新型配体1—苯基二苯并膦在丙烯氢甲酰化均相反应中的应用研究

将 1-苯基二苯并膦 (PDBP)作为膦配体用于丙烯氢甲酰化反应中 ,系统研究了反应温度、压力、铑浓度、搅拌速率对产物丁醛收率的影响 .在铑浓度为 4.0× 10 - 6 、 P/ Rh比为 15 0、温度 10 0℃、反应压力 2 .0 MPa的条件下 ,丙烯转化率可达 90 % ,催化活性为 2 6 0 9g丁醛 / (g Rh· h) ,正丁醛和异丁醛的比达 9.5 .在相同的条件下与工业上广泛采用的以三苯基膦为配体的铑催化剂相比较 ,以 PDBP为配体的铑催化剂的活性和选择性分别是它的 1.44倍和 1.90倍 .证明了 PDBP是一个很有发展前景的羰基合成的膦配体     

5H-苯基联苯膦磺化产物的薄层色谱分离

1 引 言5H－苯基联苯膦（5H-phenyl-dibenzophosphole, PDBP）的磺化产物是一种多组分的复杂混合物,在石油化学工业具有很好的应用前景。5H－苯基联苯膦是三苯基膦的衍生物,是三苯基膦经桥连反应生成。经与发烟硫酸/硼酸的无水混合物反应,氢氧化钠中和,生成PDBP磺酸钠的混合物。混合物中除了可能含有目标产物二磺化PDBP和三磺化PDBP外,还可能含有取代位置不同的一磺化产物的异构体,二磺化和三磺化PDBP的氧化物,以及Na2SO4等。有关PDBP磺化产物分离方法的研究,目前尚未见报道。作者尝试用薄层色谱法来分离该混合物,通过…     

新型配体三 (3,4-二甲氧基苯基) 膦的合成及其 Rh 配合物在 1-十二烯氢甲酰化反应中的催化性能

 将合成的三 (3,4-二甲氧基苯基) 膦 (TDMOPP) 用作 Rh 催化剂配体, 并用于 1-十二烯氢甲酰化反应, 考察了膦/铑比和反应温度对 Rh-TDMOPP 催化剂活性和选择性的影响. 结果表明, 在膦/铑比与反应温度较低时, Rh-TDMOPP 活性是 Rh-三苯基膦催化剂的 3 倍.     

新型水溶性膦配体PDBPDS的制备及在氢甲酰化反应中的应用

依据量子化学理论计算 ,设计并优化了 1-苯基二苯并膦 (1- phenydibenzophosphole,简称 PDBP)磺化制备二磺化 1-苯基二苯并膦 (5 H- phenyl- 3,13- disulfonatodibenophosphole,简称 PDBPDS)的工艺 ,重点探讨了 SO3/PDBP比、反应温度、反应时间以及硼膦比对磺化产物收率的影响 .实验结果表明 ,采用 5 0 %发烟硫酸作磺化剂、SO3/ PDBP摩尔比为 3,H3BO3/ PDBP比为 5 ,在 13～ 15℃及无水无氧条件下反应 5 0 h,磺化产物收率可达 85 % .此外 ,还将所得产物用作丙烯氢甲酰化两相反应催化剂的配体 ,大大提高了催化剂的活性和产物正异比 ,且有机相中铑含量仅为 3.6× 10 - 8,有效地控制了铑流失 .实验结果证明了新型水溶性配体 PDBPDS是一个能实现均相反应多相化的、很有开发前景的配体 .     

一种新型双膦亚磷酸酯配体的合成及在1-己烯氢甲酰化反应中的应用

以4,4'-二羟基二苯丙烷和2,4-二叔丁基苯酚为原料合成了一种新型双膦亚磷酸酯配体,并用此配体和Rh(acac)(CO)2原位形成的催化体系催化1-己烯的氢甲酰化反应.系统考察了反应温度、压力、P/Rh和溶剂四种反应参数对催化体系的催化性能影响.选择了最佳的反应条件,在铑浓度为0.75×10-3mol/L、P/Rh比为10、温度100℃、压力(H2/CO=1)2.0MPa的条件下反应1.0h,在溶剂甲苯中1-己烯的转化率可达到100%,醛选择性为98.7%,TOF为3498.6h-1.在相同的条件下与以三苯基膦和单膦亚磷酸三(2,4-二叔丁基苯基)酯为配体的铑催化剂相比较,以新型双膦亚磷酸酯为配体的铑催化剂的催化活性是PPh3的1.6倍,而与亚磷酸三(2,4-二叔丁基苯基)酯的催化活性相当.     

新型膦配体PDBPDS在氢甲酰化反应中催化剂配体性能的研究

用量子化学 AMI方法优化了 1 -苯基二苯并膦二磺化产物 ( PDBPDS)和三磺化三苯基膦 ( TPPTS)的几何构型 .比较两种化合物的空间结构和电子结构发现 ,在氢甲酰化铑膦催化反应体系中 ,PDBPDS的配体性能优于 TPPTS.首次研究了以 PDBPDS为配体的铑膦催化剂对丙烯氢甲酰化反应的催化性能 ,考察了反应温度、压力、膦铑物质的量比和搅拌速度对催化活性和选择性的影响 .结果表明 ,在 2 .0 MPa,1 0 0℃ ,膦铑物质的量比为 35 ,搅拌速度为 5 0 0 r/min及 V( H2 ) /V( CO) =1 /1的条件下 ,催化活性可达到 2 80 0 g(丁醛 ) /[g(铑 )·h],正异构产物物质的量比为 1 2 .3,在相同条件下与传统的三磺化三苯基膦 ( TPPTS)为配体的铑膦催化剂相比 ,催化活性和选择性提高了 2倍 .反应结束后 ,有机相和水相分离简单 ,有机相铑浓度仅为3.6× 1 0 - 8mol/L,有效地解决了铑流失问题 ,表明 PDBPDS是极具开发前景的新型水溶性配体     

负载型水溶性铑膦配合物催化剂的结构和性能

SiO2担载TPPTS（间-三苯基膦三磺酸钠盐）－Rh（acac）（CO）2制成的负载型水溶性催化剂进行1-己烯氢甲酰化催化反应时，引入适量水蒸气可显著提高催化活性．用魔角旋转固体核磁共振磷谱表征得到，在新制备的催化剂中，吸附于SiO2表面但未参与配位的TPPTS，约占总膦物种的70mol％以上，而位于δ=32．4处的表面配合物｛Rh（CO）（TPPTS）2｝膦物种量约为15mol％，其它膦10mol％左右．催化剂经干燥合成气在373K处理2h、或经湿合成气在较低温度（333K）下处理2h后，｛Rh（CO）（TPPTS）2｝的增加量仅约为10～15mol％，其它膦物种的变化量也较小，但催化剂经湿合成气于373K处理2h后，｛Rh（CO）（TPPTS）2｝的净增量大于40mol％；在工作态催化剂中，也观察到｛Rh（CO）（TPPTS）2）大量生成、未配位TPPTS量减小；经43h反应运转后，催化剂活性下降，归属为｛Rh（CO）（TPPTS）2）的磷谱峰宽化，揭示有部份配合物解络、部分TPPTS被氧化成OTTPTS．本研究结果证实，适量水可促进催化剂中具氢甲酰化催化活性的铑膦物种形成，提高活性，但随反应进行，配合物将逐渐解络、膦配体逐渐被氧化，从而使催化剂逐渐失活．     

顺酐催化加氢衍生物的研究（Ⅱ）琥珀酸酐加氢制γ—丁内酯

γ－丁内酯（γ－ＢＬ）是顺酐（ＭＡ）加氢的次级衍生物。作者曾报导了顺酐加氢制琥珀酸酐的研究。这里，我们研究了不同催化剂及配体对琥珀酸酐加氢生成γ－丁内酯的反应。考察了最佳钌／三苯基膦配位催化体系，对琥珀酸酐（ＳＡ）均相催化加氢生成γ－丁内酯的反应条件：催化剂及膦配体用量、温度、压力、时间、溶液对催化反应的影响。实验表明，在钌盐为０．１５ｍｍｏｌ、Ｐ／Ｒｕ＝８、１２０℃、３．０ＭＰａ氢压下，乙二醇二     

新型表面活性膦在长链烯烃氢甲酰化反应中的助催化作用

 考察了新型表面活性膦配体DPPTS(对-十二烷基苯基二苯基膦的磺酸钠盐)和OPPTS(对-辛基苯基二苯基膦的磺酸钠盐)在铑络合物催化的水/有机两相长链烯烃氢甲酰化反应中的助催化作用. 在催化烯烃氢甲酰化反应时,观察到烯烃与膦配体之间有一定的链长匹配效应; 含DPPTS的催化剂体系在低膦/铑比条件下表现出比含表面活性剂十六烷基三甲基溴化铵和水溶性配体三苯基膦三磺酸钠的催化剂体系高得多的催化活性,而且铑流失到有机相极少,仅为加入总铑量的0.8%. 这种亲水基团和磷原子处于碳链同一端的表面活性膦配体比文献报道的亲水基团和磷原子分别处于碳链两端的表面活性膦配体具有更好的助催化活性.     

新的手性双膦配体的合成及其在苯乙烯不对称氢酯基化中的应用

以甘露醇和山梨醇为原料,合成了2个新的手性膦配体,并用这些新的手性膦配体与钯原位生成的催化剂体系催化苯乙烯的不对称氢酯基化反应,得到R构型的2－苯基丙酸甲酯,其ee值分别为28.5%和13.6%。     

硅胶键合膦的制备及其对铑络合物催化1-辛烯氢甲酰化反应的影响

以硅胶为载体, 采用键合接枝法将2-(二苯膦基)乙基三乙氧基硅烷(DPPES)共价键合于硅胶表面, 制备了性能优良的硅胶键合型膦配体(以SiO₂(PPh₂)表示). 以SiO₂(PPh₂)为配体, Rh(acac)(CO)₂ (acac:乙酰丙酮)为催化前体, 负载铑膦络合物催化剂(SiO₂(PPh₂)/Rh)在1-辛烯氢甲酰化反应中原位生成. 对生成的负载型催化剂和硅胶键合型膦配体进行了傅里叶变换红外(FTIR)光谱表征, 考察了膦/铑摩尔浓度比([P]/[Rh])、温度等因素对铑催化的长链1-辛烯氢甲酰化反应的影响. 结果表明, 膦/铑摩尔浓度比的增加能显著提高反应的成醛选择性, 降低铑的流失. 在[P]/[Rh]=12、363 K、2.0 MPa、1.5 h 的温和反应条件下, 1-辛烯转化率和成醛选择性分别可达98.4%和95.3%, 其催化活性与DPPES或三苯基膦(TPP)作配体时的均相铑催化相近. 催化剂循环4 次后, 反应活性无明显下降, 1-辛烯转化率均在97.0%左右, 经电感耦合等离子体原子发射光谱(ICP-AES)检测,有机相中铑流失低于0.1%.     

阳离子表面活性剂存在下水/有机两相体系中双环戊二烯氢甲酰化

研究了在阳离子表面活性剂存在下水/有机两相中水溶性铑配合物RhCI(CO)(TPPTS)2(TPPTS:P(m-C6H4SO3Na)3)催化双环戊二烯氢甲酰化反应,考察了反应温度、催化剂浓度、不同水溶性膦配体TPPTS和TPPDS(C5H5P(m-C6H4SO3Na)2),以及表面活性剂结构对催化反应的影响.结果表明,...     

Organic Ligand‐Free Hydroformylation with Rh Particles as Catalyst†

Summary of main observation and conclusion An efficient and organic ligand-free heterogeneous catalytic system for hydroformylation of olefins is highly desirable for both academy and industry.In this study,simple Rh black was employed as a heterogeneous catalyst for hydroformylation of olefins in the absence of organic ligand.The Rh black catalyst showed good catalytic activity for a broad substrate scope including the aliphatic and aromatic olefins,affording the desired aldehydes in good yields.Taking the hydroformylation of ethylene as an example,86%yield of propanal and TOF of 200 h-1 were obtained,which was superior to the reported homogeneous catalytic systems.In addition,the catalyst could be reused five times without loss of activity under identical reaction conditions,and the Rh leaching was negligible after each cycle.     

烯烃氢甲酰化催化剂活性物种的原位1H NMR研究

The rhodium-phosphine complex catalyst Rh(CO)(acac)(PPh3)(Ⅰ) for 1-hexene hydroformylation was studied under the following reaction conditions: CO/H2=1(mole rate), pressure 1.0 MPa, temperature 25-120℃, by using the pressurized in-situ 1H NMR technique. Experimental results indicated that the formation of a rhodium hydride complex from (Ⅰ) began at room temperature and its amount increased with increasing of reaction temperature. This intermediate complex began to decompose at 100℃ and disapeared completely at 120℃. The intensity change of the proton signal was parallel to catalytical activity in hydroformylation of olefins. Under pure CO pressure the proton signal of Ph-H bond was not observed. There was a 0.2 ppm difference in proton chemical shifts of Rh-H bond under pure H2 pressure and under H2+CO pressure. The results showed that the rhodium-hydride carbonyl complex is the active intermediate in the industrial hydroformylation process.     

高稳定性无膦配体乙烯氢甲酰化催化体系研究

高活性、高稳定性的无膦配体多相氢甲酰化催化体系研究是催化化学领域的重要课题。本文以乙烯氢甲酰化这一反应为目标,发展出含有不同含氧官能团的活性炭为载体的负载纳米铑催化材料。其中,当以Rh/C-3这一材料为催化剂时,乙烯氢甲酰化反应的转化频率可以达到57889 mol/mol/h。该催化剂可以在固定床反应器上稳定运行2500小时保持活性稳定。表征发现,碳材料表面的内酯基团 (-CO2-)对催化材料的活性和稳定性具有重要的作用。这一研究对高活性、高稳定性的非膦配体多相氢甲酰化催化体系研究具有一定的启示。     

新型离子液体介质中长链烯烃氢甲酰化反应

合成和表征了离子液体[Rmim][p-CH3C6H4SO3](R=CH3(CH2)n—, n=3, 7, 11, 15), 并以所合成的离子液体为反应介质, 考察了水溶性铑膦络合物HRh(CO)(TPPTS)3[TPPTS: P(m-C6H4SO3Na)3]对长链烯烃氢甲酰化反应的催化性能. 结果表明, 离子液体[Rmim][p-CH3C6H4SO3]中R基团链长的变化对催化活性具有重要的影响；而在相同离子液体中, 氢甲酰化反应活性随着烯烃链长的增加明显下降. 与文献报道中广泛使用的离子液体[Bmim]BF4、[Bmim]PF6相比, 该催化体系对长链烯烃氢甲酰化反应具有更好的活性和化学选择性, 在3.0 MPa, 100 ℃的条件下, 1-己烯氢甲酰化反应转化频率(TOF)高达2736 h-1. 反应完成后, 水溶性铑膦络合物能很好地溶解在离子液体中, 与有机物自动分层, 催化剂的循环使用易于实现.     

Highly selective asymmetric Rh-catalyzed hydroformylation of heterocyclic olefins

A small family of new chiral hybrid, diphosphorus ligands, consisting of phosphine-phosphoramidites L1 and L2 and phosphine-phosphonites L3a-c, was synthesized for the application in Rh-catalyzed asymmetric hydroformylation of heterocyclic olefins. High-pressure (HP)-NMR and HP-IR spectroscopy under 5-10 bar of syngas has been employed to characterize the corresponding catalyst resting state with each ligand. Indole-based ligands L1 and L2 led to selective ea coordination, while the xanthene derived system L3c gave predominant ee coordination. Application of the small bite-angle ligands L1 and L2 in the highly selective asymmetric hydroformylation (AHF) of the challenging substrate 2,3-dihydrofuran (1) yielded the 2-carbaldehyde (3) as the major regioisomer in up to 68% yield (with ligand L2) along with good ee's of up to 62%. This is the first example in which the asymmetric hydroformylation of 1 is both regio- and enantioselective for isomer 3. Interestingly, use of ligand L3c in the same reaction completely changed the regioselectivity to 3-carbaldehyde (4) with a remarkably high enantioselectivity of 91%. Ligand L3c also performs very well in the Rh-catalyzed asymmetric hydroformylation of other heterocyclic olefins. Highly enantioselective conversion of the notoriously difficult substrate 2,5-dihydrofuran (2) is achieved using the same catalyst, with up to 91% ee, concomitant with complete regioselectivity to the 3-carbaldehyde product (4) under mild reaction conditions. Interestingly, the Rh-catalyst derived from L3c is thus able to produce both enantiomers of 3-carbaldehyde 4, simply by changing the substrate from 1 to 2. Furthermore, 85% ee was obtained in the hydroformylation of N-acetyl-3-pyrroline (5) with exceptionally high regioselectivities for 3-carbaldehyde 8Ac (>99%). Similarly, an ee of 86% for derivative 8Boc was accomplished using the same catalyst system in the AHF of N-(tert-butoxycarbonyl)-3-pyrroline (6). These results represent the highest ee's reported to date in the AHF of dihydrofurans (1, 2) and 3-pyrrolines (5, 6).     

Studies on the Recycling Efficiency of Thermoregulated Phase-separable Rh/PETPP Complex Catalyst

Effects on the recycling efficiency of thermoregulated phase-separable Rh/PETPP(P-[p-C6H4O(CH2CH2O)nH]3,N=3n) complex catalyst involved in hydroformylation of 1-decene are for the first time presented.It was found that the loss of Rh is dependent greatly on the composition of phosphine ligand PETPP and the organic solvent employed in the reaction.     

DFT study of the full catalytic cycle for the propene hydroformylation catalyzed by a heterobimetallic HPt(SnCl3)(PH3)2 model catalyst

DFT calculations were carried out to study the full catalytic cycle for the hydroformylation of propene, catalyzed by the heterobimetallic model catalyst trans‐Pt(H)(PH₃)₂(SnCl₃). Before the study of the full catalytic cycle, the performance of six pure GGA, one GGA with inclusion of dispersion corrections, four hybrid‐GGA, and three meta‐GGA exchange correlation functional to describe a model reaction promoted by Pt‐Sn catalyst were assessed. It is shown that the BP86 and GPW91 functionals, using extended basis set, provides reliable energetic results when compared with the CCSD(T) calculations. All intermediates and transition states along the elementary steps of the entire catalytic cycle were located and the energies involved in the catalytic cycle calculated using BP86 functional. The solvent effects along the entire catalytic cycle were evaluated using the polarizable continuum model. In contrast with the rhodium catalysts, the regioselectivity of the hydroformylation is set at the carbonylation step. The hydrogenolysis is the rate determining step of the entire cycle, with the activation energy of ～21 kcal mol^?1 in agreement with the experimental value of ～25 kcal mol^?1. The trans effect of the SnCl ligand seems to be pronounced only in the first step of the catalytic cycle, facilitating the insertion of the olefin into the Pt? H bond trans to it. The analysis of the stationary points obtained along each elementary step of the catalytic cycle is carried out separately and discussed. The BP86/cc‐pVTZ/SBKJC results shows that the pathway leading to the linear aldehyde is preferred, being in agreement with the experimental findings. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

1-丁烯氢甲酰化反应的宏观动力学研究

采用三苯基膦羰基氢化铑作为催化剂,进行1-丁烯氢甲酰化合成戊醛反应,主要考察温度、铑浓度、配体浓度、丁烯浓度、合成气中H2和CO分压等因素对反应速率的影响.动力学研究表明温度、Rh浓度、丁烯浓度和H2分压的增加均可提高反应速度,CO分压和配体量的增加使反应速度降低.给出了RhH(CO)(PPh3)3催化1-丁烯氢甲酰化的反应动力学方程,并采用非线性最小二乘法对模型进行参数估值,计算值与实验值具有较好的一致性.