CN113457746A - Catalyst and preparation method and application thereof - Google Patents

Catalyst and preparation method and application thereof Download PDF

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CN113457746A
CN113457746A CN202110739238.6A CN202110739238A CN113457746A CN 113457746 A CN113457746 A CN 113457746A CN 202110739238 A CN202110739238 A CN 202110739238A CN 113457746 A CN113457746 A CN 113457746A
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silver
bis
catalyst
dichloromethane
ligand
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CN113457746B (en
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徐晨
邢祥友
李成程
金明宇
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Southwest University of Science and Technology
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Abstract

The invention provides a catalyst and a preparation method and application thereof, wherein the structure of the catalyst is shown as a formula I: wherein R is1Selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C4-C12 aryl or substituted or unsubstituted C4-C12 heteroaryl, R2、R3Independently selected from substituted or unsubstituted C1-C12 alkyl or substituted or unsubstituted C4-C12 aryl, X is selected from any one of Cl, Br or I, L‑Selected from the group consisting of counterions. The catalyst provided by the invention has good universality, mild reaction conditions and small usage amount.

Description

Catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of a cyanohydrin hydration catalyst. In particular to a catalyst and a preparation method and application thereof, and especially relates to a catalyst with good universality and a preparation method and application thereof.
Background
The alpha-hydroxyamide compound is widely applied to the preparation of functional polymers, natural products and drug molecules, can be used as a structural unit of a natural product with physiological activity, and is an important organic synthetic intermediate. At present, alpha-hydroxyamide is mainly obtained by strong acid and strong base catalysis, boric acid catalysis and other modes, and has the defects that the application range of a substrate is greatly limited by the tolerance of a functional group, and a large amount of waste materials are generated in the reaction process due to the addition of a large amount of acid and alkali, so that the atom utilization rate is low. The method for directly preparing the alpha-hydroxyamide by hydrating the cyanohydrin has the natural advantages of simple post-reaction treatment, less experimental waste and high atom economy. However, the direct preparation of α -hydroxyamides by hydration of cyanohydrins presents a significant challenge, mainly because cyanohydrins themselves have poor stability and can easily explain the release of HCN poisoning catalysts, especially under alkaline and high temperature conditions. At present, only a few catalysts realize the hydration of the cyanohydrin compounds, but the loading capacity of the catalysts is high, the application range of the substrates is narrow, the application of the catalysts is greatly limited, and the existing alpha-hydroxyamide has low productivity, complex technical route and poor environmental protection, and needs to obtain technical breakthrough.
CN107417562A discloses a novel method for preparing chiral α -hydroxyamides, which is a series of chiral α -hydroxyamide compounds prepared by asymmetric hydrogenation of α -ketoamides with prochiral chirality using a novel tridentate phosphorane ligand, the method comprising: adding prochiral alpha-ketoamide and alkali to perform asymmetric hydrogenation reaction in the presence of a catalyst in a hydrogen atmosphere to obtain chiral alpha-hydroxyamide; the catalyst is obtained by complexing metal iridium salt and a chiral ligand. The ligand used by the method is easy to synthesize, the reaction has the characteristics of high enantioselectivity, high yield and high conversion number, most substrates obtain more than 99% of conversion rate and more than 97% -99% of ee value under the condition that the dosage of the catalyst is one ten thousandth, the highest conversion number reaches 100000, and the method has extremely high industrial value.
The production capacity of alpha-hydroxyamides is low due to the current limitations of catalysts, the technical route is complex and the environmental protection is poor. Therefore, how to provide a catalyst for catalytic synthesis of alpha-hydroxyamide with good universality becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a catalyst, a preparation method and application thereof, in particular to a catalyst with good universality, and a preparation method and application thereof. The catalyst provided by the invention has good universality, mild reaction conditions and small usage amount.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst, the structure of which is shown in formula I:
Figure BDA0003142503040000011
wherein R is1Is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C4-C12 aryl and substituted or unsubstituted C4-C12 heteroaryl, R2、R3Independently selected from substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C4-C12 aryl, X is selected from any one of Cl, Br or I, L-Selected from the group consisting of counterions.
Wherein, C1-C12 respectively represent that the structure contains one carbon atom, two carbon atoms, three carbon atoms, four carbon atoms and the like, and the description is omitted.
The catalyst with the specific structure can catalyze the reaction of the cyanohydrin compound to generate the alpha-hydroxyamide under mild conditions, and has the advantages of high conversion rate, wide substrate application range, good universality and capability of obviously reducing the equivalent weight of the catalyst.
Preferably, said R is1Is selected from
Figure BDA0003142503040000021
Preferably, said R is2Is selected from
Figure BDA0003142503040000022
Figure BDA0003142503040000023
Any one of them.
Preferably, said R is3Is selected from-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、
Figure BDA0003142503040000024
Figure BDA0003142503040000025
Any one of them.
Preferably, the counter ion is selected from OTf-、BF4 -、PF6 -、SbF6 -Or CF3COO-Any one of them.
In a second aspect, the present invention provides a process for the preparation of a catalyst as described above, comprising the steps of:
(1) mixing the precursor and the first ligand for reaction to obtain an intermediate;
(2) and (2) mixing the intermediate obtained in the step (1), a second ligand and a first silver salt for reaction to obtain the catalyst.
Wherein the structure of the precursor, the first ligand, the intermediate and the second ligand is shown as formula II:
Figure BDA0003142503040000026
wherein, X, R1、R2、R3And L-Having the same limitations as described above.
Preferably, the precursor is selected from any one of (1, 5-cyclooctadiene) platinum chloride, (1, 5-cyclooctadiene) platinum bromide or (1, 5-cyclooctadiene) platinum iodide or a combination of at least two of the above.
Preferably, the first ligand is selected from the group consisting of 6, 7-bis (5-methylfuran-2-yl) phosphonyl) naphtho [1,8-de ] [1,3] dioxin, 1, 8-bis (diphenylphosphonyl) naphthalene, 6, 7-bis (diphenylphosphonyl) naphtho [1,8-de ] [1,3] dioxin, 1, 2-bis (diphenylphosphonyl) benzene, 2, 3-bis (diphenylphosphonyl) naphthalene, 1, 2-bis (diphenylphosphino) ethane, 1, 2-bis (5-methylfuran-2-yl) phosphonyl) benzene, (4, 5-dimethoxy-1, 2-phenylene) bis (5-methylfuran-2-yl) phosphine), 1, 2-bis (5-methylfuran-2-yl) phosphonyl) ethane and 2, any one or a combination of at least two of 3-bis (5-methylfuran-2-yl) phosphonyl) naphthalene.
The second ligand is selected from any one of dimethyl phosphine oxide, diethyl phosphine oxide, diisopropyl phosphine oxide, dipropylene phosphorus oxide, dibutyl phosphorus oxide, diphenyl phosphorus oxide, bis (4-methoxyphenyl) phosphine oxide or bis (4- (trifluoromethyl) phenyl) phosphine oxide or a combination of at least two of the two.
Preferably, the first silver salt is selected from any one of silver triflate, silver tetrafluoroborate, silver hexafluoroantimonate, silver hexafluorophosphate or silver trifluoroacetate or a combination of at least two thereof.
Wherein the precursor may be a combination of (1, 5-cyclooctadiene) platinum chloride and (1, 5-cyclooctadiene) platinum bromide, a combination of (1, 5-cyclooctadiene) platinum bromide and (1, 5-cyclooctadiene) platinum iodide, a combination of (1, 5-cyclooctadiene) platinum chloride and (1, 5-cyclooctadiene) platinum iodide, or the like, and the first ligand may be a combination of 6, 7-bis (5-methylfuran-2-yl) phosphonyl) naphtho [1,8-de ] [1,3] dioxin and 1, 8-bis (diphenylphosphinyl) naphthalene, a combination of 1, 8-bis (diphenylphosphinyl) naphthalene and 6, 7-bis (diphenylphosphinyl) naphtho [1,8-de ] [1,3] dioxin, or a combination of 1, 2-bis (diphenylphosphinyl) benzene and 2, 3-bis (diphenylphosphinyl) naphthalene, etc., the second ligand may be a combination of dimethylphosphine oxide and diethylphosphine oxide, a combination of diisopropylphosphine oxide and dipropylphosphine oxide, or a combination of dibutylphosphine oxide and diphenylphosphinyloxy, etc., and the first silver salt may be a combination of silver trifluoromethanesulfonate and silver tetrafluoroborate, a combination of silver hexafluoroantimonate and silver hexafluorophosphate, or a combination of silver tetrafluoroborate and silver hexafluoroantimonate, etc., but is not limited to the above-listed combinations, and other combinations not listed within the above-mentioned combination range are also applicable.
Preferably, the molar ratio of the precursor to the first ligand is from 1:1 to 1: 1.1.
Preferably, the molar ratio of the intermediate to the second ligand is from 1:1 to 1: 1.1.
Preferably, the molar ratio of the intermediate to the first silver salt is from 1:0.9 to 1: 1.1.
Preferably, the temperature of the reaction of step (1) is 20-40 ℃.
Preferably, the temperature of the reaction of step (2) is 20-40 ℃.
Wherein the molar ratio of the precursor to the first ligand may be 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09 or 1:1.1, the molar ratio of the intermediate to the second ligand may be 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09 or 1:1.1, the molar ratio of the intermediate to the first silver salt may be 1:0.9, 1:0.95, 1:1, 1:1.05 or 1:1.1, etc., the reaction temperature in step (1) may be 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 38 ℃, 34 ℃, 38 ℃, or 38 ℃ or the reaction temperature in step (1) may be 20 ℃, 22 ℃, or the reaction temperature may be 20 ℃, 30 ℃ or the reaction temperature in step (1), but not limited to, the above-listed numerical values, and other numerical values not listed in the above numerical range are also applicable.
In a third aspect, the present invention provides the use of a catalyst as described above for the preparation of an α -hydroxy amide compound.
In a fourth aspect, the present invention also provides a method for preparing an α -hydroxyamide compound, said method comprising the steps of: and mixing the catalyst, the second silver salt and the cyanhydrin compound for reaction to obtain the alpha-hydroxy amide compound.
Preferably, the second silver salt is selected from any one or a combination of at least two of silver triflate, silver tetrafluoroborate, silver hexafluoroantimonate, silver hexafluorophosphate or silver trifluoroacetate, such as a combination of silver triflate and silver tetrafluoroborate, a combination of silver hexafluoroantimonate and silver hexafluorophosphate or a combination of silver hexafluorophosphate and silver trifluoroacetate, and the like, but is not limited to the combinations enumerated above, and other combinations not enumerated within the scope of the combinations listed above are equally applicable.
Preferably, the cyanohydrin compound is selected from
Figure BDA0003142503040000031
Figure BDA0003142503040000032
Figure BDA0003142503040000041
Figure BDA0003142503040000042
Any one or a combination of at least two of them.
Preferably, the molar percentage of the catalyst relative to the cyanohydrin compound is from 0.03 to 2 mol%.
Preferably, the molar percentage of the second silver salt relative to the cyanohydrin compound is 0.03 to 2 mol%.
The mole percentage of the catalyst to the cyanohydrin compound may be 0.03 mol%, 0.04 mol%, 0.05 mol%, 0.1 mol%, 0.3 mol%, 0.67 mol%, 0.8 mol%, 1 mol%, 1.2 mol%, 1.4 mol%, 1.6 mol%, 1.8 mol%, or 2 mol%, and the mole percentage of the second silver salt to the cyanohydrin compound may be 0.03 mol%, 0.04 mol%, 0.05 mol%, 0.1 mol%, 0.3 mol%, 0.67 mol%, 0.8 mol%, 1 mol%, 1.2 mol%, 1.4 mol%, 1.6 mol%, 1.8 mol%, or 2 mol%, but is not limited thereto, and other values not listed in the above range are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst with a specific structure provided by the invention can catalyze the reaction of the cyanohydrin compound to generate the alpha-hydroxyamide under a mild condition, has high conversion rate and wide substrate application range, can catalyze various cyanohydrin compounds to hydrolyze into the alpha-hydroxyamide compounds, has good universality, and can obviously reduce the equivalent weight of the catalyst.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
In the following preparation examples and examples, mass spectrometry was performed by using an Agilent 6200Series TOF mass spectrometer, single crystal structure testing was performed by using a Bruker D8venture X-ray diffraction tester, and nuclear magnetic testing was performed by using a Bruker AV III HD 600 spectrometer nuclear magnetic resonance tester.
Preparation example 1
This preparation provides a catalyst a, the structure of which is shown below:
Figure BDA0003142503040000051
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 6, 7-bis (5-methylfuran-2-yl) phosphonyl) naphtho [1,8-de ] [1,3] dioxin in a molar ratio of 1:1 in dichloromethane, stirring at 25 ℃ for 12 hours to obtain a first reaction liquid, filtering the first reaction liquid to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 25 ℃ for 12h to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl phosphorus oxide is 1:1.05, and the molar ratio of the intermediate to the silver trifluoromethanesulfonate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain the catalyst A, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 5. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.96(dd,J＝13.4,8.3Hz,1H),7.77(dq,J＝8.4,2.0Hz,1H),7.12(dd,J＝23.2,8.3Hz,2H),6.70(t,J＝2.3Hz,2H),6.55(t,J＝2.3Hz,2H),6.18–6.02(m,4H),5.65(s,2H),2.33(d,J＝27.0Hz,12H),1.98–1.78(m,6.0Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ162.0(dd,J＝7.1,3.6Hz),161.8(d,J＝6.3Hz),155.7,141.3(t,J＝4.3Hz),140.7(d,J＝8.3Hz),139.5(d,J＝27.5Hz),138.7(d,J＝2.9Hz),128.5(d,J＝18.1Hz),127.6(dd,J＝18.2,3.6Hz),117.3,(t,J＝11.0Hz),111.47(d,J＝9.7Hz),111.05(d,J＝12.1Hz),109.72(d,J＝8.1Hz),108.91(d,J＝7.8Hz),91.8,20.4(d,J＝39.4Hz),15.1ppm；
31P NMR(243MHz,CD2Cl2):δ96.0(dd,2Jp-p＝456.8,9.72Hz,1JPt-P＝2891.7Hz),-23.4(dd,2Jp-p＝454.4,38.9Hz,1JPt-P＝1946.4Hz),-33.1(dt,2Jp-p＝38.9,9.72Hz,1JPt-P＝3146.9Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C33H33ClO7P3Pt[M-OTf]+:864.0772,found 864.0770；
P’-Pt-P(Me2OH)＝167.52°，P-Pt-P’＝91.69°，Cl-Pt-P(Me2OH)＝89.35°。
preparation example 2
This preparation example provides a catalyst B, the structure of which is shown below:
Figure BDA0003142503040000052
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1, 2-bis (diphenylphosphinyl) benzene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst B, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.75–7.56(m,16H),7.53–7.50(m,8H),1.72(dd,J＝12.0,6.0Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ143.5(dq,J＝36.3,3.1Hz),138.0(q,J＝26.1Hz),133.8(d,J＝12.0Hz),134.2(d,J＝11.3Hz),134.1,133.0(d,J＝2.2Hz),132.6(d,J＝2.8Hz),129.7(t,J＝10.9Hz),128.1(dd,J＝57.4Hz),127.6(d,J＝67.7Hz),120.8(d,J＝319.5Hz,CF3SO3 -),18.9(dd,J＝36.6,4.9Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ100.6(dd,2Jp-p＝445.9,17.0Hz,1JPt-P＝2868.6Hz),50.2(dd,2Jp-p＝443.5,4.9Hz,1JPt-P＝2084.9Hz),42.2(dd,2Jp-p＝17.0,4.9Hz,1JPt-P＝3542.9Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C32H31ClOP3Pt[M-OTf]+:754.0919,found 754.0919；
P’-Pt-P(Me2OH)＝176.0°，P-Pt-P’＝87.0°，Cl-Pt-P(Me2OH)＝90.4°。
preparation example 3
This preparation provides a catalyst C, the structure of which is shown below:
Figure BDA0003142503040000061
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1, 2-bis (diphenylphosphino) ethane in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst C, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.85(dd,J＝13.0,7.4Hz,4H),7.71(dd,J＝12.2,7.6Hz,4H),7.66(t,J＝6.8Hz,2H),7.56(dt,J＝7.9,5.1Hz,6H),7.45(td,J＝7.7,2.5Hz,2H),4.47(d,J＝32.7Hz,4H),4.24(d,J＝2.3Hz,2H),4.11(d,J＝2.7Hz,2H),1.45(dd,J＝10.6,2.5Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.2(d,J＝11.2Hz),134.5(d,J＝11.8Hz),133.7(d,J＝2.2Hz),132.3(d,J＝2.7Hz),129.9(d,J＝11.6Hz),128.9(d,J＝10.9Hz),76.5(d,J＝10.3Hz),76.3(d,J＝11.5Hz),75.5(d,J＝7.7Hz),75.0(d,J＝8.6Hz),19.0(dd,J＝41.4,5.0Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ90.4(dd,2Jp-p＝448.3,19.4Hz,1JPt-P＝2614.7Hz),20.2(dd,2Jp-p＝445.9,9.7Hz,1JPt-P＝2291.5Hz),10.2(dd,2Jp-p＝20.4,14.8Hz,1JPt-P＝3837.0Hz)ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt+[M-SbF6 -]+:862.0581,found 862.0576。
preparation example 4
This preparation example provides a catalyst D, the structure of which is shown below:
Figure BDA0003142503040000071
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, diphenyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain a catalyst D, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2)δ7.86(dd,J＝11.8,7.6Hz,4H),7.71(dd,J＝13.0,7.6Hz,4H),7.58(dd,J＝7.5,2.0Hz,2H),7.51(td,J＝7.7,2.5Hz,4H),7.47–7.38(m,8H),7.28(dt,J＝36.0,5.0Hz,8H),4.60(s,2H),4.51(d,J＝2.3Hz,2H),4.34(t,J＝1.9Hz,2H),3.85(q,J＝1.9Hz,2H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.3(d,J＝10.8Hz),134.9(d,J＝11.5Hz),132.4(d,J＝12.1Hz),131.9(d,J＝2.6Hz),128.9(d,J＝10.9Hz),128.7(d,J＝11.9Hz),128.4(d,J＝12.0Hz),120.8(q,J＝320.3Hz,CF3SO3 -),76.6(d,J＝11.3Hz),75.8(d,J＝9.8Hz),74.9(d,J＝8.5Hz),74.5(d,J＝7.0Hz),69.9(d,J＝58.4Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ81.6(dd,2Jp-p＝481.14Hz,1JPt-P＝2971.89Hz),21.3(dd,2Jp-p＝481.14Hz,1JPt-P＝2208.87Hz),15.0(dd,2Jp-p＝21.87Hz,1JPt-P＝3807.81Hz)ppm；
19F NMR(565MHz,CD2Cl2)δ-78.9ppm；
HRMS(ESI+):calc’d for C46H39ClFeOP3Pt+[M-OTf]+:986.0894,found 986.0890。
preparation example 5
This preparation provides a catalyst E, the structure of which is shown below:
Figure BDA0003142503040000072
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1, 8-bis (5-methylfuran-2-yl) phosphino) naphthalene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain a catalyst E, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ8.22(dd,J＝11.9,8.3Hz,2H),7.98(dd,J＝13.8,7.4,Hz,1H),7.78(dd,J＝16.8,7.4Hz,1H),7.64(dt,J＝18.6,7.6Hz,2H),6.71(s,2H),6.51(s,2H),6.10(d,J＝8.4Hz,2H),2.31(d,J＝30.0Hz,12H),1.86(d,J＝10.7Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ162.1(d,J＝7.8Hz),161.9(d,J＝6.2Hz),139.4,139.2(d,J＝4.3Hz),138.7(d,J＝7.6Hz),138.5,136.5,136.2,136.1,128.7(d,J＝17.8Hz),127.8(dd,J＝17.8,9.2Hz),127.4(dd,J＝23.7,10.9Hz).109.8(d,J＝7.6Hz),109.0(d,J＝7.8Hz),20.4(dd,J＝39.1,5.4Hz),15.1ppm；
31P NMR(243MHz,CD2Cl2):δ96.2(dd,2Jp-p＝449.5,7.3Hz,1JPt-P＝2886.8Hz),-23.4(dd,2Jp-p＝432.5,38.9Hz,1JPt-P＝1934.3Hz),-33.7(dd,2Jp-p＝38.9,7.3Hz,1JPt-P＝3397.1Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C32H33ClO5P3Pt[M-OTf]+:820.0872,found 820.0870。
preparation example 6
This preparation provides a catalyst F, the structure of which is shown below:
Figure BDA0003142503040000081
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,2- (bis (5-methylfuran-2-yl) phosphonyl) benzene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction liquid, filtering the first reaction liquid to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain a catalyst F, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CDCl3):δ8.20(t,J＝8.0Hz,1H),7.81(t,J＝8.0Hz,1H),7.68–7.63(m,2H),7.18(t,J＝2.9Hz,2H),7.13(t,J＝2.9Hz,2H),6.19(d,J＝23.0Hz,4H),2.36(d,J＝10.6Hz,12H),1.92(dd,J＝11.1,2.7Hz,6H)ppm；
13C NMR(151MHz,CDCl3):δ161.1(d,J＝5.3Hz),160.7(d,J＝6.3Hz),138.1(d,J＝4.8Hz),137.5(d,J＝5.2Hz),134.3(d,J＝15.1Hz),133.4(dt,J＝11.7,7.0Hz),128.0(d,J＝22.6Hz),126.9(d,J＝19.7Hz),δ120.5(d,J＝319.7Hz,CF3SO3 -),108.95(d,J＝8.4Hz),108.61(d,J＝8.7Hz),19.0(dd,J＝38.0,5.4Hz),14.2(d,J＝16.8Hz)ppm；
31P NMR(243MHz,CDCl3):δ97.8(q,2Jp-p＝466.6,14.6Hz,1JPt-P＝2908.7Hz),14.4(dd,2Jp-p＝469.0,4.9Hz,1JPt-P＝2092.2Hz),2.9(dd,2Jp-p＝14.6,4.9Hz,1JPt-P＝3319.4Hz)ppm；
19F NMR(565MHz,CDCl3):δ-78.3ppm；
HRMS(ESI+):calc’d for C28H31ClO5P3Pt[M-OTf]+:770.0715,found 770.0712。
preparation example 7
This preparation example provides a catalyst G, the structure of which is shown below:
Figure BDA0003142503040000091
the preparation method comprises the following steps:
dissolving (1, 5-cyclooctadiene) platinum chloride and 6, 7-bis (diphenylphosphinyl) naphtho [1,8-de ] [1,3] dioxin in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction liquid, filtering the first reaction liquid to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain a catalyst G, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.54–7.37(m,6H),7.35–7.21(m,16H),6.98(dd,J＝10.1,8.1Hz,2H),5.63(s,2H),1.71(d,J＝10.6Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ155.5(d,J＝23.3Hz),142.0(t,J＝4.6Hz),141.5(d,J＝7.3Hz),140.53(dd,J＝15.1,12.2Hz),135.2(d,J＝10.9Hz),134.8(d,J＝11.8Hz),133.5(t,J＝3.6Hz),132.8(d,J＝2.0Hz),130.3(dd,J＝12.1,3.3Hz),130.0(d,J＝11.6Hz),129.3,128.9,117.4(t,J＝9.7Hz),111.4(d,J＝8.8Hz),110.8(d,J＝11.1Hz),20.3(dt,J＝38.1,5.7Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ96.1(d,2Jp-p＝437.4Hz,1JPt-P＝2920.9Hz),7.3(dd,2Jp-p＝437.4,38.9Hz,1JPt-P＝1941.6Hz),5.1(d,2Jp-p＝38.9Hz,1JPt-P＝3450.6Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C37H33ClO3P3Pt[M-OTf]+:848.0972,found 848.0973。
preparation example 8
This preparation example provides a catalyst H, the structure of which is shown below:
Figure BDA0003142503040000101
dissolving (1, 5-cyclooctadiene) platinum chloride and 1, 8-bis (diphenylphosphinyl) naphthalene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction liquid, filtering the first reaction liquid to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoromethanesulfonate in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst H, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ8.13(m,2H),7.55–7.40(m,8H),7.37–7.24(m,16H),1.68(dd,J＝10.7,2.4Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ139.6(t,J＝4.3Hz),139.2(d,J＝6.7Hz),138.1(dd,J＝12.9,10.3Hz),136.2(t,J＝7.6Hz),136.0(d,J＝10.2Hz),135.4(d,J＝11.5Hz),135.0(d,J＝11.8Hz),133.6(d,J＝3.1Hz),132.9(d,J＝2.9Hz),130.3(d,J＝12.2Hz),130.0(d,J＝11.5Hz),129.1,128.7,127.2(dd,J＝31.9,10.1Hz),20.1(dd,J＝37.7,4.6Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ96.5(dd,2Jp-p＝433.8,7.3Hz,1JPt-P＝2891.7Hz),6.98(dd,2Jp-p＝432.5,38.9Hz,1JPt-P＝1934.3Hz),5.3(dd,2Jp-p＝38.9,7.3Hz,1JPt-P＝3423.9Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.0ppm；
HRMS(ESI+):calc’d for C36H33ClOP3Pt[M-OTf]+:804.1081,found 804.1083。
preparation example 9
This preparation provides a catalyst I, the structure of which is shown below:
example (b)
Figure BDA0003142503040000102
Dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and bis (trifluoromethanesulfonyl) imide silver salt in dichloromethane, and stirring at 40 ℃ for 4 hours to obtain a second reaction solution, wherein the molar ratio of the intermediate to dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain the catalyst I, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.87(dd,J＝12.9,7.8Hz,4H),7.74(dd,J＝12.9,7.8Hz,4H),7.68–7.62(m,2H),7.60–7.54(m,6H),7.47(td,J＝7.8,2.3Hz,4H),4.49(d,J＝1.9Hz,2H),4.40(d,J＝1.9Hz,2H),4.30(d,J＝2.0Hz,2H),4.06(d,J＝2.0Hz,2H),1.54(dd,J＝10.8,2.5Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.29(d,J＝11.2Hz),134.52(d,J＝11.8Hz),133.20(d,J＝2.7Hz),132.17(d,J＝2.7Hz),129.55(d,J＝11.8Hz),128.84(d,J＝10.4Hz),120.2(d,J＝321.5Hz,CF3),76.38(d,J＝10.2Hz),76.11(d,J＝11.4Hz),75.29(d,J＝7.5Hz),74.74(d,J＝8.2Hz),19.10(dd,J＝41.0,5.0Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ93.0(dd,2Jp-p＝458.0,4.9Hz,1JPt-P 2700.9Hz),23.8(dd,2Jp-p＝459.3,14.6Hz,1JPt-P＝1807.9Hz),14.3(dd,2Jp-p＝14.6,4.9Hz,1JPt-P＝3841.8Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-79.3ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt[M-N(Tf)2 -]+:862.0581,found 862.0575。
preparation example 10
This preparation provides a catalyst J, the structure of which is shown below:
Figure BDA0003142503040000111
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoroacetate in dichloromethane, and stirring for 4 hours at 40 ℃ to obtain a second reaction liquid, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst J, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.93(dd,J＝12.9,7.6Hz,4H),7.77(dd,J＝11.7,7.7Hz,4H),7.59(t,J＝7.1Hz,2H),7.55–7.51(m,6H),7.47–7.44(m,4H),4.45(s,2H),4.40(s,2H),4.30(s,2H),3.96(s,2H),1.76(d,J＝11.7Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ160.6(q,J＝35.2Hz),135.4(d,J＝11.2Hz),134.7(d,J＝11.7Hz),132.2(d,J＝2.7Hz),131.7(d,J＝2.4Hz),128.76(d,J＝11.7Hz),128.6(d,J＝10.7Hz),116.8(q,J＝295.1Hz,CF3),76.0(d,J＝10.6Hz),75.7(d,J＝10.4Hz),74.8(d,J＝7.0Hz),74.0(d,J＝7.7Hz),20.0(dd,J＝41.5,5.6Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ56.4(t,2Jp-p＝17.6Hz,1JPt-P＝3589.1Hz),24.1(dd,2Jp-p＝459.3,17.0Hz,1JPt-P＝2058.2Hz),15.7(t,2Jp-p＝17.0Hz,1JPt-P＝4009.5Hz)ppm；
19F NMR(565MHz,CD2Cl2):δ-76.0ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt[M-CF3COO-]+:862.0581,found 862.0573。
preparation example 11
This preparation provides a catalyst K, the structure of which is shown below:
Figure BDA0003142503040000121
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver trifluoroacetate in dichloromethane, and stirring for 4 hours at 40 ℃ to obtain a second reaction liquid, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain the catalyst K, wherein the volume ratio of the dichloromethane to the n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.88(dd,J＝12.9,7.6Hz,4H),7.76(dd,J＝11.9,7.6Hz,4H),7.59(td,J＝7.3,1.8Hz,2H),7.56–7.50(m,6H),7.46(td,J＝7.8,2.4Hz,4H),4.48(s,2H),4.38(s,2H),4.35(s,2H),4.02(s,2H),1.58(d,J＝11.3Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.4(d,J＝11.1Hz),134.6(d,J＝11.7Hz),132.5(d,J＝2.8Hz),131.9(d,J＝2.6Hz),129.0(d,J＝11.8Hz),128.7(d,J＝10.1Hz),76.1(d,J＝10.6Hz),75.8(d,J＝10.7Hz),75.1(d,J＝7.3Hz),74.3(d,J＝7.9Hz),19.3(dd,J＝41.0,4.9Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ87.4(dd,2Jp-p＝469.0,19.4Hz,1JPt-P＝2790.8Hz),24.0(dd,2Jp-p＝467.8,17.0Hz,1JPt-P＝2182.1Hz),15.3(t,2Jp-p＝17.0Hz,1JPt-P＝3873.4Hz),-19.4,-144.5ppm；
19F NMR(565MHz,CD2Cl2):δ-72.8,-74.1,-81.6,-83.3ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt[M-PF6 -]+:862.0581,found 862.0577。
preparation example 12
This preparation example provides a catalyst L, the structure of which is shown below:
Figure BDA0003142503040000122
dissolving (1, 5-cyclooctadiene) platinum chloride and 1,1' -bis (diphenylphosphino) ferrocene in a molar ratio of 1:1 in dichloromethane, stirring at 40 ℃ for 4 hours to obtain a first reaction solution, filtering the first reaction solution to obtain a filtrate, carrying out reduced pressure distillation on the filtrate to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the solid, and recrystallizing to obtain an intermediate, wherein the volume ratio of dichloromethane to n-hexane is 1: 1; dissolving the obtained intermediate, dimethyl phosphorus oxide and silver hexafluoroantimonate in dichloromethane, and stirring for 4 hours at 40 ℃ to obtain a second reaction solution, wherein the molar ratio of the intermediate to the dimethyl hydroxyl phosphorus is 1:1.05, and the molar ratio of the intermediate to the silver tetrafluoroborate is 1: 1; and filtering the second reaction solution to obtain a filtrate, distilling the filtrate under reduced pressure to obtain a solid, dissolving the solid in dichloromethane, adding n-hexane into the dichloromethane, and recrystallizing to obtain a catalyst L, wherein the volume ratio of dichloromethane to n-hexane is 1: 2. The characterization data are as follows:
1H NMR(600MHz,CD2Cl2):δ7.85(dd,J＝13.0,7.4Hz,4H),7.71(dd,J＝12.2,7.6Hz,4H),7.66(t,J＝6.8Hz,2H),7.56(dt,J＝7.9,5.1Hz,6H),7.45(td,J＝7.7,2.5Hz,2H),4.47(d,J＝32.7Hz,4H),4.24(d,J＝2.3Hz,2H),4.11(d,J＝2.7Hz,2H),1.45(dd,J＝10.6,2.5Hz,6H)ppm；
13C NMR(151MHz,CD2Cl2):δ135.2(d,J＝11.2Hz),134.5(d,J＝11.8Hz),133.7(d,J＝2.2Hz),132.3(d,J＝2.7Hz),129.9(d,J＝11.6Hz),128.9(d,J＝10.9Hz),76.5(d,J＝10.3Hz),76.3(d,J＝11.5Hz),75.5(d,J＝7.7Hz),75.0(d,J＝8.6Hz),19.0(dd,J＝41.4,5.0Hz)ppm；
31P NMR(243MHz,CD2Cl2):δ90.4(dd,2Jp-p＝448.3,19.4Hz,1JPt-P＝2614.7Hz),20.2(dd,2Jp-p＝445.9,9.7Hz,1JPt-P＝2291.5Hz),10.2(dd,2Jp-p＝20.4,14.8Hz,1JPt-P＝3837.0Hz)ppm；
HRMS(ESI+):calc’d for C36H35ClFeOP3Pt[M-SbF6 -]+:862.0581,found 862.0576。
examples 1 to 45
Examples 1-45 provide methods for preparing 45 α -hydroxy amide compounds, respectively, comprising the steps of:
dissolving the catalysts A-L obtained in the preparation examples 1-11 and silver salt corresponding to counter ions in a mixed solution of tetrahydrofuran and water, uniformly mixing, adding a cyanohydrin compound A1, and stirring at the temperature represented by C1 for 4 hours to obtain an alpha-hydroxyamide compound, wherein the molar percentage of the catalysts A-L relative to a nitrile-based compound is B1, the molar percentage of the silver salt corresponding to the counter ions relative to the cyanohydrin compound is B2, and the volume ratio of the tetrahydrofuran to the water is D1; adding water into the alpha-hydroxyamide compound to obtain a dispersion, extracting the dispersion for 2 times by using ethyl acetate, and separating to obtain an organic solution; adding saturated salt solution into the organic solution to wash the organic solution, and then adding anhydrous sodium sulfate into the organic solution to dry the organic solution; filtering the washed and dried organic solution to obtain a filtrate; and carrying out reduced pressure distillation on the filtrate to obtain an alpha-hydroxy amide compound solid, and recrystallizing the alpha-hydroxy amide compound solid by adopting dichloromethane and normal hexane to obtain a purified alpha-hydroxy amide compound.
The raw materials and the mixture ratio and the preparation parameters used in the examples are as follows:
Figure BDA0003142503040000131
Figure BDA0003142503040000141
Figure BDA0003142503040000151
Figure BDA0003142503040000161
Figure BDA0003142503040000171
Figure BDA0003142503040000181
the yields of the hydration of the cyanohydrin compound to the α -hydroxy amide compound and the number of substrate molecules per active site (TON) converted in examples 1 to 45 using the catalysts a to L were measured, and the results are as follows. Wherein, the yield is obtained by a recrystallization method, and the number of the substrate molecules converted per unit active site is obtained by a method of dividing the mole number of the product by the mole number of the catalyst:
Figure BDA0003142503040000182
Figure BDA0003142503040000191
Figure BDA0003142503040000201
the characterization data of the α -hydroxyamide compounds obtained in the above examples 1-45 are shown below:
Figure BDA0003142503040000202
Figure BDA0003142503040000211
Figure BDA0003142503040000221
Figure BDA0003142503040000231
Figure BDA0003142503040000241
Figure BDA0003142503040000251
Figure BDA0003142503040000261
Figure BDA0003142503040000271
Figure BDA0003142503040000281
Figure BDA0003142503040000291
the results show that the catalyst provided by the invention has high conversion rate and wide substrate application range, can catalyze various cyanohydrin compounds to hydrolyze into alpha-hydroxy amide compounds, and has low reaction temperature and mild reaction conditions.
The applicant states that the catalyst, the preparation method and the application thereof are illustrated by the above examples, but the invention is not limited to the above examples, i.e. the invention does not mean that the invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

Claims (10)

1. A catalyst, wherein the structure of the catalyst is shown in formula I:
Figure FDA0003142503030000011
wherein R is1Is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C4-C12 aryl and substituted or unsubstituted C4-C12 heteroaryl, R2、R3Independently selected from substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C4-C12 aryl, X is selected from any one of Cl, Br or I, L-Selected from the group consisting of counterions.
2. The catalyst of claim 1, wherein R is1Is selected from
Figure FDA0003142503030000012
Preferably, said R is2Is selected from
Figure FDA0003142503030000013
Figure FDA0003142503030000014
Any one of them;
preferably, said R is3Is selected from-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、
Figure FDA0003142503030000015
Figure FDA0003142503030000016
Any one of them;
preferably, the counter ion is selected from OTf-、BF4 -、PF6 -、SbF6 -Or CF3COO-Any one of them.
3. A method for preparing a catalyst according to claim 1 or 2, characterized in that it comprises the following steps:
(1) mixing the precursor and the first ligand for reaction to obtain an intermediate;
(2) mixing the intermediate obtained in the step (1), a second ligand and a first silver salt for reaction to obtain the catalyst;
wherein the structure of the precursor, the first ligand, the intermediate and the second ligand is shown as formula II:
Figure FDA0003142503030000017
wherein, X, R1、R2、R3And L-Having the same limits as in claim 1 or 2.
4. The method for preparing a catalyst according to claim 3, wherein the precursor is selected from any one of (1, 5-cyclooctadiene) platinum chloride, (1, 5-cyclooctadiene) platinum bromide, or (1, 5-cyclooctadiene) platinum iodide or a combination of at least two thereof;
preferably, the first ligand is selected from the group consisting of 6, 7-bis (5-methylfuran-2-yl) phosphonyl) naphtho [1,8-de ] [1,3] dioxin, 1, 8-bis (diphenylphosphonyl) naphthalene, 6, 7-bis (diphenylphosphonyl) naphtho [1,8-de ] [1,3] dioxin, 1, 2-bis (diphenylphosphonyl) benzene, 2, 3-bis (diphenylphosphonyl) naphthalene, 1, 2-bis (diphenylphosphino) ethane, 1, 2-bis (5-methylfuran-2-yl) phosphonyl) benzene, (4, 5-dimethoxy-1, 2-phenylene) bis (5-methylfuran-2-yl) phosphine), 1, 2-bis (5-methylfuran-2-yl) phosphonyl) ethane and 2, any one or a combination of at least two of 3-bis (5-methylfuran-2-yl) phosphonyl) naphthalene;
the second ligand is selected from any one of dimethyl phosphine oxide, diethyl phosphine oxide, diisopropyl phosphine oxide, dipropylene phosphorus oxide, dibutyl phosphorus oxide, diphenyl phosphorus oxide, bis (4-methoxyphenyl) phosphine oxide or bis (4- (trifluoromethyl) phenyl) phosphine oxide or a combination of at least two of the two.
5. The method for preparing a catalyst according to claim 3 or 4, wherein the first silver salt is selected from any one of silver triflate, silver tetrafluoroborate, silver hexafluoroantimonate, silver hexafluorophosphate or silver trifluoroacetate or a combination of at least two thereof.
6. The method for preparing a catalyst according to any one of claims 3 to 5, wherein the molar ratio of the precursor to the first ligand is from 1:1 to 1: 1.1;
preferably, the molar ratio of the intermediate to the second ligand is 1:1 to 1: 1.1;
preferably, the molar ratio of the intermediate to the first silver salt is from 1:0.9 to 1: 1.1.
7. The method for preparing a catalyst according to any one of claims 3 to 6, wherein the temperature of the reaction of step (1) is 20 to 40 ℃;
preferably, the temperature of the reaction of step (2) is 20-40 ℃.
8. Use of a catalyst according to claim 1 or 2 for the preparation of an α -hydroxy amide compound.
9. A method for producing an α -hydroxyamide compound, said method comprising the steps of: mixing the catalyst of claim 1 or 2, a second silver salt, and a cyanohydrin compound to obtain the α -hydroxyamide compound.
10. The method for producing an α -hydroxyamide compound according to claim 9, wherein said second silver salt is selected from any one of or a combination of at least two of silver triflate, silver tetrafluoroborate, silver hexafluoroantimonate, silver hexafluorophosphate and silver trifluoroacetate;
preferably, the cyanohydrin compound is selected from
Figure FDA0003142503030000021
Figure FDA0003142503030000022
Figure FDA0003142503030000031
Figure FDA0003142503030000032
Any one or a combination of at least two of them;
preferably, the molar percentage of the catalyst relative to the cyanohydrin compound is from 0.03 to 2 mol%;
preferably, the molar percentage of the second silver salt relative to the cyanohydrin compound is 0.03 to 2 mol%.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9506389D0 (en) * 1995-03-29 1995-05-17 King S College London Catalyst and process for preparing amides
AU1281197A (en) * 1995-12-06 1997-06-27 Union Carbide Chemicals & Plastics Technology Corporation Improved metal-ligand complex catalyzed processes
CN110642895A (en) * 2018-06-27 2020-01-03 南方科技大学 Catalyst, process for producing the same, and process for producing amide compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9506389D0 (en) * 1995-03-29 1995-05-17 King S College London Catalyst and process for preparing amides
AU1281197A (en) * 1995-12-06 1997-06-27 Union Carbide Chemicals & Plastics Technology Corporation Improved metal-ligand complex catalyzed processes
CN110642895A (en) * 2018-06-27 2020-01-03 南方科技大学 Catalyst, process for producing the same, and process for producing amide compound

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Title
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