CN117003798A - Method for synthesizing ferrocene phosphine oxide compound - Google Patents

Method for synthesizing ferrocene phosphine oxide compound Download PDF

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CN117003798A
CN117003798A CN202210473591.9A CN202210473591A CN117003798A CN 117003798 A CN117003798 A CN 117003798A CN 202210473591 A CN202210473591 A CN 202210473591A CN 117003798 A CN117003798 A CN 117003798A
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ferrocene
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陈庆安
郑浩
刘倡辉
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明涉及一种合成二茂铁膦氧化合物的方法。具体为，以二茂铁取代物，二芳基膦氧为原料，在电促进下，实现二茂铁C‑H膦氧化反应。本发明有以下优点，无导向的二茂铁取代物直接作为C‑H给体，无需额外的氧化剂和金属催化剂，条件温和，广泛的底物范围，良好的收率。The invention relates to a method for synthesizing ferrocene phosphine oxide compounds. Specifically, ferrocene substituents and diarylphosphine oxygen are used as raw materials to realize ferrocene C-H phosphine oxidation reaction under the promotion of electricity. The present invention has the following advantages: unguided ferrocene substituents directly serve as C-H donors, without the need for additional oxidants and metal catalysts, mild conditions, wide substrate range, and good yields.

Description

一种合成二茂铁膦氧化合物的方法A method for synthesizing ferrocene phosphine oxide compounds

技术领域Technical field

本发明涉及一种合成二茂铁膦氧化合物的方法。The invention relates to a method for synthesizing ferrocene phosphine oxide compounds.

背景技术Background technique

带有金属茂骨架的膦化合物是一种在不对称催化反应中活性良好的配体或催化剂，以往二茂铁膦氧化合物合成方法报道，在二茂铁上引入膦基团一般需要对空气敏感的锂试剂或者当量的lewis酸，操作一般比较繁琐或者有大量的废弃物产生，而且一般需要预安装导向基团和额外金属催化。本发明以二级膦氧化物和无导向基的二茂铁取代物为原料，在电促进的自催化下，实现在金属茂C-H膦氧化反应。该反应具有广泛的底物范围、较好的收率、不需要额外昂贵的当量氧化剂和条件温和的优点。Phosphine compounds with metallocene skeletons are ligands or catalysts with good activity in asymmetric catalytic reactions. Previous synthesis methods of ferrocene phosphine oxide compounds have been reported. The introduction of phosphine groups into ferrocene generally requires air sensitivity. Lithium reagents or equivalent amounts of Lewis acid are generally cumbersome to operate or generate a large amount of waste, and generally require pre-installed directing groups and additional metal catalysis. The invention uses secondary phosphine oxides and ferrocene substituents without directing groups as raw materials, and realizes the metallocene C-H phosphine oxidation reaction under electrically promoted autocatalysis. This reaction has the advantages of wide substrate scope, good yield, no need for additional expensive equivalent oxidants, and mild conditions.

总之，本文描述了一种从简单易得原料出发，以二级膦氧化物为膦源和以无导向基二茂铁取代物为C-H供体直接合成二茂铁骨架的膦氧化合物的方法。In summary, this article describes a method for directly synthesizing phosphine oxide compounds with ferrocene skeletons starting from simple and readily available raw materials, using secondary phosphine oxides as the phosphine source and non-directing ferrocene substituents as the C-H donors.

发明内容Contents of the invention

本发明的目的在于提供一种合成二茂铁膦氧化合物的方法，是电促进的自催化的二茂铁的C-H膦氧化反应方法。The object of the present invention is to provide a method for synthesizing ferrocene phosphine oxide compounds, which is an electrically promoted autocatalytic C-H phosphine oxidation reaction method of ferrocene.

反应方程式1：二茂铁膦氧化合物的合成Reaction Equation 1: Synthesis of ferrocene phosphine oxide

具体操作步骤如下(反应方程式1)：The specific steps are as follows (reaction equation 1):

在氮气气氛下，于三口瓶中加入苯并二茂铁取代物1、二芳基膦氧化合物2、电解质和溶剂，随后加入碱，装上正负极，三口瓶RVC作为阳极(长15mm×宽10mm×厚5mm)，Pt作为阴极(长10mm×宽10mm×厚0.3mm)，电极之间的距离为25mm，两电极(阳极和阴极)长和高所在平面互相平行设置(置于反应液中的阳极和阴极相对表面的面积为85mm2)。恒定电流4.0mA，50℃下搅拌反应6h，反应生成目标产物3，反应结束后，旋干溶剂，柱层析流动相：石油醚/乙酸乙酯(体积比)Under a nitrogen atmosphere, add ferrocene substituent 1, diarylphosphine oxide compound 2, electrolyte and solvent into a three-necked flask, then add alkali, install the positive and negative electrodes, and use the three-necked flask RVC as the anode (length 15mm × Width 10mm × thickness 5mm), Pt as the cathode (length 10mm × width 10mm × thickness 0.3mm), the distance between the electrodes is 25mm, the length and height of the two electrodes (anode and cathode) are set parallel to each other (placed in the reaction solution The area of the opposing surfaces of the anode and cathode is 85mm 2 ). Constant current 4.0mA, stirring reaction at 50°C for 6 hours, the reaction generates the target product 3. After the reaction is completed, spin the solvent dry, column chromatography mobile phase: petroleum ether/ethyl acetate (volume ratio)

二茂铁取代物1与二级膦化合物2，的摩尔用量比为1:1.1-1:4，优选比为1:1.7-1:2.5。The molar ratio of ferrocene substituent 1 to secondary phosphine compound 2 is 1:1.1-1:4, and the preferred ratio is 1:1.7-1:2.5.

碱为NaOAc，Na2CO3，KH2PO4，K2HPO4，PhCO2Na，NaHCO3，NaOPiv，Et3N，TMEDA，Py，DMAP，DABCO,DBU中的一种或两种以上。碱用量为二茂铁取代物1用量的1.4-4.5摩尔当量，优选为1.5-3摩尔当量。The base is one or more of NaOAc, Na 2 CO 3 , KH 2 PO 4 , K 2 HPO 4 , PhCO 2 Na, NaHCO 3 , NaOPiv, Et 3 N, TMEDA, Py, DMAP, DABCO, and DBU. The amount of base used is 1.4-4.5 molar equivalents of the amount of ferrocene substituent 1, preferably 1.5-3 molar equivalents.

电解质为nBu4NPF6，nBu4NBF4，nBu4NCl，nBu4NOAc，nBu4NOTs，nBu4NClO4,Na ClO4中的一种或两种以上；电解质用量为二茂铁取代物1用量的0.30-2.4摩尔当量，优选0.6-1.5摩尔当量。The electrolyte is one or more of n Bu 4 NPF 6 , n Bu 4 NBF 4 , n Bu 4 NCl, n Bu 4 NOAc, n Bu 4 NOTs, n Bu 4 NClO 4 , and Na ClO 4 ; the amount of electrolyte is The amount of ferrocene substituent 1 is 0.30-2.4 molar equivalents, preferably 0.6-1.5 molar equivalents.

溶剂为丙酮，二氯甲烷、乙腈、二甲基亚砜、水、乙醇、甲醇、特戊醇、N,N-二甲基甲酰胺、三氟乙醇、六氟异丙醇一种或两种以上，优选甲醇；溶剂的用量为每毫摩尔二茂铁取代物1用溶剂2.0-8.0毫升，优选5.0毫升。The solvent is acetone, one or two of methylene chloride, acetonitrile, dimethyl sulfoxide, water, ethanol, methanol, pivalol, N,N-dimethylformamide, trifluoroethanol, and hexafluoroisopropanol. For the above, methanol is preferred; the amount of solvent used is 2.0-8.0 ml of solvent per millimole of ferrocene substituent 1, preferably 5.0 ml.

本发明有以下优点：The invention has the following advantages:

首先以二级膦氧化物和无导向基的二茂铁取代物为原料，在电促进的自催化下，实现在金属茂C-H膦氧化反应。其次该反应具有广泛的底物范围、较好的收率、不需要额外昂贵的当量氧化剂和条件温和，反应更加绿色。最后，所得产物二茂铁膦氧化合物可以一步转化得到膦配体。First, secondary phosphine oxides and ferrocene substituents without directing groups are used as raw materials, and the metallocene C-H phosphine oxidation reaction is realized under electrically promoted autocatalysis. Secondly, this reaction has a wide substrate range, good yield, does not require additional expensive equivalent oxidants, and has mild conditions, making the reaction greener. Finally, the obtained ferrocenyl phosphine oxide compound can be converted into a phosphine ligand in one step.

本发明有以下优点，无导向的二茂铁取代物直接作为C-H给体，无需额外的氧化剂和金属催化剂，条件温和，广泛的底物范围，良好的收率。The present invention has the following advantages: unguided ferrocene substituents directly serve as C-H donors without the need for additional oxidants and metal catalysts, mild conditions, wide substrate range, and good yields.

具体实施方式Detailed ways

为了更好地理解本发明，通过以下实施例进行说明。实施例1-11的反应原料及结果见表1。In order to better understand the present invention, the following examples are provided. The reaction raw materials and results of Examples 1-11 are shown in Table 1.

表1不同取代二茂铁与二苯基膦氧2的反应结果Table 1 Reaction results of different substituted ferrocenes and diphenylphosphine oxide 2

表2取代二茂铁1h与不同二级膦氧化合物的反应结果Table 2 Reaction results of substituted ferrocene with different secondary phosphine oxide compounds for 1 h

原料的合成Synthesis of raw materials

取代二茂铁1a的合成：将氯化亚铁(1.27g,10mmol)放入一个schlenk瓶中，抽换瓶中气氛为氮气三次，注入50mL的无水THF,搅拌过夜得到溶液A，另取一个schlenk瓶，抽换瓶中气氛为氮气三次，注入1,2,3,4,5-五甲基环戊二烯(1.36g,10mol)，冷却至-78℃，注入正丁基锂(2.4mol/L,4.6mL,11mol)，反应1小时得到溶液B，将溶液B转移至溶液A中，搅拌1小时后，加入的环戊二烯基钠溶液(2mol/L,5mL,10mol)，反应过夜，柱层析，用石油醚作为洗脱剂得到二茂铁取代物1a(参考文献[1]Kang,D.；Ricci,F.；White,R.J.；Plaxco,K.W.Anal.Chem.2016,88,10452-10458)。Synthesis of substituted ferrocene 1a: Put ferrous chloride (1.27g, 10mmol) into a Schlenk bottle, replace the atmosphere in the bottle with nitrogen three times, inject 50mL of anhydrous THF, stir overnight to obtain solution A, and take another A schlenk bottle, replace the atmosphere in the bottle with nitrogen three times, inject 1,2,3,4,5-pentamethylcyclopentadiene (1.36g, 10mol), cool to -78°C, and inject n-butyllithium ( 2.4mol/L, 4.6mL, 11mol), react for 1 hour to obtain solution B, transfer solution B to solution A, stir for 1 hour, then add sodium cyclopentadienyl solution (2mol/L, 5mL, 10mol) , react overnight, perform column chromatography, and use petroleum ether as the eluent to obtain ferrocene substituted product 1a (Reference [1] Kang, D.; Ricci, F.; White, R.J.; Plaxco, K.W. Anal. Chem. 2016 ,88,10452-10458).

二茂铁1b是商业购得的，1c、1d、1e、1f和1g二茂铁取代物都是通过上述方法制备获得，其操作过程和条件同上，与其不同之处在于，分别利用等摩尔量的1,2,3,4-甲基-5-乙基环戊二烯、1,2,3,4-甲基-5-异丙基环戊二烯、1,2,3,4-甲基-5-苯基环戊二烯、1,2,3,4-甲基-5-(4-氟)苯基环戊二烯和1,2,3,4-甲基-5-苯乙基环戊二烯分别替代1,2,3,4,5-五甲基环戊二烯制备得到的。Ferrocene 1b is purchased commercially, and ferrocene substituents 1c, 1d, 1e, 1f and 1g are all prepared by the above method. The operating process and conditions are the same as above. The difference is that equimolar amounts are used respectively. 1,2,3,4-methyl-5-ethylcyclopentadiene, 1,2,3,4-methyl-5-isopropylcyclopentadiene, 1,2,3,4- Methyl-5-phenylcyclopentadiene, 1,2,3,4-methyl-5-(4-fluoro)phenylcyclopentadiene and 1,2,3,4-methyl-5- It is prepared by replacing 1,2,3,4,5-pentamethylcyclopentadiene with phenethylcyclopentadiene.

二级膦氧化合物2d的合成：将镁屑(972.4mg,40mmol)放入schlenk瓶中，抽换瓶中气氛为氮气三次，注入10mL的无水THF,往其中滴入4-氯溴苯(5.74g,30mmol)，制备得到相应的格氏试剂，冷却至0℃，往其中滴入亚磷酸二乙酯(1.38g,10mmol)，搅拌一小时，然后在室温反应过夜，柱层析，用乙酸乙酯：石油醚＝2:1(体积比)作为洗脱剂得到2d二级膦氧化合物(参考文献[2]Molitor,S.；Becker,J.；Gessner,V.H.J.Am.Chem.Soc.2014,136,15517–15520)。Synthesis of secondary phosphine oxide compound 2d: Put magnesium chips (972.4 mg, 40 mmol) into a schlenk bottle, replace the atmosphere in the bottle with nitrogen three times, inject 10 mL of anhydrous THF, and drop 4-chlorobromobenzene ( 5.74g, 30mmol), prepare the corresponding Grignard reagent, cool to 0°C, drop diethyl phosphite (1.38g, 10mmol) into it, stir for one hour, then react at room temperature overnight, column chromatography, use Ethyl acetate: petroleum ether = 2:1 (volume ratio) was used as the eluent to obtain 2d secondary phosphine oxide compound (Reference [2] Molitor, S.; Becker, J.; Gessner, V.H.J.Am.Chem.Soc. 2014,136,15517–15520).

其它二级膦氧化合物的合成：二级膦氧化合物2a是商业购得的，2b、2c和2e膦氧化合物都是通过上述方法制备获得，其操作过程和条件同上，与其不同之处在于，分别利用等摩尔量的溴苯，4-甲基溴苯和3,5-二氟溴苯分别替代4-氯溴苯得到的。Synthesis of other secondary phosphine oxide compounds: Secondary phosphine oxide compound 2a is commercially available. 2b, 2c and 2e phosphine oxide compounds are all prepared by the above method. The operating process and conditions are the same as above. The difference is that, Obtained by using equimolar amounts of bromobenzene, 4-methylbromobenzene and 3,5-difluorobromobenzene respectively to replace 4-chlorobromobenzene.

实施例1Example 1

在氮气气氛下，于三口瓶中依次加入二茂铁取代物1(0.2mmol)、二级膦化合物2(0.4mmol)、nBu4NOAc(0.2mmol)、Et3N(0.4mmol)、MeOH(5.0mL)，得反应液；于三口瓶中装入阴极和阳极二电极，以RVC电极为阳极，片状Pt电极为阴极，电极之间的距离为25mm，两电极(阳极和阴极)长和高所在平面互相平行设置(阴极和阳极的下部置于反应体系的反应液中，置于反应液中的阳极和阴极相对表面的面积为85mm2)。于阴极和阳极之间通入恒定4.0mA电流，于50℃下反应，反应时间6小时；反应结束后，经过柱层析分离(流动相：石油醚/乙酸乙酯＝1:1，v/v)得到二茂铁膦氧化合物3a收率为71％，化合物经过红外、核磁(氢谱、碳谱和膦谱)、高分辨质谱鉴定结构。检测数据如下：Under a nitrogen atmosphere, add ferrocene substituent 1 (0.2mmol), secondary phosphine compound 2 (0.4mmol), n Bu 4 NOAc (0.2mmol), Et 3 N (0.4mmol), and MeOH in sequence in a three-necked flask. (5.0mL) to obtain the reaction solution; put two electrodes, cathode and anode, into a three-necked flask, with the RVC electrode as the anode and the flake Pt electrode as the cathode. The distance between the electrodes is 25mm. The two electrodes (anode and cathode) are long and the height planes are arranged parallel to each other (the lower parts of the cathode and the anode are placed in the reaction solution of the reaction system, and the area of the opposite surfaces of the anode and cathode placed in the reaction solution is 85 mm 2 ). Pass a constant 4.0mA current between the cathode and the anode, react at 50°C, and the reaction time is 6 hours; after the reaction is completed, undergo column chromatography separation (mobile phase: petroleum ether/ethyl acetate = 1:1, v/ v) Ferrocene phosphine oxide compound 3a was obtained with a yield of 71%. The structure of the compound was identified by infrared, nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum) and high-resolution mass spectrometry. The detection data is as follows:

3a:Yellow solid,mp 195.3-197.0℃,67.8mg,73％yield.1H NMR(400MHz,CDCl3)δ7.61(dd,J＝11.9,7.5Hz,4H),7.46–7.33(m,6H),3.99(s,4H),1.82(s,15H)；13C NMR(100MHz,CDCl3)δ135.6(d,J＝104.6Hz),131.5(d,J＝9.6Hz),131.1(d,J＝2.7Hz),128.1(d,J＝11.8Hz),82.0,75.8(d,J＝10.9Hz),74.2(d,J＝12.9Hz),73.2(d,J＝120.4Hz)；31PNMR(162MHz,CDCl3)δ28.0；HRMS calculated for C27H29OPNaFe[M+Na]+479.1198,found479.1199.实施例2：3a: Yellow solid, mp 195.3-197.0℃, 67.8mg, 73% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.61 (dd, J＝11.9, 7.5Hz, 4H), 7.46–7.33 (m, 6H ), 3.99 (s, 4H), 1.82 (s, 15H); 13 C NMR (100MHz, CDCl 3 ) δ 135.6 (d, J = 104.6Hz), 131.5 (d, J = 9.6Hz), 131.1 (d 31 PNMR (162MHz, CDCl 3 ) δ28.0; HRMS calculated for C 27 H 29 OPNaFe[M+Na] + 479.1198, found 479.1199. Example 2:

操作过程和条件同实施例1，与实施例1不同之处在于，见表1中表述的区别，柱层析分离(流动相：石油醚/乙酸乙酯＝1:2)产物3b收率为71％，化合物经过红外、核磁(氢谱、碳谱和膦谱)鉴定结构。The operating process and conditions are the same as Example 1. The difference from Example 1 is that, see the difference expressed in Table 1. The column chromatography separation (mobile phase: petroleum ether/ethyl acetate=1:2) product 3b yield is 71%, the structure of the compound was identified through infrared and nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum).

检测数据如下：The detection data is as follows:

3b；yellow solid,54.8mg,71％yield.1H NMR(400MHz,CDCl3)δ7.71–7.63(m,4H),7.48(m,2H),7.41(m,4H),4.46(d,J＝1.8Hz,2H),4.36(d,J＝1.9Hz,2H),4.19(s,5H)；13CNMR(100MHz,CDCl3)δ134.4(d,J＝106.4Hz),131.6(d,J＝2.8Hz),131.5(d,J＝9.9Hz),128.2(d,J＝12.1Hz),72.8(d,J＝117.6Hz),72.3(d,J＝12.9Hz),71.7(d,J＝10.5Hz),69.7.31P NMR(162MHz,CDCl3)δ29.0；3b; yellow solid, 54.8mg, 71% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.71–7.63(m,4H),7.48(m,2H),7.41(m,4H),4.46(d, J＝1.8Hz, 2H), 4.36 (d, J＝1.9Hz, 2H), 4.19 (s, 5H); 13 CNMR (100MHz, CDCl 3 ) δ 134.4 (d, J＝106.4Hz), 131.6 (d ,J＝2.8Hz),131.5(d,J＝9.9Hz),128.2(d,J＝12.1Hz),72.8(d,J＝117.6Hz),72.3(d,J＝12.9Hz),71.7(d , J=10.5Hz), 69.7. 31 P NMR (162MHz, CDCl 3 ) δ29.0;

该3b(77.6mg,0.2mmol)溶于2mL甲苯中，加入三乙胺(81.5mg,0.8mmol)和三甲基氯硅烷(65.2mg,0.6mmol)然后在油浴加热回流反应18小时，得到产率99％的膦配体4，该膦配体在选择构建C-C中有优异的活性(参考文献[3]Laulhé,S.；Blackburn,J.M.；Roizen,J.L.Org.Lett.2016,18,4440-4443。The 3b (77.6 mg, 0.2 mmol) was dissolved in 2 mL of toluene, triethylamine (81.5 mg, 0.8 mmol) and trimethylchlorosilane (65.2 mg, 0.6 mmol) were added and then heated and refluxed in an oil bath for 18 hours to obtain The yield of phosphine ligand 4 is 99%, which has excellent activity in the selective construction of C-C (Reference [3] Laulhé, S.; Blackburn, J.M.; Roizen, J.L.Org. Lett. 2016, 18, 4440 -4443.

实施例3：Example 3:

操作过程和条件同实施例1，与实施例1不同之处在于，见表1中表述的区别，产物3c收率为72％，化合物经过红外、核磁(氢谱、碳谱和膦谱)、高分辨质谱鉴定结构。The operating process and conditions are the same as Example 1. The difference from Example 1 is that, as shown in Table 1, the yield of product 3c is 72%. The compound was analyzed by infrared, nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum), Structure identification by high-resolution mass spectrometry.

检测数据如下：The detection data is as follows:

3c:Yellow solid,mp 125.6-127.2℃,67.6mg,72％yield.1H NMR(400MHz,CDCl3)δ7.65–7.57(m,4H),7.45–7.39(m,2H),7.39–7.33(m,4H),4.00(s,2H),3.99(s,2H),2.35(q,J＝7.6Hz,2H),1.83(s,6H),1.83(s,6H),0.87(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ135.5(d,J＝104.7Hz),131.5(d,J＝9.9Hz),131.1(d,J＝2.8Hz),128.0(d,J＝11.9Hz),87.7,82.3,81.5,75.6(d,J＝10.9Hz),74.0(d,J＝13.0Hz),73.1(d,J＝120.7Hz),19.9,15.3,11.3,11.1；31P NMR(162MHz,CDCl3)δ28.1；HRMS calculated forC28H31OPNaFe[M+Na]+493.1354,found 493.13593c: Yellow solid, mp 125.6-127.2℃, 67.6mg, 72% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.65–7.57(m,4H),7.45–7.39(m,2H),7.39–7.33 (m,4H),4.00(s,2H),3.99(s,2H),2.35(q,J＝7.6Hz,2H),1.83(s,6H),1.83(s,6H),0.87(t, J=7.6Hz, 3H); 13 C NMR (100MHz, CDCl 3 ) δ135.5 (d, J=104.7Hz), 131.5 (d, J=9.9Hz), 131.1 (d, J=2.8Hz), 128.0 (d,J＝11.9Hz),87.7,82.3,81.5,75.6(d,J＝10.9Hz),74.0(d,J＝13.0Hz),73.1(d,J＝120.7Hz),19.9,15.3,11.3 ,11.1; 31 P NMR (162MHz, CDCl 3 )δ28.1; HRMS calculated forC 28 H 31 OPNaFe[M+Na] + 493.1354, found 493.1359

实施例4：Example 4:

操作过程和条件同实施例1，与实施例1不同之处在于，见表1中表述的区别，产物3d收率为64％，化合物经过红外、核磁(氢谱、碳谱和膦谱)、高分辨质谱鉴定结构。The operating process and conditions are the same as Example 1. The difference from Example 1 is that, as shown in Table 1, the yield of product 3d is 64%. The compound was analyzed by infrared, nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum), Structure identification by high-resolution mass spectrometry.

检测数据如下：The detection data is as follows:

3d:Yellow solid,mp 85.5-87.0℃,62.3mg,64％yield.1H NMR(400MHz,CDCl3)δ7.64–7.55(m,4H),7.46–7.40(m,2H),7.40–7.33(m,4H),4.11(d,2H),4.08(d,J＝2.2Hz,2H),2.65(hept,J＝7.1Hz,1H),1.85(s,6H),1.79(s,6H),1.16(d,J＝7.1Hz,6H)；13C NMR(100MHz,CDCl3)δ135.3(d,J＝104.8Hz),131.4(d,J＝9.5Hz),131.2(d,J＝2.9Hz),128.1(d,J＝12.1Hz),92.0,82.5,81.0,75.4(d,J＝10.9Hz),74.0(d,J＝12.9Hz),72.7(d,J＝121.3Hz),26.8,23.3,12.0,11.3；31P NMR(162MHz,CDCl3)δ28.9；HRMS calculated forC29H33OPNaFe[M+Na]+507.1511,found 507.1507.3d: Yellow solid, mp 85.5-87.0℃, 62.3mg, 64% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.64–7.55(m,4H),7.46–7.40(m,2H),7.40–7.33 (m,4H),4.11(d,2H),4.08(d,J＝2.2Hz,2H),2.65(hept,J＝7.1Hz,1H),1.85(s,6H),1.79(s,6H) ,1.16(d,J＝7.1Hz,6H); 13 C NMR (100MHz, CDCl 3 ) δ135.3(d,J＝104.8Hz), 131.4(d,J＝9.5Hz), 131.2(d,J＝ 2.9Hz),128.1(d,J＝12.1Hz),92.0,82.5,81.0,75.4(d,J＝10.9Hz),74.0(d,J＝12.9Hz),72.7(d,J＝121.3Hz), 26.8, 23.3, 12.0, 11.3; 31 P NMR (162MHz, CDCl 3 ) δ 28.9; HRMS calculated for C 29 H 33 OPNaFe[M+Na] + 507.1511, found 507.1507.

实施例5：Example 5:

操作过程和条件同实施例1，与实施例1不同之处在于，见表1中表述的区别，产物3e收率为77％，化合物经过红外、核磁(氢谱、碳谱和膦谱)、高分辨质谱鉴定结构。The operating process and conditions are the same as Example 1. The difference from Example 1 is that, as shown in Table 1, the yield of product 3e is 77%. The compound was analyzed by infrared, nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum), Structure identification by high-resolution mass spectrometry.

检测数据如下：The detection data is as follows:

3e:Yellow solid,mp 42.9-44.2℃,79.8mg,77％yield.1H NMR(400MHz,CDCl3)δ7.67–7.59(m,4H),7.47–7.34(m,8H),7.29–7.21(m,3H),4.12(q,J＝2.0Hz,2H),4.08(q,J＝1.9Hz,2H),1.94(s,6H),1.91(s,6H).13C NMR(100MHz,CDCl3)δ136.9,135.3(d,J＝104.9Hz),131.5(d,J＝9.7Hz),131.2(d,J＝2.9Hz),131.2,128.1(d,J＝11.9Hz),127.7,126.2,88.0,83.0,82.0,76.7(d,J＝10.7Hz),75.2(d,J＝12.8Hz),73.4(d,J＝119.8Hz),12.3,11.5；31P NMR(162MHz,CDCl3)δ28.0；HRMS calculated for C32H32OPFe[M+H]+519.1535,found 519.1527.3e: Yellow solid, mp 42.9-44.2℃, 79.8mg, 77% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.67–7.59(m,4H),7.47–7.34(m,8H),7.29–7.21 (m,3H),4.12(q,J＝2.0Hz,2H),4.08(q,J＝1.9Hz,2H),1.94(s,6H),1.91(s,6H). 13 C NMR(100MHz, CDCl 3 )δ136.9,135.3(d,J＝104.9Hz),131.5(d,J＝9.7Hz),131.2(d,J＝2.9Hz),131.2,128.1(d,J＝11.9Hz),127.7,126.2 ,88.0,83.0,82.0,76.7(d,J＝10.7Hz),75.2(d,J＝12.8Hz),73.4(d,J＝119.8Hz),12.3,11.5; 31 P NMR (162MHz, CDCl 3 ) δ28.0; HRMS calculated for C 32 H 32 OPFe[M+H] + 519.1535, found 519.1527.

实施例6：Example 6:

操作过程和条件同实施例1，与实施例1不同之处在于，见表1中表述的区别，产物3f收率为63％，化合物经过红外、核磁(氢谱、碳谱和膦谱)、高分辨质谱鉴定结构。The operating process and conditions are the same as Example 1. The difference from Example 1 is that, as shown in Table 1, the yield of product 3f is 63%. The compound was analyzed by infrared, nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum), Structure identification by high-resolution mass spectrometry.

检测数据如下：The detection data is as follows:

3f:Yellow solid,mp 154.2-156.1℃,67.8mg,63％yield.1H NMR(400MHz,CDCl3)δ7.67–7.57(m,4H),7.49–7.41(m,2H),7.41–7.33(m,6H),6.97–6.90(m,2H),4.10(q,J＝2.0Hz,2H),4.07(q,J＝1.8Hz,2H),1.91(s,6H),1.88(s,6H)；13C NMR(100MHz,CDCl3)δ161.4(d,J＝245.1Hz),135.2(d,J＝105.0Hz),132.6,132.6(d,J＝7.8Hz),131.5(d,J＝9.6Hz),131.3(d,J＝2.8Hz),128.2(d,J＝12.0Hz),114.6(d,J＝21.1Hz),87.2,82.8,82.1,76.7(d,J＝10.7Hz),75.2(d,J＝12.7Hz),73.4(d,J＝119.8Hz),12.2,11.5.31P NMR(162MHz,CDCl3)δ28.1；19F NMR(376MHz,CDCl3)δ-116.5.HRMS calculated for C32H31OPFFe[M+H]+537.1440,found 537.1445.3f: Yellow solid, mp 154.2-156.1℃, 67.8mg, 63% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.67–7.57(m,4H),7.49–7.41(m,2H),7.41–7.33 (m,6H),6.97–6.90(m,2H),4.10(q,J＝2.0Hz,2H),4.07(q,J＝1.8Hz,2H),1.91(s,6H),1.88(s, 6H); 13 C NMR (100MHz, CDCl 3 ) δ 161.4 (d, J = 245.1Hz), 135.2 (d, J = 105.0Hz), 132.6, 132.6 (d, J = 7.8Hz), 131.5 (d, J＝9.6Hz),131.3(d,J＝2.8Hz),128.2(d,J＝12.0Hz),114.6(d,J＝21.1Hz),87.2,82.8,82.1,76.7(d,J＝10.7Hz ), 75.2 (d, J = 12.7Hz), 73.4 (d, J = 119.8Hz), 12.2, 11.5. 31 P NMR (162MHz, CDCl 3 ) δ28.1; 19 F NMR (376MHz, CDCl 3 ) δ- 116.5.HRMS calculated for C 32 H 31 OPFFe[M+H] + 537.1440, found 537.1445.

实施例7：Example 7:

操作过程和条件同实施例1，与实施例1不同之处在于，见表1中表述的区别，产物3g收率为53％，化合物经过红外、核磁(氢谱、碳谱和膦谱)、高分辨质谱鉴定结构。The operating process and conditions are the same as Example 1. The difference from Example 1 is that, as shown in Table 1, the yield of 3g of product is 53%. The compound was analyzed by infrared, nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum), Structure identification by high-resolution mass spectrometry.

检测数据如下：The detection data is as follows:

3g:Yellow solid,mp 50.8-51.9℃,57.3mg,52％yield,Rf＝0.40(petroleumether/ethyl acetate 20/1).1H NMR(700MHz,CDCl3)δ7.64–7.53(m,3H),7.42–7.36(m,2H),7.36–7.30(m,3H),7.28–7.22(m,2H),7.20–7.12(m,1H),7.08(d,J＝7.5Hz,2H),4.00(s,2H),3.99(s,2H),2.56(t,J＝8.1Hz,2H),2.47(t,J＝8.2Hz,2H),1.83(s,6H),1.77(s,6H).13C NMR(175MHz,CDCl3)δ142.1,135.3(d,J＝104.7Hz),131.4(d,J＝9.6Hz),131.2(d,J＝2.6Hz),128.6,128.3,128.1(d,J＝12.0Hz),125.8,85.3,82.5,81.9,75.6(d,J＝10.8Hz),74.0(d,J＝12.8Hz),73.0(d,J＝120.8Hz),37.4,29.4,11.4,11.2.31P NMR(162MHz,CDCl3)δ28.3；HRMS calculated for C34H35OPNaFe[M+Na]+569.1667,found569.1666.3g: Yellow solid, mp 50.8-51.9℃, 57.3mg, 52% yield, R f = 0.40 (petroleumether/ethyl acetate 20/1). 1 H NMR (700MHz, CDCl 3 ) δ7.64–7.53 (m, 3H ),7.42–7.36(m,2H),7.36–7.30(m,3H),7.28–7.22(m,2H),7.20–7.12(m,1H),7.08(d,J＝7.5Hz,2H), 4.00(s,2H),3.99(s,2H),2.56(t,J＝8.1Hz,2H),2.47(t,J＝8.2Hz,2H),1.83(s,6H),1.77(s,6H ). 13 C NMR (175MHz, CDCl 3 ) δ142.1, 135.3 (d, J = 104.7Hz), 131.4 (d, J = 9.6Hz), 131.2 (d, J = 2.6Hz), 128.6, 128.3, 128.1 (d ,J＝12.0Hz),125.8,85.3,82.5,81.9,75.6(d,J＝10.8Hz),74.0(d,J＝12.8Hz),73.0(d,J＝120.8Hz),37.4,29.4,11.4 ,11.2. 31 P NMR (162MHz, CDCl 3 )δ28.3; HRMS calculated for C 34 H 35 OPNaFe[M+Na] + 569.1667, found569.1666.

实施例8：Example 8:

操作过程和条件同实施例1，与实施例1不同之处在于，见表1中表述的区别，产物3h收率为40％，化合物经过红外、核磁(氢谱、碳谱和膦谱)、高分辨质谱鉴定结构。The operating process and conditions are the same as Example 1. The difference from Example 1 is that, as shown in Table 1, the yield of the product in 3 hours is 40%. The compound was analyzed by infrared, nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum), Structure identification by high-resolution mass spectrometry.

检测数据如下：The detection data is as follows:

3h:Yellow solid,mp 64.8-66.6℃,37.6mg,40％yield.1H NMR(400MHz,CDCl3)δ7.76–7.66(m,2H),7.62–7.55(m,2H),7.49–7.43(m,1H),7.42–7.32(m,4H),7.28(d,J＝7.3Hz,1H),4.21(s,1H),4.13(s,1H),4.06–4.02(m,1H),4.00(q,J＝3.0Hz,1H),3.64(d,J＝11.4Hz,3H),2.05(s,3H),2.04(s,3H),1.99(s,3H),1.97(s,3H)；13C NMR(100MHz,CDCl3)δ137.1,132.5(d,J＝132.2Hz),131.6(d,J＝2.8Hz),131.5(d,J＝9.8Hz),131.2,128.4(d,J＝12.9Hz),127.6,126.2,88.1,83.1,83.0,81.8,81.7,76.5(d,J＝12.8Hz),76.4(d,J＝11.8Hz),74.7(d,J＝17.8Hz),74.3(d,J＝12.0Hz),71.8(d,J＝165.3Hz),50.9(d,J＝5.9Hz),12.0,11.9,11.3；31P NMR(162MHz,CDCl3)δ38.6；HRMS calculated forC27H29O2PNaFe[M+Na]+495.1147,found 495.1145.3h: Yellow solid, mp 64.8-66.6℃, 37.6mg, 40% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.76–7.66(m,2H),7.62–7.55(m,2H),7.49–7.43 (m,1H),7.42–7.32(m,4H),7.28(d,J＝7.3Hz,1H),4.21(s,1H),4.13(s,1H),4.06–4.02(m,1H), 4.00(q,J＝3.0Hz,1H),3.64(d,J＝11.4Hz,3H),2.05(s,3H),2.04(s,3H),1.99(s,3H),1.97(s,3H ; _ ＝12.9Hz),127.6,126.2,88.1,83.1,83.0,81.8,81.7,76.5(d,J＝12.8Hz),76.4(d,J＝11.8Hz),74.7(d,J＝17.8Hz),74.3 (d, J=12.0Hz), 71.8 (d, J=165.3Hz), 50.9 (d, J=5.9Hz), 12.0, 11.9, 11.3; 31 P NMR (162MHz, CDCl 3 ) δ38.6; HRMS calculated forC 27 H 29 O 2 PNaFe[M+Na] + 495.1147, found 495.1145.

实施例9：Example 9:

操作过程和条件同实施例1，与实施例1不同之处在于，见表1中表述的区别，产物3i收率为65％，化合物经过红外、核磁(氢谱、碳谱和膦谱)、高分辨质谱。The operating process and conditions are the same as in Example 1. The difference from Example 1 is that, as shown in Table 1, the yield of product 3i is 65%. The compound was analyzed by infrared, nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum), High resolution mass spectrometry.

检测数据如下：The detection data is as follows:

3i:Yellow solid,mp 105.6-107.3℃,71.3mg,65％yield.1H NMR(400MHz,CDCl3)δ7.50(dd,J＝11.7,7.8Hz,4H),7.41–7.36(m,2H),7.25–7.21(m,3H),7.17(dd,J＝8.1,2.6Hz,4H),4.10(q,J＝2.0Hz,2H),4.06(q,J＝1.8Hz,2H),2.35(s,6H),1.94(s,6H),1.93(s,6H)；13C NMR(100MHz,CDCl3)δ141.4(d,J＝2.8Hz),137.0,132.3(d,J＝107.3Hz),131.5(d,J＝10.1Hz),131.2,128.8(d,J＝12.3Hz),127.6,126.1,87.9,83.0,81.9,76.5(d,J＝10.7Hz),75.2(d,J＝12.8Hz),74.0(d,J＝119.5Hz),21.6,12.3,11.6；31P NMR(162MHz,CDCl3)δ28.1；HRMS calculated for C34H35OPNaFe[M+Na]+569.1667,found 569.1693.3i: Yellow solid, mp 105.6-107.3℃, 71.3mg, 65% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.50 (dd, J＝11.7, 7.8Hz, 4H), 7.41–7.36 (m, 2H ),7.25–7.21(m,3H),7.17(dd,J＝8.1,2.6Hz,4H),4.10(q,J＝2.0Hz,2H),4.06(q,J＝1.8Hz,2H),2.35 (s, 6H), 1.94 (s, 6H), 1.93 (s, 6H); 13 C NMR (100MHz, CDCl 3 ) δ 141.4 (d, J = 2.8 Hz), 137.0, 132.3 (d, J = 107.3 Hz),131.5(d,J＝10.1Hz),131.2,128.8(d,J＝12.3Hz),127.6,126.1,87.9,83.0,81.9,76.5(d,J＝10.7Hz),75.2(d,J =12.8Hz), 74.0 (d, J = 119.5Hz), 21.6, 12.3, 11.6; 31 P NMR (162MHz, CDCl 3 ) δ28.1; HRMS calculated for C 34 H 35 OPNaFe[M+Na] + 569.1667, found 569.1693.

实施例10：Example 10:

操作过程和条件同实施例1，与实施例1不同之处在于，见表1中表述的区别，产物3j收率为72％，化合物经过核磁(氢谱、碳谱和膦谱)、高分辨质谱鉴定结构。The operating process and conditions are the same as Example 1. The difference from Example 1 is that, as shown in Table 1, the yield of product 3j is 72%. The compound was subjected to nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum), high-resolution Structure identification by mass spectrometry.

检测数据如下：The detection data is as follows:

3j:Yellow solid,mp 128.7-129.3℃,84.6mg,72％yield.1H NMR(400MHz,CDCl3)δ7.50(dd,J＝11.4,8.1Hz,4H),7.38–7.31(m,6H),7.28–7.24(m,3H),4.11(t,J＝2.0Hz,2H),4.07(t,J＝2.0Hz,2H),1.93(s,12H).13C NMR(100MHz,CDCl3)δ137.9(d,J＝3.3Hz),136.5,133.4(d,J＝106.2Hz),132.7(d,J＝10.6Hz),131.0,128.5(d,J＝12.5Hz),127.6,126.3,88.1,83.1,82.2,76.9(d,J＝11.0Hz),75.0(d,J＝13.2Hz),72.4(d,J＝122.3Hz),12.2,11.5.31P NMR(162MHz,CDCl3)δ27.1.HRMS calculated for C32H29OPCl2NaFe[M+Na]+609.0575,found 609.0578.3j: Yellow solid, mp 128.7-129.3℃, 84.6mg, 72% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.50 (dd, J＝11.4, 8.1Hz, 4H), 7.38–7.31 (m, 6H ),7.28–7.24(m,3H),4.11(t,J＝2.0Hz,2H),4.07(t,J＝2.0Hz,2H),1.93(s,12H). 13 C NMR (100MHz, CDCl 3 )δ137.9(d,J＝3.3Hz),136.5,133.4(d,J＝106.2Hz),132.7(d,J＝10.6Hz),131.0,128.5(d,J＝12.5Hz),127.6,126.3 ,88.1,83.1,82.2,76.9(d,J＝11.0Hz),75.0(d,J＝13.2Hz),72.4(d,J＝122.3Hz),12.2,11.5. 31 P NMR (162MHz, CDCl 3 ) δ27.1.HRMS calculated for C 32 H 29 OPCl 2 NaFe[M+Na] + 609.0575, found 609.0578.

实施例11：Example 11:

操作过程和条件同实施例1，与实施例1不同之处在于，除表1中表述的区别之外，产物3k收率为60％，化合物经过核磁(氢谱、碳谱和膦谱)、高分辨质谱鉴定结构。The operating process and conditions are the same as Example 1. The difference from Example 1 is that, except for the differences expressed in Table 1, the yield of product 3k is 60%. The compound was subjected to nuclear magnetic (hydrogen spectrum, carbon spectrum and phosphine spectrum), Structure identification by high-resolution mass spectrometry.

检测数据如下：The detection data is as follows:

3k:Yellow solid,mp 121.8-122.2℃,70.7mg,60％yield.1H NMR(400MHz,CDCl3)δ7.44–7.38(m,2H),7.31–7.24(m,3H),7.17–7.06(m,J＝5.0Hz,4H),6.96–6.87(m,2H),4.18-4.17(m,2H),4.12-4.10(m,2H),1.92(s,12H)；13C NMR(100MHz,CDCl3)δ162.8(ddd,J＝253.8,19.6,11.0Hz),138.6(dt,J＝103.9,6.5Hz),136.4,131.0,127.8,126.5,114.29(ddd,J＝26.0,10.2,1.6Hz)107.4(dt,J＝25.0,1.7Hz),88.5,83.4,82.4,75.0(d,J＝13.4Hz),77.4(d,J＝11.4Hz),70.7(d,J＝125.5Hz),11.9(d,J＝69.5Hz)；31P NMR(162MHz,CDCl3)δ26.2(t,J＝6.4Hz)；19F NMR(376MHz,CDCl3)δ-107.1(q,J＝6.8Hz).HRMScalculated for C32H28OPF4Fe[M+H]+591.1158,found 591.1154.3k: Yellow solid, mp 121.8-122.2℃, 70.7mg, 60% yield. 1 H NMR (400MHz, CDCl 3 ) δ7.44–7.38(m,2H),7.31–7.24(m,3H),7.17–7.06 (m,J＝5.0Hz,4H),6.96–6.87(m,2H),4.18-4.17(m,2H),4.12-4.10(m,2H),1.92(s,12H); 13 C NMR(100MHz , CDCl 3 )δ162.8(ddd,J＝253.8,19.6,11.0Hz),138.6(dt,J＝103.9,6.5Hz),136.4,131.0,127.8,126.5,114.29(ddd,J＝26.0,10.2, 1.6Hz)107.4(dt,J＝25.0,1.7Hz),88.5,83.4,82.4,75.0(d,J＝13.4Hz),77.4(d,J＝11.4Hz),70.7(d,J＝125.5Hz) ,11.9(d,J＝69.5Hz); 31 P NMR(162MHz, CDCl 3 )δ26.2(t,J＝6.4Hz); 19 F NMR(376MHz, CDCl 3 )δ-107.1(q,J＝6.8 Hz).HRMScalculated for C 32 H 28 OPF 4 Fe[M+H] + 591.1158,found 591.1154.

对比例：用当量的氧化剂代替电流：Comparative Example: Substituting an equivalent amount of oxidant for current:

a条件：1b(0.20mmol),2a(0.40mmol),nBu4NOAc(0.20mmol),Et3N(0.40mmol),氧化剂(0.4mmol),MeOH(4.0mL),50℃,6h.产率由核磁H谱以均三甲氧基苯为内标物测定。 a conditions: 1b (0.20mmol), 2a (0.40mmol), n Bu 4 NOAc (0.20mmol), Et 3 N (0.40mmol), oxidizing agent (0.4mmol), MeOH (4.0mL), 50°C, 6h. Product The rate was determined by NMR H spectrum using mesitylene trimethoxybenzene as the internal standard.

Claims (8)

1. A method for synthesizing ferrocene phosphine oxide compound is characterized in that:
ferrocene derivative 1 and secondary phosphine compound 2 shown in the following formula are used as raw materials to generate ferrocene phosphine oxide compound 3, and the reaction formula is as follows:
2R in the secondary phosphine compound 2 are respectively one or more than two of phenyl, naphthyl, phenyl containing substituent groups and methoxy, and the substituent groups on the phenyl are one or more than two of chlorine, fluorine, methyl and tert-butyl;
4R' in the derivative 1 of ferrocene are one or more than two of hydrogen, methyl, ethyl and C3-C6 alkyl; r' is one or more than two of hydrogen, methyl, ethyl, isopropyl, phenyl, phenethyl, phenyl containing substituent groups and C3-C6 alkyl, and the substituent groups on the phenyl are one or more than two of chlorine, fluorine and trifluoromethyl.
2. A method according to claim 1, characterized in that:
the specific operation steps are as follows:
in nitrogen atmosphere, adding ferrocene substituent 1, secondary phosphine compound 2, electrolyte, solvent and alkali into a container to obtain a reaction solution; the container is provided with a cathode and an anode, the anode and the cathode are arranged oppositely, the distance is 15-40mm, preferably 18-30mm, part or all of the cathode and the anode are arranged in the reaction liquid of the reaction system, and the area of the opposite surfaces of the anode and the cathode arranged in the reaction liquid is 45-120mm 2 Preferably 75-100mm 2 Then applying an electric current between the cathode and the anode;
in an electrochemical reaction: the electrochemical constant reaction current is 2.0-6.0mA (preferably 2.5-4.0), and the electrochemical constant reaction current is placed in an oil bath with the temperature of 40-70 ℃ (preferably 50-65 ℃) for 2-12 hours (preferably 4-8 hours); the reaction is carried out in a solvent in the presence of an electrolyte; the reaction produces the target product 3.
3. A method according to claim 2, characterized in that:
the molar ratio of ferrocene substituent 1 to secondary phosphine compound 2 is 1:1.1-1:4, preferably 1:1.7-1:2.5.
4. A method according to claim 2, characterized in that:
the alkali is NaOAc, na 2 CO 3 ，KH 2 PO 4 ，K 2 HPO 4 ，PhCO 2 Na (sodium benzoate), naHCO 3 NaOPiv (sodium pivalate), et 3 N, TMEDA (tetramethyl ethylenediamine), py (pyridine), DMAP 4-dimethylaminopyridine ) DABCO (triethylenediamine), DBU Diazabicyclo ring ) One or two or more of them; the amount of base is 1.4 to 4.5 molar equivalents, preferably 1.5 to 3 molar equivalents, based on the amount of ferrocene substituent 1.
5. A method according to claim 2, characterized in that:
the electrolyte is n Bu 4 NPF 6 (tetrabutylammonium hexafluorophosphate), n Bu 4 NBF 4 (tetrabutylammonium hexafluorophosphate), n Bu 4 NCl (tetrabutylammonium hexafluorophosphate), n Bu 4 NOAc (tetrabutylammonium acetate), n Bu 4 NOTS (tetrabutylammonium p-toluenesulfonate), n Bu 4 NClO 4 (tetrabutylammonium perchlorate), na ClO 4 One or two or more of (sodium perchlorate); the electrolyte is used in an amount of 0.30 to 2.4 molar equivalents, preferably 0.6 to 1.5 molar equivalents, based on the ferrocene substituent 1.
6. A method according to claim 2, characterized in that:
the solvent is one or more of acetone, dichloromethane, acetonitrile, dimethyl sulfoxide, water, ethanol, methanol, tertanol, N-dimethylformamide, trifluoroethanol and hexafluoroisopropanol, preferably methanol; the solvent is used in an amount of 10.0 to 40.0 ml, preferably 25.0 ml, per millimole of ferrocene substituent 1.
7. A method according to claim 2, characterized in that:
and after the reaction is finished, spin-drying the solvent, and purifying by column chromatography to obtain a product.
8. A method according to claim 2, characterized in that:
the reaction anode material is one or more than two of a carbon rod electrode, a carbon cloth electrode, a common glassy carbon electrode, an RVC electrode (reticular glassy carbon electrode) and a Pt electrode;
the cathode material is one or more than two of carbon rod electrode, carbon cloth electrode, common glass carbon electrode, pt electrode, fe electrode and Ni electrode.
CN202210473591.9A 2022-04-29 2022-04-29 Method for synthesizing ferrocene phosphine oxide compound Pending CN117003798A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2346364A2 (en) * 1976-03-31 1977-10-28 Inst Nat Rech Chimique Aryl substd.-ferrocenyl phosphine(s) and oxide derivs. - contg. hydroxy or carboxy gps. and prepd. by Friedel-Crafts reaction
CN107226829A (en) * 2016-03-24 2017-10-03 内蒙古大学 A kind of preparation method of the phosphine oxygen part containing ferrocene group
CN108774271A (en) * 2018-02-08 2018-11-09 浙江工业大学 A kind of chiral nitrogen nitrogen phosphine tridentate ligand and its application based on ferrocene frame having ferrocene frame

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2346364A2 (en) * 1976-03-31 1977-10-28 Inst Nat Rech Chimique Aryl substd.-ferrocenyl phosphine(s) and oxide derivs. - contg. hydroxy or carboxy gps. and prepd. by Friedel-Crafts reaction
CN107226829A (en) * 2016-03-24 2017-10-03 内蒙古大学 A kind of preparation method of the phosphine oxygen part containing ferrocene group
CN108774271A (en) * 2018-02-08 2018-11-09 浙江工业大学 A kind of chiral nitrogen nitrogen phosphine tridentate ligand and its application based on ferrocene frame having ferrocene frame

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HAO ZHENG ET AL.: "Electrochemically driven regioselective C− H phosphorylation of group 8 metallocenes", 《NATURE COMMUNICATIONS》, 17 June 2022 (2022-06-17) *
KORB, MARCUS ET AL.: "Structural Variety of Iron Carbonyl Clusters Featuring Ferrocenylphosphines", 《 EUROPEAN JOURNAL OF INORGANIC CHEMISTRY》, 7 June 2021 (2021-06-07) *

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