A method for the iron-catalyzed photoinduced preparation of cyano-inner unsaturated derivatives

Abstract

A method for the iron-catalyzed photoinduced preparation of cyano-inner unsaturated derivatives. The present invention belongs to the field of the synthesis of organic unsaturated bond compounds, and particularly relates to a method for the synthesis of cyano-inner unsaturated derivatives. The present invention aims to solve the technical problem that the current synthesis of cyano-unsaturated compounds uses dangerous inorganic or organic small molecule cyanides as raw materials, resulting in poor preparation safety. Method: Using an iron salt as a catalyst, an unsaturated sulfone reagent and a cyclic oxime acid compound as raw materials, potassium hydroxide as a base, in a toluene solvent, the reaction temperature is 30 °C, and it is placed under a 10W purple LED for photoinduced reaction to obtain the cyano-inner unsaturated compound. The catalyst involved in the synthesis method of the present invention is simple and easily available, the raw materials are green and non-toxic, the functional group compatibility is good, the reaction conditions are mild, and it has good industrial application prospects. The present invention is used for the preparation of cyano-inner unsaturated derivatives.

Description

Technical Field

[0001] The present invention belongs to the field of synthesis of organic unsaturated bond compounds, and particularly relates to a method for synthesizing unsaturated derivatives within a cyano group by iron catalysis. Background Art

[0002] Cyano unsaturated compounds are a class of organic compounds containing a cyano group and an unsaturated bond (double bond or triple bond), and they play an important role in organic synthesis. They can be prepared by various methods and can also be transformed into various functional groups to achieve purposes such as carbon chain extension, introduction of nitrogen atoms, and adjustment of unsaturation. However, since traditional methods for synthesizing cyano organic compounds generally require the use of relatively dangerous inorganic or organic small molecule cyanides, there are great challenges in the synthesis of cyano-substituted unsaturated compounds. Therefore, it is of great practical value to develop a method for synthesizing cyano unsaturated compounds using safe and reliable oxime acids as reaction raw materials under mild conditions. Summary of the Invention

[0003] The present invention aims to solve the technical problem that the current synthesis of cyano unsaturated compounds uses dangerous inorganic or organic small molecule cyanides as raw materials, resulting in poor preparation safety, and provides a method for preparing unsaturated derivatives within a cyano group by iron-catalyzed photoinduction.

[0004] The purpose of the present invention is to provide a method for synthesizing cyano unsaturated compounds of iron-catalyzed oxime acid, which uses raw materials without a cyano group to prepare compounds containing both a cyano group and an unsaturated group. The catalyst and raw materials used in this method are inexpensive, widely sourced, have high reaction efficiency, mild reaction conditions, can well tolerate various functional groups, and are simple and convenient to operate. These advantages make it have very good industrial application prospects.

[0005] A method for preparing unsaturated derivatives within a cyano group by iron-catalyzed photoinduction is specifically carried out according to the following steps:

[0006] I. Put a catalyst iron salt, an unsaturated sulfonyl reagent, a cyclic oxime acid compound, and a base into a solvent to obtain a reaction solution:

[0007] II. Under room temperature conditions, irradiate the reaction solution obtained in step I with a purple LED for reaction; after the reaction ends, remove the organic solvent using a rotary evaporator to obtain a crude product, and then separate it by silica gel column chromatography using petroleum ether and ethyl acetate as eluents to obtain unsaturated derivatives within a cyano group.

[0008] Further, the iron salt in step I is one or a mixture of several of Fe(acac)3, FeCl3, and Fe(NO3)3.

[0009] Further, the unsaturated sulfone-based reagent in Step 1 is an alkynylation reagent, an alkenylation reagent, or an allylation reagent.

[0010] Further, the structural formula of the alkynylation reagent is: Alkenylation reagent: Allylation reagent: Wherein R4 is a substituted alkyl group or a substituted aromatic ring, and R5 is a substituted alkyl group or a substituted aromatic ring.

[0011] Further, the structural formula of the cyclooxime acid compound in Step 1 is: Wherein R1 is a hydrogen atom, a substituted alkyl group or an acyl group, R2 is a hydrogen atom or a substituted alkyl group, and R3 is a hydrogen atom or a substituted alkyl group.

[0012] Further, the base in Step 1 is potassium hydroxide, potassium carbonate, sodium bicarbonate or triethylamine.

[0013] Further, the solvent in Step 1 is one or a mixture of several of acetonitrile, toluene, dichloromethane and dichloroethane.

[0014] Further, the molar ratio of the unsaturated sulfone-based reagent to the cyclooxime acid compound in Step 1 is 1:2;

[0015] The dosage of the iron salt is 5% - 20% of the molar dosage of the unsaturated sulfone-based reagent;

[0016] The dosage of the base is 50% of the molar dosage of the unsaturated sulfone-based reagent.

[0017] The synthesis method of the unsaturated sulfone-based reagent:

[0018]

[0019] Step 1: Under nitrogen protection, add sodium methylsulfinate (354 mg, 3.0 mmol, 1.2 equiv) and NaI (449 mg, 3.0 mmol, 1.2 equiv) into a dried three-necked round-bottom flask. Add anhydrous MeCN (15 mL) and alkyne (2.5 mmol, 1.0 equiv), exhaust and fill with nitrogen 3 times; then dissolve ammonium cerium(IV) nitrate (3.4 g, 6.25 mmol, 2.5 equiv) in anhydrous MeCN (25 mL) and slowly add it through a pressure-equalizing dropping funnel; Monitor the reaction by TLC, and after completion, quench the reaction with saturated brine (50 mL); then extract the reaction mixture with ethyl acetate; The organic phase is washed again with saturated brine (3 × 30 mL), dried over Na2SO4, and the solvent is removed under reduced pressure to obtain crude iodothioether; Directly used for the next step of the reaction;

[0020] Step 2: Dissolve the crude iodo sulfide in acetone (25 mL), reflux with K2CO3 (2 equiv) until the reaction is complete; monitor the reaction by TLC, filter off the carbonate after completion, remove acetone by rotary evaporation, and purify by column chromatography (EtOAc: petroleum ether 1:5) to obtain the sulfonyl alkynyl reagent product;

[0021]

[0022] In MeCN (30 mL), add I2 (1.14 g, 4.5 mmol, 1.5 equiv) to a mixture of substituted styrene (3.0 mmol, 1.0 equiv), sodium methylsulfinate (918 mg, 9.0 mmol, 3.0 equiv), and sodium acetate (612 mg, 4.5 mmol, 1.5 equiv). Stir the reaction mixture vigorously at reflux temperature for 2 hours; after completion of the reaction, add a concentrated sodium thiosulfate (Na2S2O3) solution (10 mL) to quench iodine, and then basify with a concentrated sodium bicarbonate (NaHCO3) solution (10 mL). Continue stirring and extract with ethyl acetate (3 × 20 mL); combine the organic extracts, wash with water (20 mL) and brine (20 mL), dry over anhydrous Na2SO4, filter, and concentrate under reduced pressure. The residue is purified by column chromatography (EtOAc: petroleum ether 1:3) to obtain the alkenyl sulfonyl reagent product.

[0023] The synthetic method of the cyclic oxime acid compound:

[0024]

[0025] Add ketone (5.0 mmol, 1.0 equivv) to MeOH (15 mL) in a flask to form a solution, add 2-(aminooxy)-2-methylpropanoic acid hydrochloride (778 mg, 6.0 mmol, 1.2 equiv), sodium acetate (984 mg, 12 mmol, 2.4 equiv), and reflux for 6.0 hours; then cool the mixture to room temperature, concentrate under reduced pressure, add an aqueous solution of Na2CO3 (2.0 M; 20 mL) to dissolve the product in the aqueous phase; then extract the aqueous solution once with ethyl acetate, and wash the organic phase with an aqueous solution of Na2CO3 (2.0 M; 2 × 15 mL); combine the aqueous phases, slowly add HCl solution (6.0 N) until pH < 2, and then extract with ethyl acetate (3 × 20 mL); combine the organic phases, dry over MgSO4, filter, concentrate under reduced pressure, and finally obtain the corresponding cyclic oxime acid compound product.

[0026] The synthetic route of the present invention is as follows:

[0027]

[0028] The reaction principle of the present invention is as follows:

[0029]

[0030] The carboxylic acid unit in the activating group has a coordination effect with the trivalent iron species A under the action of a base, resulting in the formation of the carboxylate-iron(III) complex B. The photoexcitation of the iron complex B will cause a ligand-to-metal charge transfer event, generating a reduced divalent iron complex and an aryloxy radical. The latter rapidly undergoes decarboxylation to generate a tertiary carbon radical intermediate D, initializing a one-way radical cascade reaction. After the N-O single bond cleavage, the key iminyl radical E is easily generated. Subsequently, through a barrier-free radical translocation and a strain-release C-C single bond cleavage, a cyanoalkyl radical F is generated. This highly reactive radical rapidly reacts with an alkynyl, alkenyl, or allyl thione to generate carbon radicals G, I, or K. A radical elimination reaction must occur to generate the corresponding fragmentation-alkynylation (H), -alkenylation (J), or -alkylation (L) products. The generated sulfonyl radical is then reduced by divalent iron to complete the iron photoreduction cycle and regenerate the catalyst.

[0031] Advantages of the present invention:

[0032] Using an iron salt as a catalyst, a sulfone reagent and a cyclooxime acid compound as raw materials, and potassium hydroxide as a base, a cyano unsaturated compound is prepared by reacting at room temperature in a toluene solvent. The catalyst involved in the synthesis method of the present invention is simple and easily available, the raw materials are green and non-toxic, the functional group compatibility is good, the reaction conditions are mild, and it has good industrial application prospects. Description of the Drawings

[0033] Figure 1 1H NMR spectrum of 6-phenylhex-5-ynenitrile prepared in Example 1;

[0034] Figure 2 13C NMR spectrum of 6-phenylhex-5-ynenitrile prepared in Example 1;

[0035] Figure 3 1H NMR spectrum of 3,6-diphenylhex-5-ynenitrile prepared in Example 2;

[0036] Figure 4 13C NMR spectrum of 3,6-diphenylhex-5-ynenitrile prepared in Example 2;

[0037] Figure 5 1H NMR spectrum of 6-(4-methylphenyl)hex-5-ynenitrile prepared in Example 6;

[0038] Figure 6 13C NMR spectrum of 6-(4-methylphenyl)hex-5-ynenitrile prepared in Example 6;

[0039] Figure 7Prepare the hydrogen spectrum of (5E)-6-phenylhex-5-enenitrile for Example 11;

[0040] Figure 8 Prepare the carbon spectrum of (5E)-6-phenylhex-5-enenitrile for Example 11;

[0041] Figure 9 Prepare the hydrogen spectrum of 6-phenylhept-6-enenitrile for Example 17;

[0042] Figure 10 Prepare the carbon spectrum of 6-phenylhept-6-enenitrile for Example 17. Detailed implementation manners

[0043] Detailed implementation manner one: A method for preparing cyano-inner unsaturated derivatives by iron-catalyzed photoinduction specifically comprises the following steps:

[0044] I. Put a catalyst iron salt, an unsaturated sulfonyl reagent, a cyclooxime acid compound, and a base into a solvent to obtain a reaction solution:

[0045] II. Under room temperature conditions, irradiate the reaction solution obtained in step I with a purple LED for reaction; after the reaction ends, remove the organic solvent by a rotary evaporator to obtain a crude product, and then separate it by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents to obtain the cyano-inner unsaturated derivative.

[0046] Detailed implementation manner two: The difference between this detailed implementation manner and detailed implementation manner one is that: the iron salt described in step I is one or a mixture of several of Fe(acac)3, FeCl3, and Fe(NO3)3. Others are the same as detailed implementation manner one.

[0047] Detailed implementation manner three: The difference between this detailed implementation manner and detailed implementation manner one or two is that: the unsaturated sulfonyl reagent described in step I is an alkynylation reagent, an alkenylation reagent, or an allylation reagent. Others are the same as detailed implementation manner one or two.

[0048] Detailed implementation manner four: The difference between this detailed implementation manner and one of detailed implementation manners one to three is that: the structural formula of the alkynylation reagent is: Alkenylation reagent: Allylation reagent: wherein R4 is a substituted alkyl group or a substituted aromatic ring, and R5 is a substituted alkyl group or a substituted aromatic ring. Others are the same as one of detailed implementation manners one to three.

[0049] Detailed implementation manner five: The difference between this detailed implementation manner and one of detailed implementation manners one to four is that: the structural formula of the cyclooxime acid compound described in step I is: Wherein, R1 is a hydrogen atom, a substituted alkyl group or an acyl group, R2 is a hydrogen atom or a substituted alkyl group, and R3 is a hydrogen atom or a substituted alkyl group. Others are the same as any one of the specific embodiments 1 to 4.

[0050] Specific Embodiment 6: The difference between this embodiment and any one of the specific embodiments 1 to 5 is that: the base in Step 1 is potassium hydroxide, potassium carbonate, sodium bicarbonate or triethylamine. It is the same as any one of the specific embodiments 1 to 5.

[0051] Specific Embodiment 7: The difference between this embodiment and any one of the specific embodiments 1 to 6 is that: the solvent in Step 1 is one or a mixture of several of acetonitrile, toluene, dichloromethane and dichloroethane. It is the same as any one of the specific embodiments 1 to 6.

[0052] Specific Embodiment 8: The difference between this embodiment and any one of the specific embodiments 1 to 7 is that: the molar ratio of the unsaturated sulfone reagent to the cyclooxime acid compound in Step 1 is 1:2;

[0053] The dosage of the iron salt is 5% - 20% of the molar dosage of the unsaturated sulfone reagent;

[0054] The dosage of the base is 50% of the molar dosage of the unsaturated sulfone reagent. It is the same as any one of the specific embodiments 1 to 7.

[0055] Specific Embodiment 9: The difference between this embodiment and any one of the specific embodiments 1 to 8 is that: the reaction in Step 2 is carried out under a nitrogen atmosphere and stirring conditions. It is the same as any one of the specific embodiments 1 to 8.

[0056] Specific Embodiment 10: The difference between this embodiment and any one of the specific embodiments 1 to 9 is that: the power of the purple LED in Step 2 is 10W, and the illumination time is 8 - 24h. It is the same as any one of the specific embodiments 1 to 9.

[0057] The content of the present invention is not limited to the content of the above embodiments, and the combination of one or several specific embodiments can also achieve the purpose of the invention.

[0058] Example 1:

[0059] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), phenylacetylenylmethyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv), and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative 6-phenylhex-5-ynenitrile was obtained, with the chemical formula as follows:

[0060]

[0061] With a purity of 99% and a yield of 88%, its NMR data are as follows 1 H NMR (400 MHz, CDCl3) δ 7.42 - 7.37 (m, 2H), 7.32 - 7.27 (m, 3H), 2.58 (dt, J = 17.8, 7.0 Hz, 4H), 1.96 (p, J = 7.0 Hz, 2H); 13 C NMR (101 MHz, CDCl3) δ 131.5, 128.2, 127.9, 123.1, 119.1, 86.8, 82.3, 24.5, 18.4, 16.1.

[0062] Example 2:

[0063] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-methyl-2-{[(3-phenylcyclobutylidene)amino]oxy}propanoic acid (0.4 mmol, 2 equiv), phenylacetylenylmethyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv), and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative 3,6-diphenylhex-5-ynenitrile was obtained, with the chemical formula as follows:

[0064]

[0065] With a purity of 99% and a yield of 61%, its NMR data are as follows: 11H NMR (400 MHz, CDCl3) δ 7.41 - 7.34 (m, 4H), 7.34 - 7.27 (m, 6H), 3.30 (p, J = 7.0 Hz, 1H), 2.99 - 2.79 (m, 4H); 13 13C NMR (101 MHz, CDCl3) δ 140.5, 131.6, 129.0, 128.4, 128.2, 127.9, 127.1, 123.1, 118.3, 86.0, 83.6, 41.2, 25.9, 23.3.

[0066] Example 3:

[0067] In a reaction tube with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-({[3-(ethoxycarbonyl)cyclobutylidene]amino}oxy)-2-methylpropanoic acid (0.4 mmol, 2 equiv), phenylacetylenyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv), and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-containing unsaturated derivative ethyl 2-(cyanomethyl)-5-phenylpent-4-ynoate was obtained, with the chemical formula as follows:

[0068]

[0069] Purity 99%, yield 64%, and the NMR data are as follows: 1 1H NMR (400 MHz, CDCl3) δ 7.41 - 7.37 (m, 2H), 7.30 (dd, J = 5.2, 2.0 Hz, 3H), 4.26 (qd, J = 7.2, 2.3 Hz, 2H), 3.02 - 2.96 (m, 1H), 2.95 - 2.84 (m, 4H), 1.31 (t, J = 7.1 Hz, 3H); 13 13C NMR (101 MHz, CDCl3) δ 170.9, 131.8, 128.4, 122.8, 117.7, 84.1, 62.0, 40.9, 21.7, 18.5, 14.3.

[0070] Example 4:

[0071] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-methyl-2-{[(7-{[(2-methylpropan-2-yl)oxy]carbonyl}-7-azaspiro[3.5]non-2-ylidene)amino]oxy}propanoic acid (0.4 mmol, 2 equiv), phenylacetylenylmethyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-containing unsaturated derivative 4-(cyanomethyl)-4-(3-phenylprop-2-ynyl)hexahydropyridine-1-carboxylic acid 2-methylprop-2-yl ester was obtained, and its chemical formula is as follows:

[0072]

[0073] The purity was 99% and the yield was 90%. The NMR data were as follows: 1 H NMR(400MHz,CDCl3)δ7.40(dd,J=6.7,3.0Hz,2H),7.30(dd,J=4.6,2.0Hz,3H),3.53(dt,J=13.9,5.4Hz,2H),3.37(ddd,J=13.8,8.2,4.1Hz,2H),2.63(s,2H),2.58(s,2H),1.68(dqd,J=17.8,9.5,3.2Hz,4H),1.46(s,10H); 13 CNMR(101MHz,CDCl3)δ154.8,131.7,128.5,128.3,123.0,117.4,84.5,84.4,80.1,35.2,33.7,28.5,27.6,26.8。

[0074] Example 5:

[0075] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-({[(2Z)-1,1-dimethylcyclopent-2-ylidene]amino}oxy)-2-methylpropanoic acid (0.4 mmol, 2 equiv), phenylacetylenylmethyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv), and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative 5,5-dimethyl-7-phenylhept-6-ynenitrile was obtained, with the chemical formula as follows:

[0076]

[0077] With a purity of 99% and a yield of 52%, its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ7.40-7.35(m,2H),7.28(m,3H),2.42(t,J=7.1Hz,2H),1.96-1.85(m,2H),1.66-1.57(m,2H),1.31(s,6H); 13 CNMR(101MHz,CDCl3)δ131.7,128.3,127.8,123.7,119.8,96.0,81.2,42.3,31.5,29.3,21.9,17.7。

[0078] Example 6:

[0079] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), p-tolylacetylenylmethyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv), and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative 6-(4-methylphenyl)hex-5-ynenitrile was obtained, with the chemical formula as follows:

[0080]

[0081] With a purity of 99% and a yield of 70%, its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ7.28(d,J=8.0Hz,2H),7.10(d,J=7.8Hz,2H),2.57(dt,J=14.4,7.0Hz,4H),2.34(s,3H),1.95(p,J=7.0Hz,2H); 13 C NMR(101MHz,CDCl3)δ138.0,131.3,128.9,120.0,119.2,86.0,82.4,24.6,21.3,18.5,16.1.

[0082] Example 7:

[0083] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), p-methoxyphenylethynyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-containing unsaturated derivative 6-(4-ethoxyphenyl)hex-5-ynenitrile was obtained. The chemical formula is as follows:

[0084]

[0085] With a purity of 99% and a yield of 64%, its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ7.31(d,J=8.7Hz,2H),6.81(d,J=8.6Hz,2H),4.01(q,J=7.0Hz,2H),2.56(dt,J=11.0,6.9Hz,4H),1.94(p,J=6.9Hz,2H),1.40(t,J=7.0Hz,3H); 13 C NMR(101MHz,CDCl3)δ158.9,133.0,119.4,115.2,114.5,85.4,82.4,63.6,24.9,18.7,16.3,14.9.

[0086] Example 8:

[0087] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), p-phenylphenylethynyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv), and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative 6-(4-phenylphenyl)hex-5-ynenitrile was obtained, with the chemical formula as follows:

[0088]

[0089] With a purity of 99% and a yield of 51%, its NMR data are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.55 (dd, J = 16.8, 7.9 Hz, 4H), 7.44 (dd, J = 13.9, 8.1 Hz, 4H), 7.35 (t, J = 7.3 Hz, 1H), 2.62 (t, J = 6.7 Hz, 2H), 2.56 (t, J = 7.2 Hz, 2H), 1.97 (p, J = 7.0 Hz, 2H); 13 C NMR (101 MHz, CDCl3) δ 140.8, 140.4, 132.1, 128.9, 127.7, 127.0, 122.1, 119.3, 87.7, 82.3, 24.7, 18.7, 16.3.

[0090] Example 9:

[0091] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), 1-nonynyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv), and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative tridec-5-ynenitrile was obtained, with the chemical formula as follows:

[0092]

[0093] With a purity of 99% and a yield of 74%, its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ2.49(t,J=7.2Hz,2H),2.33(tt,J=6.7,2.4Hz,2H),2.14(tt,J=7.2,2.4Hz,2H),1.83(p,J=7.0Hz,2H),1.48(p,J=6.9Hz,2H),1.41-1.19(m,9H),0.89(t,J=6.7Hz,3H); 13 C NMR(101MHz,CDCl3)δ119.4,82.6,31.8,29.0,28.9,28.8,25.0,22.6,18.7,18.0,16.1,14.1.

[0094] Example 10:

[0095] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), 2-thiophen-2-ylethynyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added successively. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-containing unsaturated derivative 6-(thiophen-3-yl)hex-5-ynenitrile was obtained. The chemical formula is as follows:

[0096]

[0097] With a purity of 99% and a yield of 81%, its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ7.38(d,J=2.9Hz,1H),7.26-7.23(m,1H),7.07(d,J=4.9Hz,1H),2.56(dt,J=13.8,6.9Hz,4H),1.94(p,J=7.0Hz,2H); 13 C NMR(101MHz,CDCl3)δ129.9,128.3,125.3,122.2,119.3,86.6,77.5,24.6,18.6,16.3.

[0098] Example 11:

[0099] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), styrylmethyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added in sequence. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 16 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography, and petroleum ether and ethyl acetate were used as eluents. Finally, the cyano-inner unsaturated derivative (5E)-6-phenylhex-5-enenitrile was obtained, and its chemical formula is as follows:

[0100]

[0101] With a purity of 99% and a yield of 72%, its NMR data are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.37 - 7.28 (m, 4H), 7.25 - 7.19 (m, 1H), 6.46 (d, J = 15.7 Hz, 1H), 6.18 - 6.07 (m, 1H), 2.45 - 2.35 (m, 4H), 1.85 (p, J = 7.2 Hz, 2H); 13 C NMR (101 MHz, CDCl3) δ 137.2, 132.1, 128.7, 127.7, 127.4, 126.2, 119.7, 31.7, 25.1, 16.5.

[0102] Example 12:

[0103] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), 1-(pyridin-2-yl)vinyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added in sequence. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 16 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography, and petroleum ether and ethyl acetate were used as eluents. Finally, the cyano-inner unsaturated derivative (5E)-6-(pyridin-2-yl)hex-5-enenitrile was obtained, and its chemical formula is as follows:

[0104]

[0105] With a purity of 99% and a yield of 84%, its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ8.54(d,J=4.4Hz,1H),7.63(td,J=7.7,1.8Hz,1H),7.23(d,J=7.8Hz,1H),7.13(dd,J=7.6,4.9Hz,1H),6.69(dt,J=15.7,6.9Hz,1H),6.55(d,J=15.6Hz,1H),2.44(dd,J=14.8,7.2Hz,4H),1.89(p,J=7.2Hz,2H); 13 C NMR(101MHz,CDCl3)δ155.3,149.5,136.7,132.5,131.8,122.2,121.6,119.6,31.5,24.7,16.6。

[0106] Example 13:

[0107] In a reaction tube with a magnetic stir bar, under a nitrogen atmosphere, catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), pentafluorostyrylmethyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added in sequence. After mixing evenly, the mixture was placed under a 10W purple LED for light stirring for 16 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-containing unsaturated derivative (5E)-6-(2,3,4,5,6-pentafluorophenyl)hex-5-enenitrile was obtained. The chemical formula is as follows:

[0108]

[0109] With a purity of 99% and a yield of 70%, its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ6.49(dt,J=16.3,6.8Hz,1H),6.37(d,J=16.3Hz,1H),2.50-2.39(m,4H),1.89(p,J=7.2Hz,2H); 1313C NMR (101 MHz, CDCl3) δ 146.0, 143.5, 141.1, 139.0, 138.5, 137.9, 137.8, 137.8, 137.8, 137.7, 136.5, 119.3, 116.4, 112.1, 112.0, 33.0, 24.7, 16.7; 19 19F NMR (376 MHz, CDCl3) δ -143.4, -143.4, -143.4, -143.5, -156.7, -156.7, -156.8, -162.9, -162.9, -163.0, -163.0, -163.0, -163.2.

[0110] Example 14:

[0111] In a reaction tube with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), 1,1-diphenylvinyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added successively. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 16 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-containing unsaturated derivative 6,6-diphenylhex-5-enenitrile was obtained. The chemical formula is as follows:

[0112]

[0113] Purity 99%, yield 71%, and its NMR data are as follows: 1 1H NMR (400 MHz, CDCl3) δ 7.38 (t, J = 7.3 Hz, 2H), 7.35 - 7.29 (m, 1H), 7.29 - 7.19 (m, 5H), 7.17 - 7.13 (m, 2H), 6.01 (t, J = 7.4 Hz, 1H), 2.27 (dt, J = 17.6, 7.4 Hz, 4H), 1.79 (p, J = 7.4 Hz, 2H); 13 13C NMR (101 MHz, CDCl3) δ 143.9, 142.2, 139.7, 129.8, 128.5, 128.3, 127.4, 127.3, 127.3, 126.7, 119.7, 28.8, 25.8, 16.8.

[0114] Example 15:

[0115] In a reaction tube with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), 4-methyl-1,3-thiazol-5-ylvinyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added in sequence. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 16 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative (5E)-6-(4-methyl-1,3-thiazol-5-yl)hex-5-enenitrile was obtained. The chemical formula is as follows:

[0116]

[0117] The purity is 99% and the yield is 51%. Its NMR data are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.54 (s, 1H), 6.58 (d, J = 15.6 Hz, 1H), 5.90 (dt, J = 15.5, 7.1 Hz, 1H), 2.50 - 2.38 (m, 7H), 1.87 (p, J = 7.2 Hz, 2H); 13 C NMR (101 MHz, CDCl3) δ 149.3, 130.6, 121.9, 120.4, 119.4, 31.9, 24.9, 16.6, 15.3.

[0118] Example 16:

[0119] In a reaction tube with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-({[(1Z)-2,2a,3,5a-tetrahydro-1H-cyclobuta[1,2-a][5]annulen-1-ylidene]amino}oxy)-2-methylpropanoic acid (0.4 mmol, 2 equiv), styrylmethyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added in sequence. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 16 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative {2-[(1E)-2-phenylethenyl]cyclopent-3-enyl}acetonitrile was obtained. The chemical formula is as follows:

[0120]

[0121] The purity is 99% and the yield is 65%. Its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ7.36(d,J=7.4Hz,2H),7.30(t,J=7.5Hz,2H),7.22(t,J=7.2Hz,1H),6.45(d,J=15.7Hz,1H),6.21(dd,J=15.8,7.9Hz,1H),5.91(dq,J=4.8,2.2Hz,1H),5.71(dq,J=6.0,2.0Hz,1H),2.85(dtq,J=7.3,5.0,2.4Hz,1H),2.76-2.66(m,2H),2.55(dd,J=16.8,5.2Hz,1H),2.42-2.30(m,2H); 13 C NMR(101MHz,CDCl3)δ137.0,132.8,132.0,130.9,130.8,128.7,127.5,126.2,118.7,48.7,48.3,39.5,21.7.

[0122] Example 17:

[0123] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), 2-phenylprop-2-enyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 16 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was concentrated by rotary evaporation to remove the organic solvent to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative 6-phenylhept-6-enenitrile was obtained, and its chemical formula is as follows:

[0124]

[0125] With a purity of 99% and a yield of 52%, its NMR data are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.33 (m, 5H), 5.29 (s, 1H), 5.07 (s, 1H), 2.55 (t, J = 7.2 Hz, 2H), 2.31 (t, J = 6.9 Hz, 2H), 1.70 - 1.57 (m, 4H); 13 C NMR (101 MHz, CDCl3) δ 147.5, 140.8, 128.5, 127.7, 126.2, 119.8, 113.1, 34.5, 27.2, 25.0, 17.1.

[0126] Example 18:

[0127] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), 2-(2-methylphenyl)prop-2-enyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were successively added. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 16 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was concentrated by rotary evaporation to remove the organic solvent to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-inner unsaturated derivative 6-(2-methylphenyl)hept-6-enenitrile was obtained, and its chemical formula is as follows:

[0128]

[0129] With a purity of 99% and a yield of 44%, its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ7.18 - 7.11(m,3H),7.05(d,J=6.6Hz,1H),5.19(d,J=1.6Hz,1H),4.90(d,J=1.8Hz,1H),2.37(t,J=7.6Hz,2H),2.32(t,J=7.1Hz,2H),2.29(s,3H),1.68(p,J=7.4,7.1Hz,2H),1.54(p,J=7.5,7.1Hz,2H); 13 C NMR(101MHz,CDCl3)δ149.0,142.6,134.9,130.3,128.4,127.1,125.6,119.8,114.6,36.9,26.9,25.2,20.0,17.2.

[0130] Example 19:

[0131] In a reaction tube with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2 - ({[(2Z)-1,1 - dimethylcyclopent - 2 - enyl]amino}oxy)-2 - methylpropanoic acid (0.4 mmol, 2 equiv), 2 - phenylprop - 2 - enyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added in sequence. After mixing evenly, the mixture was placed under a 10W purple LED for light - stirring for 16 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano - internal unsaturated derivative 5,5 - dimethyl - 7 - phenyloct - 7 - enenitrile was obtained. The chemical formula is as follows:

[0132]

[0133] With a purity of 99% and a yield of 35%, its NMR data are as follows: 1 H NMR(400MHz,CDCl3)δ7.37 - 7.33(m,2H),7.33 - 7.28(m,2H),7.26(s,1H),5.24(d,J=2.0Hz,1H),5.03(s,1H),2.46(s,2H),2.05(t,J=7.2Hz,2H),1.58 - 1.47(m,2H),1.25 - 1.15(m,2H),0.78(s,6H); 1313C NMR (101 MHz, CDCl3) δ 147.0, 143.8, 128.3, 127.3, 126.7, 119.9, 117.2, 46.8, 41.1, 34.3, 27.7, 20.7, 17.7。

[0134] Example 20:

[0135] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-({[(1Z)-2,2a,3,5a-tetrahydro-1H-cyclobuta[1,2-a][5]annulen-1-ylidene]amino}oxy)-2-methylpropanoic acid (0.4 mmol, 2 equiv), 2-phenylprop-2-enyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added successively. After mixing evenly, the mixture was placed under a 10 W purple LED light and stirred for 16 h, controlling the stirring rate at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent using a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the cyano-containing unsaturated derivative [2-(2-phenylprop-1-en-3-yl)cyclopent-3-enyl]acetonitrile was obtained. The chemical formula is as follows:

[0136]

[0137] Purity 99%, yield 31%, and its NMR data are as follows: 1 1H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 6.9 Hz, 2H), 7.35 (t, J = 7.4 Hz, 2H), 7.29 (d, J = 7.0 Hz, 1H), 5.84 - 5.76 (m, 1H), 5.64 - 5.57 (m, 1H), 5.32 (s, 1H), 5.10 (s, 1H), 2.77 - 2.65 (m, 2H), 2.65 - 2.51 (m, 2H), 2.31 (dd, J = 16.7, 6.0 Hz, 1H), 2.18 (dd, J = 16.6, 7.3 Hz, 1H), 2.14 - 2.02 (m, 2H); 13 13C NMR (101 MHz, CDCl3) δ 146.9, 140.7, 132.7, 130.7, 128.6, 127.8, 126.3, 119.0, 114.4, 47.9, 41.6, 41.4, 38.8, 23.0。

[0138] Example 21: Synthesis of the target product using different iron catalysts

[0139] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, iron catalyst (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), phenylacetylenyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added sequentially. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent with a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the same compound as in Example 1 was obtained.

[0140] The synthesis results of different iron catalysts in this example are shown in Table 1:

[0141] Table 1

[0142] Iron catalyst Separation yield <![CDATA[Fe(acac)3]]> 88％ <![CDATA[FeCl3]]> 74％ <![CDATA[Fe(NO3)3]]> 45％

[0143] Example 22: Synthesis of the target product with different organic solvents

[0144] In a reaction tube equipped with a magnetic stir bar, under a nitrogen atmosphere, catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), phenylacetylenyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added sequentially. After mixing evenly, the mixture was placed under a 10 W purple LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent with a rotary evaporator to obtain a crude product. The crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the same compound as in Example 1 was obtained.

[0145] The synthesis results of different organic solvents in this example are shown in Table 2:

[0146] Table 2

[0147] Organic solvent Separation yield Acetonitrile 61％ Toluene 88％ Dichloromethane 31％ Dichloroethane 65％

[0148] Example 23: Synthesis of the target product with different bases

[0149] In a reaction tube with a magnetic stir bar, under a nitrogen atmosphere, the catalyst Fe(acac)3 (0.01 mmol, 5 mol%), 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid (0.4 mmol, 2 equiv), phenyl ethynyl methyl sulfone (0.2 mmol, 1 equiv), KOH (0.1 mmol, 0.5 equiv) and toluene solvent (2 mL) were added in sequence. After mixing evenly, the mixture was placed under a purple 10 W LED for light stirring for 8 h, and the stirring rate was controlled at 500 rpm. After the reaction was completed, the reaction mixture was evaporated to remove the organic solvent by a rotary evaporator to obtain a crude product, and the crude product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, and finally the same compound as in Example 1 was obtained.

[0150] The synthesis results of different bases in this example are shown in Table 3:

[0151] Table 3

[0152] Base Separation yield Potassium hydroxide 88％ Potassium carbonate 61％ Sodium bicarbonate 65％ Triethylamine 68％

[0153] Although the present invention has been illustrated by the previous specific examples, it should not be construed as being limited thereto; rather, the present invention covers the general aspects disclosed previously. Various modifications and various embodiments can be made without departing from the spirit and scope of the present invention.

Claims

1. A method for the iron-catalyzed photoinduced preparation of cyano-inner unsaturated derivatives, characterized in that The method is specifically carried out according to the following steps: First, put the catalyst iron salt, unsaturated sulfonyl reagent, cyclooxime acid compound and base into a solvent to obtain a reaction solution: Second, irradiate the reaction solution obtained in the first step with a purple LED at room temperature; after the reaction is completed, remove the organic solvent by a rotary evaporator to obtain a crude product, and then separate it by silica gel column chromatography, using petroleum ether and ethyl acetate as eluents to prepare a cyano-containing unsaturated derivative; The catalyst iron salt is Fe(acac)3 or FeCl3; The unsaturated sulfonyl reagent is phenylethynylmethyl sulfone, p-methylphenylethynylmethyl sulfone, p-phenylphenylethynylmethyl sulfone, 1-nonynylmethyl sulfone, 2-thiophenylethynylmethyl sulfone, styrenylmethyl sulfone, 1-pyridylethynylmethyl sulfone, pentafluorophenylethynylmethyl sulfone, 1,1-diphenylethynylmethyl sulfone, 4-methyl-1,3-thiazol-5-ylvinylmethyl sulfone, 2-phenylprop-2-enylmethyl sulfone or 2-(2-methylphenyl)prop-2-enylmethyl sulfone; The cyclooxime acid compound is 2-[(cyclobutylideneamino)oxy]-2-methylpropanoic acid, 2-methyl-2-{[(3-phenylcyclobutylidene)amino]oxy}propanoic acid, 2-({[3-(ethoxycarbonyl)cyclobutylidene]amino}oxy)-2-methylpropanoic acid, 2-methyl-2-{[(7-{[(2-methylprop-2-yl)oxy]carbonyl}-7-azaspiro[3.5]non-2-ylidene)amino]oxy}propanoic acid, 2-({[(2Z)-1,1-dimethylcyclopent-2-ylidene]amino}oxy)-2-methylpropanoic acid or 2-({[(1Z)-2,2a,3,5a-tetrahydro-1H-cyclobuta[1,2-a][5]annulen-1-ylidene]amino}oxy)-2-methylpropanoic acid; The base is potassium hydroxide, potassium carbonate, sodium bicarbonate or triethylamine; The solvent is acetonitrile, toluene or dichloroethane.

2. The method for preparing an endo-unsaturated cyano derivative by iron-catalyzed photoinduction according to claim 1, wherein The molar ratio of the unsaturated sulfonyl reagent to the cyclooxime acid compound described in the first step is 1:2; The dosage of the iron salt is 5% - 20% of the molar dosage of the unsaturated sulfonyl reagent; The dosage of the base is 50% of the molar dosage of the unsaturated sulfonyl reagent.

3. The method for preparing cyano-inner unsaturated derivatives by iron-catalyzed photoinduction according to claim 1, wherein The reaction described in the second step is carried out under a nitrogen atmosphere with stirring.

4. The method for preparing cyano-inner unsaturated derivatives by iron-catalyzed photoinduction according to claim 1, wherein The power of the purple LED described in the second step is 10W, and the irradiation time is 8 - 24h.

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