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
reaction
electrode
substituent
anode
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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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Dalian Institute of Chemical Physics of CAS
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table

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Abstract

The invention relates to a method for synthesizing ferrocene phosphine oxide compound. Specifically, ferrocene substituent and diaryl phosphine oxide are used as raw materials, and the ferrocene C-H phosphine oxidation reaction is realized under the electric promotion. The invention has the advantages that the unguided ferrocene substituent is directly used as a C-H donor, no additional oxidant or metal catalyst is needed, the condition is mild, the substrate range is wide, and the yield is good.

Description

Method for synthesizing ferrocene phosphine oxide compound
Technical Field
The invention relates to a method for synthesizing ferrocene phosphine oxide compound.
Background
Phosphine compounds with metallocene skeletons are ligands or catalysts with good activity in asymmetric catalytic reactions, and previous ferrocene phosphine oxide compound synthesis methods report that introducing phosphine groups onto ferrocenes generally requires lithium reagents or equivalent lewis acids that are sensitive to air, generally requires cumbersome operations or large amounts of waste to be produced, and generally requires pre-installation of directing groups and additional metal catalysis. The invention takes secondary phosphine oxide and ferrocene substituent without guiding group as raw materials, and realizes the oxidation reaction of metallocene C-H phosphine under the self-catalysis of electric promotion. The reaction has the advantages of wide substrate range, better yield, no need of extra expensive equivalent oxidant and mild condition.
In summary, a method for the direct synthesis of ferrocenyl-skeleton phosphine oxide compounds starting from simple and readily available starting materials, with secondary phosphine oxides as phosphine source and with unguided ferrocene substituents as C-H donors, is described.
Disclosure of Invention
The invention aims to provide a method for synthesizing ferrocene phosphine oxide compound, which is an electro-promoted self-catalyzed C-H phosphine oxidation reaction method of ferrocene.
Reaction equation 1: synthesis of ferrocene phosphine oxide compound
The specific operation steps are as follows (reaction equation 1):
under nitrogen atmosphere, benzoferrocene substituent 1, diaryl phosphine oxide compound 2, electrolyte and solvent were added in a three-necked flask, followed by alkali addition, and the anode and cathode were mounted, with the three-necked flask RVC as anode (length 15 mm. Times. Width 10 mm. Times. Thickness 5 mm), pt as cathode (length 10 mm. Times. Width 10 mm. Times. Thickness 0.3 mm), the distance between the electrodes was 25mm, and the planes of the two electrodes (anode and cathode) in length and height were arranged parallel to each other (the area of the opposing surfaces of the anode and cathode placed in the reaction solution was 85 mm) 2 ). Stirring and reacting for 6h at 50 ℃ under constant current of 4.0mA to generate a target product 3, and spin-drying a solvent after the reaction is finished, wherein the mobile phase is a column chromatography: petroleum ether/ethyl acetate (volume ratio)
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.
The alkali is NaOAc, na 2 CO 3 ，KH 2 PO 4 ，K 2 HPO 4 ，PhCO 2 Na，NaHCO 3 ，NaOPiv，Et 3 One or more of N, TMEDA, py and DMAP, DABCO, DBU. 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.
The electrolyte is 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 ,Na ClO 4 One or two or more of them; 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.
The solvent is one or more of acetone, dichloromethane, acetonitrile, dimethyl sulfoxide, water, ethanol, methanol, tertbentanol, N-dimethylformamide, trifluoroethanol and hexafluoroisopropanol, preferably methanol; the amount of solvent used is 2.0-8.0 ml, preferably 5.0ml, per millimole of ferrocene substituent 1.
The invention has the following advantages:
firstly, taking a secondary phosphine oxide and a ferrocene substituent without a guide group as raw materials, and realizing the oxidation reaction of metallocene C-H phosphine under the electro-promoted self-catalysis. And secondly, the reaction has a wide substrate range, a better yield, no need of an extra expensive equivalent oxidant and mild conditions, and the reaction is more green. Finally, the obtained product ferrocene phosphine oxide compound can be converted into phosphine ligand in one step.
The invention has the advantages that the unguided ferrocene substituent is directly used as a C-H donor, no additional oxidant or metal catalyst is needed, the condition is mild, the substrate range is wide, and the yield is good.
Detailed Description
For a better understanding of the present invention, it is illustrated by the following examples. The starting materials and results for examples 1-11 are shown in Table 1.
TABLE 1 reaction results of various substituted ferrocenes with diphenylphosphinyloxy 2
TABLE 2 reaction results of substituted ferrocenes 1h with different secondary phosphine oxide compounds
Synthesis of raw materials
Synthesis of substituted ferrocene 1 a: ferrous chloride (1.27 g,10 mmol) was placed in a schlenk flask, the atmosphere in the flask was replaced with nitrogen three times, 50mL of anhydrous THF was injected, stirring was carried out overnight to obtain solution a, another schlenk flask was replaced with nitrogen three times, 1,2,3,4, 5-pentamethylcyclopentadiene (1.36 g,10 mol) was injected, cooled to-78 ℃, n-butyllithium (2.4 mol/L,4.6mL,11 mol) was injected, reaction was carried out for 1 hour to obtain solution B, solution B was transferred to solution a, after stirring for 1 hour, cyclopentadienyl sodium solution (2 mol/L,5mL,10 mol) was added, reaction was carried out overnight, column chromatography was carried out, and ferrocene substituent 1a was obtained using petroleum ether as eluent (reference document [1] kang, d.; ricci, f.; white, r.j.; plaxco, k.w.Anal. Chem. 88, 10452-10458).
Ferrocene 1b was commercially available, 1c, 1d, 1e, 1f and 1g ferrocene substituents were all prepared by the methods described above, except that 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-phenethylcyclopentadiene were prepared in equimolar amounts, respectively, in place of 1,2,3,4, 5-pentamethylcyclopentadiene.
Synthesis of secondary phosphine oxide Compound 2 d: magnesium turnings (972.4 mg,40 mmol) were placed in a schlenk flask, the atmosphere in the flask was replaced with nitrogen three times, 10mL of anhydrous THF was injected, 4-chlorobromobenzene (5.74 g,30 mmol) was added dropwise thereto to prepare the corresponding Grignard reagent, the reaction mixture was cooled to 0℃and diethyl phosphite (1.38 g,10 mmol) was added dropwise thereto, stirred for one hour, then reacted overnight at room temperature, column chromatography was performed with ethyl acetate: petroleum ether=2:1 (volume ratio) as eluent gives 2d secondary phosphine oxide compounds (ref [2] molitor, s.; becker, j.; gessner, v.h.j.am.chem.soc.2014,136, 15517-15520).
Synthesis of other secondary phosphine oxide compounds: the secondary phosphine oxide compound 2a was commercially available, and the 2b, 2c and 2e phosphine oxide compounds were all prepared by the above-mentioned method, except that the same procedure and conditions were used as above, except that bromobenzene, 4-methyl bromobenzene and 3, 5-difluorobromobenzene were used in equimolar amounts, respectively, instead of 4-chlorobromobenzene.
Example 1
In a three-necked flask, ferrocene substituent 1 (0.2 mmol), secondary phosphine compound 2 (0.4 mmol), and the like were sequentially added under nitrogen atmosphere, n Bu 4 NOAc(0.2mmol)、Et 3 N (0.4 mmol) and MeOH (5.0 mL) to obtain a reaction solution; placing two electrodes of cathode and anode in a three-mouth bottle, taking RVC electrode as anode, taking sheet Pt electrode as cathode, the distance between the electrodes is 25mm, the planes of two electrodes (anode and cathode) are parallel to each other (the lower parts of cathode and anode are placed in the reaction solution of reaction system, the area of the opposite surfaces of anode and cathode placed in the reaction solution is 85 mm) 2 ). Constant 4.0mA current is introduced between the cathode and the anode, and the reaction is carried out at 50 ℃ for 6 hours; after the reaction is finished, the ferrocene phosphine oxide compound 3a is obtained through column chromatography separation (mobile phase: petroleum ether/ethyl acetate=1:1, v/v), the yield is 71%, and the compound is subjected to infrared, nuclear magnetism (hydrogen spectrum, carbon spectrum and phosphine spectrum) and high-resolution mass spectrum identification structure. The detection data are as follows:
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 )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)； 31 P NMR(162MHz,CDCl 3 )δ28.0；HRMS calculated for C 27 H 29 OPNaFe[M+Na] + 479.1198,found 479.1199 example 2:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were seen, the yield of the column chromatography (mobile phase: petroleum ether/ethyl acetate=1:2) product 3b was 71%, and the structure was identified by infrared, nuclear magnetic (hydrogen, carbon and phosphine) spectra.
The detection data are as follows:
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 C NMR(100MHz,CDCl 3 )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. 31 P NMR(162MHz,CDCl 3 )δ29.0；
this 3b (77.6 mg,0.2 mmol) was dissolved in 2mL of toluene, triethylamine (81.5 mg,0.8 mmol) and trimethylchlorosilane (65.2 mg,0.6 mmol) were added and then reacted under reflux with heating in an oil bath for 18 hours to give phosphine ligand 4 in 99% yield, which was excellent in activity in the selection of construction C-C (ref.3 Laulh, S.; blackburn, J.M.; roizer, J.L.Org.Lett.2016,18, 4440-4443).
Example 3:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were seen, with a yield of 72% for product 3c, and the structure was identified by infrared, nuclear magnetic (hydrogen, carbon and phosphine) and high resolution mass spectrometry.
The detection data are as follows:
3c: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 for C 28 H 31 OPNaFe[M+Na] + 493.1354,found 493.1359
example 4:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were seen, the 3d yield of the product was 64%, and the structure was identified by infrared, nuclear magnetic (hydrogen, carbon and phosphine) and high resolution mass spectrometry.
The detection data are as follows:
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 )δ28.9；HRMS calculated for C 29 H 33 OPNaFe[M+Na] + 507.1511,found 507.1507.
example 5:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were seen, the yield of product 3e was 77%, and the structure was identified by infrared, nuclear magnetic (hydrogen, carbon and phosphine) and high resolution mass spectrometry.
The detection data are as follows:
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.
example 6:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were seen, the yield of product 3f was 63% and the structure was identified by infrared, nuclear magnetic (hydrogen, carbon and phosphine) and high resolution mass spectrometry.
The detection data are as follows:
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 )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. 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.
example 7:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were seen, the 3g yield of the product was 53%, and the structure was identified by infrared, nuclear magnetic (hydrogen, carbon and phosphine) and high resolution mass spectrometry.
The detection data are as follows:
3g:Yellow solid,mp 50.8-51.9℃,57.3mg,52％yield,R f ＝0.40(petroleum ether/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,found 569.1666.
example 8:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were seen, the 3h yield of the product was 40%, and the structure was identified by infrared, nuclear magnetic (hydrogen, carbon and phosphine) and high resolution mass spectrometry.
The detection data are as follows:
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)； 13 C NMR(100MHz,CDCl 3 )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； 31 P NMR(162MHz,CDCl 3 )δ38.6；HRMS calculated for C 27 H 29 O 2 PNaFe[M+Na] + 495.1147,found 495.1145.
example 9:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were seen, with a product 3i yield of 65% and the compounds were subjected to infrared, nuclear magnetic (hydrogen, carbon and phosphine) and high resolution mass spectrometry.
The detection data are as follows:
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 )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； 31 P NMR(162MHz,CDCl 3 )δ28.1；HRMS calculated for C 34 H 35 OPNaFe[M+Na] + 569.1667,found 569.1693.
example 10:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were seen, the yield of product 3j was 72%, and the structure was identified by nuclear magnetism (hydrogen spectrum, carbon spectrum and phosphine spectrum) and high resolution mass spectrometry.
The detection data are as follows:
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.
example 11:
the procedure and conditions were the same as in example 1, except that the differences described in Table 1 were followed, the 3k yield of the product was 60%, and the structure was identified by nuclear magnetism (hydrogen spectrum, carbon spectrum and phosphine spectrum), high resolution mass spectrometry.
The detection data are as follows:
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＝6.8Hz).HRMS calculated for C 32 H 28 OPF 4 Fe[M+H] + 591.1158,found 591.1154.
comparative example: replacing the current with an equivalent amount of oxidant:
a conditions are as follows: 1b (0.20 mmol), 2a (0.40 mmol), n Bu 4 NOAc(0.20mmol),Et 3 n (0.40 mmol), oxidant (0.4 mmol), meOH (4.0 mL), 50 ℃ and 6H. Yield was determined by nuclear magnetic H-spectroscopy with mesitylene as 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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