CN101450889B - 光催化1,2-二苯乙烯类似物发生顺反异构化反应的方法 - Google Patents
光催化1,2-二苯乙烯类似物发生顺反异构化反应的方法 Download PDFInfo
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Abstract
本发明属于催化剂领域,特别涉及提供一种利用光化学催化剂加快1,2-二苯乙烯类似物发生顺反异构化反应的方法。在催化量多吡啶二价铂配合物催化剂的存在下,且在惰性气体氛围中,利用可见光照射含有反式-1,2-二苯乙烯类似物或者顺式和反式-1,2-二苯乙烯类似物的混合物的反应溶液,得到顺式1,2-二苯乙烯类似物或以顺式1,2-二苯乙烯类似物为主的产物。本发明的方法反应快速高效、反应体系分离简单、催化剂可回收利用。
Description
技术领域
本发明属于催化剂领域,特别涉及一种利用光化学催化剂加快1,2-二苯乙烯类似物(analogues)发生顺反异构化反应的方法。
背景技术
1,2-二苯乙烯类似物具有顺式和反式两种异构体,由于反式异构体能量较低、顺式异构体能量较高,1,2-二苯乙烯类似物多以反式构型存在。合成1,2-二苯乙烯类似物现有的合成路线,如Wittig反应及其各种改进方法、芳醛制得的腙与负碳离子缩合、羰基化合物的还原偶合、α-锂代苄基苯砜的自身偶合等等,得到都是以反式异构体为主的产物,顺式异构体不易得到。然而,顺式异构体往往具有与反式异构体不同的性质,如中国专利公开号:CN1732884A中公开的:顺式-1,2-二苯乙烯衍生物可用于预防和治疗糖尿病;美国专利5,525,632中公开:顺式-1,2-二苯乙烯结构的风车子碱(combrestatin)类化合物具有抗肿瘤活性。因此,合成顺式-1,2-二苯乙烯类似物具有重要的价值。
在光照条件下,1,2-二苯乙烯类似物的顺式和反式异构体之间可以相互转化,发生基于单重态或三重态的顺反异构化反应。如:美国的Hanmmond,G,、Satiel,J.等研究了紫外光直接照射下,单重态的1,2-二苯乙烯到达反应平衡时,顺式和反式异构体的比例取决于两个异构体在该波长下的摩尔消光系数(J.Am.Chem.Soc.1964,86,3197;J.Am.Chem.Soc.1972,94,2742),但反应的量子效率低;美国的Hammond,G,、Satiel,J.等使用小分子(如二苯酮等)为敏化剂,敏化1,2-二苯乙烯到达激发三重态,使顺反异构化反应发生在1,2-二苯乙烯的三重态势能面上,反应到达平衡时,顺式和反式异构体的比例取决于敏化剂与顺式和反式异构体的能量差(J.Am.Chem.Soc.1972,94,3449;J.Am.Chem.Soc.1968,90,6394;J.Am.Chem.Soc.1984,106,3144;Adv.Photochem.1988,14,1),但由于激发态的敏化剂分子与二苯乙烯分子的作用程度小,及反应过程中敏化剂发生光漂白作用等常常会导致光敏反应的量子产率低、反应时间长,反应产物复杂;为了提高1,2-二苯乙烯类似物顺反异构化反应的反应速度,美国的Whitten等利用金属卟啉化合物及双二联吡啶钌作为敏化剂,大大提高了1,2-二苯乙烯类似物顺反异构化反应的速度,获得了以反式异构体为主的产物(J.Am.Chem.Soc 1972,94,7811;J.Am.Chem.Soc1973,95,4367;J.Am.Chem.Soc.1978,100,2620,);最近,美国的Wilcox等将三联吡啶钌配合物和二苯酮敏化剂与1,2-二苯乙烯类似物共价相连,研究了其顺反异构化反应的动力学(J.Am.Chem.Soc 2006,128,250,J.Am.Chem.Soc 2007,129,3966);在极特定的条件下,光照1,2-二苯乙烯类似物能够发生单向的顺反异构化反应,如:1973年荷兰的Eenkhoom等发现了单重态1-(2-吡啶基)-2-(2-吲哚基)乙烯发生单向反式→顺式异构化反应(Can.J.Chem.1973,51,792.),Lewis等证明这是由于在基态顺式异构体存在分子内氢键,从而引起反式→顺式的单向异构化反应的发生(J.Am.Chem.Soc.1995,117,3029)。1983年日本的Arai,Tokumam等人发现三重态敏化蒽基取代的烯烃发生单向的顺式→反式的异构化反应(Tetrahedron Lett.1983,24,2873)。
可以看出,虽然研究1,2-二苯乙烯类似物顺反异构化反应的历史不短,但能够实现快速敏化、获得高能量顺式-1,2-二苯乙烯类似物的例子很少。本发明采用多吡啶二价铂配合物作为催化剂,利用可见光的照射有效提高了顺反异构化反应的速度,光稳态时得到了顺式-1,2-二苯乙烯类似物或顺式-1,2-二苯乙烯类似物为主的产物。
发明内容
本发明的目的是提供一种高效光催化1,2-二苯乙烯类似物发生顺反异构化反应的方法,其特点是使用催化量的催化剂,利用可见光即可快速实现1,2-二苯乙烯类似物的顺反异构化反应,催化剂可以回收利用。
本发明的光催化1,2-二苯乙烯类似物发生顺反异构化反应的方法,是在催化量多吡啶二价铂配合物催化剂的存在下,且在惰性气体(如氩气或氮气等)氛围中,利用可见光照射含有反式-1,2-二苯乙烯类似物或者顺式和反式-1,2-二苯乙烯类似物混合物的反应溶液,得到顺式-1,2-二苯乙烯类似物或以顺式1,2-二苯乙烯类似物为主的产物。
本发明的反应路线是:
本发明的光催化1,2-二苯乙烯类似物发生顺反异构化反应的方法包括以下步骤:
1)将催化剂多吡啶二价铂配合物和反式-1,2-二苯乙烯类似物或者顺式和反式-1,2-二苯乙烯类似物的混合物溶入有机溶剂中(如选自乙腈、二氯甲烷、苯、甲苯中的一种或大于一种的混合物),得到反应溶液;
2)在惰性气体(如氩气或氮气等)氛围中,用可见光350nm<λ<600nm的光照射步骤1)的反应溶液,光照时间随反应溶液浓度和体积的不同而不同,通过气谱监测反应进程,反应结束时得到顺式-1,2-二苯乙烯类似物,或者以顺式-1,2-二苯乙烯类似物为主的产物。
步骤1)中反式-1,2-二苯乙烯类似物或者顺式和反式-1,2-二苯乙烯类似物的混合物在反应溶液中的浓度范围是10-5mol/l至饱和,催化剂多吡啶二价铂配合物在反应溶液中的优选浓度大约为10-3~10-7mol/l。
本发明涉及反式-1,2-二苯乙烯类似物、顺式-1,2-二苯乙烯类似物具有以下结构:
其中:R1为苯基,R2为苯基、2-吡啶基、3-吡啶基、4-吡啶基、2-呋喃基、4-甲基苯基、4-甲氧基苯基或4-硝基苯基;或R1为2-噻吩基,R2为2-噻吩基、苯基、4-甲基苯基或4-甲氧基苯基;或R1为3-噻吩基,R2为苯基、4-甲基苯基或4-甲氧基苯基;或R1为2-吡啶基,R2为2-吡啶基、4-吡啶基、4-甲基苯基、4-甲氧基苯基或2-萘基;或R1为4-吡啶基,R2为4-吡啶基、4-甲基苯基、4-甲氧基苯基或2-萘基;或R1,R2独立的为4-甲基苯基或4-甲氧基苯基。
本发明涉及的多吡啶二价铂配合物催化剂是2,2’:6’,2”-三联吡啶二价铂配合物、6-苯基-2,2′-二联吡啶二价铂配合物、2,2′-二联吡啶二价铂配合物或菲啰啉二价铂配合物。
所述的2,2’:6’,2”-三联吡啶二价铂配合物具有以下结构:
式中R1为C6H4OCH3-4,R2为C≡CC6H4 C≡CC6H5-4,R3、R4独立的为H;或R1为C6H4OCH3-4,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4CH3-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CCH2OH,R3、R4独立的为H;或R1为H,R2为C≡CCH2CH2CH3,R3、R4独立的为H;或R1为C(CH3)3,R2为C≡CC6H5,R3、R4独立的为H;或R1为C(CH3)3,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H5,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4OCH3-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4Cl-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4OCOCH3,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CSi(CH3)3,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡C(CH2)nCH3(n为1~16的正整数),R3、R4独立的为H;或R1为H,R2为C≡CCH2OCOCH3,R3、R4独立的为H;或R1为H,R2为Cl,R3、R4独立的为H;或R1为H,R2为C≡CSi(CH3)3,R3、R4独立的为H;或R1为H,R2为C≡C(CH2)nCH3(n为1-1 6的正整数),R3、R4独立的为H;或R1为H,R2为C6H5,R3、R4独立的为H;或R1、R3、R4独立的为C(CH3)3,R2为Cl;或R1、R3、R4独立的为C(CH3)3,R2为C≡CC6H5;
所述的6-苯基-2,2′-二联吡啶二价铂配合物具有以下结构:
式中R1为H,R2为Cl,R3、R4独立的为H;或R1为C6H5,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4CH3-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H;或R1为C6H4OCH3-4,R2为Cl,R3、R4独立的为H;或R1为C6H4OCH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H;或R1为C6H4OCH3-4,R2为C≡CC6H5,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H5,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4Cl-4,R3、R4独立的为H;
所述的2,2’-二联吡啶二价铂配合物具有以下结构:
式中R1为H、CH3、Cl、OCH3或C(CH3)3;R2为Cl、C≡CC6H4CH3-4、C≡CC6H4C≡CC6H5-4、C≡CCH2OH、C≡CC6H5、C≡CC6H4OCH3-4、C≡CC6H4OCOCH3、C≡CSi(CH3)3或C≡C(CH2)nCH3(n为1~16的正整数);
所述的菲啰啉二价铂配合物具有以下结构:
式中R1为H或CH3;R2为Cl、C≡CC6H4CH3-4、C≡CC6H4C≡CC6H5-4、C≡CCH2OH、C≡CC6H5、C≡CC6H4OCH3-4、C≡CC6H4OCOCH3、C≡CSi(CH3)3或C≡C(CH2)nCH3(n为1~16的正整数)。
本发明采用多吡啶二价铂配合物作为催化剂,利用可见光快速实现1,2-二苯乙烯类似物的顺反异构化反应,由于多吡啶二价铂配合物催化剂的特殊性质,反应所得的顺式-1,2-二苯乙烯类似物或顺式-1,2-二苯乙烯类似物为主的产物容易与催化剂分离,催化剂能够重复利用。
附图说明
图1.本发明实施例1用波长350nm<λ<600nm的光照射氩气或氮气氛围下的反式-二苯乙烯类似物(其中R1为苯基,R2为苯基)及催化剂2,2’:6’,2”-三联吡啶二价铂配合物(其中催化剂中的R1为C6H4OCH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H)乙腈溶液的透明容器,溶液紫外吸收的变化随光照时间的变化,总的光照时间为10分钟,其中小图是差谱;箭头表示吸收光谱随时间的变化方向;曲线1~6由上到下的光照时间分别为0,20,40,60,90,150秒钟。
图2.本发明实施例2在氩气或氮气氛围下,反式-4-吡啶基苯乙烯类似物(其中R1为苯基,R2为4-吡啶基)和催化剂2,2’:6’,2”-三联吡啶二价铂配合物(其中催化剂中的R1为C6H4OCH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H)的氘代乙腈溶液光照前后1H NMR谱图的变化。
具体实施方式
下面以具体实施例来对本发明进行详细说明,但并不是对本发明的具体限制。
实施例1.
以2,2’:6’,2”-三联吡啶二价铂配合物为催化剂(其中催化剂中的R1为C6H4OCH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H),反式-1,2-二苯乙烯(其中R1为苯基,R2为苯基)为底物,用500 W高压汞灯照射其乙腈溶液,使用400nm的玻璃滤光片。
向透明玻璃器皿中加入20ml含有3.6mg反式-1,2-二苯乙烯(其中R1为苯基,R2为苯基)的乙腈溶液,反式-1,2-二苯乙烯在乙腈溶液中的浓度为1×10-2mol/l,然后加入2,2’:6’,2”-三联吡啶二价铂配合物(其中催化剂中的R1为C6H4OCH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H),2,2’:6’,2”-三联吡啶二价铂配合物在乙腈溶液中的浓度为1×10-5mol/l,在氩气或氮气氛围中,使用400nm的玻璃滤光片进行照射,总的光照时间为10分钟。用紫外一可见吸收光谱监测光照过程,溶液的吸收光谱变化如图1所示,光照结束后气谱检测结果显示,90%的反式-1,2-二苯乙烯(其中R1为苯基,R2为苯基)异构化为顺式-1,2-二苯乙烯,反应结束后,蒸除溶剂,加入乙酸乙酯萃取,过滤,回收不溶的催化剂,滤液旋干,对产物进行分离后得到顺式产物,回收不溶的催化剂。
实施例2.
以2,2’:6’,2”-三联吡啶二价铂配合物为催化剂(其中催化剂中的R1为C6H4OCH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H),反式-4-吡啶基苯乙烯为底物(其中R1为苯基,R2为4-吡啶基),用500W高压汞灯照射其氘代乙腈溶液,使用400nm的玻璃滤光片。
向0.6ml浓度为1×10-5mol/l的2,2’:6’,2”-三联吡啶二价铂配合物(其中R1为C6H4OCH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H)的氘代乙腈溶液中加入1.0mg反式-4-吡啶基苯乙烯(其中R1为苯基,R2为4-吡啶基),在氮气氛围中用500W高压汞灯照射上述混合溶液,使用400nm的玻璃滤光片,照射时间30分钟。用1H NMR检测光照前后的核磁变化,如图2所示。核磁图谱变化表明底物几乎完全转化为相对应的产物。反应结束后,蒸除溶剂,加入乙酸乙酯萃取,过滤,滤液旋干,即可得到顺式产物,回收不溶的催化剂。
实施例3.
以6-苯基-2,2′-二联吡啶二价铂配合物(其中催化剂中的R1为C6H4CH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H)为催化剂,反式-1,2-二苯乙烯(其中R1为苯基,R2为苯基)为底物,用500W高压汞灯照射其苯溶液,使用400nm的玻璃滤光片。
在透明玻璃器皿中,氮气氛围中用500W高压汞灯照射含有1.80mg反式-1,2-二苯乙烯(其中R1为苯基,R2为苯基;在苯溶液中的浓度为10-3mol/l)与催化量6-苯基-2,2′-二联吡啶二价铂配合物(其中催化剂中的R1为C6H4CH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H;在苯溶液中的浓度为1×10-5mol/l)的苯溶液10ml,使用350nm的玻璃滤光片,反应过程用气谱监测,照射30分钟后,反应结束,气谱显示约83%的反式-1,2-二苯乙烯转化为顺式-1,2-二苯乙烯。蒸除溶剂,加入乙酸乙酯萃取,过滤,回收不溶的催化剂,滤液旋干,对产物进行分离后,得到顺式-1,2-二苯乙烯。
实施例4.
以菲啰啉二价铂配合物(其中催化剂中的R1为H;R2为Cl)为催化剂,反式-1,2-二苯基乙烯为底物(其中R1为苯基,R2为苯基),用500W高压汞灯照射其乙腈溶液,使用350nm的玻璃滤光片。
在透明玻璃器皿中,氮气保护下,用500W高压汞灯照射含有7.2mg反式-1,2-二苯基乙烯为底物(其中R1为苯基,R2为苯基;在乙腈溶液中的浓度为2×10-3mol/l)与催化量菲啰啉二价铂配合物(其中催化剂中的R1为H;R2为Cl,在乙腈溶液中的浓度为1×10-5mol/l)的乙腈溶液20ml,使用350nm的玻璃滤光片,用气谱监测反应。反应1小时后结束,气谱显示约67%的反式-1,2-二苯基乙烯(其中R1为苯基,R2为苯基)转化为顺式产物,蒸除溶剂,加入乙酸乙酯萃取,过滤,回收不溶的催化剂,滤液旋干,对产物进行分离后,得到顺式产物。
实施例5.
以2,2’:6’,2”-三联吡啶二价铂配合物为催化剂(其中催化剂中的R1为C6H4CH3-4,R2为C≡C(CH2)2CH3,R3、R4独立的为H),底物为反式2-萘乙烯基吡啶(其中R1为4-吡啶基,R2为2-萘基),用500W高压汞灯照射其甲苯溶液,使用400nm的玻璃滤光片。
在透明玻璃器皿中,氩气或氮气保护下,用500W高压汞灯照射含有4.62mg的反式-2-萘乙烯基吡啶(其中R1为4-吡啶基,R2为2-萘基;在乙腈溶液中的浓度为10-3mol/l)与催化量的2,2’:6’,2”-三联吡啶二价铂配合物(其中催化剂中的R1为C6H4CH3-4,R2为C≡C(CH2)2CH3,R3、R4独立的为H;在乙腈溶液中的浓度为10-5mol/l)的乙腈溶液,使用400nm的玻璃滤光片,用气谱监测反应进行。反应1小时后结束,气谱显示约63%的反式-2-萘乙烯基吡啶转化为顺式产物,蒸除溶剂,加入乙酸乙酯萃取,过滤,回收不溶的催化剂,滤液旋干,对产物进行分离后,得到顺式产物。
实施例6.
以2,2’:6’,2”-三联吡啶二价铂配合物为催化剂(其中催化剂中R1为C6H4CH3-4,R2为C≡CC6H4CH3-4,R3、R4独立的为H),反式和顺式-1,2-二苯乙烯混合物(其中R1为苯基,R2为苯基)为底物,用500W高压汞灯照射其乙腈溶液,使用400nm的玻璃滤光片。
向透明玻璃器皿中加入20ml含有1.8mg反式-1,2-二苯乙烯(其中R1为苯基,R2为苯基)和1.8mg顺式-1,2-二苯乙烯(其中R1为苯基,R2为苯基)混合物的乙腈溶液,反式和顺式-1,2-二苯乙烯在乙腈溶液中的浓度均为5×10-3mol/l,总的1,2-二苯乙烯在乙腈溶液中的浓度为1×10-3mol/l),然后加入2,2’:6’,2”-三联吡啶二价铂配合物(其中催化剂中R1为C6H4CH3-4,R2为C≡CC6H4CH3-4,R3、R4独立的为H),2,2’:6’,2”-三联吡啶二价铂配合物在乙腈溶液中的浓度为1×10-5mol/l,在氩气或氮气氛围中,使用400nm的玻璃滤光片进行照射,光照结束后气谱检测结果显示,产物中顺式-1,2-二苯乙烯的比例为94%。反应结束后,蒸除溶剂,加入乙酸乙酯萃取,过滤,回收不溶的催化剂,滤液旋干,对产物进行过硅胶柱分离后得到顺式产物,回收不溶的催化剂。
Claims (7)
1.一种光催化1,2-二苯乙烯类似物发生顺反异构化反应的方法,其中1,2-二苯乙烯类似物的结构如式一、式二所示,其特征是:在催化量多吡啶二价铂配合物催化剂的存在下,且在惰性气体氛围中,利用可见光照射含有反式-1,2-二苯乙烯类似物或者顺式和反式-1,2-二苯乙烯类似物的混合物的反应溶液,得到顺式-1,2-二苯乙烯类似物或以顺式-1,2-二苯乙烯类似物为主的产物;
所述的反式-1,2-二苯乙烯类似物具有以下结构:
所述的顺式-1,2-二苯乙烯类似物具有以下结构:
其中上述反式-1,2-二苯乙烯类似物或者顺式-1,2-二苯乙烯类似物结构中的R1为苯基,R2为苯基、2-吡啶基、3-吡啶基、4-吡啶基、2-呋喃基、4-甲基苯基、4-甲氧基苯基或4-硝基苯基;或R1为2-噻吩基,R2为2-噻吩基、苯基、4-甲基苯基或4-甲氧基苯基;或R1为3-噻吩基,R2为苯基、4-甲基苯基或4-甲氧基苯基;或R1为2-吡啶基,R2为2-吡啶基、4-吡啶基、4-甲基苯基、4-甲氧基苯基或2-萘基;或R1为4-吡啶基,R2为4-吡啶基、4-甲基苯基、4-甲氧基苯基或2-萘基;或R1,R2独立的为4-甲基苯基或4-甲氧基苯基。
2.根据权利要求1所述的方法,其特征是:所述的含有反式-1,2-二苯乙烯类似物或者顺式和反式-1,2-二苯乙烯类似物的混合物的反应溶液,是将多吡啶二价铂配合物催化剂、反式-1,2-二苯乙烯类似物或者顺式和反式-1,2-二苯乙烯类似物的混合物溶入有机溶剂中,得到含有多吡啶二价铂配合物催化剂、反式-1,2-二苯乙烯类似物或者顺式和反式-1,2-二苯乙烯类似物的混合物的反应溶液,其中多吡啶二价铂配合物催化剂在反应溶液中的浓度为10-3~10-7mol/l。
3.根据权利要求1或2所述的方法,其特征是:所述的反式-1,2-二苯乙烯类似物或者顺式和反式-1,2-二苯乙烯类似物的混合物在反应溶液中的浓度范围为10-5mol/l至饱和。
4.根据权利要求2所述的方法,其特征是:所述的有机溶剂选自乙腈、二氯甲烷、苯、甲苯中的一种或大于一种的混合物。
5.根据权利要求1所述的方法,其特征是:所述的可见光波长为350nm<λ<600nm。
6.根据权利要求1或2所述的方法,其特征是:所述的多吡啶二价铂配合物催化剂是2,2’:6’,2”-三联吡啶二价铂配合物、6-苯基-2,2′-二联吡啶二价铂配合物、2,2′-二联吡啶二价铂配合物或菲啰啉二价铂配合物。
7.根据权利要求6所述的方法,其特征是:所述的2,2’:6’,2”-三联吡啶二价铂配合物具有以下结构:
式中R1为C6H4OCH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H;或R1为C6H4OCH3-4,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4CH3-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CCH2OH,R3、R4独立的为H;或R1为H,R2为C≡CCH2CH2CH3,R3、R4独立的为H;或R1为C(CH3)3,R2为C≡CC6H5,R3、R4独立的为H;或R1为C(CH3)3,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H5,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4OCH3-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4Cl-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4OCOCH3,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CSi(CH3)3,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡C(CH2)nCH3,其中n为1~16的正整数,R3、R4独立的为H;或R1为H,R2为C≡CCH2OCOCH3,R3、R4独立的为H;或R1为H,R2为Cl,R3、R4独立的为H;或R1为H,R2为C≡CSi(CH3)3,R3、R4独立的为H;或R1为H,R2为C≡C(CH2)nCH3,其中n为1~16的正整数,R3、R4独立的为H;或R1为H,R2为C6H5,R3、R4独立的为H;或R1、R3、R4独立的为C(CH3)3,R2为Cl;或R1、R3、R4独立的为C(CH3)3,R2为C≡CC6H5;
所述的6-苯基-2,2′-二联吡啶二价铂配合物具有以下结构:
式中R1为H,R2为Cl,R3、R4独立的为H;或R1为C6H5,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4CH3-4,R3、R4独立的为H;或R1为C6H4CH3-4,R2为Cl,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H;或R1为C6H4OCH3-4,R2为Cl,R3、R4独立的为H;或R1为C6H4OCH3-4,R2为C≡CC6H4C≡CC6H5-4,R3、R4独立的为H;或R1为C6H4OCH3-4,R2为C≡CC6H5,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H5,R3、R4独立的为H;或R1为C6H4CH3-4,R2为C≡CC6H4Cl-4,R3、R4独立的为H;
所述的2,2’-二联吡啶二价铂配合物具有以下结构:
式中R1为H、CH3、Cl、OCH3或C(CH3)3;R2为Cl、C≡CC6H4CH3-4、C≡CC6H4C≡CC6H5-4、C≡CCH2OH、C≡CC6H5、C≡CC6H4OCH3-4、C≡CC6H4OCOCH3、C≡CSi(CH3)3或C≡C(CH2)nCH3,其中n为1~16的正整数;
所述的菲啰啉二价铂配合物具有以下结构:
式中R1为H或CH3;R2为Cl、C≡CC6H4CH3-4、C≡CC6H4C≡CC6H5-4、C≡CCH2OH、C≡CC6H5、C≡CC6H4OCH3-4、C≡CC6H4OCOCH3、C≡CSi(CH3)3或C≡C(CH2)nCH3,其中n为1~16的正整数。
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DE2041221A1 (de) * | 1970-08-19 | 1972-03-02 | Basf Ag | Cis-trans-Isomerisierung von 1,2-substituierten AEthylenen |
US3792109A (en) * | 1972-09-11 | 1974-02-12 | Phillips Petroleum Co | Isomerization of 1-olefins or transolefins to internal cis-olefins |
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DE2041221A1 (de) * | 1970-08-19 | 1972-03-02 | Basf Ag | Cis-trans-Isomerisierung von 1,2-substituierten AEthylenen |
US3792109A (en) * | 1972-09-11 | 1974-02-12 | Phillips Petroleum Co | Isomerization of 1-olefins or transolefins to internal cis-olefins |
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David G. Whitten等;.Photochemistry of Metalloporphyrin Complexes. Ligand Photoisomerization via Intramolecular Energy Transfer.《Journal of the American Society》.1972,第94卷(第22期),7811-7823. * |
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