Method for isomerizing trans-1, 2-diarylethene into cis-1, 2-diarylethene

Abstract

The invention discloses a method for isomerizing trans-1, 2-diarylethene into cis-1, 2-diarylethene, and belongs to the technical field of organic synthesis.The method comprises the steps that in an organic solvent, trans-1, 2-diarylethene serves as a substrate, a rhodium complex serves as a catalyst, an isomerization reaction is conducted in the air atmosphere under visible blue light irradiation, and the cis-1, 2-diarylethene is obtained; the catalyst is 1, 2-diarylethene; the rhodium complex is a pentamethyl cyclopentadienyl rhodium complex coordinated with an eta < 6 >-aromatic ring or a derivative of the pentamethyl cyclopentadienyl rhodium complex; the method is easy to operate, inert gas protection is not needed, additional additives are not needed, the trans-1, 2-diarylethene raw material is rich in source and relatively low in price, and the rhodium complex catalyst can be recycled and accords with the concept of green chemistry. The method provided by the invention provides an efficient and reliable path for the acquisition of cis-1, 2-diarylethene.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene. Background Art

[0002] At present, in organic reactions carried out under light conditions, the metal catalysts used are mainly concentrated on organic ligand-metal complexes with ruthenium or iridium as the central metal (Prier, CK; Randic, DA; MacMillan, DWC Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis. Chem. Rev. 2013, 113, 5322-5363.). 6 -The photochemical properties of metal complexes coordinated by aromatic rings (with a coordination Haptor number of 6) have not been fully developed. The application of such metal complexes in photochemical transformation is mainly concentrated in photolysis reactions, that is, aromatic rings coordinated to metals in the form of a coordination Haptor number of 6 dissociate under light conditions to obtain aromatic compounds without metal coordination (McGrew, GI; Temaismithi, J.; Carroll, PJ; Walsh, PJ Synthesis of Polyarylated Methanes through Cross-Coupling of Tricarbonylchromium-Activated Benzyllithiums. Angew. Chem., Int. Ed. 2010, 49, 5541-5544.). However, in such reactions, stoichiometric organometallic reagents must be used, which is not in line with the concept of green chemistry.

[0003] On the other hand, olefins are an important structural unit in the field of organic chemistry, and most reactions for synthesizing olefin compounds tend to obtain thermodynamically more stable trans (E) olefins (such as Chinese patent documents with publication numbers CN118146061A and CN111978142A, etc.), while cis (Z) olefins, as a type of thermodynamically less stable structure, have relatively few synthesis methods. Therefore, the isomerization reaction of olefins under light conditions is a very important reaction, and trans (E) olefins can be used as starting materials to prepare thermodynamically more unstable cis (Z) olefins. Cis (Z) olefins have important applications in the fields of medicine, agriculture, and organic synthesis, and can be used as intermediates for the synthesis of drugs and functional chemicals.

[0004] A Chinese patent document with publication number CN116251580A discloses a chromium-based catalyst and its application in the cis-trans isomerization reaction of olefins. The invention develops a specific chromium-based catalyst, which can simultaneously improve the conversion rate of raw materials and the selectivity of products in the cis-trans isomerization reaction of olefins, especially the isomerization reaction of trans olefins to cis olefins. However, the preparation method of the chromium-based catalyst is complicated and the raw material types are many.

[0005] In the prior art, there is no use of sandwich type η 6 -Aromatic ring-coordinated metal complexes are reported as catalysts for the isomerization of trans (E) olefins to cis (Z) olefins under light irradiation. Summary of the invention

[0006] The invention provides a method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene. The method is simple and efficient, and can realize efficient conversion of trans (E) olefins to cis (Z) olefins under light conditions.

[0007] The specific technical solutions adopted are as follows:

[0008] A method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene, comprising:

[0009] In an organic solvent, trans-1,2-diarylethene is used as a substrate and a rhodium complex is used as a catalyst. An isomerization reaction is carried out in an air atmosphere under visible blue light irradiation to obtain cis-1,2-diarylethene; the rhodium complex is η 6 - Aromatic ring coordinated pentamethylcyclopentadienyl rhodium complex or its derivatives;

[0010] The structure of trans-1,2-diarylethene is shown in formula (I) (trans E structure):

[0011]

[0012] In formula (I), Ar 1 and Ar 2 The same or different, each independently is phenyl, substituted phenyl or heteroaryl.

[0013] Taking into account the easy availability of raw materials, preferably, in formula (I), in the substituted phenyl group, the substituent of the phenyl group is a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxyl group, a halogen atom, an ester group, an acyl group, a cyano group or a trifluoromethoxy group.

[0014] The reaction principle of the method of the present invention is: 6-Aromatic ring coordinated pentamethylcyclopentadienyl rhodium complex or its derivative is used as a catalyst, which can form an electron donor acceptor (EDA) complex with trans-1,2-diarylethene, and form an excited state EDA complex under the irradiation of visible blue light. The excited state complex will release the first triplet excited state intermediate of diarylethene after relaxation, and the intermediate will further isomerize to cis-1,2-diarylethene, while releasing the ground state rhodium catalyst to participate in the next catalytic cycle.

[0015] The coordinating anion of the rhodium complex (X - ) is trifluoromethanesulfonate ion (OTf - ), bis(trifluoromethylsulfonyl)imide ion (NTf2 - ), tetrafluoroborate ion (BF4 - ), hexafluoroantimonate ion (SbF6 - ), hexafluorophosphate ion (PF6 - ), methanesulfonate (OMs - ) or p-toluenesulfonate (OTs - ).

[0016] Preferably, the structural formula of the rhodium complex is any one of the following:

[0017]

[0018] Among them, X - Same definition as above.

[0019] Most preferably, the structural formula of the rhodium complex is Coordinate anion X - is the trifluoromethanesulfonate ion OTf - or bis(trifluoromethylsulfonyl)imide ion NTf2 - .

[0020] Preferably, the organic solvent is at least one of nitromethane, acetonitrile, acetone, ethyl acetate and tetrahydrofuran; based on the molar amount of trans-1,2-diarylethene, the amount of the organic solvent is 0.5-10 L / mol; more preferably, the amount of the organic solvent is 1-10 L / mol.

[0021] Preferably, the wavelength range of the visible blue light is 380-500 nm, and the irradiation power of the visible blue light is 10-100 W.

[0022] Preferably, the reaction temperature of the isomerization reaction is 0-40°C, and the reaction time is 12-36h; more preferably, the reaction temperature is 25°C, and the reaction time is 24-36h.

[0023] Considering the yield and cost, preferably, the molar ratio of the rhodium complex to trans-1,2-diarylethene diarylethene is 1:10-50, more preferably 1:20-50.

[0024] Furthermore, after the isomerization reaction is completed, the reaction solution is concentrated and separated by silica gel column chromatography to obtain thermodynamically unstable cis-1,2-diarylethene.

[0025] The reaction equation of the method of the present invention can be expressed as follows:

[0026]

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) In the present invention, n 6 The preparation method of the aromatic ring coordinated pentamethylcyclopentadienyl rhodium complex and its derivatives is simple and efficient, and is prepared by a one-step reaction using commercially available raw materials, and is easy to operate and handle.

[0029] (2) The present invention utilizes η 6 -Aromatic ring coordinated pentamethylcyclopentadienyl rhodium complexes and their derivatives are used as catalysts to catalyze the isomerization reaction of diarylethenes and can be used to prepare thermodynamically unstable cis (Z) diarylethenes.

[0030] (3) The isomerization reaction of diarylethenes in the present invention is simple to operate, does not require inert gas protection, and does not require additional additives. The reaction can be carried out efficiently under visible blue light conditions at room temperature. At the same time, the catalyst can be recycled and reused, which is in line with the concept of green chemistry. DETAILED DESCRIPTION

[0031] The present invention will be further illustrated below in conjunction with the examples. It should be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. The operating methods in the following examples that do not specify specific conditions are usually performed under normal conditions or according to the conditions recommended by the manufacturer. The content that is not described in detail in this specification sheet belongs to the prior art known to professionals in the field. The experimental materials used in the following examples, if not otherwise specified, can be purchased by conventional biochemical reagent companies.

[0032] Example 1

[0033]

[0034] Dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer ([Cp*RhCl2]2) (0.1mmol, 62.8mg), silver bis(trifluoromethanesulfonyl imide) (AgNTf2) (0.4mmol, 155.2mg) and nitromethane (4.0mL) were added to the reaction flask in sequence and stirred at room temperature (about 25°C) for 1 hour. The silver chloride precipitate was then filtered off, and hexamethylbenzene (0.3mmol, 48.7mg) was added to the filtrate, and stirring was continued at 50°C for 12 hours. After the reaction was completed, the reaction was cooled to room temperature, concentrated to remove the solvent, and the crude product was washed three times with acetone (0.5mL) and ether (4.0mL), and the catalyst Cp*Rhη was obtained after drying. 6 -(hexamethylbenzene)(NTf2)2(cat.4), yield 68%, 66.3 mg.

[0035] Catalyst Cp*Rhη 6 The characterization results of -(hexamethylbenzene)(NTf2)2 are: 1 H NMR (500MHz, Acetone-d6) δ2.58(s,18H),2.14(s,15H). 13 C NMR (126MHz, Acetone-d6) δ 121.08 (q, J = 321.3Hz), 119.08 (d, J = 4.6Hz), 109.54 (d, J = 7.8Hz), 16.18, 8.71. 19 F NMR (471MHz, Acetone-d6) δ-79.87 (12F).

[0036] Example 2

[0037]

[0038] Add the raw material trans-1,2-stilbene (E-1) (0.2mmol, 36.1mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at 25℃ for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-1 with a yield of 92%, 33.3mg, and Z-1 / E-1=91 / 9.

[0039] The characterization results of the target product Z-1 are: 1 H NMR (500MHz, CDCl3) δ7.22–7.07(m,10H),6.52(s,2H).13 C NMR (126MHz, CDCl3) δ137.2, 130.2, 128.9, 128.2, 127.1.

[0040] Amplification preparation: Add the raw material trans-1,2-diphenylethylene E-1 (4.0mmol, 721.0mg), cat.4 (0.12mmol, 115.3mg) and acetone (12.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated, and the resulting residue is washed three times with ether (15mL), the organic layers are combined, concentrated, and separated by column chromatography to obtain the target product Z-1 with a yield of 98%, 705.1mg, and Z-1 / E-1=91 / 9. In addition, the rhodium catalyst residue obtained after washing with ether can be further used to catalyze the isomerization reaction of trans-1,2-diphenylethylene. By adding the catalyst residue to a reaction of the same scale and repeating the above steps, the target product Z-1 can be obtained again with a yield of 96%, 693.5 mg, and Z-1 / E-1=88 / 12; the above steps are repeated for the third time to re-catalyze the isomerization reaction of trans-(Z)-1,2-diphenylethylene with the catalyst residue to obtain the target product Z-1 with a yield of 95%, 687.1 mg, and Z-1 / E-1=88 / 12.

[0041] Example 3

[0042]

[0043] Add the raw material trans-1,2-di-m-tolylethylene E-2 (0.2mmol, 41.7mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-2 with a yield of 89%, 36.9mg, and Z-2 / E-2=90 / 10.

[0044] The characterization results of the target product Z-2 are: 1 H NMR (500MHz, CDCl3) δ7.13–7.03 (m, 6H), 6.99 (d, J = 7.3Hz, 2H), 6.53 (s, 2H), 2.26 (s, 6H). 13C NMR (126MHz, CDCl3) δ137.7,137.2,130.1,129.6,128.0,127.8,125.8,21.3.

[0045] Example 4

[0046]

[0047] Add the raw material trans-1,2-di-o-tolylethylene E-3 (0.2mmol, 41.7mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-3 with a yield of 94%, 39.2mg, and Z-3 / E-3=90 / 10.

[0048] The characterization results of the target product Z-3 are: 1 H NMR (500MHz, CDCl3) δ7.13 (d, J = 7.5Hz, 2H), 7.10–7.03 (m, 2H), 6.97–6.86 (m, 4H), 6.71 (s, 2H), 2.28 (s, 6H). 13 C NMR (126MHz, CDCl3) δ136.5,136.1,129.9,129.4,129.1,127.0,125.4,19.9.

[0049] Example 5

[0050]

[0051] Add the raw material trans-1,2-bis(3-methoxyphenyl)ethylene E-4 (0.2mmol, 48.1mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-4 with a yield of 91%, 43.6mg, and Z-4 / E-4=88 / 12.

[0052] The characterization results of the target product Z-4 are: 1H NMR (500MHz, CDCl3) δ7.14(t,J=7.9Hz,2H),6.85(d,J=7.6Hz,2H),6.82–6.77(m,2H),6.76–6.70(m,2H),6.57(s,2H),3.65(s,6H). 13 C NMR (126MHz, CDCl3) δ159.3,138.5,130.3,129.2,121.5,113.8,113.3,55.0.

[0053] Example 6

[0054]

[0055] Add the raw material trans-3,3'-(ethylene-1,2-diyl)diphenol E-5 (0.2mmol, 42.4mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-5 with a yield of 94%, 39.8mg, and Z-5 / E-5=81 / 19.

[0056] The characterization results of the target product Z-5 are: 1 H NMR (500MHz, Acetone-d6) δ8.23(s,2H),7.08(t,J=7.8Hz,2H),6.78(s,2H),6.74(d,J=7.7Hz,2H),6.70(dd,J=8.2,2.5Hz,2H),6.52(s,2H). 13 C NMR (126MHz, Acetone-d6) δ158.2, 139.6, 131.0, 130.2, 121.1, 116.3, 115.2.

[0057] Example 7

[0058]

[0059] Add the raw material trans-1,2-bis(3-fluorophenyl)ethylene E-6 (0.2mmol, 43.2mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-6, with a yield of 91%, 39.4mg, and Z-6 / E-6=82 / 18.

[0060] The characterization results of the target product Z-6 are: 1 H NMR (500MHz, CDCl3) δ7.19 (q, J = 8.0Hz, 2H), 6.99 (d, J = 7.7Hz, 2H), 6.95–6.83 (m, 4H), 6.59 (s, 2H). 13 CNMR (126MHz, CDCl3) δ162.7 (d, J = 245.7Hz), 138.9 (d, J = 7.8Hz), 130.1 (d, J = 2.3Hz) ,129.8(d,J=8.3Hz), 124.6(d,J=2.8Hz), 115.5(d,J=21.6Hz), 114.3(d,J=21.2Hz). 19 F NMR(471MHz, CDCl3)δ-113.20–-113.30(m,1F).

[0061] Example 8

[0062]

[0063] Add the raw material trans-1,2-bis(4-chlorophenyl)ethylene E-7 (0.2mmol, 49.8mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-7 with a yield of 95%, 47.1mg, and Z-7 / E-7=89 / 11.

[0064] The characterization results of the target product Z-7 are: 1 H NMR (500MHz, CDCl3) δ7.20 (d, J = 8.3Hz, 4H), 7.13 (d, J = 8.6Hz, 4H), 6.54 (s, 2H). 13C NMR (126MHz CDCl3) δ135.2, 133.0, 130.1, 129.6, 128.5.

[0065] Example 9

[0066]

[0067] Add the raw material trans-1,2-bis(4-bromophenyl)ethylene E-8 (0.2mmol, 67.6mg), cat.4 (0.006mmol, 5.8mg), tetrahydrofuran (0.2mL) and acetone (0.8mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-8 with a yield of 68%, 46.3mg, and Z-8 / E-8=83 / 17.

[0068] The characterization results of the target product Z-8 are: 1 H NMR (500MHz, CDCl3) δ7.41–7.31(m,4H),7.12–7.03(m,4H),6.53(s,2H). 13 C NMR (126MHz, CDCl3) δ135.7, 131.5, 130.4, 129.7, 121.2.

[0069] Example 10

[0070]

[0071] Add the raw material trans-1-methoxy-3-phenylene E-9 (0.2mmol, 42.1mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-9 with a yield of 99%, 41.6mg, and Z-9 / E-9=90 / 10.

[0072] The characterization results of the target product Z-9 are: 1H NMR (500MHz, CDCl3) δ7.29–7.20(m,4H),7.20–7.16(m,1H),7.14(t,J=7.9Hz,1H),6.86–6.81(m,1H),6.78 (t,J=2.1Hz,1H),6.74(dd,J=8.0,2.1Hz,1H),6.61(d,J=12.2Hz,1H),6.56(d,J=12.2Hz,1H),3.64(s,3H). 13 C NMR (126MHz, CDCl3) δ159.3,138.5,137.2,130.5,130.1,129.2,128.9,128.2,127.1,121.5,113.7,113.3,55.0.

[0073] Embodiment 11

[0074]

[0075] Add the raw material trans-1-fluoro-3-phenylene E-10 (0.2mmol, 39.6mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-10, with a yield of 91%, 36.2mg, and Z-10 / E-10=85 / 15.

[0076] The characterization results of the target product Z-10 are: 1 H NMR (500MHz, CDCl3) δ7.27–7.14(m,6H),7.00(d,J=7.7Hz,1H),6.92(d,J=10.2Hz ,1H),6.87(td,J=8.5,2.6Hz,1H),6.64(d,J=12.2Hz,1H),6.54(d,J=12.2Hz,1H). 13 C NMR (126MHz, CDCl3) δ162.7 (d, J = 245.3Hz), 139.4 (d, J = 7.8Hz), 136.7, 131.4, 129.6 (d, J = 8.3Hz), 12 8.9 (d, J = 2.3Hz), 128.8, 128.3, 127.4, 124.7 (d, J = 2.8Hz), 115.5 (d, J = 21.7Hz), 114.0 (d, J = 21.2Hz). 19F NMR (471MHz, CDCl3) δ-113.5 (td, J=9.2, 5.8Hz, 1F).

[0077] Example 12

[0078]

[0079] Add the raw material trans-1-chloro-4-phenylene E-11 (0.2mmol, 42.9mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-11 with a yield of 97%, 41.8mg, and Z-11 / E-11=90 / 10.

[0080] The characterization results of the target product Z-11 are: 1 H NMR (500MHz, CDCl3) δ7.30–7.09(m,9H),6.62(d,J=12.1Hz,1H),6.52(d,J=12.2Hz,1H). 13 C NMR (126MHz, CDCl3) δ136.8,135.6,132.7,130.9,130.2,128.9,128.8,128.4,128.3,127.3.

[0081] Example 13

[0082]

[0083] Add the raw material trans-4-phenylbenzene benzoic acid methyl ester E-12 (0.2mmol, 47.7mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After the reaction bottle is sealed, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-12, with a yield of 92%, 43.7mg, and Z-12 / E-12=93 / 7.

[0084] The characterization results of the target product Z-12 are: 1H NMR (500MHz, CDCl3) δ7.81(d,J=8.3Hz,2H),7.22(d,J=8.0Hz,2H),7.18–7.07(m,5H),6.62(d,J=12.3Hz,1H),6.52(d,J=12.2Hz,1H),3.81(s,3H). 13 C NMR (126MHz, CDCl3) δ166.9,142.1,136.6,132.2,129.5,129.2,128.8,128.6,128.3,127.5,52.0.

[0085] Embodiment 14

[0086]

[0087] Add the raw material trans-3-phenylbenzene benzoic acid methyl ester E-13 (0.2mmol, 47.7mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After the reaction bottle is sealed, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-13, with a yield of 93%, 44.5mg, and Z-13 / E-13=92 / 8.

[0088] The characterization results of the target product Z-13 are: 1 H NMR(500MHz, CDCl3)δ7.93(s,1H),7.86(d,J=7.8Hz,1H),7.41(d,J=7.8Hz,1H),7.28–7.2 5(m,1H),7.24–7.17(m,5H),6.67(d,J=12.2Hz,1H),6.61(d,J=12.2Hz,1H),3.87(s,3H). 13 C NMR (126MHz, CDCl3) δ166.9,137.6,136.7,133.2,131.4,130.3,130.1,129.1,128.8,128.3,128.2,127.3,52.1.

[0089] Embodiment 15

[0090]

[0091] Add the raw material trans-1-(3-phenylvinylphenyl)ethan-1-one E-14 (0.2mmol, 44.5mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-14, with a yield of 91%, 40.3mg, and Z-14 / E-14=88 / 12.

[0092] The characterization results of the target product Z-14 are: 1 H NMR (500MHz, CDCl3) δ7.85–7.73(m,2H),7.42(d,J=7.6Hz,1H),7.30(t,J=7.7Hz,1 H),7.27–7.15(m,5H),6.70(d,J=12.1Hz,1H),6.62(d,J=12.1Hz,1H),2.42(s,3H). 13 C NMR (126MHz, CDCl3) δ198.0,137.5,137.0,136.8,133.5,131.5,129.1,129.1,128.7,128.5,128.4,127.4,126.7,26.5.

[0093] Example 16

[0094]

[0095] Add trans-3-phenylvinylcarbonitrile E-15 (0.2mmol, 41.1mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-15 with a yield of 91%, 37.5mg, and Z-15 / E-15=84 / 16.

[0096] The characterization results of the target product Z-15 are: 1H NMR(500MHz, CDCl3)δ7.50(s,1H),7.45(dd,J=9.8,8.2Hz,2H),7.30(t,J=7.8Hz,1H), 7.28–7.21(m,3H),7.27–7.21(m,2H),6.73(d,J=12.2Hz,1H),6.54(d,J=12.2Hz,1H). 13 C NMR (126MHz, CDCl3) δ138.5,136.1,133.2,132.7,132.4,130.5,129.0,128.7,128.5,127.8,127.7,118.7,112.4.

[0097] Embodiment 17

[0098]

[0099] Add the raw material trans-1-phenylvinyl-3-(trifluoromethoxy)benzene E-16 (0.2mmol, 52.8mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After the reaction bottle is sealed, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-16, with a yield of 88%, 46.3mg, and Z-16 / E-16=88 / 12.

[0100] The characterization results of the target product Z-16 are: 1 H NMR (500MHz, CDCl3) δ7.27–7.18(m,6H),7.15(d,J=7.7Hz,1H),7.08(s,1H),7.03(d,J=7.9Hz,1H),6.67(d,J=12.2Hz,1H),6.55(d,J=12.2Hz,1H). 19 F NMR (471MHz, CDCl3) δ-57.8 (s, 1F). 13 C NMR (126MHz, CDCl3) δ 149.1 (q, J = 1.9Hz), 139.2, 136.5, 131.8, 129.5, 128.7, 128.6, 128.4, 127.5, 127.3, 121.3, 120.4 (d, J = 257.1Hz), 119.6.

[0101] Embodiment 18

[0102]

[0103] Add the raw material trans-3-(3-methylphenylvinyl)benzonitrile E-17 (0.2mmol, 43.9mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-17, with a yield of 91%, 39.9mg, and Z-17 / E-17=88 / 12.

[0104] The characterization results of the target product Z-17 are: 1 H NMR (500MHz, CDCl3) δ7.52(s,1H),7.48–7.42(m,2H),7.30(t,J=7.8Hz,1H),7.12(t,J=7.6Hz,1H),7.05(d,J =7.7Hz,1H),7.01(s,1H),6.96(d,J=7.6Hz,1H),6.70(d,J=12.2Hz,1H),6.51(d,J=12.2Hz,1H),2.27(s,3H). 13 CNMR (126MHz, CDCl3) δ138.60,138.16,136.04,133.23,132.85,132.39,130. 47,129.39,128.93,128.54,128.37,127.50,125.66,118.73,112.35,21.31.

[0105] Embodiment 19

[0106]

[0107] Add the raw material trans-1-(4-chlorophenylvinyl)-3-methoxybenzene E-18 (0.2mmol, 48.9mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-18 with a yield of 92%, 44.8mg, and Z-18 / E-18=88 / 12.

[0108] The characterization results of the target product Z-18 are: 1H NMR (500MHz, CDCl3) δ7.25–7.10(m,5H),6.80(d,J=7.6Hz,1H),6.75(d,J=6.4Hz,2H),6.59(d,J=12.2Hz,1H),6.52(d,J=12.2Hz,1H),3.68(s,3H). 13 C NMR (126MHz, CDCl3) δ159.5,138.2,135.6,132.8,130.8,130.2,129.3,129.1,128.4,121.3,113.9,113.2,55.1.

[0109] Embodiment 20

[0110]

[0111] Add the raw material trans-1-chloro-3-(3-methoxyphenylvinyl)benzene E-19 (0.2mmol, 48.9mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-19 with a yield of 93%, 45.7mg, and Z-19 / E-19=89 / 11.

[0112] The characterization results of the target product Z-19 are: 1 H NMR (500MHz, CDCl3) δ7.26–7.22(m,1H),7.19–7.06(m,4H),6.81(d,J=7.7Hz,1H) ,6.79–6.72(m,2H),6.61(d,J=12.2Hz,1H),6.52(d,J=12.2Hz,1H),3.66(s,3H). 13 C NMR (126MHz, CDCl3) δ159.4,139.1,137.9,134.0,131.4,129.4,129.3,128.9,128.8,127.2,127.0,121.4,113.7,113.6,55.1.

[0113] Embodiment 21

[0114]

[0115] Add the raw material trans-4-(3-methylphenylvinyl)phenyl acetate E-20 (0.2mmol, 50.5mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-20, with a yield of 86%, 43.4mg, and Z-20 / E-20=88 / 12.

[0116] The characterization results of the target product Z-20 are: 1 H NMR(500MHz, CDCl3)δ7.25(d,J=8.6Hz,2H),7.11(t,J=7.5Hz,1H),7.08–7.03(m,2H),7.01(d,J=7.5Hz ,1H),6.93(d,J=8.2Hz,2H),6.57(d,J=12.2Hz,1H),6.52(d,J=12.2Hz,1H),2.27(s,3H),2.26(s,3H). 13 C NMR (126MHz, CDCl3) δ169.4,149.5,137.9,136.9,134.9,130.6,129.9,129.5,129.0,128.1,127.9,125.8,121.2,21.3,21.1.

[0117] Embodiment 22

[0118]

[0119] Add the raw material trans-4-methyl-3-phenylphenylbenzoic acid methyl ester E-21 (0.2mmol, 50.5mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After the reaction bottle is sealed, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-21 with a yield of 83%, 41.8mg, and Z-21 / E-21=94 / 6.

[0120] The characterization results of the target product Z-21 are: 1H NMR(500MHz, CDCl3)δ7.88–7.76(m,2H),7.25(d,J=8.2Hz,1H),7.17–7.09(m,3H),7.08 –7.00(m,2H),6.67(d,J=12.2Hz,1H),6.61(d,J=12.2Hz,1H),3.82(s,3H),2.27(s,3H). 13 C NMR (126MHz, CDCl3) δ167.0,141.6,137.5,136.6,131.6,130.2,130.1,128.7,128.3,128.2,127.8,127.3,51.9,20.1.

[0121] Embodiment 23

[0122]

[0123] Add the raw material trans-2-methyl-5-phenylvinylbenzoic acid methyl ester E-22 (0.2mmol, 50.5mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After the reaction bottle is sealed, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-22, with a yield of 93%, 46.9mg, and Z-22 / E-22=91 / 9.

[0124] The characterization results of the target product Z-22 are: 1 H NMR (500MHz, CDCl3) δ7.80(s,1H),7.30–7.15(m,6H),7.04(d,J=7.9Hz,1H),6.62(d,J=12.2Hz,1H),6.55(d,J=12.2Hz,1H),3.82(s,3H),2.55(s,3H). 13 C NMR (126MHz, CDCl3) δ167.9,139.0,137.0,134.8,132.1,131.5,131.2,130.7,129.5,129.0,128.7,128.3,127.2,51.7,21.4.

[0125] Embodiment 24

[0126]

[0127] Add the raw material trans-2-methyl-5-phenylphenylbenzoic acid methyl ester E-23 (0.2mmol, 42.5mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After the reaction bottle is sealed, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-23, with a yield of 98%, 41.6mg, and Z-23 / E-23=86 / 14.

[0128] The characterization results of the target product Z-23 are: 1 H NMR(500MHz, CDCl3)δ7.29–7.13(m,5H),7.05(d,J=7.5Hz,1H),7.03–6.97(m,1H), 6.82(t,J=9.0Hz,1H),6.55(d,J=12.2Hz,1H),6.50(d,J=12.2Hz,1H),2.17(s,3H). 13 C NMR (126MHz, CDCl3) δ160.4 (d, J = 245.3Hz), 137.1, 132.9 (d, J = 3.9Hz), 132.0 (d, J = 5.0Hz), 129.9, 129.3 ,128.8,128.2,127.7(d,J=7.9Hz),127.1,124.5(d,J=17.4Hz),114.7(d,J=22.3Hz),14.4(d,J=3.6Hz). 19 F NMR(471MHz, CDCl3)δ-119.0–-119.2(m,1H).

[0129] Embodiment 25

[0130]

[0131] Add the raw material trans-1-fluoro-4-methyl-2-phenylethylene E-24 (0.2mmol, 42.5mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-24 with a yield of 94%, 39.9mg, and Z-24 / E-24=91 / 9.

[0132] The characterization results of the target product Z-24 are: 1H NMR (500MHz, CDCl3) δ7.26–7.15(m,5H),7.03–6.95(m,2H),6.93–6.87(m,1H),6.68(d,J=12.3Hz,1H),6.56(d,J=12.3Hz,1H),2.15(s,3H). 13 C NMR (126MHz, CDCl3) δ158.4 (d, J = 245.1Hz), 136.9, 132.9 (d, J = 3.6Hz), 132.0, 130.6 (d, J = 3.3Hz), 129.4 (d,J=8.0Hz),128.7,128.1,127.3,124.5(d,J=14.7Hz),122.7(d,J=2.8Hz),115.2(d,J=22.1Hz),20.5. 19 F NMR(471MHz, CDCl3)δ-120.0–-120.1(m,1F).

[0133] Embodiment 26

[0134]

[0135] Add the raw material trans-4-(3-chlorophenylvinyl)-1-fluoro-2-toluene E-25 (0.2mmol, 49.3mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-25 with a yield of 90%, 44.5mg, and Z-25 / E-25=88 / 12.

[0136] The characterization results of the target product Z-25 are: 1 H NMR(500MHz, CDCl3)δ7.22(s,1H),7.19–7.11(m,2H),7.09(d,J=7.4Hz,1H),7.04(d,J=7.2Hz,1H),7 .01–6.94(m,1H),6.84(t,J=9.0Hz,1H),6.55(d,J=12.2Hz,1H),6.47(d,J=12.2Hz,1H),2.18(s,3H). 13C NMR (126MHz, CDCl3) δ160.6 (d, J = 246.0Hz), 139.0, 134.1, 132.3 (d, J = 3.8Hz), 132.0 (d, J = 5.1Hz), 130.6, 129.4 ,128.8,128.4,127.7(d,J=7.9Hz),127.2,126.9,124.7(d,J=17.5Hz),114.9(d,J=22.4Hz),14.4(d,J=3.6Hz). 19 F NMR(471MHz, CDCl3)δ-118.4–-118.5(m,1F).

[0137] Embodiment 27

[0138]

[0139] Add the raw material trans-4-(4-fluoro-3-methylphenyl)acetate E-26 (0.2mmol, 54.1mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After the reaction bottle is sealed, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-26, with a yield of 89%, 48.3mg, and Z-26 / E-26=82 / 18.

[0140] The characterization results of the target product Z-26 are: 1 H NMR (500MHz, CDCl3) δ7.23(d,J=8.5Hz,2H),7.08–6.99(m,2H),6.95(d,J=8.3Hz,2H),6.84(t,J=9.0Hz,1H),6.51(s,2H),2.28(s,3H),2.18(s,3H). 13 C NMR (126MHz, CDCl3) δ 169.3, 160.4 (d, J = 245.7Hz), 149.6, 134.7, 132.7 (d, J = 4.0Hz), 131.9 (d, J = 5.2Hz), 129. 9,129.5,128.9,127.7(d,J=7.8Hz),124.6(d,J=17.4Hz),121.3,114.8(d,J=22.5Hz),21.1,14.4(d,J=3.6Hz). 19 F NMR(471MHz, CDCl3)δ-118.8–-118.9(m,1F).

[0141] Embodiment 28

[0142]

[0143] Add the raw material trans-4-(3-chloro-4-methylphenylvinyl)phenyl acetate E-27 (0.2mmol, 57.4mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After the reaction bottle is sealed, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-27, with a yield of 85%, 48.9mg, and Z-27 / E-27=86 / 14.

[0144] The characterization results of the target product Z-27 are: 1 H NMR (500MHz, CDCl3) δ7.24(d,J=9.2Hz,3H),7.05(d,J=7.9Hz,1H),7.01(d,J=7.9Hz,1H),6.9 6(d,J=8.3Hz,2H),6.55(d,J=12.2Hz,1H),6.49(d,J=12.2Hz,1H),2.33(s,3H),2.28(s,3H). 13 C NMR (126MHz, CDCl3) δ169.3,149.7,136.2,134.9,134.5,134.2,130.7,129.9,129.8,129.2,128.9,127.0,121.4,21.1,19.8.

[0145] Embodiment 29

[0146]

[0147] Add the raw material trans-4-(2-fluoro-5-methylphenyl)acetate E-28 (0.2mmol, 54.1mg), cat.4 (0.006mmol, 5.8mg) and acetone (1.0mL) to the reaction bottle in sequence. After sealing the reaction bottle, place it under a blue light with a power of 40W and a wavelength range of about 427nm at room temperature (about 25°C) for 24 hours (the reaction temperature is maintained at room temperature by a fan device). After the reaction is completed, the reaction solution is concentrated and directly separated by column chromatography to obtain the target product Z-28, with a yield of 93%, 50.4mg, and Z-28 / E-28=89 / 11.

[0148] The characterization results of the target product Z-28 are: 1H NMR(500MHz, CDCl3)δ7.23(d,J=8.6Hz,2H),7.03–6.96(m,2H),6.96–6.86(m, 3H),6.64(d,J=12.2Hz,1H),6.56(d,J=12.2Hz,1H),2.26(s,3H),2.16(s,3H). 13 C NMR (126MHz, CDCl3) δ169.3,158.4(d,J=245.1Hz),149.7,134.5,133.0(d,J=3.5Hz),131.0,130.6(d,J=3.3Hz ), 129.7, 129.5 (d, J = 7.8Hz), 124.3 (d, J = 15.0Hz), 123.0 (d, J = 2.7Hz), 121.2, 115.2 (d, J = 22.0Hz), 21.1, 20.5. 19 F NMR(471MHz, CDCl3)δ-119.8–-119.9(m,1F).

[0149] The embodiments described above provide a detailed description of the technical solutions of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements or similar substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene, characterized in that: include: In an organic solvent, trans-1,2-diarylethene is used as a substrate and a rhodium complex is used as a catalyst. An isomerization reaction is carried out in an air atmosphere under visible blue light irradiation to obtain cis-1,2-diarylethene; the rhodium complex is η 6 - Aromatic ring coordinated pentamethylcyclopentadienyl rhodium complex or its derivatives; The structure of trans-1,2-diarylethene is shown in formula (I): In formula (I), Ar 1 and Ar 2 The same or different, each independently is phenyl, substituted phenyl or heteroaryl.

2. The method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene according to claim 1, characterized in that: In the substituted phenyl group, the substituent of the phenyl group is a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxyl group, a halogen atom, an ester group, an acyl group, a cyano group or a trifluoromethoxy group.

3. The method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene according to claim 1, characterized in that: Rhodium complex anion X - is the trifluoromethanesulfonate ion OTf - , bis(trifluoromethylsulfonyl)imide ion NTf2 - , tetrafluoroborate ion BF4 - , hexafluoroantimonate ion SbF6 - , hexafluorophosphate ion PF6 - , methanesulfonate OMs - or p-toluenesulfonate OTs - The structural formula of the rhodium complex is any one of the following, X - is as defined above; 4. The method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene according to claim 1, characterized in that: The structural formula of the rhodium complex is Coordinate anion X - is the trifluoromethanesulfonate ion OTf - or bis(trifluoromethylsulfonyl)imide ion NTf2 - .

5. The method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene according to claim 1, characterized in that: The organic solvent is at least one of nitromethane, acetonitrile, acetone, ethyl acetate and tetrahydrofuran; and the amount of the organic solvent is 0.5-10 L / mol based on the molar amount of trans-1,2-diarylethene.

6. The method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene according to claim 1, characterized in that: The wavelength range of visible blue light is 380-500nm, and the irradiation power of visible blue light is 10-100W.

7. The method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene according to claim 1, characterized in that: The reaction temperature of the isomerization reaction is 0-40°C, and the reaction time is 12-36h.

8. The method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene according to claim 1, characterized in that: The molar ratio of the rhodium complex to the trans-1,2-diarylethene diarylethene is 1:10-50.

9. The method for isomerizing trans-1,2-diarylethene to cis-1,2-diarylethene according to claim 1, characterized in that: After the isomerization reaction is completed, the reaction solution is concentrated and separated by silica gel column chromatography to obtain cis-1,2-diarylethene.

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