A method for hydrodehalogenation of halogenated alkane

Abstract

The present invention provides a method for hydrogenating and dehalogenating halogenated alkanes, and belongs to the technical field of organic synthesis. The method for hydrogenating and dehalogenating halogenated alkanes of the present invention comprises the following steps: mixing halogenated alkanes, titanium metal catalysts, borane compounds and organic solvents, and performing hydrogenating and dehalogenating reaction under heating conditions in a protective atmosphere to obtain alkane compounds corresponding to the halogenated alkanes. The present invention uses borane compounds as reducing agents to reduce titanium metal catalysts in a high oxidation state to generate metal hydride intermediates (titanium hydrogen compounds), and the metal hydride intermediates further reduce halogenated alkanes to generate target alkanes. The method of the present invention is simple to operate, low in cost and high in yield.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for hydrogenating and dehalogenating halogenated alkane. Background Art

[0002] Halogenated organic matter is a common environmental pollutant. Traditional halogenated organic pollutants mainly include organic pesticides (such as chlordane, DDT, chlorobenzene, etc.), which pose a potential threat to the health of animals and plants. With the advancement of science and technology, the widespread use of organic halides has led to a significant increase in their content in the environment. Dehydrohalogenation can effectively promote the degradation of halogenated organic matter and reduce the harm of organic halides to humans and the environment. The use of transition metals to catalyze the dehydrohalogenation of halogenated alkanes can effectively avoid the use of toxic and explosive reagents, the generation of stoichiometric metal waste, poor selectivity and poor compatibility with low functional groups brought about by equivalent metal-halogen exchange or metal (such as zinc)-mediated dehydrohalogenation processes. However, transition metal-catalyzed dehydrohalogenation generally requires the participation of precious metals such as palladium, platinum, ruthenium, rhodium and nickel.

[0003] Early transition metals are abundant in the earth's crust and are cheap. However, due to their special properties (such as high oxidation state), early transition metal catalytic hydrogenation is difficult. Therefore, it is challenging to apply cheap early transition metals to the catalytic hydrogenation process of halogenated alkanes instead of precious metals. Summary of the invention

[0004] The object of the present invention is to provide a method for hydrodehalogenation of halogenated alkanes, which has the advantages of simple operation, low cost and high safety.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for hydrodehalogenation of halogenated alkanes, comprising the following steps:

[0007] The halogenated alkane, titanium metal catalyst, borane compound and organic solvent are mixed, and a hydrogenation dehalogenation reaction is carried out under heating conditions in a protective atmosphere to obtain an alkane compound corresponding to the halogenated alkane.

[0008] Preferably, the halogenated alkane has a structure shown in Formula 1:

[0009]

[0010] In formula 1, R 1 includes aryl, heteroaryl, alkyl, substituted aryl or substituted alkyl; R 2 includes alkyl or hydrogen; or R 1 and R 2 is independently cycloalkyl; X includes chlorine or bromine.

[0011] Preferably, the substituent in the substituted aryl group is methyl, tert-butyl, phenyl, methylthio, methoxy, benzyloxy, diphenylamino, chlorine, bromine, iodine or pinacol borate substituent, and the substituent in the substituted alkyl group is one or more of aryl, ether, silicon, carbazole and amino.

[0012] Preferably, the titanium metal catalyst comprises bis(cyclopentadienyl)titanium dichloride or bis(trifluoromethanesulfonate)titanocene.

[0013] Preferably, the mixing further comprises adding an alkali compound, and the alkali compound comprises lithium methoxide.

[0014] Preferably, the borane compound comprises a borane-ammine complex.

[0015] Preferably, the organic solvent is tetrahydrofuran or 1,4-dioxane.

[0016] Preferably, the molar ratio of the halogenated alkane, the titanium metal catalyst, the base compound and the borane compound is 1:(0.01-0.1):(0-1):(3-5).

[0017] Preferably, the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.

[0018] Preferably, the temperature of the hydrodehalogenation reaction is 35-100° C. and the time is 12 hours.

[0019] The present invention provides a method for hydrogenating and dehalogenating halogenated alkanes, comprising the following steps: mixing halogenated alkanes, titanium metal catalysts, borane compounds and organic solvents, and performing hydrogenating and dehalogenating reactions under heating conditions in a protective atmosphere to obtain alkane compounds corresponding to the halogenated alkanes. The present invention uses borane compounds as reducing agents to reduce titanium metal catalysts in a high oxidation state to generate metal hydride intermediates (titanium hydrogen compounds), and then uses the metal hydride intermediates to further reduce the halogenated alkanes to generate target alkanes, thereby realizing the application of pre-transition metals (titanium) in the field of catalytic hydrogenation. The method of the present invention is simple to operate, has a high yield, and has relatively mild reaction conditions, and thus has good functional group tolerance and a wide range of substrates.

[0020] The present invention uses relatively cheap titanium metal which is widely present in nature as a catalyst, thereby reducing the reaction cost.

[0021] The reaction product of the present invention has good selectivity and single product, which is conducive to separation and purification of the product. DETAILED DESCRIPTION

[0022] The present invention provides a method for hydrodehalogenation of halogenated alkanes, comprising the following steps:

[0023] The halogenated alkane, titanium metal catalyst, borane compound and organic solvent are mixed, and a hydrogenation dehalogenation reaction is carried out under heating conditions in a protective atmosphere to obtain an alkane compound corresponding to the halogenated alkane.

[0024] In the present invention, unless otherwise specified, the required raw materials or instruments are commercially available products well known to those skilled in the art.

[0025] In the present invention, the halogenated alkane preferably has a structure shown in Formula 1:

[0026]

[0027] In formula 1, R 1 includes aryl, heteroaryl, alkyl, substituted aryl or substituted alkyl; R 2 includes alkyl or hydrogen; or R 1 and R 2 is independently cycloalkyl; X includes chlorine or bromine.

[0028] In the present invention, the substituent in the substituted aryl is preferably a methyl, tert-butyl, phenyl, methylthio, methoxy, benzyloxy, diphenylamino, chlorine, bromine, iodine or pinacol borate substituent, and the substituent in the substituted alkyl is preferably one or more of an aryl, ether, silicon, carbazole and amino group; when the substituent is two or more of the above, the present invention has no special limitation on the specific positions of different types of substituents, which can be adjusted according to the specific raw materials. The halogenated alkanes described in the present invention are all commercially available products well known in the art.

[0029] In the present invention, the halogenated alkane is preferably benzyl bromide, benzyl chloride, p-methylbenzyl bromide, p-methylbenzyl chloride, 3-methylbenzyl bromide, p-tert-butylbenzyl bromide, p-tert-butylbenzyl chloride, 3-methoxybenzyl bromide, 3-methoxybenzyl chloride, p-phenylbenzyl bromide, p-phenylbenzyl chloride, p-methylthiobenzyl bromide, 3-benzyloxybenzyl bromide, p-chlorobenzyl bromide, 3-chlorobenzyl bromide, 3-chlorobenzyl chloride, p-bromobenzyl bromide, p-bromobenzyl chloride, 3-bromobenzyl bromide, p-iodobenzyl bromide, 4-bromomethylphenylboronic acid pinacol ester, 4-(bromomethyl)-N,N-diphenylaniline, 2-bromomethylnaphthalene, 2-chloromethylnaphthalene, 1-bromo-2 -(bromomethyl)naphthalene, 1-bromomethylnaphthalene, 9-bromomethylanthracene, triphenylmethane bromide, 1-bromooctane, 1-chlorooctane, 5-(2-bromoethyl)-2,3-dihydrobenzofuran, phenethyl bromide, phenhexyl bromide, benzyl 5-bromopentyl ether, 3,3-diphenylpropyl bromide, 3-bromopropyl-2-naphthyl ether, 9-(5-bromopentyl)carbazole, 2-(6-bromohexyloxy)tetrahydro-2H-pyran, 2-bromomethyl-1,4-benzodioxane, (6-bromohexyloxy)-tert-butyldimethylsilane, 2-bromooctane, bromocycloheptane or 1-bromoadamantane.

[0030] In the present invention, the titanium metal catalyst preferably includes bis(cyclopentadienyl)titanium dichloride or bis(trifluoromethanesulfonate)titanocene.

[0031] In the present invention, the mixing preferably further comprises adding a base compound, and the base compound preferably comprises lithium methoxide. The present invention utilizes a base compound to activate the high-valent titanium metal catalyst, which is beneficial for its reduction by the borane compound, thereby inducing free radicals and achieving dehalogenation.

[0032] In the present invention, the borane compound preferably includes a borane ammonia complex.

[0033] In the present invention, the molar ratio of the halogenated alkane, titanium metal catalyst, base compound and borane compound is preferably 1:(0.01-0.1):(0-1):(3-5), more preferably 1:(0.01-0.05):1:4, and further preferably 1:(0.025-0.075):1:4.

[0034] In the present invention, the organic solvent is preferably tetrahydrofuran or 1,4-dioxane; the volume ratio of the molar amount of the halogenated alkane to the organic solvent is preferably (0.1-0.2) mmol: (0.2-2) mL, more preferably 0.2 mmol: 0.5-1 mL.

[0035] The present invention has no special limitation on the mixing of the halogenated alkane, titanium metal catalyst, alkali compound, borane compound and organic solvent. The materials can be mixed uniformly according to the process well known in the art.

[0036] In the present invention, the protective atmosphere is preferably a nitrogen atmosphere or an argon atmosphere; the pressure of the protective atmosphere is preferably 1 atm.

[0037] In the present invention, the temperature of the hydrodehalogenation reaction is preferably 35-100°C, more preferably 40-80°C, more preferably 60°C, and the time is preferably 12h; the hydrodehalogenation reaction is preferably carried out under stirring conditions. The present invention does not have any special restrictions on the stirring conditions, and the process familiar to those skilled in the art can be used.

[0038] In the present invention, the reaction formula of the hydrodehalogenation reaction is

[0039]

[0040] After the hydrodehalogenation reaction is completed, the present invention also preferably includes cooling the obtained reaction product to room temperature, sequentially performing column chromatography and decompression spin drying, and the present invention has no special restrictions on the column chromatography and decompression spin drying, and column chromatography and decompression spin drying well known to those skilled in the art can be used. In an embodiment of the present invention, the reaction product is specifically purified by silica gel column chromatography, eluted with an eluent, and then the solvent is decompressed and spin dried; the eluent is petroleum ether or a petroleum ether-ethyl acetate mixed solvent; the volume ratio of petroleum ether to ethyl acetate in the petroleum ether-ethyl acetate mixed solvent is 10:1 or 40:1.

[0041] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0042] In the following examples, all raw materials are commercially available products well known to those skilled in the art. In Examples 1 to 24, 27, 29 to 35, 38, 39, 41, 44, 45, 47, 56, and 57, no separation was performed, and a product system of alkane compounds was directly obtained. Due to the low boiling point of the product, the reaction system was analyzed by GC-MS to confirm the formation of the target product, and the yield of the alkane compound in the product system was determined by gas phase detection (dodecane as an internal standard) or nuclear magnetic resonance analysis (benzyl benzoate as an internal standard).

[0043] Example 1

[0044] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), lithium methoxide (denoted as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), benzyl bromide (denoted as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (denoted as THF, 1mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a structural compound (toluene) represented by formula 3a. The yield detected by GC-MS was 58%.

[0045] The chemical reaction formula of the above preparation process is:

[0046]

[0047] Example 2

[0048] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 35°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 73%.

[0049] The chemical reaction formula of the above preparation process is:

[0050]

[0051] Example 3

[0052] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.6mmol, 18.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 35°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 66%.

[0053] The chemical reaction formula of the above preparation process is:

[0054]

[0055] Example 4

[0056] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 1.0mmol, 30.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 76%.

[0057] The chemical reaction formula of the above preparation process is:

[0058]

[0059] Example 5

[0060] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 40°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 67%.

[0061] The chemical reaction formula of the above preparation process is:

[0062]

[0063] Example 6

[0064] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 60°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 65%.

[0065] The chemical reaction formula of the above preparation process is:

[0066]

[0067] Example 7

[0068] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 80°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 54%.

[0069] The chemical reaction formula of the above preparation process is:

[0070]

[0071] Example 8

[0072] Bis(trifluoromethanesulfonic acid)titanium dichloride (denoted as Cp 2 Ti(OTf) 2, 0.02mmol, 9.6mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 35°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 76%.

[0073] The chemical reaction formula of the above preparation process is:

[0074]

[0075] Example 9

[0076] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.002mmol, 0.5mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 35°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 64%.

[0077] The chemical reaction formula of the above preparation process is:

[0078]

[0079] Example 10

[0080] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 35°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 86%.

[0081] The chemical reaction formula of the above preparation process is:

[0082]

[0083] Embodiment 11

[0084] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.01mmol, 2.5mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 35°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield determined by GC-MS was 80%.

[0085] The chemical reaction formula of the above preparation process is:

[0086]

[0087] Example 12

[0088] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.015mmol, 3.8mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 1mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 76%.

[0089] The chemical reaction formula of the above preparation process is:

[0090]

[0091] Example 13

[0092] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and 1,4-dioxane (referred to as 1,4-dioxane, 1mL) were mixed and stirred at 35°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 74%.

[0093] The chemical reaction formula of the above preparation process is:

[0094]

[0095] Embodiment 14

[0096] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 0.2mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 73%.

[0097] The chemical reaction formula of the above preparation process is:

[0098]

[0099] Embodiment 15

[0100] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under an argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 79%.

[0101] The chemical reaction formula of the above preparation process is:

[0102]

[0103] Example 16

[0104] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl bromide (referred to as 1a, 0.2mmol, 34.0mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by the structure of formula 3a. The yield detected by GC-MS was 88%.

[0105] The chemical reaction formula of the above preparation process is:

[0106]

[0107] Embodiment 17

[0108] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl chloride (referred to as 1b, 0.2mmol, 25.2mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound (toluene) represented by formula 3a. The yield detected by GC-MS was 91%.

[0109] The chemical reaction formula of the above preparation process is:

[0110]

[0111] Embodiment 18

[0112] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), p-methylbenzyl bromide (referred to as 1c, 0.2mmol, 36.8mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound (p-xylene) represented by formula 3c. The yield detected by GC-MS was 80%.

[0113] The chemical reaction formula of the above preparation process is:

[0114]

[0115] Embodiment 19

[0116] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), p-methylbenzyl chloride (referred to as 1d, 0.2mmol, 28.0mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound (p-xylene) represented by formula 3c. The yield detected by GC-MS was 94%.

[0117] The chemical reaction formula of the above preparation process is:

[0118]

[0119] Embodiment 20

[0120] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl2 , 0.005mmol, 1.3mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), 3-methylbenzyl bromide (denoted as 1e, 0.2mmol, 36.8mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3e (meta-xylene). The yield detected by GC-MS was 82%.

[0121] The chemical reaction formula of the above preparation process is:

[0122]

[0123] Embodiment 21

[0124] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), p-tert-butylbenzyl bromide (referred to as 1f, 0.2mmol, 45.2mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3f (p-tert-butyltoluene). The yield according to NMR analysis was 54%.

[0125] The chemical reaction formula of the above preparation process is:

[0126]

[0127] Embodiment 22

[0128] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), p-tert-butylbenzyl chloride (referred to as 1g, 0.2mmol, 36.4mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3f (p-tert-butyltoluene). The yield according to NMR analysis was 81%.

[0129] The chemical reaction formula of the above preparation process is:

[0130]

[0131] Embodiment 23

[0132] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp2 TiCl 2 , 0.005 mmol, 1.3 mg), borane ammonia complex (denoted as 2a, 0.8 mmol, 24.0 mg), 3-methoxybenzyl bromide (denoted as 1h, 0.2 mmol, 40.0 mg) and tetrahydrofuran (denoted as THF, 0.5 mL) were mixed and stirred at 35 °C for 12 h under an argon (1 atm) atmosphere to obtain a product system containing the compound with the structure shown in Formula 3h (3-methoxytoluene). The yield analyzed by NMR was 70%.

[0133] The chemical reaction equation for the above preparation process is as follows:

[0134]

[0135] Example 24

[0136] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02 mmol, 5.0 mg), borane ammonia complex (denoted as 2a, 0.8 mmol, 24.0 mg), 3-methoxybenzyl chloride (denoted as 1i, 0.2 mmol, 31.2 mg) and tetrahydrofuran (denoted as THF, 0.5 mL) were mixed and stirred at 35 °C for 12 h under an argon (1 atm) atmosphere to obtain a product system containing the compound with the structure shown in Formula 3h (3-methoxytoluene). The yield analyzed by NMR was 93%.

[0137] The chemical reaction equation for the above preparation process is as follows:

[0138]

[0139] Example 25

[0140] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005 mmol, 1.3 mg), borane ammonia complex (denoted as 2a, 0.8 mmol, 24.0 mg), p-phenylbenzyl bromide (denoted as 1j, 0.2 mmol, 49.2 mg) and tetrahydrofuran (denoted as THF, 0.5 mL) were mixed and stirred at 35 °C for 12 h under an argon (1 atm) atmosphere. Then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography. After elution with petroleum ether as the eluent, the solvent was evaporated under reduced pressure to obtain the compound with the structure shown in Formula 3j (p-phenyltoluene). The separation yield was 78%.

[0141] The chemical reaction equation for the above preparation process is as follows:

[0142]

[0143] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ7.63(d,J=7.3Hz,2H),7.55(d,J=7.9Hz,2H),7.47(t,J=7.6Hz,2H),7.37(t,J=7.3Hz,1H),7.30(d,J=7.7Hz,2H),2.45(s,3H). 13 C NMR (101MHz, Chloroform-d) δ141.3,138.5,137.1,129.6,128.9,127.2,127.1,21.2.

[0144] Embodiment 26

[0145] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), p-phenylbenzyl chloride (referred to as 1k, 0.2mmol, 40.4mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 35°C for 12h under argon (1atm) atmosphere, then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound shown in formula 3j (p-phenyltoluene). The isolated yield was 59%.

[0146] The chemical reaction formula of the above preparation process is:

[0147]

[0148] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ7.63(d,J=7.3Hz,2H),7.55(d,J=7.9Hz,2H),7.47(t,J=7.6Hz,2H),7.37(t,J=7.3Hz,1H),7.30(d,J=7.7Hz,2H),2.45(s,3H). 13 C NMR (101MHz, Chloroform-d) δ141.3,138.5,137.1,129.6,128.9,127.2,127.1,21.2.

[0149] Embodiment 27

[0150] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), p-methylthiobenzyl bromide (referred to as 1l, 0.2mmol, 43.2mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3l (p-methylthiotoluene). The yield according to NMR analysis was 90%.

[0151] The chemical reaction formula of the above preparation process is:

[0152]

[0153] Embodiment 28

[0154] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 3-benzyloxybenzyl bromide (referred to as 1m, 0.2mmol, 55.2mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 35°C for 12h under argon (1atm) atmosphere, then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound shown in formula 3m (4-benzyloxytoluene). The isolated yield was 73%.

[0155] The chemical reaction formula of the above preparation process is:

[0156]

[0157] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ7.47-7.26(m,5H),7.16(t,J=7.8Hz,1H),6.84-6.72(m,3H),5.03(s,2H),2.32(s,3H). 13 C NMR (101MHz, Chloroform-d) δ159.0,139.6,137.3,129.3,128.7,128.0,127.6,121.9,115.9,111.8,70.0,21.7.

[0158] Embodiment 29

[0159] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.005mmol, 1.3mg), borane ammonia complex (denoted as 2a, 0.8mmol, 40.6mg), p-chlorobenzyl bromide (denoted as 1n, 0.2mmol, 28.0mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3n (p-chlorotoluene). The yield according to NMR analysis was 61%.

[0160] The chemical reaction formula of the above preparation process is:

[0161]

[0162] Embodiment 30

[0163] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), 3-chlorobenzyl bromide (denoted as 1o, 0.2mmol, 40.6mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3o (3-chlorotoluene). The yield according to NMR analysis was 88%.

[0164] The chemical reaction formula of the above preparation process is:

[0165]

[0166] Embodiment 31

[0167] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 3-chlorobenzyl chloride (referred to as 1p, 0.2mmol, 32.0mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3o (3-chlorotoluene). The yield according to NMR analysis was 45%.

[0168] The chemical reaction formula of the above preparation process is:

[0169]

[0170] Embodiment 32

[0171] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl2 , 0.005mmol, 1.3mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), p-bromobenzyl bromide (denoted as 1q, 0.2mmol, 49.6mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3q (p-bromotoluene). The yield according to NMR analysis was 66%.

[0172] The chemical reaction formula of the above preparation process is:

[0173]

[0174] Embodiment 33

[0175] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.02mmol, 5.0mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), p-bromobenzyl chloride (denoted as 1r, 0.2mmol, 40.8mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3q (p-bromotoluene). The yield according to NMR analysis was 97%.

[0176] The chemical reaction formula of the above preparation process is:

[0177]

[0178] Embodiment 34

[0179] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), 3-bromobenzyl bromide (denoted as 1s, 0.2mmol, 49.6mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3s (3-bromotoluene). The yield according to NMR analysis was 90%.

[0180] The chemical reaction formula of the above preparation process is:

[0181]

[0182] Embodiment 35

[0183] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl2 , 0.005mmol, 1.3mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), p-iodobenzyl bromide (denoted as 1t, 0.2mmol, 59.2mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound of the structure shown in formula 3t (p-iodotoluene). The yield according to NMR analysis was 95%.

[0184] The chemical reaction formula of the above preparation process is:

[0185]

[0186] Embodiment 36

[0187] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 4-bromomethylphenylboronic acid pinacol ester (referred to as 1u, 0.2mmol, 59.4mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 35°C for 12h under argon (1atm) atmosphere, and then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, and after elution with petroleum ether: ethyl acetate (V:V=40:1) as eluent, the solvent was decompressed and dried to obtain the structural compound shown in formula 3u (4-methylphenylboronic acid pinacol ester). The isolated yield was 61%.

[0188] The chemical reaction formula of the above preparation process is:

[0189]

[0190] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ7.63 (d, J = 7.8Hz, 2H), 7.10 (d, J = 7.7Hz, 2H), 2.28 (s, 3H), 1.25 (s, 12H). 13 C NMR (101MHz, Chloroform-d) δ 141.5, 135.0, 128.7, 83.7, 25.0, 21.8.

[0191] Embodiment 37

[0192] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 4-(bromomethyl)-N,N-diphenylaniline (referred to as 1v, 0.2mmol, 67.4mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 35°C for 12h under argon (1atm) atmosphere, and then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography. After elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound shown in formula 3v (4-methyl-N,N-diphenylaniline). The isolated yield was 50%.

[0193] The chemical reaction formula of the above preparation process is:

[0194]

[0195] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ7.25-7.16(m,4H),7.09-7.03(m,6H),7.02-6.92(m,4H),2.30(s,3H). 13 C NMR (101MHz, Chloroform-d) δ 148.2, 145.4, 132.9, 130.1, 129.3, 125.1, 123.7, 122.4, 21.0.

[0196] Embodiment 38

[0197] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 2-bromomethylnaphthalene (referred to as 1w, 0.2mmol, 44.0mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound (2-methylnaphthalene) represented by the structure of formula 3w. The yield according to NMR analysis was 54%.

[0198] The chemical reaction formula of the above preparation process is:

[0199]

[0200] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.02 mmol, 5.0 mg), borane ammonia complex (denoted as 2a, 0.8 mmol, 24.0 mg), 2-chloromethylnaphthalene (denoted as 1x, 0.2 mmol, 35.2 mg) and tetrahydrofuran (denoted as THF, 0.5 mL) were mixed and stirred at 35 °C for 12 h under an argon (1 atm) atmosphere to obtain a product system containing the compound with the structure shown in formula 3w (2-methylnaphthalene). The yield determined by NMR analysis was 73%.

[0201] The chemical reaction equation for the above preparation process is:

[0202]

[0203] Example 40

[0204] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005 mmol, 1.3 mg), borane ammonia complex (denoted as 2a, 0.8 mmol, 24.0 mg), 1-bromo-2-(bromomethyl)naphthalene (denoted as 1y, 0.2 mmol, 59.6 mg) and tetrahydrofuran (denoted as THF, 0.5 mL) were mixed and stirred at 35 °C for 12 h under an argon (1 atm) atmosphere. Then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography. After elution with petroleum ether as the eluent, the solvent was rotary evaporated under reduced pressure to obtain the compound with the structure shown in formula 3y (1-bromo-2-methylnaphthalene). The isolated yield was 68%.

[0205] The chemical reaction equation for the above preparation process is:

[0206]

[0207] Characterization data are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 8.29 (d, J = 8.5 Hz, 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.69 (d, J = 8.3 Hz, 1H), 7.55 (ddd, J = 8.4, 6.8, 1.3 Hz, 1H), 7.45 (ddd, J = 8.1, 6.9, 1.2 Hz, 1H), 7.33 (d, J = 8.3 Hz, 1H), 2.62 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 136.1, 133.1, 132.7, 128.9, 128.1, 127.4, 127.4, 127.1, 125.8, 124.2, 24.3.

[0208] Example 41

[0209] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), 1-bromomethylnaphthalene (denoted as 1z, 0.2mmol, 44.0mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a structural compound (1-methylnaphthalene) shown in formula 3z. The yield according to nuclear magnetic analysis was 63%.

[0210] The chemical reaction formula of the above preparation process is:

[0211]

[0212] Embodiment 42

[0213] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 9-bromomethylanthracene (referred to as 1aa, 0.2mmol, 54.0mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 35°C for 12h under argon (1atm) atmosphere, then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound (9-methylanthracene) shown in formula 3aa. The isolated yield was 53%.

[0214] The chemical reaction formula of the above preparation process is:

[0215]

[0216] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ8.35-8.20 (m, 3H), 7.97 (d, J = 8.2Hz, 2H), 7.56-7.37 (m, 4H), 3.07 (s, 3H). 13 C NMR (101MHz, Chloroform-d)) δ 131.6, 130.2, 129.2, 125.4, 125.4, 125.0, 124.8, 14.0.

[0217] Embodiment 43

[0218] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), triphenylmethane bromide (referred to as 1ab, 0.2mmol, 64.4mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 35°C for 12h under argon (1atm) atmosphere, then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound (triphenylmethane) shown in formula 3ab. The isolated yield was 81%.

[0219] The chemical reaction formula of the above preparation process is:

[0220]

[0221] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ7.26 (dd, J=8.2, 6.5Hz, 6H), 7.22-7.15 (m, 3H), 7.14-7.07 (m, 6H), 5.54 (s, 1H). 13 C NMR (101MHz, Chloroform-d) δ144.0, 129.6, 128.4, 126.4, 57.0.

[0222] Embodiment 44

[0223] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), lithium methoxide (denoted as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), 1-bromooctane (denoted as 4a, 0.2mmol, 38.4mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 60°C for 12h under argon (1atm) atmosphere to obtain a product system containing a structural compound (n-octane) shown in formula 5a. The yield detected by GC-MS was 93%.

[0224] The chemical reaction formula of the above preparation process is:

[0225]

[0226] Embodiment 45

[0227] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.02mmol, 5.0mg), lithium methoxide (denoted as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (denoted as 2a, 0.8mmol, 29.6mg), 1-chlorooctane (denoted as 4b, 0.2mmol, 28.0mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 100°C for 12h under argon (1atm) atmosphere to obtain a product system containing a structural compound (n-octane) shown in formula 5a. The yield detected by GC-MS was 88%.

[0228] The chemical reaction formula of the above preparation process is:

[0229]

[0230] Embodiment 46

[0231] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), lithium methoxide (denoted as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (denoted as 2a, 0.8mmol, 24.0mg), 5-(2-bromoethyl)-2,3-dihydrobenzofuran (denoted as 4c, 0.2mmol, 45.2mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 60°C for 12h under argon (1atm) atmosphere to obtain a product system containing the structural compound shown in formula 5c (5-ethyl-2,3-dihydrobenzofuran). The isolated yield was 71%.

[0232] The chemical reaction formula of the above preparation process is:

[0233]

[0234] The characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.03(s,1H),6.92(d,J=8.1Hz,1H),6.70(d,J=8.1Hz,1H),4 .53(t,J=8.7Hz,2H),3.17(t,J=8.6Hz,2H),2.57(q,J=7.6Hz,2H),1.20(t,J=7.6Hz,3H). 13 C NMR (101MHz, Chloroform-d) δ 158.2, 136.5, 127.3, 127.0, 124.5, 109.0, 71.2, 30.0, 28.4, 16.3.

[0235] Embodiment 47

[0236] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), lithium methoxide (referred to as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), phenethyl bromide (referred to as 4d, 0.2mmol, 36.8mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 60°C for 12h under argon (1atm) atmosphere, then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound shown in formula 5d (ethylbenzene). The yield detected by GC-MS was 92%.

[0237] The chemical reaction formula of the above preparation process is:

[0238]

[0239] Embodiment 48

[0240] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), lithium methoxide (referred to as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), phenylhexyl bromide (referred to as 4e, 0.2mmol, 48.0mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 60°C for 12h under an argon (1atm) atmosphere, and then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, and after elution with petroleum ether as an eluent, the solvent was decompressed and dried to obtain a structural compound (hexylbenzene) shown in formula 5e. The isolated yield was 86%.

[0241] The chemical reaction formula of the above preparation process is:

[0242]

[0243] The characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.27(t,J=7.5Hz,2H),7.17(d,J=7.4Hz,3H),2.68–2 .50(m,2H),1.61(p,J=7.6Hz,2H),1.31(pd,J=8.4,4.5Hz,6H),0.97–0.78(m,3H). 13C NMR (101MHz, Chloroform-d) δ143.1,128.6,128.4,125.7,36.2,31.9,31.7,29.2,22.8,14.2.

[0244] Embodiment 49

[0245] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), lithium methoxide (referred to as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), benzyl 5-bromopentyl ether (referred to as 4f, 0.2mmol, 51.2mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 60°C for 12h under argon (1atm) atmosphere, then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound shown in formula 5f (benzylpentyl ether). The isolated yield was 96%.

[0246] The chemical reaction formula of the above preparation process is:

[0247]

[0248] The characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.34(d,J=4.4Hz,4H),7.28(p,J=5.0,4.5Hz,1H),4.50(s,2H),3 .46(t,J=6.7Hz,2H),1.62(p,J=6.1Hz,2H),1.34(tt,J=6.2,2.9Hz,4H),0.90(t,J=7.0Hz,3H). 13 C NMR (101MHz, Chloroform-d) δ138.9,128.5,127.7,127.6,73.0,70.7,29.6,28.5,22.7,14.2.

[0249] Embodiment 50

[0250] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.005mmol, 1.3mg), lithium methoxide (referred to as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 3,3-diphenylpropyl bromide (referred to as 4g, 0.2mmol, 54.8mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 60°C for 12h under argon (1atm) atmosphere, then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound (3,3-diphenylpropane) shown in formula 5g. The isolated yield was 93%.

[0251] The chemical reaction formula of the above preparation process is:

[0252]

[0253] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ7.30–7.19(m,8H),7.18–7.11(m,2H),3.78(t,J=7.8Hz,1H),2.06(p,J=7.4Hz,2H),0.89(t,J=7.3Hz,3H). 13 C NMR (101MHz, Chloroform-d) δ145.3,128.5,128.1,126.2,53.4,28.7,12.9.

[0254] Embodiment 51

[0255] 2-Naphthol (denoted as 6a, 10mmol, 1.4g), 1,3-dibromopropane (denoted as 7a, 12mmol, 2.4g,) were mixed with potassium hydroxide (denoted as KOH, 12mmol, 672mg) and N,N-dimethylformamide (denoted as DMF, 10mL), stirred at room temperature for 24h under argon (1atrm) atmosphere, 20mL of ethyl acetate was added to the obtained reaction solution for dilution, and washed three times with saturated brine, the organic phase solvent was decompressed and spin-dried to obtain a crude product of the structure shown in formula 4h (3-bromopropyl-2-naphthyl ether), the structure of 4h was determined by GC-MS analysis, and it can be directly used for the dehalogenation reduction in the next step without separation;

[0256] The chemical reaction formula of the above preparation process is:

[0257]

[0258] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.005 mmol, 1.3 mg), lithium methoxide (denoted as MeOLi, 0.2 mmol, 7.6 mg), borane ammonia complex (denoted as 2a, 0.8 mmol, 24.0 mg), 3-bromopropyl-2-naphthyl ether (denoted as 4h, 0.2 mmol, 52.8 mg) and tetrahydrofuran (denoted as THF, 0.5 mL) were mixed and stirred at 60 °C for 12 h under an argon (1 atm) atmosphere. Then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography. After elution with petroleum ether as the eluent, the solvent was rotary evaporated under reduced pressure to obtain the compound (2-naphthyl propyl ether) with the structure shown in Formula 5h. The separation yield was 97%.

[0259] The chemical reaction equation for the above preparation process is:

[0260]

[0261] The characterization data are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.79–7.65 (m, 3H), 7.41 (ddd, J = 8.3, 6.9, 1.3 Hz, 1H), 7.30 (ddd, J = 8.1, 6.8, 1.3 Hz, 1H), 7.17–7.08 (m, 2H), 4.00 (t, J = 6.6 Hz, 2H), 1.85 (h, J = 7.3 Hz, 2H), 1.06 (t, J = 7.4 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 157.2, 134.7, 129.4, 129.0, 127.7, 126.8, 126.4, 123.5, 119.1, 106.6, 69.6, 22.7, 10.7.

[0262] Example 52

[0263] Carbazole (denoted as 6b, 10 mmol, 1.7 g), 1,3-dibromopentane (denoted as 7b, 12 mmol, 2.6 g), potassium hydroxide (denoted as KOH, 12 mmol, 672 mg) and N,N-dimethylformamide (denoted as DMF, 10 mL) were mixed and stirred at room temperature for 24 h under an argon (1 atm) atmosphere. 20 mL of ethyl acetate was added to the resulting reaction solution for dilution, and it was washed three times with saturated brine. The organic phase solvent was rotary evaporated under reduced pressure to obtain the crude product with the structure shown in Formula 4i (9-(5-bromopentyl)carbazole). The structure of 4i was determined by GC-MS analysis and could be directly used for the next dehalogenation reduction without separation;

[0264]

[0265] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp2 TiCl 2 , 0.005mmol, 1.3mg), lithium methoxide (referred to as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 9-(5-bromopentyl)carbazole (referred to as 4i, 0.2mmol, 62.8mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 60°C for 12h under argon (1atm) atmosphere, then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound (9-pentylcarbazole) shown in formula 5i. The isolated yield was 80%.

[0266] The chemical reaction formula of the above preparation process is:

[0267]

[0268] The characterization data are: 1 H NMR(400MHz,Chloroform-d)δ8.08(d,J=7.8Hz,2H),7.43(ddd,J=8.3,6.9,1.2Hz,2H),7.36(d,J=8.2Hz,2H),7.20 (t,J=7.4Hz,2H),4.22(t,J=7.3Hz,2H),1.82(p,J=7.3Hz,2H),1.32(dt,J=7.3,3.8Hz,4H),0.84(t,J=7.0Hz,3H). 13 C NMR (101MHz, Chloroform-d) δ140.5,125.7,122.9,120.5,118.8,108.8,43.1,29.5,28.8,22.6,14.1.

[0269] Embodiment 53

[0270] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.005mmol, 1.3mg), lithium methoxide (referred to as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 2-(6-bromohexyloxy)tetrahydro-2H-pyran (referred to as 4j, 0.2mmol, 52.8mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 60°C for 12h under argon (1atm) atmosphere, then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound shown in formula 5j (2-hexyloxytetrahydro-2H-pyran). The isolated yield was 74%.

[0271] The chemical reaction formula of the above preparation process is:

[0272]

[0273] The characterization data are: 1 H NMR(400MHz,Chloroform-d)δ4.62–4.50(m,1H),3.86(ddd,J=11.1,7.5,3.3Hz,1H),3.72(dt,J=9.5,6.9Hz,1H),3.48(dt,J=10.7,5.0Hz,1 H),3.37(dt,J=9.5,6.7Hz,1H),1.82(qt,J=8.8,3.9Hz,1H),1.76–1.65(m,1H),1.61–1.46(m,6H),1.41–1.20(m,6H),0.87(t,J=6.8Hz,3H). 13 C NMR (101MHz, Chloroform-d) δ99.0,67.8,62.4,31.8,30.9,29.8,26.0,25.6,22.7,19.8,14.2.

[0274] Embodiment 54

[0275] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2, 0.005mmol, 1.3mg), lithium methoxide (referred to as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), 2-bromomethyl-1,4-benzodioxane (referred to as 4k, 0.2mmol, 45.6mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 100°C for 12h under argon (1atm) atmosphere, and then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography, and after elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound shown in formula 5k (2-methyl-1,4-benzodioxane). The isolated yield was 87%.

[0276] The chemical reaction formula of the above preparation process is:

[0277]

[0278] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ6.73–6.80(m,4H),4.24–4.15(m,1H),4.12(dd,J=11.2,2.1Hz,1H),3.74(dd,J=11.2,8.1Hz,1H),1.27(d,J=6.4Hz,3H). 13 C NMR (101MHz, Chloroform-d) δ143.6,143.2,121.6,121.3,117.4,117.1,69.4,69.2,16.7.

[0279] Embodiment 55

[0280] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), lithium methoxide (referred to as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (referred to as 2a, 0.8mmol, 24.0mg), (6-bromohexyloxy)-tert-butyldimethylsilane (referred to as 4l, 0.2mmol, 58.4mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed, stirred at 60°C for 12h under argon (1atm) atmosphere, and then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography. After elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound (hexyloxy tert-butyldimethylsilane) system shown in formula 5l. The isolated yield was 86%.

[0281] The chemical reaction formula of the above preparation process is:

[0282]

[0283] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ3.62 (s, 2H), 1.58–1.44 (m, 2H), 1.39–1.18 (m, 6H), 0.89 (d, J = 3.8Hz, 12H), 0.05 (s, 6H). 13 C NMR(101MHz,Chloroform-d)δ63.5,33.0,31.8,26.1,25.6,22.8,18.5,14.2,-5.1. 29 Si NMR (79MHz, Chloroform-d) δ18.28.

[0284] Embodiment 56

[0285] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (referred to as 2a, 0.8mmol, 38.4mg), 2-bromooctane (referred to as 4m, 0.2mmol, 28.0mg) and tetrahydrofuran (referred to as THF, 0.5mL) were mixed and stirred at 60°C for 12h under argon (1atm) atmosphere to obtain a product system containing a compound (n-octane) represented by formula 5a. The yield detected by GC-MS was 96%.

[0286] The chemical reaction formula of the above preparation process is:

[0287]

[0288] Embodiment 57

[0289] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), borane ammonia complex (denoted as 2a, 0.8mmol, 35.2mg), bromocycloheptane (denoted as 4n, 0.2mmol, 28.0mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed and stirred at 35°C for 12h under argon (1atm) atmosphere to obtain a product system containing a structural compound (cycloheptane) represented by formula 5n. The yield detected by GC-MS was 87%.

[0290] The chemical reaction formula of the above preparation process is:

[0291]

[0292] Embodiment 58

[0293] Bis(cyclopentadienyl)titanium dichloride (denoted as Cp 2 TiCl 2 , 0.005mmol, 1.3mg), lithium methoxide (denoted as MeOLi, 0.2mmol, 7.6mg), borane ammonia complex (denoted as 2a, 0.8mmol, 22.8mg), 1-bromoadamantane (denoted as 4o, 0.2mmol, 28.0mg) and tetrahydrofuran (denoted as THF, 0.5mL) were mixed, stirred at 100°C for 12h under argon (1atm) atmosphere, and then the reaction temperature was lowered to room temperature and the product was purified by silica gel column chromatography. After elution with petroleum ether as eluent, the solvent was decompressed and dried to obtain the structural compound (adamantane) shown in formula 5o. The isolation yield was 85%.

[0294] The chemical reaction formula of the above preparation process is:

[0295]

[0296] The characterization data are: 1 H NMR (400MHz, Chloroform-d) δ1.87 (s, 4H), 1.75 (t, J = 3.3Hz, 12H). 13 C NMR (101MHz, Chloroform-d) δ37.9,28.5.

[0297] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for hydrodehalogenating halogenated alkanes, The following steps are involved: Mixing a halogenated alkane, a titanium metal catalyst, a borane compound and an organic solvent, and performing a hydrodehalogenation reaction under heating conditions in a protective atmosphere to obtain an alkane compound corresponding to the halogenated alkane; The halogenated alkane is benzyl bromide, benzyl chloride, p-methylbenzyl bromide, p-methylbenzyl chloride, 3-methylbenzyl bromide, p-tert-butylbenzyl bromide, p-tert-butylbenzyl chloride, 3-methoxybenzyl bromide, 3-methoxybenzyl chloride, p-phenylbenzyl bromide, p-phenylbenzyl chloride, p-methylthiobenzyl bromide, 3-benzyloxybenzyl bromide, p-chlorobenzyl bromide, 3-chlorobenzyl bromide, 3-chlorobenzyl chloride, p-bromobenzyl bromide, p-bromobenzyl chloride, 3-bromobenzyl bromide, p-iodobenzyl bromide, 4-bromomethylphenylboronic acid pinacol ester, 4-(bromomethyl)-N,N-diphenylaniline, 2-bromomethylnaphthalene, 2-chloromethylnaphthalene, 1-bromo-2-(bromomethyl)- 1-bromomethylnaphthalene, 9-bromomethylanthracene, triphenylmethane, 1-bromooctane, 1-chlorooctane, 5-(2-bromoethyl)-2,3-dihydrobenzofuran, phenethyl bromide, phenhexyl bromide, benzyl 5-bromopentyl ether, 3,3-diphenylpropyl bromide, 3-bromopropyl-2-naphthyl ether, 9-(5-bromopentyl)carbazole, 2-(6-bromohexyloxy)tetrahydro-2H-pyran, 2-bromomethyl-1,4-benzodioxane, (6-bromohexyloxy)-tert-butyldimethylsilane, 2-bromooctane, bromocycloheptane or 1-bromoadamantane; The titanium metal catalyst is bis(cyclopentadiene)titanium dichloride or bis(trifluoromethanesulfonic acid)titanocene; The mixing further comprises adding an alkali compound, wherein the alkali compound is lithium methoxide; The borane compound is a borane ammonia complex.

2. The method according to claim 1, It is characterized in that The organic solvent is tetrahydrofuran or 1,4-dioxane.

3. The method according to claim 1, It is characterized in that The molar ratio of the halogenated alkane, the titanium metal catalyst, the base compound and the borane compound is 1:(0.01-0.1):(0-1):(3-5).

4. The method according to claim 1, It is characterized in that The protective atmosphere is a nitrogen atmosphere or an argon atmosphere.

5. The method according to claim 1, It is characterized in that The temperature of the hydrodehalogenation reaction is 35-100° C. and the time is 12 hours.

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