The latter problem can be solved by generating bromine in situ by reaction between hydrogen peroxide and bromide ions or hydrogen bromide, but this inevitably increases the exposure of the alcohol to HBr/Br.sup.-. The selectivity of the process towards non-substituted oxidation depending upon the inherent deactivation or reactivity of the alcohol can be improved by irradiating the reactants with light of suitable frequency to generate bromine radicals in the mixture, and/or by controlling the rate of introduction of the hydrogen peroxide and controlling the extent to which mole ratio of HBr:alcohol is substoichiometric. Selectivity can also be improved by employing a two-phase reaction mixture, the alcohol being present to a considerable extent in the organic phase with HBr/Bromide being retained to a great extent in the aqueous phase.It is particularly beneficial for the selective oxidation of alcohols that are substituted by adjacent electronegative groups, for example chloropropanols.

摘要翻译： 使用溴将醇氧化成酮类受到形成溴化物取代产物的相当速度的副反应。 此外，使用溴作为试剂是相对令人不快的，并且造成主要的废物处理问题。 后一个问题可以通过过氧化氢和溴离子或溴化氢之间的反应原位产生溴来解决，但这必然会增加酒精暴露于HBr / Br-。 可以通过用合适频率的光照射反应物以在混合物中产生溴自由基，和/或通过控制引入速率来提高该方法对于未取代的氧化的选择性，这取决于醇的固有的失活或反应性 过氧化氢和控制HBr：酒精的摩尔比是亚化学计量的程度。 还可以通过使用两相反应混合物来改善选择性，醇在有机相中相当程度地存在，HBr /溴化物在水相中被很大程度地保留。 对由相邻的电负性基团例如氯丙醇取代的醇的选择性氧化特别有利。