CN1356335A - 亚磷酸酯衍生物,其制备方法以及含亚磷酸酯的催化剂前体 - Google Patents
亚磷酸酯衍生物,其制备方法以及含亚磷酸酯的催化剂前体 Download PDFInfo
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- CN1356335A CN1356335A CN01120879.1A CN01120879A CN1356335A CN 1356335 A CN1356335 A CN 1356335A CN 01120879 A CN01120879 A CN 01120879A CN 1356335 A CN1356335 A CN 1356335A
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- 239000003054 catalyst Substances 0.000 title description 31
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- 239000003446 ligand Substances 0.000 claims abstract description 100
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 67
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- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 14
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- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明提供了一种多齿亚磷酸酯配位体以及含有该多齿亚磷酸酯配位体和零价镍的催化剂前体组合物,所述多齿亚磷酸酯如说明书中的化学式I、III、IV、VI、VIII、IX、X、XI、XII、XIII、XIV和XV所表示的化合物。本发明还提供氯亚磷酸酯的制备方法以及N,N-二烷基二芳基亚磷酸酯制备方法。
Description
发明领域
本发明一般涉及用于氢氰化二烯烃化合物制备非共轭的无环腈的改进的液相方法,还涉及将上述腈异构化为3-和/或4-直链单烯腈的液相方法。改进在于方法是在零价镍和多齿亚磷酸酯配位体存在下进行。
发明背景
催化氢氰化体系特别是涉及烯烃的氢氰化在本领域中是公知的,例如,用于将丁二烯氢氰化生成戊烯腈(PN)的液相体系在本领域中是公知的。例如,Drinkard的US 3,496,215公开了使用单齿亚磷酸镍催化剂氢氰化丁二烯。在上述专利和将在本文中使用的术语“戊烯腈”是指氰基丁烯,同样,“丁烯腈”是指氰基丙烯。正如Baker等人,J.Chem.Soc.,Chem.Commun.,1991,p803-804所描述的,现已知二齿亚磷酸酯配位体与零价镍和铂配合可用于丁二烯的液相氢氰化。
所生成的戌烯腈进行进一步氢氰化和/或异构化生成己二腈(ADN),己二腈是一种制造尼龙的重要工业原料。例如,Drinkard的US 3,536,748公开了在零价镍配合物存在下液相异构化2-甲基-3-丁烯腈,Chia的US 3,676,481公开了另外利用三(烃基)硼促进剂的改进方法。
活化的烯烃如共轭烯烃(例如丁二烯和苯乙烯)和应变烯烃(例如降冰片烯)的氢氰化可不必使用路易斯酸促进剂,而未活化的烯烃如1-辛烯和3-戌烯腈的氢氰化通常需要使用路易斯酸促进剂。有关在氢氰化反应中使用促进剂的教导例如参见US 3,496,217。
在本发明中用于氢氰化二烯烃的某些多齿亚磷酸酯配位体已经用于单烯烃的氢氰化。普通转让的共同未决申请08/424,351(1995年4月26日申请)和共同未决申请U.S.08/505,137(1995年7月21日申请)公开了优选与路易斯酸促进剂结合的二齿亚磷酸酯配位体用于氢氰化单烯烃。
本发明提供了一种氢氰化二烯烃化合物如丁二烯和异构化未共轭无环腈的改进方法,不必使用路易斯酸促进剂,而利用零价镍和多齿亚磷酸酯配位体。对于本领域技术人员来说,本发明的其它目的和优点可通过参考下面本发明的详细描述而显而易见。
发明概述
本发明提供了一种液相氢氰化二烯烃化合物和异构化所得的非共轭无环腈的改进方法,包括使无环脂肪二烯烃化合物优选丁二烯与HCN源反应,其中所述改进包括在催化剂前体组合物存在下进行氢氰化和/或异构化反应,所述催化剂前体组合物包括零价镍和至少一种多齿亚磷酸酯配位体,该配位体选自下列式I、II、III、IV、V、VI、VII、VIII、IX、X、XI、XII、XIII、XIV和XV表示的化合物:其中:
各R1各自独立地为支链或直链的至多12个碳原子的烷基,或OR4,其中R4为C1-C12烷基;
各R5各自独立地为至多12个碳原子的叔取代的烃(tertiarysubstituted hydrocarbon);其中:
各R6和R7各自独立地为至多12个碳原子的叔取代的烃;和
各R8各自独立为H或支链或直链的至多12个碳原子的烷基,或OR4,其中R4为C1-C12烷基;其中:
各R9各自独立为H或支链或直链的至多12个碳原子的烷基,或OR4,其中R4为C1-C12烷基;和
各R10各自独立地为至多12个碳原子的叔取代的烃;其中:
各R14各自独立地为至多12个碳原子的叔取代的烃,或Si(R11)3,其中R11各自独立为支链或直链的至多12个碳原子的烷基或苯基或R14可以是CO2R3″,其中R3″为至多6个碳原子的仲烷基;其中:
R12为H或支链或直链的至多12个碳原子的烷基;和
各R1各自独立地为H、卤素、C1-C12烷基或OR3,其中R3为C1-C12烷基;
各R2′各自独立地为H或位于氧的间位或对位的1-12个碳原子的伯、仲或叔烃基,或位于苯氧基环的氧的间位或对位的CN,CO2R4″或OR4″,其中R4″为C1-C6烷基;
各R5′各自独立地为H或1-3个碳原子的伯或仲烃基;对于式VI和IX来说,R5′也可为OR4″,其中R4″为C1-C6烷基;对于式X和XI来说,R5′也可为CO2R4″,其中R4″为C1-C6烷基;和
各X各自独立地为O或CH(R4′),其中R4′为H,取代的苯基或C1-C12烷基;并且其中所述反应最后制得3和/或4-直链单烯腈。
本发明提供了一种液相氢氰化二烯烃化合物的改进方法,包括使无环脂肪二烯烃化合物优选丁二烯与HCN源反应,其中所述改进包括在催化剂前体组合物存在下进行氢氰化反应,所述催化剂前体组合物包括零价镍和至少一种多齿亚磷酸酯配位体,该配位体选自下列式I、II、III、IV、V、VI、VII、VIII、IX、X、XI、XII、XIII、XIV和XV表示的化合物:其中:
各R1各自独立地为支链或直链的至多12个碳原子的烷基,或OR4,其中R4为C1-C12烷基;
各R6和R7各自独立地为至多12个碳原子的叔取代的烃;和
各R8各自独立为H或支链或直链的至多12个碳原子的烷基,或OR4,其中R4为C1-C12烷基;其中:
各R9各自独立为H或支链或直链的至多12个碳原子的烷基,或OR4,其中R4为C1-C12烷基;和
R12为H或支链或直链的至多12个碳原子的烷基;和
各R1各自独立地为H、卤素、C1-C12烷基或OR3,其中R3为C1-C12烷基;
各R2各自独立地为3-12个碳原子的仲或叔烃基,或OR4″,其中R4″为C1-C6烷基或苄基;或下式的环状基团:其与苯基环连接形成5元环,其中RW为H或CH3,和Z为-O-或-CH2-;
各R2′各自独立地为H或位于氧的间位或对位的1-12个碳原子的伯、仲或叔烃基,或位于苯氧基环的氧的间位或对位的CN,CO2R4″或OR4″,其中R4″为C1-C6烷基;
各R5′各自独立地为H或1-3个碳原子的伯或仲烃基;对于式VI和IX来说,R5′也可为OR4″,其中R4″为C1-C6烷基;对于式X和XI来说,R5′也可为CO2R4″,其中R4″为C1-C6烷基;
各X各自独立地为O或CH(R4′),其中R4′为H,取代的苯基或C1-C12烷基;并且其中所述反应最后制得3和/或4-直链单烯腈和2-烷基-3-单烯腈。
本文所用的术语“仲”和“叔”是指与芳环键连的碳原子。
反应最适宜从起始原料二烯的氢氰化至最后的3-和/或4-直链单烯腈连续地进行。然而,本方法也可分步进行,即在异构化之前,就地分离出由氢氰化反应所得的非共轭无环腈。另外,由任意方法制备的非共轭无环腈可用作本发明异构化的起始原料。
本发明还提供了在本发明方法中使用的一些多齿亚磷酸酯配位体和由它制备的催化剂前体组合物,以及制备氯亚磷酸酯的新方法。
具体地,制备氯亚磷酸酯的方法包括使式N(R18)2P(OR19)2化合物(其中R19为取代的芳基)与氯化氢气体(HCl)反应制得HN(R18)2·HCl和(R19O)2PCl。反应优选在无过量的HCl下进行,或者如果有过量的HCl存在,在反应完成后,迅速除去HCl,防止(R19O)2PCl产物的分解。
本发明还提供了制备N,N-二烷基二芳基氨基亚磷酸酯的方法,包括在惰性溶剂如己烷或甲苯中使一当量PCl3与一当量仲胺如二异丙基胺和至少一当量叔胺如三乙胺优选在大约5-大约35℃的范围内进行反应,接着加入大约1.9当量的取代的苯酚和大约2.1当量的叔胺如三乙胺,优选在亲核催化剂如4-二甲基氨基吡啶存在下,然后使各组份在大约25-大约90℃下反应。实施上述方法可避免需要分离出中间体(R18)2NPCl2。
优选实施方案的详细描述
本发明方法中所用的催化剂前体组合物包括多齿亚磷酸酯配位体和零价镍。本发明的优选配位体(用于氢氰化二烯烃化合物,接着和/或独立地异构化非共轭无环腈为3-和/或4-直链单烯腈)可用如下的式I表示,其中各R1各自独立地为支链或直链的含有至多12个碳原子的烷基,或OR4,其中R4为C1-C12烷基,R4可以是伯、仲或叔烷基;实例包括甲基、乙基、异丙基和叔丁基。各R1可相同或不同。在较优选的配位体中,两个R1基团都为OR4,其中R4为甲基,R5为含有至多12个单键碳原子的叔取代的烃基。最优选的是,各R1各自为OCH3,和各R5各自为叔丁基。对于就地将二烯烃化合物氢氰化为非共轭无环腈来说,R5可扩展包括至多12个碳原子的仲和伯烷基和OR4″,其中R″为C1-C6烷基。
催化剂组合物称为“前体”仅是指在大多数情况下在氢氰化反应中活性催化剂组合物的结构事实上可与烯烃配合。
这些配位体可用本领域公知的各种方法制备,例如,参见WO93,03839,US4,769,498;US4,688,651,J.Amer.Chem.Soc.,1993,115,2066中所描述的方法。2,2′-联苯酚与三氯化磷反应得到氯亚磷酸1,1′-联苯-2,2′-二基酯。该氯亚磷酸酯与2,2′-二羟基-3,3′-二叔丁基-5,5′-二甲氧基-1,1′-联苯在三乙胺存在下反应得到其中R1为甲氧基的最优选的配位体。
氯亚磷酸酯可用本领域公知的各种方法制备,例如,参见Polymer,1992,33,161;Inorganic Synthesis,1966,8,68;US 5,210,260;Z.Anorg.Allg.Chem.,1986,535,221所述。有大的邻位取代的苯酚(例如2-叔丁基苯酚)、氯亚磷酸酯可就地由PCl3和苯酚制备,有较少基团的苯酚(例如2,3-二甲氧基苯酚),一般必须通过高真空蒸馏纯化。高真空蒸馏难以大规模操作。
制备氯亚磷酸酯的改进方法包括用HCl处理N,N-二烷基二芳基氨基亚磷酸酯,用此方法已经制备了ClP(OMe)2,参见Z.Naturforsch,1972,27B,1429;然而,以前没有使用该方法制备过由取代的苯酚衍生的氯亚磷酸酯。N,N-二烷基二芳基氨基亚磷酸酯可用本领域公知的方法制备,例如参见Tetrahedron Letters,1993,34,6451和Aust.J.Chem.1993,233所述。
可用上述的式II-XV描述本发明的其它多齿亚磷酸酯,尽管这些配位体不如式I优选,但它们仍然可被认为是本发明有用的配位体。目前,尽管式I是最优选的,但式VII和XI优选于其它剩余的配位体。
可按照本领域公知的技术制备或生产零价镍(US 3,496,217;3,631,191;3,846,461;3,847,959和3,903,120,这些专利在此引入作为参考)。含有配位体(该配位体可被有机磷配位体置换)的零价镍化合物为优选的零价镍源。两种优选的零价镍化合物为Ni(COD)2(COD为1,5-环辛二烯)和Ni(P(O-邻-C6H4CH3)2)(C2H4),这两种化合物在本领域中是公知的。另外,两价镍化合物可与还原剂混合,然后作为在反应中合适的零价镍源。合适的两价镍化合物包括式NiY2其中Y为卤素、羧酸基或乙酰丙酮基,合适的还原剂包括金属硼氢化物,金属氢化铝,烷基金属,Zn,Fe,Al,Na或H2。当与卤代催化剂(如US3,903,120所述)混合时,元素镍优选镍粉末也可是合适的零价镍源。
实际的催化剂前体为零价镍与多齿配位体(当两种物质混合时所形成的)的配合物,有效的催化剂对于一克原子零价镍需要至少两摩尔P原子。
在本发明中使用的二烯烃反应物包括含有4-10个碳原子的主要共轭的二烯烃;例如,1,3-丁二烯和顺式和反式-2,4-己二烯,由于丁二烯在生产己二腈中工业上很重要,因此特别优选丁二烯。其它合适的二烯烃化合物包括被不使催化剂减活的基团取代的二烯烃化合物,例如顺式和反式-1,3-戊二烯。
下列式XVI和XVII表示合适的代表性起始二烯烃化合物;式XVIII、XIX和XX表示由1,3-丁二烯和HCN得到的产物。
CH2=CH-CH=CH2
(1,3-丁二烯) R15CH=CH-CH=CHR16
很明显化合物XVI是式XVII的一种特殊情况,其中R15和R16各自为氢。
按照本发明,在实施二烯烃的氢氰化中,应用下列描述:
氢氰化反应可在有或没有溶剂下进行,在反应温度下溶剂可以是液体并且对不饱和化合物和催化剂是惰性的。一般地,这些溶剂是烃如苯、二甲苯或腈如乙腈、苄腈和己二腈。
所用的反应温度在一定程度上取决于所用的具体催化剂,所用的具体不饱和化合物和所需的速度。一般地,可使用-25℃至200℃的温度,优选0℃至150℃。
反应可通过将所有的反应物装入反应器中进行或优选地,将催化剂或催化剂组份、不饱和化合物和所用的溶剂装入反应器,使氢化氰气体吹过反应混合物表面或鼓泡通过所述反应混合物。如果需要的话,当使用不饱和的有机化合物气体时,可将氢化氰和不饱和的有机化合物一起加入到反应介质中。对于间歇操作来说,HCN与催化剂的摩尔比一般为大约10∶1至100,000∶1,优选100∶1至5,000∶1。在连续操作中,例如当使用固定床催化剂类型操作时,可使用较高比例的催化剂如5∶1至100,000∶1,优选100∶1至5,000∶1的HCN∶催化剂。
优选地,将反应混合物搅动如搅拌或振荡。
氰化的产物可通过常规技术如从溶液中结晶产物或通过蒸馏来回收。
可以分离出由二烯烃的氢氰化制备的2一烷基-3-单烯腈或在同样的反应条件下连续进行异构化。
用作本发明异构化的起始原料的2-烷基-3-单烯腈可由上述二烯烃的氢氰化得到或由任何其它来源得到。用作本发明异构化的起始原料2-烷基-3-单烯腈中的烯烃双键不能与氰基的三键共轭。合适的起始原料2-烷基-3-单烯腈可带有不攻击催化剂的基团,例如另外的氰基。优选地,除了任何其它取代基外,起始原料2-烷基-3-单烯腈含有5-8个碳原子。2-甲基-3-丁烯腈在己二腈生产中特别重要,其它代表性的腈包括2-乙基-3-丁烯腈和2-丙基-3-丁烯腈。
R17是H或C1-C3烷基。
CH2=CH-CH2-CH2CN CH3-CH2=CH-CH2CN
式XXIII 和 式XXIV
很明显化合物XXI是式XXII的一种特殊情况,其中R17为氢。
本发明的异构化方法例如可在常压和10-200℃优选60-150℃的范围中的任意温度下进行。压力不是关键,然而如果需要的话可以高于或低于常压。任何常规的间歇或连续流动方法可用于液相或气相(相对于相对挥发性的2-甲基-3-丁烯腈反应物和直链戌烯腈产物)。反应器可以是任何耐机械和化学材料,通常为玻璃或惰性金属或合金,例如镍、铜、银、金、铂、不锈钢、Monel,Hastelloy等。
反应通常在“净样”即没有加入稀释剂或溶剂中进行。可使用对催化剂无破坏作用的任何溶剂或稀释剂,然而,合适的溶剂包括脂肪烃和芳香烃(己烷,环己烷,苯),醚(乙醚,四氢呋喃,二氧六环,乙二醇二甲醚,苯甲醚),酯(乙酸乙酯,苯甲酸甲酯),腈(乙腈,苄腈)等。
为了防止催化剂的氧化减活需要非氧化环境,因此,通常和优选使用惰性气氛例如氮气,但需要时也可使用空气,只是要以氧化损耗部分催化剂为代价。
当反应为在有或没有溶剂的液相中的典型间歇操作时,催化剂镍配合物在操作范围内的温度下在一定程度上是可溶解的,通常在最优选操作温度下完全可溶。然而,镍配合物必须是不挥发的,而2-甲基-3-丁烯腈反应物和直链戊烯腈产物具有相对的挥发性。因此,在连续流动反应中,催化剂可以是完全液相操作中流动体系的一个成分,它可以处于半蒸汽相操作中的流动非流液相,或可以处于常规流动蒸汽相操作中的固定床状态(通常在固体载体上)。
在反应中的时间要素不是关键,通常可通过实际操作得到。将2-甲基-3-丁烯腈转化为直链戊烯腈的实际水平所需的时间取决于反应温度,即在低温下操作一般比高温下操作需要较长的时间,实际反应时间可在几秒至几小时,这取决于具体条件和操作方法。
对于间歇或连续操作来说,2-甲基-3-丁烯腈与催化剂的摩尔比一般大于1∶1,通常为大约5∶1至20,000∶1,优选100∶1至5,000∶1。
实施例
本发明用下列某些优选的具体实施方案的非限定实例说明,其中所有的份数、比例和百分数均为重量,除非另有说明。在实施例中,配位体“A”为式I配位体,其中各R1各自为OCH3,各R5各自为叔丁基。
实施例1
丁二烯氢氰化
通过将11.52g 1,3-丁二烯真空转移到34.56g丁腈中制得25wt%1,3-丁二烯溶液,通过将2.51g HCN加入到7.50g丙腈中制得25wt%HCN溶液。通过将0.014g Ni(COD)2((COD)=1,5-环辛二烯)和0.118g配位体“A”加入到9.87g丙腈制得催化剂溶液。用这些溶液,在装有微型搅拌棒的2ml GC管形瓶中制备下列反应混合物:
试样1 试样2 试样3丁二烯溶液 0.201g 0.201g 0.203gHCN溶液 0.080g 0.082g 0.082g催化剂溶液 0.077g 0.076g 0.076g
用装有合适大小的Nordel橡胶片的帽卷曲密封GC管形瓶有助于确保所含有的反应混合物。将管形瓶置于80℃的热块搅拌器中,反应时间1小时后,移出试样1,反应时间2小时后,移出试样2,反应时间3小时后,移出试样3。在每一种情况下通过用作为产品分析的GC(气相色谱)溶剂二甘醇二甲醚稀释反应混合物中止反应,反应混合物中的丙腈用作为GC产物分析的内标,分析结果如表1所示。
如表1所示,在本发明实例2-5中,基本上按照上述实例1所述进行丁二烯氢氰化实验,只是实施例4和5在140℃下进行,需要较长的反应时间,结果也列于表1中。
对比实施例A
通过将11.52g 1,3-丁二烯真空转移到34.56g丁腈中制得25wt%13-丁二烯溶液,通过将2.50g HCN加入到7.50g丙腈中制得25wt%HCN溶液。通过将0.298g Ni(pTTP)4(pTTP=对三甲苯基亚磷酸酯)和0.157g pTTP加入到9.565g丙腈制得催化剂溶液。用这些溶液,在装有微型搅拌棒的2ml GC管形瓶中制备下列反应混合物:
试样1 试样2 试样3丁二烯溶液 0.203g 0.215g 0.200gHCN溶液 0.083g 0.087g 0.089g催化剂溶液 0.078g 0.081g 0.078g
用装有合适大小的Nordel橡胶片的帽卷曲密封GC管形瓶有助于确保所含有的反应混合物。将管形瓶置于80℃的热决搅拌器中,反应时间1小时后,移出试样1,反应时间2小时后,移出试样2,反应时间3小时后,移出试样3。在每一种情况下通过用作为产品分析的GC溶剂二甘醇二甲醚稀释反应混合物中止反应,反应混合物中的丙腈用作为GC产物分析的内标,分析结果如表1所示。
在对比实施例B中,基本上按照上述对比实施例A所描述的方法进行丁二烯氢氰化实验,结果也列于表1中。
在对比实施例C-G中,按照上述本发明实施例1-5所描述的方法进行丁二烯氢氰化实验,只是使用“Pringle配位体”(式I化合物其中R1和R5=H)代替配位体“A”,结果也列于表1中。
实施例6
2M3BN(2-甲基-3-丁烯腈)异构化
通过将0.014g Ni(COD)2和0.118配位体“A”加入到9.87g丙腈中制得催化剂溶液,由Fluka Chemie AG,Buchs,Switzerland得到样品2M3BN,并且在氮气氛下在100%的2,6-二叔丁基-4-甲基苯酚存在下蒸馏。样品的GC分析表明它为81% 2M3BN。用这些混合物,在装有微型搅拌棒的2ml GC管形瓶中制备下列反应混合物:
试样1 试样2 试样3催化剂溶液 0.103g 0.100g 0.100g2M3BN 0.105g 0.101g 0.100g
用装有合适大小的Nordel橡胶片的帽卷曲密封GC管形瓶有助于确保所含有的反应混合物。将试样1-3置于125℃的热决搅拌器中,反应时间1小时后,移出试样1,反应时间2小时后,移出试样2,反应时间3小时后,移出试样3。在每一种情况下通过用作为产品分析的GC溶剂二甘醇二甲醚稀释反应混合物中止反应,反应混合物中的丙腈用作为GC产物分析的内标,分析结果如表2所示。
在本发明的实施例7和8中,基本上按照上述实例6所述的方法进行异构化实验,结果也列于表2中。
对比实施例H
通过将0.298g Ni(pTTP)4和0.157g pTTP加入到9.565g丙腈中制得催化剂溶液,由Fluka Chemie AG,Buchs,Switzerland得到样品2M3BN,并且在氮气氛下蒸馏成100 PPM的2,6-二叔丁基-4-甲基苯酚。样品的GC分析表明它为82% 2M3BN。用这些混合物,在装有微型搅拌棒的2ml GC管形瓶中制备下列反应混合物:
试样1 试样2 试样3催化剂溶液 0.100g 0.102g 0.105g2M3BN 0.103g 0.106g 0.100g
用装有合适大小的Nordel橡胶片的帽卷曲密封GC管形瓶有助于确保所含有的反应混合物。将试样1-3置于125℃的热块搅拌器中,反应时间1小时后,移出试样1,反应时间2小时后,移出试样2,反应时间3小时后,移出试样3。在每一种情况下通过用作为产品分析的GC溶剂二甘醇二甲醚稀释反应混合物中止反应,反应混合物中的丙腈用作为GC产物分析的内标,分析结果如表2所示。
在对比实施例I中,基本上按照上述实施例H所述的方法进行2M3BN异构化实验,结果也列于表2中。
在对比实施例J和K中,基本上按照上述本发明实施例6所述的方法进行2M3BN异构化实验,只是使用“Pringle配位体”代替配位体“A”,结果列于表2中。
按照下列方式制备合适于具体实验的用于本发明实施例9-53和60所用的反应物和催化剂的原料溶液:
1,3-丁二烯溶液(BD):通过将已知量的丁二烯真空转移到三倍量的腈溶剂中制得25wt%丁二烯在腈溶剂(选自丙腈、丁腈和己腈)中的溶液,所得的溶液在密封的容器中在-35℃下贮存,直至在实验中使用。
HCN溶液:在手套箱中通过称出2.50g液体HCN加入到7.50g溶剂中一般制得25wt% HCN在腈溶剂(选自如上)中的溶液,所得的溶液在-35℃下贮存,直至在实验中使用。
催化剂溶液:对于典型的多齿亚磷酸酯配位体来说,将1.2mmol P原子和0.055g Ni(COD)2(0.2mmol)在一定量的腈溶剂(选自如上)中混合,使得总溶液重量为10.00g。在混合后,通常马上使用所得的催化剂溶液。
2-甲基-3-丁烯腈混合物(2M3BN):制备2M3BN试样,它为戊烯腈异构体混合物,含有81-82% 2M3BN。
在本发明的实施例9-31和53中,进行丁二烯氢氰化实验如下,结果列于表3中。
向装有微型搅拌棒的2ml GC管形瓶中,加入0.075g Ni催化剂溶液(1.5μmol Ni)、0.080g HCN原料溶液(740μmol HCN)和0.200g BD原料溶液(925μmol BD)。GC管形瓶帽装有合适大小的Nordel橡胶片,在卷曲密封后有助于确保所含有的反应混合物,将管形瓶置于80℃的热块搅拌器中。在合适的时间点移出试样并且通过冷却至-35℃中止反应。然后反应混合物在用于产品分析的GC溶剂(选自戊二腈、二甘醇二甲醚或丙酮)中稀释,当测量腈反应溶剂时所述溶剂作为内标。
在本发明实施例32-52和60中,2M3BN异构化实验进行如下,结果列于表4中。
向装有微型搅拌棒的2mL GC管形瓶中,加入0.100gNi催化剂溶液(2.0μmol Ni)和0.100g含有2M3BN的混合物(1.0mmol,2M3BN)。GC管形瓶帽装有合适大小的Nordel橡胶片,在卷曲密封后有助于确保所含有的反应混合物。将管形瓶置于125℃的热块搅拌器中,在合适的时间点移出试样,并且在作为GC溶剂的丙酮中稀释,腈反应溶剂用作分析和计量3PN和2M3BN反应产物混合物的内标,
在表3和4中,符号“OA”表示2-异丙基苯氧基,其中氧与磷连接,符号“OC”表示2-异丙基-5-甲基苯氧基,其中氧与磷连接。
在本发明实施例54-59,59A,61-66和66A中,按照下列方式制备合适于具体实验的反应物和催化剂的原料溶液:
1.3-丁二烯溶液(BD):通过将已知量的丁二烯真空转移到三倍量的甲苯中制得25wt%丁二烯溶液,所得的溶液在密封的容器中在-35℃下贮存,直至在实验中使用。
HCN溶液:在手套箱中通过称出2.50g液体HCN加入到7.50g戊腈中一般制得25wt%HCN溶液,所得的溶液在-35℃下贮存,直至在实验中使用。
催化剂溶液:时于典型的多齿亚磷酸酯配位体来说,将0.84mmol P原子和0.040g Ni(COD)2(0.14mmol)在一定量的甲苯或四氢呋喃中混合,使得总溶液重量为5.00g。在混合后,通常马上使用所得的催化剂溶液。
2-甲基-3-丁烯腈混合物(2M3BN):制备2M3BN试样,它为戊烯腈异构体混合物,含有81-82% 2M3BN。向0.930g该混合物中,加入0.070g戊腈作为2M3BN异构化反应的内标。
丁二烯的氢氧化
在本发明实施例54-59和59A中,丁二烯氢氰化实验进行如下,结果列于表5中。
向装有微型搅拌棒的4mL螺帽管形瓶中,加入0.060g Ni催化剂溶液(1.68μmol Ni)、0.090g HCN原料溶液(832μmol HCN)和0.200gBD原料溶液(925μmol BD)。管形瓶用隔膜帽密封确保含有的反应混合物,然后将管形瓶置于80℃的热决搅拌器中,在合适的时间点移出试样,通过冷却至-35℃中止反应,然后反应混合物在用于产品分析的GC溶剂乙醚中稀释,在反应混合物中的戊腈用作内标。
比较实施例I
通过将5.37g 1,3-丁二烯转移到16.11g甲苯中制得25wt%1,3-丁二烯溶液,通过将1.25g HCN加入到3.75g戊腈中制备25wt%溶液,通过将0.297g Ni(pTTP)4和0.155g pTTP加入到6.71g甲苯中制得催化剂溶液,用这些溶液,在装有微型搅拌棒的4mL螺帽管形瓶中制备下列反应混合物:
试样1 试样2丁二烯溶液 0.207g 0.208gHCN溶液 0.091g 0.089g催化剂溶液 0.059g 0.077g
管形瓶用隔膜帽密封确保含有的反应混合物,然后将管形瓶置于80℃的热块搅拌器中,在1.5h的反应时间后移出试样1,在2.5h反应时间后移出试样2,在每一种情况下通过冷却反应混合物至-35℃中止反应,然后反应混合物在用于产品分析的GC溶剂乙醚中稀释,反应混合物中的戊腈用作内标,分析结果列于表5中。
在比较实施例M中,基本上按照上述实施例L所述方法进行丁二烯氢氰化实验,结果也列于表5中。
2M3BN的异构化
在本发明实施例61-66和66A中,2M3BN的异构化实验进行如下,结果列于表6中。
向装有微型搅拌棒的4mL螺帽管形瓶中加入0.070g Ni催化剂溶液(2.0μmol Ni)和0.107g含有2M3BN的混合物(1.0mmol 2M3BN)。管形瓶用隔膜帽密封确保含有的反应混合物,然后将管形瓶置于125℃的热块搅拌器中,在合适的时间点移出试样,通过冷却至-35℃中止反应,然后反应混合物在用于产品分析的GC溶剂乙醚中稀释,在反应混合物中的戊腈用作分析和计量3PN和2M3BN反应产物混合物的内标。
比较实施例N
通过将5.37g 1,3-丁二烯转移到16.11g甲苯中制得25wt%1,3-丁二烯溶液,通过将1.25g HCN加入到3.75g戊腈中制备25wt% HCN溶液,通过将0.297g Ni(pTTP)4和0.155g pTTP加入到6.71g甲苯中制得催化剂溶液,用这些溶液,在装有微型搅拌棒的4mL螺帽管形瓶中制备下列反应混合物:
试样1 试样2催化剂溶液 0.074g 0.073g2M3BN 0.106g 0.106g
管形瓶用隔膜帽密封确保含有的反应混合物,然后将管形瓶置于125℃的热块搅拌器中,在1.5h的反应时间后移出试样1,在2.5h反应时间后移出试样2,在每一种情况下通过冷却反应混合物至-35℃中止反应,然后反应混合物在用于产品分析的GC溶剂乙醚中稀释,反应混合物中的戊腈用作分析和计量3PN和2M3BN反应产物混合物内标,分析结果列于表6中。
在比较实施例O中,基本上按照上述实施例N所述方法进行2M3BN异构化实验,结果也列于表6中。
表1
步骤1-氢氰化反应
摩尔比 摩尔比 反应时间 %产率 %产率 %产率实施例 催化剂 P/Ni HCN/Ni 温度 3PN 2M3BN 总PN1 配位体A 6 2000 1hr 80℃ 19.1 75.5 94.7
Ni(COD)2 3hr 21.5 76.3 97.82 配位体A 6 2000 1hr 80℃ 17.3 71.2 88.5
Ni(COD)2 3hr 18.3 73.3 91.63 配位体A 6 2000 1hr 80℃ 18.8 76.9 95.6
Ni(COD)2A Ni(pTTP)4 6 500 1hr 80℃ 2.1 1.6 3.7
pTTP 2hr 3.5 2.4 6.0
3hr 4.7 3.0 7.7B Ni(pTTP)4 6 500 1hr 80℃ 2.8 1.7 4.5
pTTP 2hr 4.7 2.8 7.5
3hr 6.3 3.7 10.1C Pringle配位体 6 2000 1hr 80℃ 0.0 0.0 0.0
Ni(COD)2 2hr 0.0 0.0 0.0
3hr 0.0 0.0 0.0D Pringle配位体 6 2000 1hr 80℃ 0.0 0.0 0.0
Ni(COD)2 2hr 0.0 0.0 0.0
3hr 0.0 0.0 0.04 配位体A 6 2000 1hr 140℃ 26.2 63.4 89.6
Ni(COD)2 5hr 26.8 64.1 90.9
摩尔比 摩尔比 反应时间 %产率 %产率 %产率实施例 催化剂 P/Ni HCN/Ni 温度 3PN 2M3BN 总PN5 Ligand A 6 2000 5hr 140℃ 31.7 59.6 91.3
Ni(COD)2E Pringle Ligand 6 2000 1hr 140℃ 2.1 2.0 4.1
Ni(COD)2 5hr 5.3 4.8 10.1F Pringle Ligand 6 2000 1hr 140℃ 2.1 2.0 4.1
Ni(COD)2 5hr 5.1 4.6 9.7G Pringle Ligand 6 2000 1hr 140℃ 1.0 1.0 2.0
Ni(COD)2 5hr 6.8 6.0 12.8配位体A =式I化合物,其中R1=OCH3和R5=叔丁基Pringle配位体=式I化合物,其中R1和R5=H,按Baker等人,J.Chem.Soc.Chem.Commun.,1991,pp.803-804的方法制备。pTTP=对甲苯基亚磷酸酯催化剂,它在U.S.P.3,536,748中提到。
表2
步骤2-异构化反应
摩尔比 开始比例 反应时间 比例 3PN 3PN+2M3BN实施例 催化剂 P/Ni 2M3BN/Ni 温度 3PN/2M3BN 3PN+2M3BN 计量6 配位体A 6 2000 1hr 125℃ 0.6 39.0% 98.9%
Ni(COD)2 2hr 2.9 74.4% 100.0%
3hr 12.9 92.8% 100.0%7 配位体A 6 2000 2hr 125℃ 12.0 92.3% 96.3%
Ni(COD)2 3hr 13.8 93.2% 100.0%8 配位体A 6 2000 1hr 125℃ 3.7 78.6% 100.0%
Ni(COD)2 2hr 10.1 91.0% 100.0%H Ni(pTTP)4 6 500 1hr 125℃ 0.1 10.7% 100.0%
pTTP 2hr 0.2 17.5% 100.0%
3hr 0.3 24.6% 99.8%I Ni(pTTP)4 6 500 1hr 125C 0.2 14.3% 92.6%
pTTP 2hr 0.4 30.3% 86.5%J Pringle配位体 6 2000 1hr 125℃ 0.0 0.5% 100.0%
Ni(COD)2 2hr 0.0 0.5% 94.2%
4hr 0.0 0.5% 82.3%K Pringle配位体 6 2000 1hr 125℃ 0.0 0.5% 98.1%
Ni(COD)2 2hr 0.0 0.5% 100.0%配位体A=式I化合物,其中R1=OCH3和R5=叔丁基Pringle配位体=式I化合物,其中R1和R5=H,按Baker等人,J.Chem.Soc.Chem.Commun.,1991,pp.803-804的方法制备。pTTP=对甲苯基亚磷酸酯催化剂,它在U.S.P.3,536,748中提到。
表3
步骤1-氢氰化反应
%产率 %产率 %产率实施例 配位体 反应时间 3PN 2M3BN 总 PN
%产率 %产率 %产率实施例 配位体 反应时间 3PN 2M3BN 总 PN
表4
步骤2-异构化反应
%产率 %产率 比例 2PN+2M3BN实施例 配位体 反应时间 2M3BN 3PN 3PN/2M3BN 计量
%产率 %产率 比例 2PN+2M3BN实施例 配位体 反应时间 2M3BN 3PN 3PN/2M3BN 计量
%产率 %产率 比例 2PN+2M3BN实施例 配位体 反应时间 2M3BN 3PN 3PN/2M3BN 计量
%产率 %产率 比例 2PN+2M3BN实施例 配位体 反应时间 2M3BN 3PN 3PN/2M3BN 计量
表5
BD氢氰化
%产率 %产率实施例 配位体 反应时间 3PN 2M3 总计
%产率 %产率实施例 配位体 反应时间 3PN 2M3 总计
%产率 %产率对比实施例 催化剂 反应时间 PN 2M3 总计
L Ni(pTTP)4/pTTP 1.5hr 7.4 4.1 11.5
2.5hr 12.3 6.6 18.9
M Ni(pTTP)4/pTTP 2hr 3.8 1.7 5.5
3hr 8.2 4.5 12.7
表6
2M3异构化
%产率 %产率 %3PN/2M3实施例 配位体 反应时间 2M3 3PN 比例 计量
%产率 %产率 3PN/2M3催化剂 对比实施例 反应时间 2M3 3PN 比例 计量N Ni(pTp)4/pTTP 1.5hr 58.5 32.1 0.55 90.6
2.5hr 61.7 33.4 0.54 95.1O Ni(pTTO)4/pTTP 2hr 64.8 31.5 0.49 96.3
3hr 49.5 44.0 0.89 93.4下面给出含有邻位取代的含氧基团配位体的制备:
由PCl3和2,3-二氢-2,2-二甲基-7-苯并呋喃醇就地制备由2,3-二氢-2,2-二甲基-7-苯并呋喃醇衍生的氯亚酯。将含有0.55g(4mmo1)PCl3和1.314g(8mmol)2,3-二氢-2,2-二甲基-7-苯并呋喃醇的甲苯溶液冷却至-30℃,向上述溶液中缓慢滴加入含有1.0g(10mmol)NEt3的冷甲苯溶液(-30℃),将混合物搅拌过夜得到氯亚酯溶液(31P nmr的甲苯/CDCl3:165ppm),加入含有0.372g(2mmol)2,2′-联苯酚和0.6g(6mmol)NEt3的甲苯溶液,混合物搅拌过夜,用硅藻土过滤混合物,用甲苯洗涤,除去溶剂得到1.84g所需产物。31P nmr在C6D6中:由于杂质在146,133,132ppm处有带有小峰的131.9 ppm。FABMS(快速原子轰击质谱):实测值:899.23;计算值M+H,M=C52H52O10P2:899.31。
实施例68
配位体C;式XI,其中R2为环状基团,-O-C(CH3)2-CH2-
配位体C的制备类似于配位体B。用0.57g(2mmol)1,1′-联-2-萘酚代替联苯酚,常规后处理后,得到1.97g产物,为白色固体。31P(ppm,C6D6):在147.3,133.1,131.5和131.0处有带有小峰的131.26。FABMS(快速原子轰击质谱):实测值:999.24;计算值M+H,M=C60H56O10P2:999.33。
实施例69
配位体D;式XI,其中,R2为OMe
由PCl3和愈创木酚就地制备由愈创木酚衍生的氯亚酯。将含有0.55g(4mmol)PCl3和0.993g(8mmol)愈创木酚溶液冷却至-30℃,向上述溶液中缓慢滴加入含有1.0g(10mmol)NEt3的冷甲苯溶液(-30℃),将混合物在室温下搅拌45分钟得到氯亚酯溶液(31P(C6D6/甲苯):166.17),加入含有0.573g(2mmol)1,1′-联-2-萘酚和0.6g(6mmol)NEt3的甲苯溶液,混合物搅拌过夜,用硅藻土过滤混合物,用甲苯洗涤,除去溶剂得到1.67g所需产物。31P nmr在C6D6中:由于杂质在147,133,128ppm处有带有小峰的131.7 ppm。通过快速硅胶柱色谱纯化产物,用10-20%EtOAc/己烷洗脱,得到白色糊状的产物。1H nmr(δ,CDCl3):3.61(s,6H),3.62(s,6H),6.62-7.92(m,28H)。31P nmr(ppm,CDCl3):132.04。FABMS(快速原子轰击质谱):实测值:837.03;计算值M-H,M=C48H40O10P2:837.21。
实施例70
上述化合物的制备类似于配位体B,但是使用1.602g 2-(苄氧基)苯酚代替2,3-二氢-2,2-二甲基-7-苯并呋喃醇和541mg(1.9mmol)2,2′-亚丙基双(4,6-二甲基苯酚)(按照Yamada等人,Bull.Chem.Soc.Jpn.,62,3603(1989))代替2,2′-联苯酚。常规处理后,得到2.167g淡褐色糊状物。31P(ppm,C6D6):在132.8处带有小峰的135.73。FABMS(快速原子轰击质谱):实测值:1139.27;计算值M-H,M=C71H66O10P2:1139.40。
实施例71
上述化合物的制备类似于配位体B,但是使用1.602g 2-(苄氧基)苯酚代替2,3-二氢-2,2-二甲基-7-苯并呋喃醇。常规处理后,得到2.099g淡褐色糊状物。31P(ppm,C6D6):在146.6,132.9处有带有小峰的131.95。FABMS(快速原子轰击质谱):实测值:1043.24;计算值M+H,M=C64H52O10P2:1043.31。
实施例72和73描述了使用N,N-二烷基二芳基氨基亚磷酸酯制备氯亚磷酸酯。
实施例72A.双[(2-异丙基-5-甲基)苯基]N,N-二异丙基氨基亚磷酸酯:
向25.0g PCl3的350ml无水甲苯溶液中加入19.1g无水二异丙胺,同时保持在5-7℃的温度下,然后加入19.4g三乙胺,同时保持在5-8℃的温度下。混合物在室温下搅拌16小时,然后在低于40℃下加入52.4g百里酚在38.2g三乙胺和50ml无水甲苯溶液,接着加入0.25g4-二甲氨基吡啶的40ml甲苯溶液混合物在80℃下加热2小时,冷却至12℃,先后用水、氯化钠水溶液洗涤,再用水洗涤。在减压下在60-70℃之间蒸馏200ml溶剂干燥氨基亚磷酸酯溶液,得到产物的溶液,通过气相色谱和31P-NMR分析(δ143ppm)纯度为90-95%。B.双(2-异丙基苯基)N,N-二异丙基氨基亚磷酸酯:
在室温下,向15.0g2-异丙基苯酚和10.5g三乙胺的100ml己烷溶液中加入60mL N,N-二异丙基酰氨基二氯(0.825M的己烷溶液),历时45分钟。将混合物在室温下搅拌至少16小时,过滤出三乙胺盐酸盐,用两份100mL己烷洗涤,合并滤液,浓缩洗涤液得到19.2g油状产物,将一份产物(11g)用20mL冷甲醇结晶,用两份5mL冷甲醇洗涤,抽吸干燥得到7.35g纯的氨基亚磷酸酯,为晶状固体。mp 35℃,31P-NMR(C6D6)δ142.2ppm;1H-NMR(C6D6)δ1.25(m,24H),3.6(七重峰,2H),3.9(m,2H),7.0(m,4H),7.2(m,4H)和7.35(m,2H)。C.双(2-异丙基苯基)氯亚磷酸酯:
将7.21g实施例72B产物的200ml环己烷溶液冷却至0℃,将无水HCl气体鼓泡通入,历时大约20分钟。通过将无水氮气鼓泡通过溶液冲洗过量的HCl,历时10分钟。在干燥箱中过滤出二异丙胺盐酸盐,用50mL环己烷洗涤,合并滤液,真空浓缩洗涤液至干,得到5.40g油状粗产物氯亚磷酸酯,通过31P-NMR分析判断纯度为90%。31P-NMR(C6D6)δ162.4ppm。对应于亚磷酸三芳基酯和膦酸氢二芳基酯的少量(各为5%)峰表明有杂质存在,但氯亚酯是足够纯,可用于接着的配位体合成。
实施例73
双(2,3-二甲氧基苯基)氯亚磷酸酯的制备
在装有冷凝器、温度计和加料漏斗的250mL三颈烧瓶中加入21.547g2,3-二甲氧基苯酚,14.2g NEt3和140mg 4-N,N-二甲基氨基吡啶的35mL环己烷溶液,在40分钟内滴加入139.8mL 0.5M N,N-二异丙基二氯氨基亚磷酸酯的己烷溶液,将混合物加热至65℃,在此温度下保持3.5小时。通过硅胶过滤混合物,用环己烷洗涤,在冰浴中冷却溶液,在45分钟内加入140mL 1M HCl的乙醚溶液。将混合物搅拌过夜,过滤,用甲苯洗涤,除去溶剂得到15.98g所需产物,为澄清的浅黄色液体,31PNMR(ppm,C6D6):169.9。
尽管在上面描述中已经说明了本发明的具体实施方案,但本领域技术人员能够理解到在不违背本发明精神和必需的特征的情况下可对发明作出各种修饰、取代和重排。关于本发明的范围,应参考所附的权利要求,而不是上述说明书。
Claims (9)
各R1各自独立地为支链和直链的至多12个碳原子的烷基,或OR4,其中R4为C1-C12烷基;
各R5各自独立地为至多12个碳原子的仲链或直链烷基或OR4″,其中R4″为C1-C6烷基;其中:
各R9各自独立为H或支链和直链的至多12个碳原子的烷基,或OR4,其中R4为C1-C12烷基;
各R10各自独立地为的至多12个碳原子的仲链或直链烷基,或OR4″,其中R4″为C1-C6烷基;其中:
各R1各自独立地为H、卤素、C1-C12烷基或OR3,其中R3为C1-C12烷基;
各R2各自独立地为OR4″,其中R4″为C1-C6烷基或苄基;或下式的环状基团:其与苯基环连接形成5元环,其中RW为H或CH3,和Z为-O-或-CH2-;对于式XII、XIII、XIV和XV来说,
各R2′各自独立地为位于苯氧基环的氧的间位或对位的CN或CO2R″,其中R4″为C1-C6烷基;
对于式XII、XIII、XIV和XV来说,R2′也可为OR4″,其中R4″为C1-C6烷基,或独立为H,卤素或1-6个碳原子的伯、仲或叔烃基;
各R5′各自独立为H或1-6个碳原子的伯、仲或叔烃基;对于式VI和IX来说,R5′也可为OR4″,其中R4″为C1-C6烷基;对于式X和IX来说,R5′也可为CO2R4″,其中R4″为C1-C6烷基;和
各X各自独立地为O或CH(R4′),其中R4′为H,取代的苯基或C1-C12烷基。
2.一种催化剂前体组合物,包括零价镍和权利要求1的多齿亚磷酸酯配位体。
3.权利要求2的催化剂前体组合物,其中多齿亚磷酸酯配位体选自式I、IV、VII和XI表示的化合物。
4.权利要求3的催化剂前体组合物,其中多齿亚磷酸酯配位体用式XI表示,其中R2为OR4″,其中R4″为C1-C6烷基。
5.权利要求4的催化剂前体组合物,其中多齿亚磷酸酯配位体用式XI表示,其中R2为OCH3,其中R2′和R5′为H。
6.制备氯亚磷酸酯的方法,包括使其中R19为取代的芳基式N(R18)2P(OR19)2化合物与氯化氢气体反应,得到HN(R18)2·HCl和(R19O)2PCl。
7.权利要求6的方法,其中HCl不以过量存在。
8.制备N,N-二烷基二芳基氨基亚磷酸酯的方法,包括在惰性溶剂中使一当量的PCl3与一当量仲胺和至少一当量叔胺反应,接着加入大约1.9当量的取代的苯酚和大约2.1当量叔胺。
9.权利要求8的方法,其中溶剂为甲苯。
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US37942995A | 1995-01-27 | 1995-01-27 | |
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US08/563,718 US5821378A (en) | 1995-01-27 | 1995-11-28 | Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles |
US08/563718 | 1995-11-28 |
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CN96191601A Expired - Lifetime CN1076342C (zh) | 1995-01-27 | 1996-01-17 | 二烯烃的氢氰化和非共轭的2-烷基-3-单烯腈的异构化 |
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CA (1) | CA2208040A1 (zh) |
DE (2) | DE69605398T2 (zh) |
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Families Citing this family (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5710306A (en) * | 1996-03-15 | 1998-01-20 | Dsm N.V. | Process to prepare a multidentate phosphite compound |
DE19717359B4 (de) * | 1996-04-30 | 2014-10-30 | Mitsubishi Chemical Corp. | Bisphosphitverbindungen und Verfahren zu deren Herstellung |
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ZA986369B (en) * | 1997-07-29 | 2000-01-17 | Du Pont | Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles. |
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US5847191A (en) * | 1997-07-29 | 1998-12-08 | E. I. Du Pont De Nemours And Company | Process for the hydrocyanation of monoolefins using bidentate phosphite ligands and zero-valent nickel |
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WO2009075692A2 (en) | 2007-05-14 | 2009-06-18 | Invista Technologies S.A.R.L. | High efficiency reactor and process |
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FR2932477B1 (fr) | 2008-06-17 | 2013-01-18 | Rhodia Operations | Procede de fabrication de composes nitriles a partir de composes a insaturation ethylenique |
FR2937321B1 (fr) | 2008-10-21 | 2010-10-22 | Rhodia Operations | Procede de fabrication de composes comprenant des fonctions nitriles |
FR2941455B1 (fr) | 2009-01-29 | 2011-02-11 | Rhodia Operations | Procede de fabrication de composes comprenant des fonctions nitriles |
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EP2771347B1 (en) | 2011-10-26 | 2016-07-27 | Invista Technologies S.à.r.l. | Methods for producing organodiphosphites from phosphorochloridites characterized by measuring side-product levels to determine further additions |
CN105753906A (zh) * | 2014-12-18 | 2016-07-13 | 中国科学院兰州化学物理研究所 | 环己二醇衍生的手性双齿亚磷酸酯配体及其制备方法和应用 |
Family Cites Families (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2934564A (en) * | 1957-11-08 | 1960-04-26 | American Potash & Chem Corp | Organohalophosphines |
GB1084599A (en) * | 1964-10-15 | 1967-09-27 | Asahi Chemical Ind | Process for the preparation of unsaturated aliphatic nitriles |
US3853948A (en) * | 1965-11-23 | 1974-12-10 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentene-nitriles |
US3536748A (en) * | 1965-11-23 | 1970-10-27 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles |
US3496215A (en) * | 1965-11-23 | 1970-02-17 | Du Pont | Hydrocyanation of olefins using selected nickel phosphite catalysts |
GB1112539A (en) * | 1965-11-26 | 1968-05-08 | Du Pont | Preparation of organic nitriles |
US3485917A (en) * | 1966-04-14 | 1969-12-23 | Janssen Pharmaceutica Nv | Composition and method for combating fungus with imidazole carboxylates |
US3496210A (en) * | 1966-07-28 | 1970-02-17 | Du Pont | Hydrocyanation of terminal alkynes |
US3496217A (en) * | 1967-05-23 | 1970-02-17 | Du Pont | Hydrocyanation of olefins |
US3578695A (en) * | 1967-07-26 | 1971-05-11 | Standard Oil Co Ohio | Olefinic nitriles by the catalytic oxidation of olefins using hydrogen cyanide |
US3775461A (en) * | 1967-11-06 | 1973-11-27 | Du Pont | Hydrocyanation of olefins |
US3869500A (en) * | 1968-03-23 | 1975-03-04 | Asahi Chemical Ind | Process for the production of unsaturated aliphatic nitriles |
US3584029A (en) * | 1968-04-09 | 1971-06-08 | Asahi Chemical Ind | Process for the production of lower saturated aliphatic nitriles |
US3655723A (en) * | 1969-10-31 | 1972-04-11 | Du Pont | Hydrocyanation of olefins |
NL6916495A (en) * | 1969-11-01 | 1971-05-04 | Pivalonitrile from isobutene and hcn | |
US3631191A (en) * | 1970-04-08 | 1971-12-28 | Du Pont | Synthesis of zero valent nickel-tetrakis triaryl phosphite complexes |
JPS4928495B1 (zh) * | 1970-06-16 | 1974-07-26 | ||
US3676481A (en) * | 1970-06-29 | 1972-07-11 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles in the presence of certain metal salt and/or tri(hydrocarbyl)boron promoters |
US3739011A (en) * | 1971-04-30 | 1973-06-12 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles |
US3766231A (en) * | 1971-08-02 | 1973-10-16 | Du Pont | Compounds of zero valent nickel containing n bonded nitriles |
US3798256A (en) * | 1971-08-02 | 1974-03-19 | Du Pont | Hydrocyanation of olefins |
US3925445A (en) * | 1971-08-02 | 1975-12-09 | Du Pont | Hydrocyanation of olefins |
US3766237A (en) * | 1972-01-25 | 1973-10-16 | Du Pont | Hydrocyanation of olefins |
GB1417554A (en) * | 1972-02-07 | 1975-12-10 | Ici Ltd | Organo metal complexes |
US3773809A (en) * | 1972-06-28 | 1973-11-20 | Du Pont | Separation of organic phosphorus compounds and their metal complexes from organic nitriles in the hydrocyanation of olefins |
US3846461A (en) * | 1972-10-25 | 1974-11-05 | Du Pont | Process of preparing a zerovalent nickel complex with organic phosphorus compounds |
US3847959A (en) * | 1972-10-25 | 1974-11-12 | Du Pont | Process of preparing a zerovalent nickel complex with organic phosphorus compounds |
US3903120A (en) * | 1973-06-19 | 1975-09-02 | Du Pont | Preparation of zerovalent nickel complexes from elemental nickel |
US3852325A (en) * | 1973-08-29 | 1974-12-03 | Du Pont | Selective isomerization of pentenenitriles |
US3852328A (en) * | 1973-09-26 | 1974-12-03 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to a linear pentenenitrile |
US3852329A (en) * | 1973-10-02 | 1974-12-03 | Du Pont | Process for isomerization of 2-methyl-3-butene-nitrile to a linear pentenenitrile |
DE2960925D1 (en) * | 1978-05-18 | 1981-12-17 | Ciba Geigy Ag | Dioxaphosphepines, their preparation and use as stabilisers for organic materials |
US4298546A (en) * | 1980-08-05 | 1981-11-03 | E. I. Du Pont De Nemours And Company | Isomerization of 2-methyl-3-butenenitrile |
US4371474A (en) * | 1982-01-13 | 1983-02-01 | E. I. Du Pont De Nemours And Company | Hydrocyanation of olefins |
US4599206A (en) * | 1984-02-17 | 1986-07-08 | Union Carbide Corporation | Transition metal complex catalyzed reactions |
US4737588A (en) * | 1984-12-28 | 1988-04-12 | Union Carbide Corporation | Transition metal complex catalyzed reactions |
US4668651A (en) * | 1985-09-05 | 1987-05-26 | Union Carbide Corporation | Transition metal complex catalyzed processes |
US4774353A (en) * | 1986-06-05 | 1988-09-27 | E. I. Du Pont De Nemours And Company | Triorganotin catalyst promoters for hydrocyanation |
US4739000A (en) * | 1986-07-22 | 1988-04-19 | Ethyl Corporation | Antioxidant aromatic tetraphosphites |
US4705881A (en) * | 1986-11-17 | 1987-11-10 | E. I. Du Pont De Nemours And Company | Continuous hydrocyanation process using zinc halide promoter |
US4714773A (en) * | 1987-01-09 | 1987-12-22 | E. I. Du Pont De Nemours And Company | Hydrocyanation of butadiene |
US4783546A (en) * | 1987-06-02 | 1988-11-08 | E. I. Du Pont De Nemours And Company | Preparation of 4-pentenenitrile by isomerization |
US4874884A (en) * | 1988-03-31 | 1989-10-17 | E. I. Du Pont De Nemours And Company | Promoter synergism in pentenenitrile hydrocyanation |
DE4026406A1 (de) * | 1990-08-21 | 1992-02-27 | Basf Ag | Rhodiumhydroformylierungskatalysatoren mit bis-phosphit-liganden |
JP3416956B2 (ja) * | 1991-06-11 | 2003-06-16 | 三菱化学株式会社 | ヒドロホルミル化法およびビスホスファイト化合物 |
TW213465B (zh) * | 1991-06-11 | 1993-09-21 | Mitsubishi Chemicals Co Ltd | |
US5360938A (en) * | 1991-08-21 | 1994-11-01 | Union Carbide Chemicals & Plastics Technology Corporation | Asymmetric syntheses |
US5175335A (en) * | 1991-11-12 | 1992-12-29 | E. I. Du Pont De Nemours And Company | Enantioselective hydrocyanation of aromatic vinyl compounds |
US5292785A (en) * | 1992-05-05 | 1994-03-08 | Ciba-Geigy Corporation | Bis-phosphite stabilized compositions |
US5288918A (en) * | 1992-09-29 | 1994-02-22 | Union Carbide Chemicals & Plastics Technology Corporation | Hydroformylation process |
BR9408151A (pt) * | 1993-11-23 | 1997-08-05 | Du Pont | Processos de hidrocianação de precursor de catalisador |
US5512695A (en) * | 1994-04-14 | 1996-04-30 | E. I. Du Pont De Nemours And Company | Bidentate phosphite and nickel catalyst compositions for hydrocyanation of monoolefins |
US5543536A (en) * | 1994-04-26 | 1996-08-06 | E. I. Du Pont De Nemours And Company | Monodentate phosphite and nickel catalyst composition for monoolefin hydrocyanation |
US5512696A (en) * | 1995-07-21 | 1996-04-30 | E. I. Du Pont De Nemours And Company | Hydrocyanation process and multidentate phosphite and nickel catalyst composition therefor |
US5440067A (en) * | 1994-11-18 | 1995-08-08 | E. I. Dupont De Nemours And Company | Catalyzed gas phase isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles |
US5449807A (en) * | 1994-11-18 | 1995-09-12 | E. I. Du Pont De Nemours And Company | Catalyzed vapor phase hydrocyanation of diolefinic compounds |
-
1996
- 1996-01-08 IN IN36CA1996 patent/IN187044B/en unknown
- 1996-01-17 AT AT98203601T patent/ATE236172T1/de not_active IP Right Cessation
- 1996-01-17 ES ES96902689T patent/ES2141474T3/es not_active Expired - Lifetime
- 1996-01-17 DE DE69605398T patent/DE69605398T2/de not_active Expired - Lifetime
- 1996-01-17 ES ES98203601T patent/ES2196481T3/es not_active Expired - Lifetime
- 1996-01-17 CN CNB011208791A patent/CN100427495C/zh not_active Expired - Lifetime
- 1996-01-17 WO PCT/US1996/000548 patent/WO1996022968A1/en active IP Right Grant
- 1996-01-17 AT AT96902689T patent/ATE187161T1/de not_active IP Right Cessation
- 1996-01-17 BR BRPI9606718-7A patent/BR9606718B1/pt not_active IP Right Cessation
- 1996-01-17 DE DE69627207T patent/DE69627207T2/de not_active Expired - Lifetime
- 1996-01-17 CN CN96191601A patent/CN1076342C/zh not_active Expired - Lifetime
- 1996-01-17 JP JP52290296A patent/JP3959111B2/ja not_active Expired - Fee Related
- 1996-01-17 EP EP96902689A patent/EP0804412B1/en not_active Expired - Lifetime
- 1996-01-17 CA CA002208040A patent/CA2208040A1/en not_active Abandoned
- 1996-01-26 ID IDP20000245A patent/ID24513A/id unknown
- 1996-10-11 US US08/729,457 patent/US5696280A/en not_active Expired - Lifetime
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US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
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WO2023060929A1 (zh) * | 2021-10-15 | 2023-04-20 | 浙江大学 | 一种多齿亚磷酸酯配体在催化合成己二腈中的应用 |
CN113912516B (zh) * | 2021-10-15 | 2023-06-27 | 浙江新和成股份有限公司 | 一种多齿亚磷酸酯配体在催化合成己二腈中的应用 |
Also Published As
Publication number | Publication date |
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ATE187161T1 (de) | 1999-12-15 |
WO1996022968A1 (en) | 1996-08-01 |
JPH10512879A (ja) | 1998-12-08 |
BR9606718A (pt) | 1998-01-13 |
IN187044B (zh) | 2002-01-05 |
ATE236172T1 (de) | 2003-04-15 |
DE69605398T2 (de) | 2000-07-27 |
BR9606718B1 (pt) | 2009-01-13 |
CN1076342C (zh) | 2001-12-19 |
DE69627207T2 (de) | 2004-01-15 |
ES2141474T3 (es) | 2000-03-16 |
ID24513A (id) | 1996-07-25 |
JP3959111B2 (ja) | 2007-08-15 |
US5696280A (en) | 1997-12-09 |
DE69605398D1 (de) | 2000-01-05 |
ES2196481T3 (es) | 2003-12-16 |
EP0804412A1 (en) | 1997-11-05 |
CA2208040A1 (en) | 1996-08-01 |
EP0804412B1 (en) | 1999-12-01 |
CN100427495C (zh) | 2008-10-22 |
DE69627207D1 (de) | 2003-05-08 |
CN1169143A (zh) | 1997-12-31 |
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