A NNN-pyridine-quinoline type cobalt complex and its preparation method, and a catalyzed hydrosilylation reaction of alkynes.

Abstract

This invention relates to an NNN-pyridine-quinoline type cobalt complex, its preparation method, and a catalytic hydrosilylation reaction of alkynes. The hydrosilylation reaction of alkynes catalyzed by the NNN-pyridine-quinoline type cobalt complex includes the following steps: dissolving alkynes, diphenylsilane, and additives in an organic solvent; using the NNN-pyridine-quinoline type cobalt complex as a catalyst; and conducting the hydrosilylation reaction of alkynes to obtain a martensitic olefin addition product. The NNN-pyridine-quinoline type cobalt complex and its preparation method described in this invention, along with the catalytic hydrosilylation reaction of alkynes, offer a simple and low-cost synthesis method for the NNN-pyridine-quinoline type cobalt complex, exhibiting high catalytic activity. It overcomes the drawback of traditional hydrosilylation reactions requiring precious metals such as platinum, providing a new approach for industrial hydrosilylation reactions.

Description

Technical Field

[0001] This invention belongs to the field of organic chemical synthesis technology, specifically relating to an NNN-pyridine-quinoline type cobalt complex and its preparation method, and a catalyzed hydrosilylation reaction of alkynes. Background Technology

[0002] Alkenes and silicon compounds are an important class of organic compounds with abundant chemical reactivity and diverse structures, finding wide applications in organic synthesis, organometallic chemistry, and materials chemistry. The hydrosilylation reaction of alkynes with silane reagents is an efficient synthetic method for alkenes due to its atom economy and step economy. Through the hydrosilylation reaction of alkynes, a variety of organic compounds with biological activity or industrial applications can be synthesized, such as pharmaceuticals, pesticides, and polymer materials.

[0003] With the advancement of the reaction, transition metal-catalyzed hydrosilylation of alkynes has achieved great success. However, traditional catalysts such as platinum catalysts, although having good catalytic effects, are expensive and difficult to recover. In recent years, inexpensive metal catalysts such as cobalt or iron catalysts have made good progress in the hydrosilylation of alkynes, but they still have problems such as poor chemoselectivity and regioselectivity, and a narrow range of substrate applications. Therefore, it is necessary to develop inexpensive metal catalysts with good chemoselectivity and broad substrate applicability for the hydrosilylation of alkynes.

[0004] In view of this, the present invention proposes a novel catalyst—NNN-pyridine-quinoline type cobalt complex, its preparation method, and its application in the hydrosilylation reaction of alkynes. Summary of the Invention

[0005] The first objective of this invention is to provide an NNN-pyridine-quinoline type cobalt complex that can be used as a catalyst for catalyzing the hydrosilylation reaction of alkynes.

[0006] To achieve the above objectives, the following technical solution is adopted:

[0007] An NNN-pyridine-quinoline type cobalt complex has the following structural formula:

[0008]

[0009] In the structural formula, X is Cl or Br.

[0010] The second objective of this invention is to provide a method for preparing the above-mentioned NNN-pyridine-quinoline cobalt complex, which is simple and low in cost.

[0011] To achieve the above objectives, the following technical solution is adopted:

[0012] The preparation method of the above-mentioned NNN-pyridine-quinoline type cobalt complex, wherein the chemical reaction formula of the preparation method is as follows:

[0013]

[0014] Furthermore, the specific steps include:

[0015] (1) 2-(chloromethyl)pyridine is coupled with an 8-aminopyridine compound to generate intermediate 1, namely N-(pyridin-2-ylmethyl)quinoline-8-amine;

[0016] (2) The intermediate 1 is coordinated with a cobalt salt at room temperature to obtain an NNN-pyridine-quinoline type cobalt complex; the cobalt salt is CoCl2 or CoBr2.

[0017] The third objective of this invention is to provide a hydrosilylation reaction of alkynes catalyzed by an NNN-pyridine-quinoline type cobalt complex. Using the aforementioned NNN-pyridine-quinoline type cobalt complex as a catalyst is inexpensive and readily available, and can replace noble metal catalysts in the hydrosilylation reaction of alkynes. It has a wide range of substrate applications, not only applicable to terminal alkynes, but also to aryl internal alkynes, aliphatic internal alkynes, and asymmetric internal alkynes, etc., and has high regioselectivity and chemoselectivity, providing a new approach for industrial hydrosilylation reactions.

[0018] To achieve the above objectives, the following technical solution is adopted:

[0019] A hydrosilylation reaction of alkynes catalyzed by an NNN-pyridine-quinoline type cobalt complex has the following chemical reaction formula:

[0020]

[0021] In the reaction formula, R1 is an aliphatic chain or a benzene ring substituent; R2 is an aliphatic chain, a benzene ring substituent, or H.

[0022] Furthermore, this includes the following steps:

[0023] Alkynes, diphenylsilane, and additives are dissolved in an organic solvent, and an NNN-pyridine-quinoline cobalt complex is used as a catalyst to carry out a hydrosilylation reaction of alkynes to obtain a martensitic olefin addition product.

[0024] The NNN-pyridine-quinoline type cobalt complex is the aforementioned NNN-pyridine-quinoline type cobalt complex.

[0025] Furthermore, the alkyne is one of the following: phenylacetylene, o-phenylacetylene, m-phenylacetylene, p-phenylacetylene, o-methoxyphenylacetylene, m-methoxyphenylacetylene, p-methoxyphenylacetylene, 4-bromophenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 2-acetylenthiophene, 3-acetylenthiophene, 3,5-dimethoxyphenylacetylene, 3,4-dimethoxyphenylacetylene, 4-tert-butylphenylacetylene, 3-aminophenylacetylene, 2-aminophenylacetylene, 1-acetylenylnaphthalene, 9-acetylenylphenanthrene, cyclohexyne, 1-ynylcyclohex-1-ene, 1-pentyne, 1-heptyne, diphenylacetylene, 1-phenyl-propyne, 1-phenyl-butyne, 1-phenyl-pentyne, 1-phenyl-hexyne, and 1-ethyl-4-(p-tolylynyl)benzene.

[0026] Furthermore, the additive is one of sodium tert-butoxide, potassium tert-butoxide, sodium triethylborohydride, and lithium triethylborohydride.

[0027] The organic solvent is one of N,N-dimethylformamide, acetonitrile, toluene, 1,4-dioxane, tetrahydrofuran, and diethyl ether.

[0028] The hydrosilylation reaction is carried out under nitrogen or inert conditions.

[0029] Furthermore, the molar ratio of the additives, catalysts and diphenylsilane is 2.5-5:0.5-5:100.

[0030] Furthermore, the hydrosilylation reaction is carried out at a temperature of room temperature to 70°C for a time of 12-24 hours.

[0031] Furthermore, the hydrosilylation reaction is carried out at a temperature of 60°C for 24 hours.

[0032] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0033] 1. The technical solution of the present invention utilizes inexpensive and commercially available 8-aminoquinoline and halogenated methylpyridine hydrochloride as reactants to synthesize an NNN-pyridine-quinoline type ligand, which is then coordinated with a cobalt metal salt to obtain the complex. The method is inexpensive and easy to operate.

[0034] 2. The technical solution of the present invention uses NNN-pyridine-quinoline type cobalt complex as catalyst, the synthesis steps of hydrosilylation reaction are simple, the raw materials are inexpensive, and it has good stability.

[0035] 3. The technical solution of the present invention uses NNN-pyridine-quinoline type cobalt complex as a catalyst, which has good substrate universality for participating in alkyne hydrosilylation reactions and can be applied to alkynes such as internal alkynes, aromatic alkynes, and aliphatic alkynes.

[0036] 4. The technical solution of this invention uses NNN-pyridine-quinoline type cobalt complex as a catalyst. The hydrosilylation reaction has the advantages of mild conditions, high selectivity and high yield. It breaks the traditional characteristics of using precious metals to produce organosilicon products and provides a new experimental idea for realizing cheap and efficient silicon chemical production. Detailed Implementation

[0037] To further illustrate the present invention's NNN-pyridine-quinoline type cobalt complex and its preparation method, as well as the catalyzed hydrosilylation reaction of alkynes, and to achieve the intended objectives of the invention, the following detailed description, in conjunction with preferred embodiments, details the specific implementation methods, structures, features, and effects of the NNN-pyridine-quinoline type cobalt complex and its preparation method, as well as the catalyzed hydrosilylation reaction of alkynes proposed in this invention. In the following description, different "examples" or "examples" do not necessarily refer to the same example. Furthermore, specific features, structures, or characteristics in one or more examples can be combined in any suitable manner.

[0038] The following will provide a more detailed description of the NNN-pyridine-quinoline type cobalt complex, its preparation method, and the catalyzed hydrosilylation reaction of alkynes according to the present invention, with reference to specific embodiments:

[0039] In this invention, a novel NNN-pyridine-quinoline cobalt complex is synthesized using inexpensive, commercially available 8-aminoquinoline and halogenated methylpyridine hydrochloride as reactants to synthesize an NNN-pyridine-quinoline ligand. Using CoCl2 or CoBr2 as the metal salt, the NNN-pyridine-quinoline cobalt complex is synthesized. After the reaction, only simple processing is required; column chromatography purification is unnecessary to obtain a high-purity catalyst. After obtaining the cobalt complex, it can be used to achieve hydrosilylation reactions of different types of substituted aromatic alkynes, yielding the corresponding primary addition Markovnikov products in high yield. Aliphatic alkynes and internal alkynes can also be readily converted to their corresponding primary addition products. The technical solution of this invention is as follows:

[0040] An NNN-pyridine-quinoline type cobalt complex has the following structural formula:

[0041]

[0042] In the structural formula, X is Cl or Br.

[0043] The chemical reaction formula for the preparation method of the above-mentioned NNN-pyridine-quinoline type cobalt complex is as follows:

[0044]

[0045] Preferably, it includes the following steps:

[0046] (1) 2-(chloromethyl)pyridine is coupled with an 8-aminopyridine compound to generate intermediate 1, namely N-(pyridin-2-ylmethyl)quinoline-8-amine;

[0047] (2) The intermediate 1 is coordinated with a cobalt salt at room temperature to obtain an NNN-pyridine-quinoline type cobalt complex; the cobalt salt is CoCl2 or CoBr2.

[0048] A hydrosilylation reaction of alkynes catalyzed by an NNN-pyridine-quinoline type cobalt complex, wherein the chemical reaction formula for the hydrosilylation reaction is as follows:

[0049]

[0050] In the reaction formula, R1 is an aliphatic chain or a benzene ring substituent; R2 is an aliphatic chain, a benzene ring substituent, or H.

[0051] Preferably, it includes the following steps:

[0052] Alkynes, diphenylsilane, and additives are dissolved in an organic solvent, and an NNN-pyridine-quinoline cobalt complex is used as a catalyst to carry out a hydrosilylation reaction of alkynes to obtain a martensitic olefin addition product.

[0053] More preferably, the alkyne is one of phenylacetylene, o-phenylacetylene, m-phenylacetylene, p-phenylacetylene, o-methoxyphenylacetylene, m-methoxyphenylacetylene, p-methoxyphenylacetylene, 4-bromophenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 2-acetylenthiophene, 3-acetylenthiophene, 3,5-dimethoxyphenylacetylene, 3,4-dimethoxyphenylacetylene, 4-tert-butylphenylacetylene, 3-aminophenylacetylene, 2-aminophenylacetylene, 1-acetylenylnaphthalene, 9-acetylenylphenanthrene, cyclohexyne, 1-ynylcyclohexyl-1-ene, 1-pentyne, 1-heptyne, diphenylacetylene, 1-phenyl-propyne, 1-phenyl-butyne, 1-phenyl-pentyne, 1-phenyl-hexyne, and 1-ethyl-4-(p-tolylynyl)benzene.

[0054] In the above technical solutions, the alkynes are all commercially available and require no further processing. This invention does not have special requirements for the alkynes; any alkynes or similar structures that meet the above requirements are acceptable.

[0055] More preferably, the additive is one of sodium tert-butoxide, potassium tert-butoxide, sodium triethylborohydride, and lithium triethylborohydride;

[0056] The organic solvent is one of N,N-dimethylformamide, acetonitrile, toluene, 1,4-dioxane, tetrahydrofuran, and diethyl ether.

[0057] In the above technical solutions, silanes, additives, and organic solvents can be commercially available products well-known in the field.

[0058] The hydrosilylation reaction is carried out under nitrogen or inert initiation conditions.

[0059] In the above technical solution, the present invention mixes the hydrogen-containing silane, alkyne, additive, and complex by first adding the solid, and then adding the liquid raw material under oxygen-free conditions. The specific mixing sequence is: complex, additive, hydrogen-containing silane, alkyne, and organic solvent, followed by a hydrosilylation reaction.

[0060] More preferably, the molar ratio of the additive, catalyst and silane is 2.5-5:0.5-5:100.

[0061] More preferably, the hydrosilylation reaction is carried out at a temperature of room temperature to 70°C for a time of 12-24 hours.

[0062] More preferably, the hydrosilylation reaction is carried out at a temperature of 60°C for 24 hours.

[0063] Example 1: Synthesis of NNN-pyridine-quinoline type cobalt complex

[0064] Using commercially available 8-aminoquinoline and halogenated methylpyridine hydrochloride as reactants, NNN-pyridine-quinoline ligands were synthesized. NNN-pyridine-quinoline cobalt complexes were then synthesized using CoCl2 or CoBr2 as metal salts. The synthesis of the cobalt complexes consisted of two steps, and the specific synthetic route is shown below:

[0065]

[0066] The specific operating steps are as follows:

[0067] First, 2-(chloromethyl)pyridine undergoes a coupling reaction with an 8-aminopyridine compound to generate N-(pyridin-2-ylmethyl)quinoline-8-amine (compound 1).

[0068] Then, at room temperature, compound 1 was coordinated with a cobalt salt (CoCl2 or CoBr2) to obtain a cobalt NNN clamp-shaped cobalt complex (2). The pure cobalt complex can be obtained by simple washing, and its structural formula is shown below:

[0069]

[0070] In the structural formula, X is either Cl or Br.

[0071] Examples 2-14.

[0072] The hydrosilylation reaction of alkynes catalyzed by the NNN-pyridine-quinoline cobalt complex prepared in Example 1 includes the following steps: reacting different types of alkynes with diphenylsilanes (mainly aromatic alkynes, aliphatic alkynes, and aromatic internal alkynes) to obtain martensitic olefin addition products. The reaction equation is as follows:

[0073]

[0074] In the reaction formula, R1 is an aliphatic chain or a benzene ring substituent; R2 is an aliphatic chain, a benzene ring substituent, or H.

[0075] The specific steps are as follows:

[0076] Alkynes, diphenylsilane, and additives are dissolved in an organic solvent, and an NNN-pyridine-quinoline cobalt complex is used as a catalyst to carry out a hydrosilylation reaction of alkynes to obtain a martensitic olefin addition product.

[0077] The alkyne is one of the following: phenylacetylene, o-phenylacetylene, m-phenylacetylene, p-phenylacetylene, o-methoxyphenylacetylene, m-methoxyphenylacetylene, p-methoxyphenylacetylene, 4-bromophenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 2-acetylenthiophene, 3-acetylenthiophene, 3,5-dimethoxyphenylacetylene, 3,4-dimethoxyphenylacetylene, 4-tert-butylphenylacetylene, 3-aminophenylacetylene, 2-aminophenylacetylene, 1-acetylenylnaphthalene, 9-acetylenylphenanthrene, cyclohexyne, 1-ynylcyclohex-1-ene, 1-pentyne, 1-heptyne, diphenylacetylene, 1-phenyl-propyne, 1-phenyl-butyne, 1-phenyl-pentyne, 1-phenyl-hexyne, and 1-ethyl-4-(p-tolylynyl)benzene.

[0078] The additive is one of sodium tert-butoxide, potassium tert-butoxide, sodium triethylborohydride, and lithium triethylborohydride;

[0079] The organic solvent is one of N,N-dimethylformamide, acetonitrile, toluene, 1,4-dioxane, tetrahydrofuran, and diethyl ether.

[0080] The mixing order is: complex, additive, hydrogen-containing silane, alkyne and organic solvent, followed by hydrosilylation reaction.

[0081] The molar ratio of additives, catalysts and diphenylsilane is 2.5-5:0.5-5:100.

[0082] The hydrosilylation reaction is carried out under nitrogen or inert initiation conditions.

[0083] The hydrosilylation reaction is carried out at a temperature of room temperature to 70°C for 12-24 hours. Preferably, the hydrosilylation reaction is carried out at a temperature of 60°C for 24 hours.

[0084] In Examples 2-14, X in the cobalt complex is Cl.

[0085] The reaction formula is as follows:

[0086]

[0087] The specific operating steps are as follows:

[0088] 1.0 mmol diphenylsilane, 1.1 mmol phenylacetylene, 0.5 mol% cobalt complex, 2.5 mol% sodium tert-butoxide, and 2 mL tetrahydrofuran solvent were mixed and heated to 60 °C, then reacted for 24 h. After the reaction was completed, the product was obtained by column chromatography with a yield of 95% and a selectivity of 93:7.

[0089] Note: Selectivity refers to Markovnikov products and anti-Markovnikov products.

[0090] NMR data for the product diphenyl(1-phenylvinyl)silane: 1 H NMR (400MHz, CDCl3): δ7.43 (dd, J=7.8, 1.5Hz, 4H), 7.26-7.20 (m, 8H), 7.09 (ddd ,J=7.9,4.6,3.2Hz,3H),6.16-6.13(m,1H),5.55(d,J=2.4Hz,1H),5.27(s,1H). 13 C NMR (101MHz, CDCl3): δ146.02,143.05,135.91,133.17,132.27,129.94,128.54,128.19,127.22,126.86.

[0091] Example 3.

[0092] The reaction formula is as follows:

[0093]

[0094] The specific operating steps are as follows:

[0095] 1.5 mmol of diphenylsilane, 1.1 mmol of 3-methylphenylacetylene, 0.5 mol% of cobalt complex, 2.5 mol% of sodium tert-butoxide, and 2 mL of tetrahydrofuran solvent were mixed and heated to 60 °C, then reacted for 24 h. After the reaction was completed, the product was obtained by column chromatography with a yield of 93% and a selectivity of 93:7.

[0096] The NMR data for the product diphenyl(1-(m-methylbenzene)vinyl)silane are as follows:

[0097] 1H NMR (400MHz, CDCl3) δ7.45-7.42(m,4H),7.27-7.22(m,6H),7.04-6.99(m,3H),6.91- 6.88(m,1H),6.13(t,J=3.2Hz,1H),5.53(d,J=2.4Hz,1H),5.26(s,1H),2.15(s,3H).

[0098] 13 C NMR (101MHz, CDCl3) δ150.11,147.01,142.77,140.38,137.45,137.20,135.05,133.61,133.48,133.22,131.80,128.44,26.24.

[0099] Example 4.

[0100] The reaction formula is as follows:

[0101]

[0102] The specific operating steps are as follows:

[0103] 1.0 mmol of diphenylsilane, 1.1 mmol of 2-methylphenylacetylene, 0.5 mol% cobalt complex, 2.5 mol% sodium tert-butoxide, and 2 mL of tetrahydrofuran solvent were mixed and heated to 60 °C, then reacted for 24 h. After the reaction was completed, the product diphenyl(1-(o-methylphenyl)vinyl)silane was obtained by column chromatography with a yield of 93% and a selectivity of 95:5.

[0104] NMR data for the product diphenyl(1-(o-methylbenzene)vinyl)silane:

[0105] 1 H NMR (400MHz, CDCl3) δ7.48-7.45(m,4H),7.31-7.25(m,6H),7.03-6.94(m,3H),6.85(t ,J=6.9Hz,1H),5.86(d,J=3.0Hz,1H),5.80(d,J=3.1Hz,1H),5.12(s,1H),2.11(s,3H).

[0106] 13 C NMR (101MHz, CDCl3): δ152.53,148.08,140.43,139.96,139.08,138.68,137.42,135.31,133.44,132.76,131.76,130.76,25.22.

[0107] Example 5.

[0108] The reaction formula is as follows:

[0109]

[0110] The specific operating steps are as follows:

[0111] 1.0 mmol of diphenylsilane, 1.1 mmol of 4-methylphenylacetylene, 0.5 mol% of cobalt complex, 2.5 mol% of sodium tert-butoxide, and 2 mL of tetrahydrofuran solvent were mixed and heated to 60 °C, then reacted for 24 h. After the reaction was completed, the product was separated by column chromatography with a yield of 93% and a selectivity of 94:6.

[0112] NMR data for the product diphenyl(1-(p-methylbenzene)vinyl)silane:

[0113] 1 H NMR (400MHz, CDCl3): δ7.48(d,J=6.6Hz,4H),7.27(dd,J=12.8,5.6Hz,6H),7.17(d,J=8.1Hz,2H),6.96( t,J=8.9Hz,2H),6.17(dd,J=9.6,5.0Hz,1H),5.55(d,J=2.3Hz,1H),5.31(s,1H),2.20(d,J=4.7Hz,3H).

[0114] 13 C NMR (101MHz, CDCl3): δ149.82,144.24,141.87,140.53,137.59,136.56,135.29,134.37,133.49,131.45,25.74.

[0115] Example 6.

[0116] The specific operating steps are as follows:

[0117] The reaction formula is as follows:

[0118]

[0119] (1) 1.0 mmol diphenylsilane, 1.1 mmol 4-bromophenylacetylene, 0.5 mol% cobalt complex, 2.5 mol% sodium tert-butoxide and 2 mL tetrahydrofuran solvent were mixed, heated to 60 °C, and reacted for 24 h. After the reaction was completed, the product was separated by column chromatography with a yield of 96% and a selectivity of 89:11.

[0120] NMR data for the product (1-(4-bromophenyl)vinyl)diphenylsilane:

[0121] 1 H NMR (400MHz, CDCl3): δ7.46 (d, J = 6.5 Hz, 4H), 7.28 (d, J = 7.1 Hz, 8H), 7.10 (d, J = 7.6 Hz, 2H), 6.17 (s, 1H), 5.62 (s, 1H), 5.28 (s, 1H).

[0122] 13 C NMR (101MHz, CDCl3) δ145.12,141.99,135.86,135.29,134.49,132.76,131.63,130.10,128.27,121.25.

[0123] (2) 4-fluorophenylacetylene and 4-chlorophenylacetylene were substituted for 4-bromophenylacetylene and reacted with diphenylsilane, respectively, following the same steps as in (1). NMR analysis yielded martensitic olefin addition products. The product yields were all greater than 90%.

[0124] Example 7.

[0125] The specific operating steps are as follows:

[0126] The reaction formula is as follows:

[0127]

[0128] (1) 1.0 mmol diphenylsilane, 1.1 mmol 3-acetylenthiophene, 0.5 mol% cobalt complex, 2.5 mol% sodium tert-butoxide and 2 mL tetrahydrofuran solvent were mixed, heated to 60 °C, and reacted for 24 h. After the reaction was completed, the product was separated by column chromatography with a yield of 96% and a selectivity of 96:4.

[0129] NMR data for the product diphenyl(1-(thiophen-3-yl)vinyl)silane:

[0130] 1 H NMR (400MHz, CDCl3): δ7.44 (dd, J=7.8, 1.4Hz, 4H), 7.27-7.22 (m, 6H), 7.07 (dt, J=5.0, 3.0Hz ,2H),6.97(dd,J=2.6,1.4Hz,1H),6.20(t,J=3.9Hz,1H),5.49(d,J=2.4Hz,1H),5.24(s,1H).

[0131] 13C NMR (101MHz, CDCl3): δ148.01,143.81,140.56,138.85,137.34,135.37,133.53,131.77,130.88,127.26.

[0132] (2) 2-Acetylthiophene was substituted for 3-acetylthiophene, and reacted with diphenylsilane, following the same steps as (1). NMR analysis also yielded a martensitic olefin addition product. The product yield was 95%.

[0133] Example 8.

[0134] The specific operating steps are as follows:

[0135] (1) The reaction formula is as follows:

[0136]

[0137] 1.0 mmol of diphenylsilane, 1.1 mmol of 1-phenyl-1-propyne, 0.5 mol% of cobalt complex, 2.5 mol% of sodium tert-butoxide, and 2 mL of tetrahydrofuran solvent were mixed and heated to 60 °C, then reacted for 24 h. After the reaction was completed, the product was separated by column chromatography with a yield of 85% and a selectivity of >99:1.

[0138] NMR data for product (Z)-diphenyl(2-phenylpropyl-1-en-1-yl)silane:

[0139] 1 H NMR (400MHz, CDCl3): δ7.54-7.52(m,1H),7.41(dd,J=13.6,5.5Hz,3H),7.32-7.23(m,8H),7.14(t,J=7.5Hz,2H),6.9 2(d,J=7.6Hz,1H), 6.22(dq,J=13.3,6.6Hz,1H), 5.10(d,J=7.4Hz,1H), 1.98(d,J=0.8Hz,1H), 1.63(d,J=6.7Hz,2H).

[0140] 13 C NMR (101MHz, CDCl3): δ142.88,142.12,141.10,135.80,133.60,129.75,129.63,129.15,128.48,128.14,127.93,127.05,125.87,17.58,16.38.

[0141] (2) 1-Phenylacetylene, 1-phenyl-pentylacetylene, 1-phenyl-hexylacetylene, and 1-ethyl-4-(p-tolylynyl)benzene were substituted for 1-phenyl-1-propyne and reacted with diphenylsilane, following the same steps as in (1). NMR analysis yielded martensitic olefin addition products. The product yields were all greater than 80%.

[0142] Example 9.

[0143] The specific operating steps are as follows:

[0144] (1) 1.0 mmol diphenylsilane, 1.1 mmol 1-pentyne, 1.0 mol% cobalt complex, 5 mol% sodium tert-butoxide and 0.5 mL tetrahydrofuran solvent were mixed, heated to 60 °C, and reacted for 24 h. After the reaction was completed, the product was separated by column chromatography with a yield of 75% and a selectivity of 97:3.

[0145] (2) 1-Pentyne was substituted with 1-ynylcyclohexyl-1-ene, 1-heptyne, and diphenylacetylene, and reacted with diphenylsilane, following the same steps as in (1). NMR analysis yielded martensitic olefin addition products. The product yields were all greater than 65%.

[0146] Example 10.

[0147] The specific operating steps are as follows:

[0148] (1) 1.0 mmol of diphenylsilane, 1.1 mmol of o-methoxyphenylacetylene, 5 mol% cobalt complex, 5 mol% potassium tert-butoxide, and 4 mL of N,N-dimethylformamide solvent were mixed and reacted at room temperature for 24 h. After the reaction was completed, the product was obtained by column chromatography. The olefin addition product with a martensitic structure was obtained by NMR determination.

[0149] (2) o-methoxyphenylacetylene was substituted with m-methoxyphenylacetylene and p-methoxyphenylacetylene, and reacted with diphenylsilane, with the remaining steps the same as in (1). NMR analysis yielded martensitic olefin addition products. The product yields were all greater than 90%.

[0150] Example 11.

[0151] The specific operating steps are as follows:

[0152] (1) 1.0 mmol of diphenylsilane, 1.1 mmol of 3,5-dimethoxyphenylacetylene, 2.0 mol% cobalt complex, 3.5 mol% sodium tert-butoxide, and 3 mL of acetonitrile solvent were mixed and reacted at 60 °C for 24 h. After the reaction was completed, the product was obtained by column chromatography. The olefin addition product with a martensitic structure was obtained by NMR determination.

[0153] (2) 3,5-Dimethoxyphenylacetylene was replaced with 3,4-dimethoxyphenylacetylene and 4-tert-butylphenylacetylene, respectively, and reacted with diphenylsilane. The remaining steps were the same as in (1). NMR analysis also yielded martensitic olefin addition products.

[0154] The product yields were all greater than 85%.

[0155] Example 12.

[0156] The specific operating steps are as follows:

[0157] (1) 1.0 mmol diphenylsilane, 1.1 mmol 3-aminophenylacetylene, 0.5 mol% cobalt complex, 2.5 mol% triethylborohydride, and 3 mL toluene solvent were mixed and reacted at 60 °C for 24 h. After the reaction was completed, the product was obtained by column chromatography. The olefin addition product with a martensitic structure was obtained by NMR determination.

[0158] (2) 3-Aminophenylacetylene was replaced with 2-aminophenylacetylene and reacted with diphenylsilane. The remaining steps were the same as in (1). NMR analysis also yielded a martensitic olefin addition product.

[0159] The product yields were all greater than 80%.

[0160] Example 13.

[0161] The specific operating steps are as follows:

[0162] (1) 1.0 mmol of diphenylsilane, 1.1 mmol of 1-ethynylnaphthalene, 0.5 mol% of cobalt complex, 2.5 mol% of triethyl borohydride, and 3 mL of diethyl ether solvent were mixed and reacted at 60 °C for 24 h. After the reaction was completed, the product was obtained by column chromatography. The olefin addition product with a martensitic structure was obtained by NMR determination.

[0163] (2) Using diethyl ether as a solvent, cyclohexyne replaced 1-ethynylnaphthalene and reacted with diphenylsilane. The remaining steps were the same as in (1). NMR analysis also yielded a martensitic olefin addition product.

[0164] The product yields were all greater than 70%.

[0165] Example 14.

[0166] The specific operating steps are as follows:

[0167] 1.0 mmol of diphenylsilane, 1.1 mmol of 9-ethynylphenanthrene, 0.5 mol% cobalt complex, 2.5 mol% sodium tert-butoxide, and 4 mL of 1,4-dioxane solvent were mixed and reacted at 70 °C for 12 h. After the reaction was complete, the products were separated by column chromatography. NMR analysis revealed the presence of martensitic olefin addition products. The yields of all products were greater than 70%.

[0168] Example 15.

[0169] The specific operating steps are as follows:

[0170] 1.0 mmol of diphenylsilane, 1.1 mmol of cyclohexyne, 0.5 mol% of cobalt complex (X = Br), 2.5 mol% of sodium tert-butoxide, and 2 mL of tetrahydrofuran solvent were mixed and reacted at 70 °C for 20 h. After the reaction was completed, the products were separated by column chromatography. NMR analysis revealed the presence of martensitic olefin addition products. The yields of all products were greater than 70%.

[0171] As can be seen from the above embodiments, this invention provides a method for synthesizing NNN-pyridine-quinoline type cobalt complexes and their participation in the hydrosilylation reaction of alkynes. By reacting diphenylsilane with different alkynes, using sodium tert-butoxide as an additive, the corresponding hydrosilylation products were obtained. The results varied depending on the type of alkyne reacted with; aromatic alkynes showed the best effect, followed by internal alkynes, while aliphatic alkynes showed moderate effect. The yields of the obtained hydrosilylation products ranged from 50% to 96%, with selectivity ranging from 50:50 to 99:1.

[0172] Organosilicon refers to a class of silicon-containing organic compounds with great application prospects. With the development of science and technology, the organosilicon industry has become one of the world's strategic emerging industries, and its market prospects are increasingly broad. Hydrosilylation is one of the important methods for synthesizing organosilicon, and the products produced are environmentally friendly. Commonly used hydrogen-containing silanes include benzylsilanes, diphenylsilanes, and alkoxysilanes. Considering hydrolysis and the reactivity of hydrogen, the experiment mainly focuses on diphenylsilanes and benzylsilanes, using a phenylacetylene-based alkyne reaction model to explore hydrosilylation reactions under the catalysis of synthesized cobalt complexes. This invention utilizes inexpensive and commercially available 8-aminoquinoline and halogenated methylpyridine hydrochloride as reactants to synthesize an NNN-pyridine-quinoline ligand, which is then coordinated with a cobalt metal salt to obtain the complex. This method has simple synthesis steps, inexpensive and readily available raw materials, and good stability. The cobalt complex of this invention has the advantages of mild conditions, high reaction selectivity and reactivity, and good substrate universality in the hydrosilylation reaction of alkynes. It breaks the traditional characteristics of using precious metals to produce organosilicon products and provides a new experimental approach for achieving inexpensive and efficient silicon chemical production.

[0173] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A NNN-pyrido-quinoline type cobalt complex characterized in that, The structural formula of the NNN-pyridine-quinoline type cobalt complex is shown as follows: In the structural formula, X is Cl or Br.

2. The method of producing the NNN-pyridine-quinoline type cobalt complex according to claim 1, characterized by, The preparation method comprises the following steps: (1) coupling 2-(chloromethyl)pyridine with 8-aminoquinoline compound to generate intermediate 1, i.e. N-(pyridin-2-ylmethyl)quinolin-8-amine; (2) coordinating the intermediate 1 with cobalt salt at room temperature to obtain the NNN-pyridine-quinoline type cobalt complex; the cobalt salt is CoCl2 or CoBr2.

3. A NNN-pyrido-quinoline type cobalt complex-catalyzed hydrosilylation of alkyne, characterized by, The alkyne hydrosilylation reaction comprises the following steps: dissolving alkyne, diphenylsilane and additive in an organic solvent, using the NNN-pyridine-quinoline type cobalt complex as a catalyst to perform alkyne hydrosilylation reaction, and obtaining Markovnikov configuration olefin addition product; The NNN-pyridine-quinoline type cobalt complex is the NNN-pyridine-quinoline type cobalt complex synthesized by the preparation method in claim 1 or claim 2.

4. The alkyne hydrosilylation reaction according to claim 3, wherein the alkyne is one of phenylacetylene, o-methylphenylacetylene, m-methylphenylacetylene, p-methylphenylacetylene, o-methoxyphenylacetylene, m-methoxyphenylacetylene, p-methoxyphenylacetylene, 4-bromophenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 2-ethynylthiophene, 3-ethynylthiophene, 3,5-dimethoxyphenylacetylene, 3,4-dimethoxyphenylacetylene, 4-tert-butylphenylacetylene, 3-aminophenylacetylene, 2-aminophenylacetylene, 1-ethynyl naphthalene, 9-ethynylphenanthrene, cyclohexyne, 1-alkynylcyclohex-1-ene, 1-pentyn, 1-heptyne, diphenylacetylene, 1-phenyl-propyne, 1-phenyl-butyne, 1-phenyl-pentyne, 1-phenyl-hexyne, 1-ethyl-4-(p-tolylalkynyl)benzene.

5. The alkyne hydrosilylation reaction according to claim 3, wherein the additive is one of sodium tert-butoxide, potassium tert-butoxide, sodium triethylborohydride and lithium triethylborohydride; the organic solvent is one of N,N-dimethylformamide, acetonitrile, toluene, 1,4-dioxane, tetrahydrofuran and diethyl ether; and the hydrosilylation reaction is performed under inert condition.

6. The alkyne hydrosilylation reaction according to claim 5, wherein the hydrosilylation reaction is performed under nitrogen condition.

7. The alkyne hydrosilylation reaction according to claim 5, wherein the molar ratio of the additive, the catalyst and diphenylsilane is 2.5-5:0.5-5:

100.

8. The alkyne hydrosilylation reaction according to claim 3, wherein the temperature of the hydrosilylation reaction is room temperature-70℃, and the time is 12-24h.

9. The alkyne hydrosilylation reaction according to claim 8, wherein the temperature of the hydrosilylation reaction is 60℃, and the time is 24h. ​ ​ ​ ​ ​ ​ ​ ​

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