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公开(公告)号：US4801738A
公开(公告)日：1989-01-31
申请号：US608460
申请日：1984-05-09
IPC分类号： C07C67/313 , B01J29/12 , B01J31/00 , B01J31/20 , C07B61/00 , C07C67/333 , C07C67/38 , C07C69/67
CPC分类号： C07C67/347
摘要： .delta.-Formylvalerates are prepared by a process wherein a 3-pentenoate is treated with an isomerization catalyst at elevated temperatures and a 4-pentenoate is distilled off, and the resulting 4-pentenoate is reacted with carbon monoxide and hydrogen at from 80 to 160.degree. C. under from 1 to 30 bar in the presence of a rhodium carbonyl complex which has been modified with tertiary organic phosphines or phosphites.
摘要翻译： δ-甲酸戊酯通过其中3-异戊烯酸酯在高温下用异构化催化剂处理并蒸馏除去4-戊烯酸酯的方法制备，所得4-戊烯酸酯与一氧化碳和氢气在80至160℃下反应。 在1至30巴下，在用叔有机膦或亚磷酸酯改性的羰基铑络合物的存在下。
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22.发明授权Isolation of methyl 4-pentenoate from mixtures containing this and methyl 3-pentenoate 失效从含有此和3-戊烯酸甲酯的混合物中分离4-戊烯酸甲酯
公开(公告)号：US4561942A
公开(公告)日：1985-12-31
申请号：US717108
申请日：1985-03-28
IPC分类号： C07C67/54 , C07C69/533 , B01D3/36
CPC分类号： C07C67/54
摘要： Methyl 4-pentenoate is isolated from mixtures containing this and methyl 3-pentenoate by a process in which from 0.25 to 0.4 part by weight of water is added per part by weight of methyl 4-pentenoate, and the azeotrope of methyl 4-pentenoate and water is distilled off.
摘要翻译： 4-戊烯酸甲酯由含有该戊烯酸甲酯和3-戊烯酸甲酯的混合物中分离，其中每重量份4-戊烯酸甲酯中加入0.25至0.4重量份的水，以及4-戊烯酸甲酯的共沸物和 水被蒸馏掉。
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公开(公告)号：US4169956A
公开(公告)日：1979-10-02
申请号：US940463
申请日：1978-09-08
CPC分类号： C07C67/38
摘要： A process for the manufacture of butanedicarboxylic acid esters, wherein(a) an aqueous cobalt salt solution is treated with carbon monoxide and hydrogen in the presence of active charcoal,(b) the resulting aqueous solution is extracted with butadiene or with a hydrocarbon mixture containing butadiene,(c) the butadiene, or butadiene/hydrocarbon mixture, containing cobalt carbonyl hydride, cobalt carbonyl and butenyl-cobalt tricarbonyl, is reacted with carbon monoxide and an excess of an alkanol of 1 to 4 carbon atoms in the presence of a tertiary nitrogen base,(d) the tertiary nitrogen bases contained in the resulting reaction mixture are removed from the latter to the extent of leaving from 0.1 to 0.3 mole per mole of pentenoic acid ester, excess hydrocarbons are also removed, the pentenoic acid ester remaining in the reaction mixture is reacted with carbon monoxide and an alkanol of 1 to 4 carbon atoms, and thereafter excess alkanol and free nitrogen base are distilled off and(e) the residual reaction mixture, containing cobalt catalysts, butanedicarboxylic acids and by-products is treated with an oxidizing agent in an aqueous acid medium and the mixture is separated into an organic phase, from which butanedicarboxylic acid esters are isolated by distillation, and an aqueous phase containing cobalt salts, which phase is extracted with a water-immiscible solvent.
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公开(公告)号：US4745228A
公开(公告)日：1988-05-17
申请号：US65959
申请日：1987-06-24
申请人： Martin Decker , Rolf Fischer , Wolfgang Franzischka , Rudolf Kummer , Heinz-Walter Schneider , Uwe Vagt
发明人： Martin Decker , Rolf Fischer , Wolfgang Franzischka , Rudolf Kummer , Heinz-Walter Schneider , Uwe Vagt
CPC分类号： C07C45/48
摘要： Cyclic ketones of the formula ##STR1## where n is an integer from 4 to 6, are prepared by converting an aliphatic dicarboxylate of the formulaR.sup.1 OCC--(CH.sub.2).sub.n --COOR.sup.2 IIwhere n has the above meaning, R.sup.1 and R.sup.2 are each alkyl, cycloalkyl, aralkyl or aryl and R.sup.2 may furthermore be hydrogen, at from 150.degree. to 450.degree. C. over a solid oxide catalyst.
摘要翻译： 通过将式R 1 OCC-（CH 2）n -COOR 2 II的脂肪族二羧酸酯转化为其中n具有上述含义，R1和R2各自为烷基，其中n为4-6的整数，其中n为4至6的整数的式 ，环烷基，芳烷基或芳基，R2可以为氢，在固体氧化物催化剂上为150-450℃。
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公开(公告)号：US4586987A
公开(公告)日：1986-05-06
申请号：US721810
申请日：1985-04-10
申请人： Heinz-Walter Schneider , Rudolf Kummer , Otto Leman , Paul Panitz
发明人： Heinz-Walter Schneider , Rudolf Kummer , Otto Leman , Paul Panitz
CPC分类号： C07C67/54
摘要： C.sub.1 -C.sub.4 -alkyl pentenoates are obtained from reaction mixtures which contain this and which are obtained by reacting butadiene, or a butadiene-containing hydrocarbon mixture, with carbon monoxide and a C.sub.1 -C.sub.4 -alkanol, in the presence of a cobalt carbonyl catalyst and a tertiary nitrogen base at elevated temperatures and under superatmospheric pressure by a process in which(a) the liquid reaction mixture freed from excess carbon monoxide is treated with hydrogen at elevated temperatures and under from 5 to 80 bar,(b) hydrocarbons are distilled off from the resulting liquid reaction mixture,(c) the C.sub.1 -C.sub.4 -alkyl pentenoate, the alkanol and the nitrogen base are then distilled off under reduced pressure, and(d) the C.sub.1 -C.sub.4 -alkyl pentenoate is obtained by fractional distillation from the distillate containing this compound, the alkanol and the tertiary nitrogen base.
摘要翻译： 由含有这一点的反应混合物获得戊烯酸C 1 -C 4烷基酯，其通过使丁二烯或含丁二烯的烃混合物与一氧化碳和C 1 -C 4烷醇在羰基钴催化剂存在下反应获得， 在高温和超大气压下，通过一种方法，（a）在高温和5至80巴下用氢处理脱除过量一氧化碳的液体反应混合物，（b）将烃蒸馏掉， 从所得液体反应混合物中，（c）戊烯酸C 1 -C 4烷基酯，然后在减压下蒸馏除去链烷醇和氮碱，并且（d）戊烯酸C1-C4烷基酯是通过从 含有该化合物的馏出物，链烷醇和叔氮碱。
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公开(公告)号：US4537987A
公开(公告)日：1985-08-27
申请号：US629766
申请日：1984-07-11
IPC分类号： B01J31/00 , B01J31/20 , B01J31/24 , C07B61/00 , C07C67/313 , C07C67/38 , C07C67/39 , C07C69/44 , C07C69/67
CPC分类号： C07C67/39
摘要： Pure monoesters of adipic acid are prepared by a process in which(a) a pentenoate is reacted with carbon monoxide and hydrogen at from 90.degree. to 140.degree. C. and under from 5 to 300 bar in the presence of a carbonyl complex of cobalt or of rhodium, and a 5-formylvalerate is separated off, and(b) the 5-formylvalerate thus obtained is oxidized with molecular oxygen, or with a gas containing this, at from 20.degree. to 100.degree. C. under from 1 to 10 bar.
摘要翻译： 己二酸的纯单酯通过以下方法制备，其中（a）戊烯酸酯与一氧化碳和氢气在90至140℃和5至300巴下在钴或羰基络合物存在下反应 的铑，并分离出5-甲酰基戊酸酯，（b）将所得的5-甲酰基戊酸酯用分子氧或含有该气体的气体在20至100℃下在1至10巴 。
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公开(公告)号：US4360692A
公开(公告)日：1982-11-23
申请号：US205569
申请日：1980-11-10
CPC分类号： C07C67/347 , C07C67/38
摘要： An improved process for the preparation of alkyl formylvalerates, wherein butadiene or a butadiene-containing hydrocarbon mixture is reacted, in a first stage, with carbon monoxide and alkanols in the presence of cobalt carbonyl complexes and, per mole of butadiene, from 0.5 to 2 moles of tertiary nitrogen bases having a pK.sub.a of from 3 to 11, at from 80.degree. to 150.degree. C. and from 300 to 2,000 bar, and, in a second stage, the resulting alkyl pentenoate is reacted with carbon monoxide and hydrogen in the presence of cobalt carbonyl complexes at from 100.degree. to 160.degree. C. and from 100 to 300 bar, the improvement being that tertiary nitrogen bases, excess alkanols and any unconverted hydrocarbons are distilled off from the reaction mixture obtained in the first stage, with the proviso that the reaction mixture is treated, before or during the distillation, with gases containing molecular oxygen, and the residual reaction mixture containing alkyl pentenoate and cobalt catalyst is used in the second stage.
摘要翻译： 一种改进的制备烷基甲酰基戊酸酯的方法，其中丁二烯或含丁二烯的烃混合物在第一阶段中与一氧化碳和链烷醇在钴羰基络合物和每摩尔丁二烯的存在下反应，为0.5至2 具有pKa为3至11，80至150℃和300至2,000巴的叔氮碱的摩尔数，并且在第二阶段中，使得到的戊烯酸烷基酯与一氧化碳和氢气在 在100至160℃和100至300巴存在钴羰基络合物，其改进是从第一阶段获得的反应混合物中蒸馏掉叔氮碱，过量链烷醇和任何未转化的烃， 条件是反应混合物在蒸馏之前或期间用含有分子氧的气体进行处理，并且含有戊烯酸烷基酯和钴催化剂的残余反应混合物用于 第二阶段
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公开(公告)号：US4310686A
公开(公告)日：1982-01-12
申请号：US153572
申请日：1980-05-27
IPC分类号： C07C67/08 , B01J31/00 , B01J31/20 , C07B61/00 , C07C67/38 , C07C67/58 , C07C69/34 , C07C69/44
摘要： A process for the preparation of butanedicarboxylic acid esters, wherein(a) an aqueous cobalt salt solution is treated with excess carbon monoxide and hydrogen in the presence of active charcoal laden with cobalt carbonyl,(b) the resulting aqueous solution of cobalt carbonyl hydride is extracted with butadiene or a butadiene containing hydrocarbon mixture and the aqueous phase is separated off,(c) the butadiene, or butadiene/hydrocarbon mixture, containing cobalt carbonyl hydride, cobalt carbonyl and butenyl-cobalt tricarbonyl, is reacted with carbon monoxide and excess C.sub.1 -C.sub.4 -alkanol in the presence of a tertiary nitrogen base,(d) the resulting reaction mixture is freed from the tertiary nitrogen base contained therein, down to a content of from 0.1 to 0.3 mole per mole of pentenoic acid ester, and from excess hydrocarbons, and the pentenoic acid ester remaining in the reaction mixture is reacted with carbon monoxide and excess C.sub.1 -C.sub.4 -alkanol in the presence of the cobalt carbonyl and tertiary nitrogen base contained in the reaction mixture,(e) the reaction mixture is treated with an oxidizing agent in the presence of the aqueous acid solution which has been separated off in stage (b), and the mixture is separated into an organic phase, from which butanedicarboxylic acid esters are isolated by distillation, and an aqueous phase, and(f) the aqueous phase is extracted with water-immiscible solvents, the phases are separated, and the resulting aqueous phase is freed from alkanols and tertiary nitrogen base and is recycled to stage (a).
摘要翻译： 制备丁烷二羧酸酯的方法，其中（a）钴水溶液在过量的一氧化碳和氢气的存在下，在负载有羰基钴的活性炭存在下处理，（b）得到的氢化羰基碳水溶液为 用丁二烯或含丁二烯的烃混合物萃取并分离出水相，（c）含有羰基氢化钴，羰基钴和三丁基钴的三羰基化合物的丁二烯或丁二烯/烃混合物与一氧化碳和过量的C1 -C 4 - 链烷醇，（d）将所得反应混合物与其中所含的叔氮碱脱除，至每摩尔戊烯酸酯为0.1至0.3摩尔，过量 碳氢化合物和残留在反应混合物中的戊烯酸酯在羰基钴a存在下与一氧化碳和过量的C 1 -C 4烷醇反应 （e）反应混合物在步骤（b）中分离的酸性水溶液存在下用氧化剂处理，并将混合物分离成有机相 通过蒸馏分离丁二羧酸酯和水相，（f）水相用不与水混溶的溶剂萃取，分离相，所得水相脱离链烷醇和叔氮碱， 被回收到舞台（a）。
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公开(公告)号：US4529815A
公开(公告)日：1985-07-16
申请号：US608459
申请日：1984-05-09
IPC分类号： B01J29/00 , B01J29/06 , B01J31/00 , B01J31/26 , C07B61/00 , C07C67/333 , C07C69/533
CPC分类号： C07C67/333
摘要： 4-Pentenoates are prepared by isomerization of isomeric pentenoates in the presence of a catalyst, by a process in which isomeric pentenoates are treated at elevated temperatures with an acidic ion exchanger or acidic zeolite which contains a noble metal of group eight of the periodic table, and the 4-pentenoate is distilled off from the reaction mixture.
摘要翻译： 通过在酸性离子交换剂或包含元素周期表第八族的贵金属的酸性沸石的高温下处理异构戊烯酸酯的方法，在催化剂存在下异构戊烯酸酯制备4-戊烯酸酯， 并从反应混合物中蒸馏出4-戊烯酸酯。
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30.发明授权Purification of carboxylates containing aldehydes, acetals and/or unsaturated compounds 失效含醛，缩醛和/或不饱和化合物的羧酸盐的纯化
公开(公告)号：US4523027A
公开(公告)日：1985-06-11
申请号：US518006
申请日：1983-07-28
CPC分类号： C07C67/60
摘要： Carboxylates which contain aldehydes, acetals and/or unsaturated compounds and are obtained by reacting an olefinically unsaturated compound with carbon monoxide and an alkanol are purified by a process wherein the said carboxylates are treated with hydrogen at elevated temperatures in the presence of an acidic ion exchanger or zeolite doped with one or more metals of group VIII of the periodic table, and the resulting low and/or high boilers are separated off by distillation.
摘要翻译： 通过使烯属不饱和化合物与一氧化碳和链烷醇反应得到的含醛，缩醛和/或不饱和化合物的羧酸盐通过其中所述羧酸盐在酸性离子交换剂存在下在高温下用氢处理的方法进行纯化 或掺杂有周期表第Ⅷ族的一种或多种金属的沸石，并通过蒸馏分离得到的低和/或高沸点。
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