Use of silicon compounds in cyclization reactions

1 . A method for preparation of 4,5-dichloro-4-methoxypentanenitrile, comprising: performing a cyclization reaction on 4,5-dichloro-4-methoxypentanenitrile in presence of a silicon compound and an acylamide compound to provide 2-chloro-5-chloromethylpyridine, wherein a reaction equation of the cycllization reaction is as follows:

wherein the silicon compound is selected from one or more of compounds having a chemical structural formula shown below:

wherein R 3 , R 4 , and R 5 are each independently selected from H, Ph, C1-C4 alkyl, Cl, and Br,

Y is O or is not present,

n is selected from 0, 1, 2, 3, 4, and 5, and

X is selected from Cl and Br.

2 . The method for preparation of 2-chloro-5-chloromethylpyridine of claim 1 , wherein in the compound of formula V, R 3 , R 4 , and R 5 are each independently selected from H, Ph, C1-C2 alkyl, Cl, and Br,

n is selected from 0 and 1, and

X is selected from Cl and Br.

3 . The method for preparation of 2-chloro-5-chloromethylpyridine of claim 1 , wherein the silicon compound is selected from one or more of methyltrichlorosilane, dichlorodiethylsilane, dichlorodimethylsilane, trimethylchlorosilane, 1,1,2,2-tetrachloro-1,2-dimethyldisilane, silicon tetrachloride, dibromo (dimethyl) silane, bromotrimethylsilane, and 1,3-dichloro-1,1,3,3-tetramethyldisiloxane.

4 . The method for preparation of 2-chloro-5-chloromethylpyridine of claim 1 , wherein the acylamide compound has a chemical structural formula shown as RCONR 1 R 2 ,

wherein R is selected from hydrogen, saturated or unsaturated C1 to C8 aliphatic groups, and substituted or unsubstituted phenyl, R 1 and R 2 are each independently selected from saturated or unsaturated C1 to C8 aliphatic groups and phenyl, or R and R 1 , or R and R 2 together with their attached atoms form a five- or six-membered heterocyclic group,

and/or, in the cyclization reaction, a molar ratio of the compound of formula I to the acylamide compound is 1: (0.1-1.5);

and/or, the cyclization reaction is carried out in the presence of a solvent, wherein the solvent is a nonprotonic solvent;

and/or, the cyclization reaction is carried out at a temperature of 70 to 150° C.;

and/or, in the cyclization reaction, a molar ratio of the compound of formula I to the silicon compound is 1: (0.5-2.0);

and/or, a post-treatment of the cyclization reaction comprises: quenching with water, adjusting pH of reaction system, performing solid-liquid separation, and removing organic solvent.

5 . The method for preparation of 2-chloro-5-chloromethylpyridine of claim 4 , further comprising: performing a reaction on a solid phase substance under an alkaline condition to obtain a silicon-oxygen compound.

6 . A method for preparation of 2-(chloromethyl)-5-(trifluoromethyl)-1,3,4-oxadiazole, comprising: performing a cyclization reaction on 1-(chloroacetyl)-2-(trifluoroacetyl) hydrazine in presence of a silicon compound and an acylamide compound to provide 2-(chloromethyl)-5-(trifluoromethyl)-1,3,4-oxadiazole, wherein a reaction equation of the cyclization reaction is as follows:

wherein the silicon compound is selected from one or more of compounds having a chemical structural formula shown below:

wherein R 3 , R 4 , and R 5 are each independently selected from H, Ph, C1-C4 alkyl, Cl, and Br,

Y is O or is not present,

n is selected from 0, 1, 2, 3, 4, and 5, and

X is selected from Cl and Br.

7 . The method for preparation of 2-(chloromethyl)-5-(trifluoromethyl)-1,3,4-oxadiazole of claim 6 , wherein in the compound of formula V, R 3 , R 4 , and R 5 are each independently selected from H, C1-C2 alkyl, Cl, and Br,

n is selected from 0 and 1, and

X is selected from Cl and Br.

8 . The method for preparation of 2-(chloromethyl)-5-(trifluoromethyl)-1,3,4-oxadiazole of claim 6 , wherein the silicon compound is selected from one or more of methyltrichlorosilane, dichlorodiethylsilane, dichlorodimethylsilane, trimethylchlorosilane, 1, 1,2,2-tetrachloro-1,2-dimethyldisilane, silicon tetrachloride, dibromo (dimethyl) silane, bromotrimethylsilane, and 1,3-dichloro-1,1,3,3-tetramethyldisiloxane.

9 . The method for preparation of 2-(chloromethyl)-5-(trifluoromethyl)-1,3,4-oxadiazole of claim 1 , wherein the acylamide compound has a chemical structural formula shown as RCONR 1 R 2 ,

wherein R is selected from hydrogen, saturated or unsaturated C1 to C8 aliphatic groups, and substituted or unsubstituted phenyl, R 1 and R 2 are each independently selected from saturated or unsaturated C1 to C8 aliphatic groups and phenyl, or R and R 1 , or R and R 2 together with their attached atoms form a five- or six-membered heterocyclic group,

and/or, in the cyclization reaction, a molar ratio of the compound of formula III to the acylamide compound is 1: (0.1-1.5);

and/or, the cyclization reaction is carried out in the presence of a solvent, wherein the solvent is a nonprotonic solvent;

and/or, the cyclization reaction is carried out at a temperature of 70 to 150° C.;

and/or, in the cyclization reaction, a molar ratio of the compound of formula III to the silicon compound is 1: (0.5-2.0);

and/or, a post-treatment of the cyclization reaction comprises: quenching with water, adjusting pH of reaction system, performing solid-liquid separation, and removing organic solvent.

10 . The method for preparation of 2-(chloromethyl)-5-(trifluoromethyl)-1,3,4-oxadiazole of claim 9 , further comprising: performing a reaction on a solid phase substance under an alkaline condition to obtain a silicon-oxygen compound.

11 . The method for preparation of 2-chloro-5-chloromethylpyridine of claim 4 , wherein the acylamide compound is selected from one or more of N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-diethylpropionamide, N,N-dimethylpropionamide, N,N-diphenylformamide, N,N-diphenylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone;

and/or, the solvent is an aromatic hydrocarbon solvent.

12 . The method for preparation of 2-chloro-5-chloromethylpyridine of claim 5 , wherein the silicon-oxygen compound is selected from silicates.

13 . The method for preparation of 2-(chloromethyl)-5-(trifluoromethyl)-1,3,4-oxadiazole of claim 9 , wherein the acylamide compound is selected from one or more of N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-diethylpropionamide, N,N-dimethylpropionamide, N,N-diphenylformamide, N,N-diphenylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone;

and/or, the solvent is an aromatic hydrocarbon solvent.

14 . The method for preparation of 2-(chloromethyl)-5-(trifluoromethyl)-1,3,4-oxadiazole of claim 10 , wherein the silicon-oxygen compound is selected from silicates.