A method for preparing an organostannane compound catalyzed by diethylzinc

Abstract

The present invention provides a method for preparing an organostannane compound catalyzed by diethylzinc, belonging to the technical field of preparing stannane compounds. The method can solve the problems urgently needed to be solved in the preparation method of such stannane compounds. The method comprises: mixing an acetylene compound, a tin hydrogen compound, and a diethylzinc catalyst under an inert atmosphere; reacting the reaction system at 60 to 70°C for 18 to 24 hours, then exposing the reaction system to air to terminate the reaction, and purifying the organostannane compound by column chromatography, wherein the inert atmosphere is nitrogen. The stannane compound is a vinyl stannane compound or an ethynyl stannane compound, and the acetylene compound is an aliphatic acetylene compound or an aromatic acetylene compound. The present invention solves the problems urgently needed to be solved in the preparation method of such organostannane compounds, such as the high cost of the catalyst used, the environmentally unfriendly nature of the catalyst, and the complex operation process.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of organostannane compounds, in particular to a method for preparing organostannane compounds catalyzed by diethyl zinc. Background Art

[0002] Organostannanes are a valuable class of organometallic compounds with a wide range of applications in industry, agriculture, biology, and organic synthesis. Organostannanes are insensitive to oxygen and water, maintaining stable chemical properties during long-term storage and use, making them essential versatile organometallic reagents in organic synthesis.

[0003] Vinylstannanes are important synthetic intermediates that can be coupled with a variety of electrophiles. Alkynylstannanes can be transformed into various targets and have also been used as organometallic reagents. For the hydrotinylation of alkynes, free radical hydrotinylation, strong Lewis acid-mediated, and transition metal-catalyzed methods have been developed to provide (Z)- and (E)-vinylstannanes, respectively. The synthetic advantages of organostannanes involving alkynylstannanes can be attributed to the favorable balance of reactivity and stability that other organostannanes lack. One method for achieving cross-coupling at sp-hybridized carbon atoms is the Stille reaction. The necessary coupling reagent is an alkynyl-substituted tin compound, typically prepared by reacting an alkaline (earth) metal acetylide with a tin electrophile such as R3SnCl and R3SnBr (R is alkyl or aryl). Alkynylstannanes can also be synthesized by direct bonding of tin amides and alkoxides with terminal acetylenes.

[0004] The most direct and atom-economical route to vinylstannanes and alkynylstannanes is the direct reaction of R3Sn-H with alkynes. The most commonly used tin hydride reagent is tri-n-butyltin hydride (Bu3SnH) due to its low cost, ease of handling, and high reactivity. Trimethyltin hydride and triphenyltin hydride are also widely used, but the former is toxic and volatile, while the latter adds more slowly to alkynes than tri-n-butyltin hydride.

[0005] The literature reports that metal Zn catalysis is used to simultaneously synthesize vinyl stannane and alkynyl stannane compounds in a one-step reaction (Kai, Y.; Oku, S.; Tani, T.; Sakurai, K.; Tsuchimoto, T, Advanced Synthesis & Catalysis 2019, 361(18), 4314-4323). This method uses Zn(OTf)2 as a catalyst under an inert atmosphere and reacts at 70°C for 8 hours to carry out the organotin reaction of phenylacetylene. This method uses a variety of catalysts. First, Zn(OTf)2 (7.27 mg, 20.0 μmol) is placed in a 20 mL Schlenk bottle, heated at 150°C in vacuum for 1.5 hours, cooled to room temperature, and filled with argon. EtCN (0.40 mL) is added to the bottle and stirred at room temperature for 3 minutes. To this, phenylacetylene (0.400 mmol), tri-n-butyltin hydride (140 mg, 0.480 mmol), and pyridine (3.16 mg, 40.0 μmol) were added. The mixture was stirred at 70°C for 8 h, and then a saturated aqueous NH4F solution (0.5 mL) was added. The aqueous phase was extracted with ethyl acetate (5 mL x 3). The resulting oily mixture was dried over anhydrous sodium sulfate and then purified by silica gel column chromatography to obtain vinylstannane and alkynylstannane, respectively. Furthermore, this method requires a relatively large amount of pyridine during the reaction, accounting for 10% of the molar amount of the acetylenic compound. Furthermore, pyridine is highly toxic and poses a significant environmental risk.

[0006] The urgent problems to be solved in the preparation method of acetylene compounds are to use environmentally friendly metal catalysts, simplify the operation process and reduce costs. Summary of the Invention

[0007] The purpose of the present invention is to provide a method for preparing an organic stannane compound, which adopts a commercialized, environmentally friendly catalyst, reduces the types of catalysts, simplifies the operation process, and solves the urgent problems to be solved in the preparation method of the organic stannane compound.

[0008] The technical solutions of the present invention are as follows:

[0009] A method for preparing an organotin compound catalyzed by diethyl zinc, characterized by comprising the following steps:

[0010] Step 1: Under an inert atmosphere, an acetylene compound and a tin hydride compound are mixed, and then diethylzinc is added;

[0011] Step 2: The reaction system is reacted at 60-70° C. for 18-24 hours, and then exposed to air to terminate the reaction to obtain the organotin compound.

[0012] The inert atmosphere in step 1 is nitrogen.

[0013] The acetylene compound is an aromatic acetylene compound or an aliphatic acetylene compound.

[0014] The aromatic acetylene compound is phenylacetylene, 2-fluorophenylacetylene, 3-fluorophenylacetylene, 4-fluorophenylacetylene, 2-methylphenylacetylene, 3-methylphenylacetylene, 4-methylphenylacetylene, 2-(trifluoromethyl)phenylacetylene, 3-(trifluoromethyl)phenylacetylene, 4-(trifluoromethyl)phenylacetylene, 4-methoxyphenylacetylene or 4-tert-butylphenylacetylene.

[0015] The aliphatic acetylene compound is 1-ethynylcyclohexene.

[0016] The tin hydrogen compound is tri-n-butyltin hydrogen.

[0017] The molar ratio of the acetylene compound to the tin hydrogen compound is (1.05-1.1):1.

[0018] The molar amount of the diethyl zinc is 4-5% of the molar amount of the tin hydrogen.

[0019] The invention provides a method for preparing vinylstannane compounds and alkynylstannane compounds catalyzed by diethyl zinc. Zinc is a common metal, not a rare earth metal, and is easily available and inexpensive. The catalyst is also environmentally friendly, thus solving the problems that need to be solved, such as environmental pollution, high catalyst cost, and difficulty in obtaining the catalyst used in the preparation method of such organotin compounds. DETAILED DESCRIPTION

[0020] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0021] Example 1

[0022] According to the technical solution of the present invention, a specific application method includes the following steps:

[0023] (1) In an inert atmosphere, i.e., in a nitrogen-protected glove box, a tin hydrogen compound and an acetylene compound are mixed in a molar ratio, and then a catalyst, diethylzinc, is added;

[0024] (2) reacting the mixed system obtained in (1) at 60-70° C. for 18-24 hours, and then exposing it to air to terminate the reaction, thereby obtaining the organotin compound.

[0025] Wherein, the tin hydride is preferably tri-n-butyltin hydride, and its reaction formula is as follows:

[0026]

[0027] Among them, R 1 Alkyl or aryl, R 2 Any one selected from H, alkyl, or aryl.

[0028] The reaction of phenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0029] Step 1: In a nitrogen-protected glove box, phenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction bottle, and then 0.05 mL (5 mmol%) of 1 mol / L diethylzinc was added via syringe;

[0030] Step 2: The obtained mixture was heated in an oil bath at 65°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13 C NMR and 119 Sn NMR test, the nuclear magnetic data of the obtained product are as follows:

[0031] 1 H NMR (400MHz, CDCl3) δ7.41(d,J=7.6Hz,2H),7.31(t,J=7.4Hz,2H),7.22(d,J=8.2Hz,1H), 6.95–6.78(m,2H),1.55(p,J=8.3,7.9Hz,6H),1.34(q,J=7.4Hz,6H),1.00–0.94(m,15H).

[0032] 13 C NMR (101MHz, CDCl3) δ146.07,138.89,129.58,128.47,127.50,126.00,29.15,27.32,13.72,9.64.

[0033] 119 SnNMR(149MHz, CDCl3)δ-43.58,-56.27,-64.29.

[0034] Calculated product 1 The H NMR yield was 99%, (α / β = 99:1, E / Z = 90:10, C 20 H 32 Sn:C 20 H 34 Sn=72:28).

[0035] Example 2

[0036] Vinylstannane and ethynylstannane compounds were prepared by the process of Example 1, except that the mixture was heated in an oil bath at 60°C for 24 hours and then exposed to air to terminate the reaction. The vinylstannane compound was obtained by dissolving the product with CDCl3. The product was calculated. 1 The H-NMR yield was 88% (α / β=99:1, E / Z=85:15, C 20 H 32 Sn:C 20 H 34 Sn=70:30).

[0037] Example 3

[0038] Vinylstannane and ethynylstannane compounds were prepared by the process of Example 1, except that 0.04 mL (4 mmol%) of 1 mol / L diethylzinc was added, and then heated in a 70°C oil bath for 24 h. The reaction was terminated by exposure to air to obtain vinylstannane compounds. The products were dissolved in CDCl3 and the product was calculated. 1 The H-NMR yield was 95% (α / β=99:1, E / Z=88:12, C 20 H 32 Sn:C 20 H 34 Sn=83:17).

[0039] Example 4

[0040] Vinylstannane and ethynylstannane compounds were prepared by the process of Example 1, except that the mixture was heated in an oil bath at 70°C for 18 h and then exposed to air to terminate the reaction. Vinylstannane and ethynylstannane compounds were obtained. The products were dissolved in CDCl3 and the product was calculated. 1 The H-NMR yield was 85% (α / β=99:1, E / Z=80:20, C 20 H 32 Sn:C 20 H 34 Sn=80:20).

[0041] Example 5

[0042] Vinylstannane and ethynylstannane compounds were prepared by the process of Example 1, except that the mixture was heated in an oil bath at 70°C for 20 h and the reaction was terminated by exposure to air to obtain vinylstannane compounds. The products were dissolved in CDCl3 and the product was calculated. 1 The H-NMR yield was 90% (α / β=99:1, E / Z=85:15, C 20 H 32Sn:C 20 H 34 Sn=80:20).

[0043] Example 6

[0044] Vinylstannane and ethynylstannane compounds were prepared by the process of Example 1, except that the mixture was heated in an oil bath at 70°C for 22 hours and then exposed to air to terminate the reaction. Vinylstannane and ethynylstannane compounds were obtained. The products were dissolved in CDCl3 and the product was calculated. 1 The H-NMR yield was 95% (α / β=99:1, E / Z=90:10, C 20 H 32 Sn:C 20 H 34 Sn=85:15).

[0045] Example 7

[0046] Vinylstannane and ethynylstannane compounds were prepared by the process of Example 1, except that 1 mmol of phenylacetylene was added. The mixture was then heated in an oil bath at 70°C for 24 h and exposed to air to terminate the reaction. Vinylstannane and ethynylstannane compounds were obtained. The products were dissolved in CDCl3 and the product was calculated. 1 The H-NMR yield was 80% (α / β=99:1, E / Z=75:25, C 20 H 32 Sn:C 20 H 34 Sn=80:20).

[0047] Example 8

[0048] Vinylstannane and ethynylstannane compounds were prepared by the process of Example 1, except that 1 ml of toluene was added as the reaction solvent, and then heated in a 70°C oil bath for 24 h. The reaction was terminated by exposure to air to obtain vinylstannane compounds. The products were dissolved in CDCl3 and the product was calculated. 1 The H-NMR yield was 70% (α / β=99:1, E / Z=70:30, C 20 H 32 Sn:C 20 H 34 Sn=60:40).

[0049] Example 9

[0050] The reaction of 4-fluorophenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0051] Step 1: In a nitrogen-protected glove box, 4-fluorophenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction bottle, and then 0.05 mL (5 mmol%) of 1 mol / L diethylzinc was added via syringe;

[0052] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0053] 1 H NMR (400MHz, CDCl3) δ: 7.29 (dd, J=8.6, 5.6Hz, 2H), 6.92 (t, J=8.7Hz, 2H), 6.7 2(d,J=16.0Hz,2H),1.52-1.42(m,6H),1.31-1.13(m,6H),0.92-0.71(m,15H).

[0054] 13 C NMR (101MHz, CDCl3) δ: 162.55, 160.10, 143.69, 134.12, 128.20, 126.39, 114.37, 28.10, 26.28, 12.67, 8.60.

[0055] 119 Sn NMR(149MHz, CDCl3)δ:-36.40,-48.12,-64.26.

[0056] Calculated product 1 The H-NMR yield was 92% (α / β=99:1, E / Z=87:13, C 20 H 32 Sn:C 20 H 34 Sn=26:74).

[0057] Example 10

[0058] The reaction of 4-(trifluoromethyl)phenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0059] Step 1: In a nitrogen-protected glove box, 4-(trifluoromethyl)phenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction bottle, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe;

[0060] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0061] 1 H NMR (400MHz, CDCl3) δ7.59(d,J=8.3Hz,2H),7.51(d,J=8.1Hz,2H),7.10–6.86(m,2 H),1.64–1.53(m,6H),1.41–1.34(m,6H),1.05–1.00(m,6H),0.94(t,J=7.3Hz,9H).

[0062] 13 C NMR (101MHz, CDCl3) δ144.72,142.16,133.95,127.51,126.28,125.62,125.58,29.29,27.47,13.85,9.83.

[0063] 119 Sn NMR(149MHz, CDCl3)δ-43.15,-55.91,-64.74.

[0064] Calculated product 1 The H-NMR yield was 92% (α / β=99:1, E / Z=87:13, C 20 H 32 Sn:C 20 H 34 Sn=6:94).

[0065] Example 11

[0066] The reaction of 4-tert-butylphenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0067] Step 1: In a nitrogen-protected glove box, 4-tert-butylphenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction bottle, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe.

[0068] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0069] 1 H NMR (400MHz, CDCl3) δ7.37 (s, 4H), 6.93–6.74 (m, 2H), 1.60–1.50 (m, 6H), 1.33 (d, J = 1.3Hz, 15H), 0.94 (dt, J = 22.3, 7.7Hz, 16H).

[0070] 13 C NMR (101MHz, CDCl3) δ150.75,147.35,145.97,136.38,128.54,125.83,34.70,31.47,29.28,27.45,13.87,9.77.

[0071] 119 SnNMR(149MHz, CDCl3)δ-43.29,-56.33,-64.21.

[0072] Calculated product 1 The H-NMR yield was 97% (α / β=99:1, E / Z=84:16, C 20 H 32 Sn:C 20 H 34 Sn=6:94).

[0073] Example 12

[0074] The reaction of 4-methoxyphenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0075] Step 1: In a nitrogen-protected glove box, 4-methoxyphenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction vial, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe.

[0076] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0077] 1 H NMR (400MHz, CDCl3) δ7.26 (dd, J = 8.9, 2.7Hz, 2H), 6.81–6.53 (m, 4H), 3.70 (s, 3H), 1.55–1.37 (m, 6H), 1.26 (q, J = 7.3Hz, 6H), 0.95–0.71 (m, 15H).

[0078] 13 C NMR (101MHz, CDCl3) δ159.29,145.47,132.06,127.17,126.41,113.88,55.28,29.18,27.34,13.73,9.64.

[0079] 119 Sn NMR(149MHz, CDCl3)δ-43.24,-56.41,-66.33.

[0080] Calculated product 1 The H-NMR yield was 98% (α / β=99:1, E / Z=88:12, C 20 H 32 Sn:C 20 H 34 Sn=13:87).

[0081] Example 13

[0082] The reaction of 3-fluorophenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0083] Step 1: In a nitrogen-protected glove box, 3-fluorophenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction vial, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe.

[0084] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0085] 1 H NMR (400MHz, CDCl3) δ7.22–7.16(m,1H),7.10–6.94(m,2H),6.92–6.69(m,3H),1.53–1.39(m,6H),1.27(q,J=7.3Hz,6H),0.93–0.73(m,15H).

[0086] 13 C NMR (101MHz, CDCl3) δ164.48,162.05,144.75,141.20,131.69,129.88,121.93,114.11,112.39,29.11,27.29,13.69,9.65.

[0087] 119 Sn NMR(149MHz, CDCl3)δ-43.21,-56.08,-64.43.

[0088] Calculated product 1 The H-NMR yield was 87% (α / β=99:1, E / Z=92:8, C 20 H 32 Sn:C 20 H 34 Sn=17:83).

[0089] Example 14

[0090] The reaction of 3-(trifluoromethyl)phenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0091] Step 1: In a nitrogen-protected glove box, 3-(trifluoromethyl)phenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction vial, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe.

[0092] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0093] 1 H NMR (400MHz, CDCl3) δ7.66 (s, 1H), 7.58 (d, J = 7.3Hz, 1H), 7.49–7.42 (m, 2H), 7.06–6.83(m,2H),1.63–1.51(m,6H),1.41–1.33(m,6H),1.05–0.90(m,15H).

[0094] 13 C NMR (101MHz, CDCl3) δ144.21,139.23,132.41,129.03,128.76,123.88,122.52,29.01,27.11,13.58,9.53.

[0095] 119 Sn NMR(149MHz,Chloroform-d)δ-43.01,-55.82,-64.67.

[0096] Calculated product 1 The H-NMR yield was 97% (α / β=99:1, E / Z=92:8, C 20 H 32 Sn:C 20 H 34 Sn=39:61).

[0097] Example 15

[0098] The reaction of 3-methylphenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0099] Step 1: In a nitrogen-protected glove box, 3-methylphenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction vial, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe.

[0100] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. Vinylstannane and ethynylstannane compounds were purified by column chromatography using petroleum ether as the elution system. The products were dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0101] 1 H NMR (400MHz, CDCl3) δ7.17–6.94(m,4H),6.86–6.67(m,2H),2.27(s,3H),1.51–1.41(m,6H),1.32–1.22(m,6H),0.91–0.73(m,15H).

[0102] 13 C NMR (101MHz, CDCl3) δ146.19,138.85,138.00,129.23,128.38,128.30,126.72,123.18,29.15,27.32,21.41,13.72,9.63.

[0103] 119 Sn NMR(149MHz, CDCl3)δ-43.57,-56.34,-65.89.

[0104] Calculated product 1 The H-NMR yield was 82% (α / β=99:1, E / Z=86:14, C 20 H 32 Sn:C 20 H 34 Sn=20:80).

[0105] Example 16

[0106] The reaction of 2-fluorophenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0107] Step 1: In a nitrogen-protected glove box, 2-fluorophenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction vial, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe.

[0108] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0109] 1 H NMR (400MHz, CDCl3) δ7.50(dd,J=7.7,1.7Hz,1H),7.26–7.22(m,1H),7.17(dd,J=4.4,1.3Hz,1H),7.15–7.12(m,1H),7. 07(td,J=7.6,1.8Hz,1H),6.80(d,J=19.4Hz,1H),1.52–1.44(m,6H),1.30–1.24(m,6H),0.88(dt,J=31.9,7.7Hz,15H).

[0110] 13 C NMR (101MHz, CDCl3) δ142.00,136.89,133.65,132.67,129.59,128.36,126.73,126.59,29.12,27.29,13.71,9.77.

[0111] 119 Sn NMR(149MHz, CDCl3)δ-42.75,-55.69,-63.82.

[0112] Calculated product 1 The H-NMR yield was 88% (α / β=99:1, E / Z=96:4, C 20 H 32 Sn:C 20 H 34 Sn=16:84).

[0113] Example 17

[0114] The reaction of 2-methylphenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0115] Step 1: In a nitrogen-protected glove box, 2-methylphenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction bottle, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe.

[0116] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0117] 1 H NMR (400MHz, CDCl3) δ7.46(d,J=7.4Hz,1H),7.19–7.12(m,3H),7.10(d,J=19.4Hz,1H),6.71(d,J=19. 4Hz,1H),2.35(s,3H),1.59–1.52(m,6H),1.38–1.30(m,6H),0.99–0.95(m,6H),0.91(t,J=7.3Hz,9H).

[0118] 13 C NMR (101MHz, CDCl3) δ144.32,138.61,134.87,131.49,130.36,127.45,126.21,125.39,29.31,27.45,19.78,13.88,9.85.

[0119] 119 Sn NMR(149MHz, CDCl3)δ-43.85,56.32,-63.78.

[0120] Calculated product 1 The H-NMR yield was 98% (α / β=99:1, E / Z=96:4, C 20 H 32 Sn:C 20 H 34 Sn=26:74).

[0121] Example 18

[0122] The reaction of 2-(trifluoromethyl)phenylacetylene with tri-n-butyltin hydride catalyzed by diethylzinc

[0123] Step 1: In a nitrogen-protected glove box, 2-(trifluoromethyl)phenylacetylene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction vial, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe.

[0124] Step 2: The obtained mixture was heated in an oil bath at 70°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain the vinyl stannane compound. The product was dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0125] 1H NMR(400MHz, CDCl3):7.67(d,J=7.8Hz,1H),7.60(d,J=7.8Hz,1H),7.50(t,J=7.6Hz,1H),7.35–7.22( m,2H),6.99–6.81(m,1H),1.61–1.50(m,6H),1.42–1.25(m,6H),1.03–0.96(m,6H),0.940.88(m,9H).

[0126] 13 C NMR (101MHz, CDCl3): 141.7, 138.2, 135.7, 131.7, 127.0, 126.9, 125.4, 125.4, 29.1, 29.0, 27.2, 13.6, 9.7.

[0127] 119 Sn NMR(149MHz, CDCl3)δ-44.15,-56.50,-64.39.

[0128] Calculated product 1 The H-NMR yield was 98% (α / β=99:1, E / Z=35.5:64.5, C 20 H 32 Sn:C 20 H 34 Sn=26:74).

[0129] Example 19

[0130] Reaction of 1-ethynylcyclohexene with tri-n-butyltin hydride catalyzed by diethylzinc

[0131] Step 1: In a nitrogen-protected glove box, 1-ethynylcyclohexene (1.1 mmol) and tri-n-butyltin hydride (1 mmol) were mixed in a 10 mL reaction bottle, followed by the addition of 0.05 mL (5 mmol%) of 1 mol / L diethylzinc via syringe.

[0132] Step 2: The obtained mixture was heated in an oil bath at 60°C for 24 h, and then exposed to air to terminate the reaction. The crude product was purified by column chromatography using petroleum ether as the elution system to obtain vinyl stannane and ethynyl stannane compounds. The product was dissolved in CDCl3, sampled, and subjected to 1 H NMR, 13 C NMR and 119 Sn NMR spectrum test, the nuclear magnetic data of the obtained product are as follows:

[0133] 1 H NMR (400MHz, CDCl3) δ6.45(d,J=19.4Hz,1H),5.97(d,J=19.4Hz,1H),5.67(d,J=4.7Hz,1H),2.08(dt,J=6.4,3 .1Hz,4H),1.56-1.50(m,4H),1.42(dd,J=7.5,3.0Hz,6H),1.24(dd,J=7.5,3.1Hz,6H),0.82(t,J=7.1Hz,15H).

[0134] 13 C NMR (101MHz, CDCl3) δ148.85,136.65,128.38,122.57,28.12,26.30,24.85,22.87,21.70,21.53,12.67,8.47.

[0135] 119 Sn NMR(149MHz, CDCl3)δ-44.15,-56.50,-65.32.

[0136] Calculated product 1 The H-NMR yield was 92% (α / β=99:1, E / Z=60:40, C 20 H 32 Sn:C 20 H 34 Sn=41:59).

Claims

1. A method for preparing an organostannane compound catalyzed by diethyl zinc, characterized in that The following steps are involved: Step 1: Under an inert atmosphere, an acetylene compound and a tin hydride compound are mixed, and then diethyl zinc is added, wherein the acetylene compound is an aromatic acetylene compound or an aliphatic acetylene compound, the aromatic acetylene compound is phenylacetylene, 2-fluorophenylacetylene, 3-fluorophenylacetylene, 4-fluorophenylacetylene, 2-methylphenylacetylene, 3-methylphenylacetylene, 4-methylphenylacetylene, 2-(trifluoromethyl)phenylacetylene, 3-(trifluoromethyl)phenylacetylene, 4-(trifluoromethyl)phenylacetylene, 4-methoxyphenylacetylene or 4-tert-butylphenylacetylene, the aliphatic acetylene compound is 1-ethynylcyclohexene, and the tin hydride compound is tri-n-butyltin hydride; Step 2: The reaction system is reacted at 60-70° C. for 18-24 hours, and then exposed to air to terminate the reaction to obtain the organic stannane compound.

2. The method for preparing an organostanyl compound according to claim 1, wherein : The inert atmosphere in step 1 is nitrogen.

3. The method for preparing an organostanyl compound according to claim 1, wherein :The molar ratio of the acetylene compound to the tin hydrogen compound is (1.05-1.1):

1.

4. The method for preparing an organostanyl compound according to claim 1, wherein The molar amount of the diethyl zinc is 3 to 5% of the molar amount of the acetylene compound.

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