阅读说明：本技术 一种一步法合成烷基硫氰酸酯的方法 (Method for synthesizing alkyl thiocyanate by one-step method ) 是由 陈甫雪 吴迪 于 2021-09-01 设计创作，主要内容包括：本发明涉及一种一步法合成烷基硫氰酸酯的方法,属于化学合成技术领域。所述方法如下：将化合物I、引发剂和氮-硫氰基酰亚胺试剂溶解于有机溶剂中,在40℃～150℃的温度下反应2h～6h,反应结束后,去除有机溶剂,纯化,得到一种烷基硫氰酸酯；所述化合物I的结构通式为或其中,R～(1)为烃基或者被取代的烃基；R～(2)和R～(3)分别独立为氢、卤素、烷基、芳基、被取代的芳基、烷氧基或被取代的烷氧基；R～(4)为烷基,R～(5)为烷基或者氢；R～(6)为烷基；n＝0或者1。所述方法通过一步法就能够合成出烷基硫氰酸酯,方法简单,产率高；且随着反应步骤的减少,减少了化学试剂的适用,经济性好。(The invention relates to a method for synthesizing alkyl thiocyanate by a one-step method, belonging to the technical field of chemical synthesis. The method comprises the following steps: dissolving a compound I, an initiator and a nitrogen-thiocyano imide reagent in an organic solvent, reacting for 2-6 h at the temperature of 40-150 ℃, removing the organic solvent after the reaction is finished, and purifying to obtain alkyl thiocyanate; the general structural formula of the compound I is Or Wherein R is 1 Is a hydrocarbyl or substituted hydrocarbyl group; r 2 And R 3 Each independently is hydrogen, halogen, alkyl, aryl, substituted aryl, alkoxy, or substituted alkoxy; r 4 Is alkyl, R 5 Is alkyl or hydrogen; r 6 Is an alkyl group; n is 0 or 1. The method can synthesize the alkyl thiocyanate through a one-step method, and is simple and high in yield; and with the reduction of reaction steps, the application of chemical reagents is reduced, and the economy is good.)

1. A method for synthesizing alkyl thiocyanate by one-step method is characterized in that: the method comprises the following steps:

dissolving a compound I, an initiator and a nitrogen-thiocyano imide reagent in an organic solvent, reacting for 2-6 h at the temperature of 40-150 ℃, removing the organic solvent after the reaction is finished, and purifying to obtain alkyl thiocyanate;

the general structural formula of the compound I is

Wherein R is¹Is a hydrocarbyl or substituted hydrocarbyl group; r²And R³Each being bonded to a different carbon atom of the benzene ring, not includingOn the benzene ring with R¹A bonded carbon atom; r²And R³Each independently is hydrogen, halogen, alkyl, aryl, substituted aryl, alkoxy, or substituted alkoxy;

R⁴and R⁵Each being bound to a different carbon atom of the heterocyclic ring, R⁴Is alkyl, R⁵Is alkyl or hydrogen;

R⁶to any alpha carbon or to any beta carbon of the naphthalene ring, R⁶Is an alkyl group;

n is 0 or 1;

the initiator is an azo initiator or a peroxide initiator;

the nitrogen-sulfur cyano imide reagent is nitrogen-sulfur cyano succinimide, nitrogen-sulfur cyano phthalimide, nitrogen-sulfur cyano saccharin or nitrogen-sulfur cyano bisbenzenesulfonimide;

the organic solvent is an organic solvent which does not react with the initiator, the nitrogen-thiocyanoimide reagent and the compound I.

2. The one-step method for synthesizing alkyl thiocyanate according to claim 1, wherein: the compound I is

3. The one-step method for synthesizing alkyl thiocyanate according to claim 1, wherein: the initiator is an azo initiator; the organic solvent is an aromatic hydrocarbon solvent or an ether solvent.

4. The one-step method for synthesizing alkyl thiocyanate according to claim 3, wherein: the initiator is azodiisobutyronitrile; the organic solvent is benzene or 1, 4-dioxane; the nitrogen-sulfur cyano imide reagent is nitrogen-sulfur cyano saccharin.

5. The one-step method for synthesizing alkyl thiocyanate according to claim 1, wherein: the ratio of the amounts of the nitrogen-thiocyaneimide reagent to the amount of the compound I is 1:1 to 7, and the ratio of the amounts of the initiator to the amount of the nitrogen-thiocyaneimide reagent is 1:1 to 10.

6. The one-step method for synthesizing alkyl thiocyanate according to claim 5, wherein: the ratio of the amounts of the nitrogen-thiocyaneimide reagent to the amount of the compound I is 1:3 to 5, and the ratio of the amounts of the initiator to the amount of the nitrogen-thiocyaneimide reagent is 1:2 to 5.

7. The one-step method for synthesizing alkyl thiocyanate according to claim 1, wherein: the concentration of the nitrogen-thiocyano imide reagent in the organic solvent is 40 mg/mL-70 mg/mL.

8. The one-step method for synthesizing alkyl thiocyanate according to claim 1, wherein: the reaction temperature is 50-90 ℃ and the reaction time is 4 h.

9. The one-step method for synthesizing alkyl thiocyanate according to claim 1, wherein: the compound I is

The initiator is an azo initiator; the organic solvent is an aromatic hydrocarbon solvent or an ether solvent;

the mass ratio of the nitrogen-thiocyaneimide reagent to the compound I is 1:1 to 7, and the mass ratio of the initiator to the nitrogen-thiocyaneimide reagent is 1:1 to 10;

the concentration of the nitrogen-sulfur cyano imide reagent in the organic solvent is 40 mg/mL-70 mg/mL;

the reaction temperature is 50-90 ℃ and the reaction time is 4 h.

10. The one-step method for synthesizing alkyl thiocyanate according to claim 9, wherein: the initiator is azodiisobutyronitrile; the organic solvent is benzene or 1, 4-dioxane; the nitrogen-thiocyano imide reagent is nitrogen-thiocyano saccharin;

the ratio of the amounts of the nitrogen-thiocyaneimide reagent to the amount of the compound I is 1:3 to 5, and the ratio of the amounts of the initiator to the amount of the nitrogen-thiocyaneimide reagent is 1:2 to 5.

Technical Field

The invention relates to a method for synthesizing alkyl thiocyanate by a one-step method, belonging to the technical field of chemical synthesis.

Background

The sulfur-containing cyano compounds are widely present in natural products and bioactive molecules, and are also important intermediates for synthesizing other sulfur-containing compounds. The alkyl thiocyanate compound is one of sulfur-containing cyano compounds, and has important potential application value in the fields of cancer resistance and antibiosis. The synthesis of alkyl thiocyanate compounds usually requires the introduction of a functional group, such as halogen, hydroxyl, trimethylsiloxy, boronic acid, thiol or thioether, onto a substrate molecule, and the substrate molecule introduced with the functional group undergoes a substitution reaction with an anionic thiocyano source to produce alkyl thiocyanate by virtue of the dissociative nature of the functional group. The method has multiple reaction steps and is not simple and convenient enough; and the chemical reagents are used more and the economy is not good.

Disclosure of Invention

In view of the above, the present invention aims to provide a one-step method for synthesizing alkyl thiocyanate, which can synthesize alkyl thiocyanate by one-step method, and has the advantages of simple method and high yield; and with the reduction of reaction steps, the application of chemical reagents is reduced, and the economy is good.

In order to achieve the purpose of the invention, the following technical scheme is provided.

A one-step method for synthesizing alkyl thiocyanate, comprising the following steps: dissolving a compound I, an initiator and a nitrogen-thiocyano imide reagent in an organic solvent, reacting for 2-6 h at the temperature of 40-150 ℃, removing the organic solvent after the reaction is finished, and purifying to obtain the alkyl thiocyanate.

The general structural formula of the compound I is

Wherein the content of the first and second substances,R¹is a hydrocarbyl or substituted hydrocarbyl group such as methyl, butyl or allyl; r²And R³Each of which is bonded to a different carbon atom of the benzene ring, excluding the carbon atoms of the benzene ring bonded to R¹A bonded carbon atom; r²Is hydrogen, halogen, alkyl, aryl, substituted aryl, alkoxy or substituted alkoxy; r³Is hydrogen, halogen, alkyl, aryl, substituted aryl, alkoxy or substituted alkoxy; aryl such as phenyl, naphthyl, tetrahydronaphthyl or biphenyl, and substituted alkoxy such as allylalkoxy, benzyloxy;

R⁴and R⁵Each being bound to a different carbon atom of the heterocyclic ring, R⁴Is alkyl, R⁵Is alkyl or hydrogen;

R⁶to any alpha carbon or to any beta carbon of the naphthalene ring, R⁶Is an alkyl group.

n is 0 or 1.

Preferably, the compound I is(R¹Is methyl, R²And R³All are hydrogen),(R¹Is methyl, R²Is methyl, R³Is hydrogen),(R¹Is methyl, R²Is methyl, R³Is hydrogen),(R¹Is methyl, R²Is methyl, R³Is hydrogen),(R¹Is methyl, R²Is OMe, R³Is hydrogen),(R¹Is methyl, R²Is tert-butyl, R³Is hydrogen),(R¹Is ethyl, R²And R³All are hydrogen),(R¹Is butyl, R²And R³All are hydrogen),(R¹Is methyl, R²Is chlorine, R³Is hydrogen),(R¹Is methyl, R²Is chlorine, R³Is hydrogen),(R¹Is methyl, R²Is Br, R³Is hydrogen),(R¹Is methyl, R²Is Br, R³Is hydrogen),(R¹Is methyl, R²Is Br, R³Is methyl group)(R¹Is methyl, R²And R³All are methyl),(R¹Is ethyl, R²Is methyl, R³Is hydrogen),(R⁶Is methyl group)(R⁶Is methyl group)(R¹Is toluene, R²And R³All are hydrogen),(n＝1)、(n＝0)、(R⁴Is methyl, R⁵Is hydrogen),(R⁴And R⁵All are methyl),(R⁴Is methyl, R⁵Is hydrogen),(R¹Is propionic acid, R²Is butyl, R³Is hydrogen) or(R¹Is allyl, R²And R³Is hydrogen).

The initiator is azo initiator or peroxide initiator.

Preferably, the initiator is an azo initiator.

More preferably, the initiator is azobisisobutyronitrile.

The nitrogen-thiocyano imide reagent is nitrogen-thiocyano succinimide (N-thiocyanato succinimide), nitrogen-thiocyano phthalimide (N-thiocyanato phthalimide), nitrogen-thiocyano saccharin (N-thiocyanato saccharan) or nitrogen-thiocyanato bisbenzenesulfonimide (N-thiocyanato dibenzylsulfonimide).

The structural formula of the nitrogen-sulfur cyano succinimide is as follows:the structural formula of the nitrogen-thiocyano phthalimide is as follows:the structural formula of the nitrogen-thiocyano saccharin is as follows:the structural formula of the nitrogen-thiocyano bis-benzenesulfonylimine is as follows:

preferably, the nitrogen-thiocyanoimide reagent is nitrogen-thiocyanosol.

The organic solvent is an organic solvent which does not react with the initiator, the nitrogen-thiocyanoimide reagent and the compound I.

Preferably, the organic solvent is an aromatic hydrocarbon solvent or an ether solvent.

More preferably, the organic solvent is benzene or 1, 4-dioxane.

Preferably, the ratio of the amount of the nitrogen-thiocyaneimide reagent to the amount of the substance of the compound I is 1 (1 to 7), and the ratio of the amount of the initiator to the amount of the substance of the nitrogen-thiocyaneimide reagent is 1 (1 to 10).

More preferably, the ratio of the amount of the nitrogen-thiocyaneimide reagent to the amount of the substance of the compound I is 1 (3-5), and the ratio of the amount of the initiator to the amount of the substance of the nitrogen-thiocyaneimide reagent is 1 (2-5).

More preferably, the concentration of the nitrogen-thiocyaneimide reagent in the organic solvent is from 40mg/mL to 70 mg/mL.

Preferably, the reaction temperature is 50-90 ℃ and the reaction time is 4 h.

Advantageous effects

The invention provides a method for synthesizing alkyl thiocyanate by a one-step method, wherein a nitrogen-thiocyanimide reagent used in the method is a thiocyanato source, a compound I provides alkyl, the nitrogen-thiocyanimide reagent and the compound I directly perform thiocyanidation reaction under the action of an initiator, a leaving functional group is not required to be introduced on the compound I in advance through an intermediate reaction, and the synthesis steps are reduced. The reaction mechanism of the invention is as follows: under the heating condition, the initiator generates free radicals, the free radicals further react with the nitrogen-thiocyanimide reagent to generate thiocyano free radicals, and the thiocyano free radicals react with the compound I through free radicals to generate the alkyl thiocyanate compound.

The invention provides a one-step method for synthesizing alkyl thiocyanate, which adopts an optimized nitrogen-thiocyano imide reagent for reaction, and the yield of the prepared alkyl thiocyanate is high.

The invention provides a one-step method for synthesizing alkyl thiocyanate, which can synthesize the alkyl thiocyanate by a one-step method without intermediate reaction, thereby reducing the use of chemical reagents in the reaction process, reducing the waste of the chemical reagents and having good economical efficiency.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of thiocyanomethylbenzene prepared in example 1.

FIG. 2 is a nuclear magnetic carbon spectrum of thiocyanomethylbenzene prepared in example 1.

FIG. 3 is a nuclear magnetic hydrogen spectrum of 3- (thiocyanomethyl) thiophene prepared in example 23.

FIG. 4 is a nuclear magnetic carbon spectrum of 3- (thiocyanomethyl) thiophene prepared in example 23.

Detailed Description

The invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available or may be prepared from literature.

Example 1

One-step synthesis of thiocyanomethylbenzeneThe method of (1), the method steps are as follows:

toluene (92mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) were dissolved in benzene (1.0mL) under air, and after 4h of reaction under reflux at 80 ℃, benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, the eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1, and the final product was obtained after the purification was completed and was a yellow oily liquid.

The final product obtained in this example was tested as follows:

(1) the obtained test results are shown in figure 1 and figure 2 respectively after the nuclear magnetic resonance hydrogen spectrum test and the nuclear magnetic resonance carbon spectrum test, and the nuclear magnetic hydrogen spectrum result of the final product is¹H NMR(400MHz,CDCl₃) Delta 7.40-7.36 (m,5H),4.17(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) Delta 134.3,129.1,128.9,128.9,111.9, 38.3; comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of thiocyanomethylbenzene, the final product is thiocyanomethylbenzene.

(2) The thiocyanomethylbenzene obtained in this example had a mass of 27mg and a yield of 93%.

(3) The purity of the thiocyanomethylbenzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 2

One-step synthesis method of 1-methyl-2-thiocyanomethylbenzeneThe method of (1), the method steps are as follows:

dissolving o-xylene (106mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyanatosaccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 deg.C for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the remaining residue with silica gel column, eluting with petroleum ether and ethyl acetate at a volume ratio of 10:1, and purifying to obtain the final product as colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) Delta 7.25-7.17 (m,4H),4.18(s,2H),2.37(s, 3H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 136.8,131.9,131.0,130.2,129.3,126.7,111.9,36.6 and 19.0. Comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1-methyl-2-thiocyanomethylbenzene, the final product is 1-methyl-2-thiocyanomethylbenzene.

(2) The mass of 1-methyl-2-thiocyanomethylbenzene produced in this example was 30mg, and the yield was 92%.

(3) The purity of the 1-methyl-2-thiocyanomethylbenzene is more than 95 percent through nuclear magnetic hydrogen spectrum test.

Example 3

One-step synthesis method of 1-methyl-3-thiocyanomethylbenzeneThe method of (1), the method steps are as follows:

dissolving m-xylene (106mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyanatosaccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 deg.C for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance with silica gel column, eluting with petroleum ether and ethyl acetate at a volume ratio of 10:1, and purifying to obtain the final product which is colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) performing hydrogen spectrum test and carbon spectrum test by nuclear magnetic resonanceIt can be seen that the end product has a nuclear magnetic hydrogen spectrum result of¹H NMR(400MHz,CDCl₃) Delta 7.25-7.11 (m,4H),4.09(s,2H),2.33(s, 3H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 138.9,134.1,129.7,129.6,129.0,126.0,112.0,38.4 and 21.3. Comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1-methyl-3-thiocyanomethylbenzene, the final product is 1-methyl-3-thiocyanomethylbenzene.

(2) The mass of 1-methyl-3-thiocyanomethylbenzene produced in this example was 33mg, and the yield was 100%.

(3) The purity of the 1-methyl-3-thiocyanomethyl benzene is more than 95 percent through nuclear magnetic hydrogen spectrum test.

Example 4

One-step synthesis method of 1-methyl-4-thiocyanomethylbenzeneThe method of (1), the method steps are as follows:

p-xylene (106mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) were dissolved in benzene (1.0mL) under air conditions, and after 4h of reaction under reflux at 80 ℃, benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, an eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1, and the final product was obtained after the purification was completed and was a colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) δ 7.26(d, J ═ 8.0Hz,2H),7.19(d, J ═ 8.0Hz,2H),4.14(s,2H),2.36(s, 3H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 138.9,131.2,129.8,128.9,112.1,38.2 and 21.2. The two results are compared with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1-methyl-4-thiocyanomethylbenzene, and the final product is obtainedThe product is 1-methyl-4-thiocyanomethylbenzene.

(2) The mass of 1-methyl-4-thiocyanomethylbenzene produced in this example was 32mg, and the yield was 98%.

(3) The purity of the 1-methyl-4-thiocyanomethyl benzene is more than 95 percent through nuclear magnetic hydrogen spectrum test.

Example 5

One-step synthesis of 4-thiocyanomethyl anisoleThe method of (1), the method steps are as follows:

dissolving 4-methylanisole (122mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) in benzene (1.0mL) under air conditions, refluxing and stirring at 80 ℃ for 4 hours, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance by a silica gel column, and obtaining a final product after purification, wherein the final product is a yellow oily liquid after purification, and the eluent for purification consists of petroleum ether and ethyl acetate according to a volume ratio of 10: 1.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) δ 7.29(d, J ═ 8.4Hz,2H),6.90(d, J ═ 8.4Hz,2H),4.15(s,2H),3.82(s, J ═ 3H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) 160.0,130.3,128.2,114.5,112.2,55.3 and 38.2. Comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 4-thiocyanomethyl anisole, the final product is 4-thiocyanomethyl anisole.

(2) The mass of 4-thiocyanomethylanisole obtained in this example was 36mg, and the yield was 100%.

(3) The purity of the 4-thiocyanomethyl anisole is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 6

One-step method for synthesizing 1-tert-butyl4-thiocyanomethyl-benzene radicalThe method of (1), the method steps are as follows:

tert-butyl benzene (148mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) were dissolved in benzene (1.0mL) under air conditions, and after 4h of reaction under reflux at 80 ℃, the benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, the eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1, and the final product was obtained after the purification was completed and was a colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) δ 7.41(d, J ═ 8.4Hz,2H),7.30(d, J ═ 8.4Hz,2H),4.16(s,2H),1.33(s, 9H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 152.0,131.2,128.7,126.1,38.2,34.7 and 31.2. Comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1-tert-butyl-4-thiocyanomethylbenzene, the final product is 1-tert-butyl-4-thiocyanomethylbenzene.

(2) The mass of 1-tert-butyl-4-thiocyanomethylbenzene obtained in this example was 38mg, and the yield was 93%.

(3) The purity of the 1-tert-butyl-4-thiocyanomethylbenzene is more than 95 percent through nuclear magnetic hydrogen spectrum test.

Example 7

One-step synthesis of (1-thiocyanoethyl) benzeneThe method of (1), the method steps are as follows:

dissolving ethylbenzene (106mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyanatosaccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance by silica gel column, wherein an eluent for purification consists of petroleum ether and ethyl acetate according to a volume ratio of 10:1, and obtaining a final product after the purification is finished, wherein the final product is colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) δ 7.40-7.35 (m,5H),6.61(q, J ═ 6.8Hz,1H),1.89(d, J ═ 6.8Hz, 3H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 139.0,129.0,128.9,127.0,111.7,48.4 and 21.9. The two results are compared with the published nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of (1-thiocyanoethyl) benzene, and the final product is (1-thiocyanoethyl) benzene.

(2) The mass of (1-thiocyanoethyl) benzene produced in this example was 33mg, and the yield was 100%.

(3) The purity of the (1-thiocyanoethyl) benzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 8

One-step synthesis of (1-thiocyanobutyl) benzeneThe method of (1), the method steps are as follows:

butylbenzene (134mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) were dissolved in benzene (1.0mL) under air conditions, and after 4h of reaction under reflux at 80 ℃, the benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, the eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1, and the final product was obtained after the purification was completed and was a colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) hydrogen and carbon nuclear magnetic resonance spectroscopyThe result of nuclear magnetic hydrogen spectrum of the final product is shown as follows¹H NMR(400MHz,CDCl₃) δ 7.41-7.33 (m,5H),4.35(t, J ═ 7.6Hz,1H), 2.17-2.11 (m,2H), 1.45-1.29 (m,2H),0.95(t, J ═ 7.2Hz, 3H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 138.3,129.0,128.8,127.4,111.7,53.4,37.7,20.6 and 13.4. The two results are compared with the published nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of (1-thiocyanobutyl) benzene, and the final product is (1-thiocyanobutyl) benzene.

(2) The mass of (1-thiocyanobutyl) benzene prepared in this example was 36mg, with a yield of 94%.

(3) The purity of the (1-thiocyanobenzyl) benzene is more than 95 percent through nuclear magnetic hydrogen spectrum tests.

Example 9

One-step synthesis method of 1-chloro-2- (thiocyanomethyl) benzeneThe method of (1), the method steps are as follows:

dissolving 1-chloro-2-methylbenzene (126mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, stirring at 80 ℃ for 4 hours, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance by a silica gel column, wherein an eluent for purification consists of petroleum ether and ethyl acetate in a volume ratio of 10:1, and obtaining a final product after the purification is finished, wherein the final product is colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) Delta 7.46-7.40 (m,2H), 7.36-7.29 (m,2H),4.25(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 134.2,132.3,131.1,130.5,130.1,127.5,111.8, 36.2. The two results are combined with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1-chloro-2- (thiocyanomethyl) benzeneBy comparison, the final product is 1-chloro-2- (thiocyanomethyl) benzene.

(2) The mass of 1-chloro-2- (thiocyanomethyl) benzene obtained in this example was 14mg, and the yield was 38%.

(3) The purity of the 1-chloro-2- (thiocyanomethyl) benzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 10

One-step synthesis method of 1-chloro-4- (thiocyanomethyl) benzeneThe method of (1), the method steps are as follows:

dissolving 1-chloro-4-methylbenzene (126mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, removing benzene by rotary evaporation under reduced pressure, purifying the remaining residue with a silica gel column, eluting with a purifying agent consisting of petroleum ether and ethyl acetate in a volume ratio of 10:1, and obtaining the final product after purification, wherein the final product is yellow oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) δ 7.37(d, J ═ 8.8Hz,2H),7.30(d, J ═ 8.8Hz,2H),4.12(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) 135.0,132.9,130.3,129.4,111.5, 37.6. Comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1-chloro-4- (thiocyanomethyl) benzene, the final product is 1-chloro-4- (thiocyanomethyl) benzene.

(2) The mass of 1-chloro-4- (thiocyanomethyl) benzene obtained in this example was 19mg, and the yield was 52%.

(3) The purity of the 1-chloro-4- (thiocyanomethyl) benzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 11

One-step methodSynthesis of 1-bromo-4- (thiocyanomethyl) benzeneThe method of (1), the method steps are as follows:

dissolving 1-bromo-4-methylbenzene (170mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the remaining residue by a silica gel column, wherein an eluent for purification consists of petroleum ether and ethyl acetate in a volume ratio of 10:1, and obtaining a final product after the purification is finished, wherein the final product is a colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) δ 7.53(d, J ═ 8.4Hz,2H),7.24(d, J ═ 8.4Hz,2H),4.10(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 133.4,132.3,130.5,123.1,111.5, 37.6. Comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1-bromo-4- (thiocyanomethyl) benzene, the final product is 1-bromo-4- (thiocyanomethyl) benzene.

(2) The mass of 1-bromo-4- (thiocyanomethyl) benzene prepared in this example was 30mg, and the yield was 66%.

(3) The purity of the 1-bromo-4- (thiocyanomethyl) benzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 12

One-step synthesis method of 1-bromo-3- (thiocyanomethyl) benzeneThe method of (1), the method steps are as follows:

dissolving 1-bromo-3-methylbenzene (170mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the remaining residue by a silica gel column, wherein an eluent for purification consists of petroleum ether and ethyl acetate in a volume ratio of 10:1, and obtaining a final product after the purification is finished, wherein the final product is a colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) Delta 7.54-7.52 (m,2H), 7.35-7.28 (m,2H),4.13(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 136.5,132.1,131.9,127.6,123.0,111.4, 37.4. Comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1-bromo-3- (thiocyanomethyl) benzene, the final product is 1-bromo-3- (thiocyanomethyl) benzene.

(2) The mass of 1-bromo-3- (thiocyanomethyl) benzene prepared in this example was 21mg, and the yield was 46%.

(3) The purity of the 1-bromo-3- (thiocyanomethyl) benzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 13

One-step synthesis method of 1-bromo-3-methyl-5- (thiocyanomethyl) benzeneThe method of (1), the method steps are as follows:

dissolving 1-bromo-3, 5-dimethylbenzene (184mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyanatosaccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance with a silica gel column, wherein an eluent for purification consists of petroleum ether and ethyl acetate in a volume ratio of 10:1, and obtaining a final product after purification, wherein the final product is a white solid and has a melting point of 50-52 ℃ as measured by a digital micro melting point apparatus.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum, infrared spectrum and High Resolution Mass Spectrum (HRMS) tests¹H NMR(400MHz,CDCl₃) δ 7.33(s,1H),7.31(s,1H),7.10(s,1H),4.07(s,2H),2.35(s, 3H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) Delta 141.0,136.1,132.7,128.9,122.7,111.5,37.5, 21.1; the infrared spectrum result is that the IR (KBr) is 2916,2152,1597,1566,1442,1257cm^-1，2152cm^-1The peak at (A) is a characteristic peak of thiocyano (-SCN); the result of high resolution mass spectrometry is HRMS (APCI) m/z calculated value C₉H₉BrNS[M+H]⁺It was 241.9634 and the experimental value was 241.9634. According to the four results, the final product is 1-bromo-3-methyl-5- (thiocyanomethyl) benzene.

(2) The mass of 1-bromo-3-methyl-5- (thiocyanomethyl) benzene obtained in this example was 44mg, and the yield was 91%.

(3) The purity of the 1-bromo-3-methyl-5- (thiocyanomethyl) benzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 14

One-step synthesis method of 1, 3-dimethyl-5- (thiocyanomethyl) benzeneThe method of (1), the method steps are as follows:

dissolving 1,3, 5-trimethylbenzene (121mg, 1.00mmol), azodiisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyanatosaccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance with a silica gel column, wherein an eluent for purification consists of petroleum ether and ethyl acetate in a volume ratio of 10:1, and obtaining a final product after purification, wherein the final product is a white solid and has a melting point of 47-49 ℃ as measured by a digital micro melting point apparatus.

The final product obtained in this example was tested as follows:

(1) hydrogen spectrum, carbon spectrum and red spectrum by nuclear magnetic resonanceThe nuclear magnetic hydrogen spectrum result of the final product is shown by external spectrum and High Resolution Mass Spectrum (HRMS) tests¹H NMR(400MHz,CDCl₃) δ 6.99(s,1H),6.97(s,2H),4.11(s,2H),2.33(s, 6H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) Delta 138.8,134.0,130.6,126.7,112.2,38.4, 21.2; the infrared spectrum result is that the IR (KBr) is 2916,2152,1604,1466cm^-1，2152cm^-1The peak at (A) is a characteristic peak of thiocyano (-SCN); the result of high resolution mass spectrometry is HRMS (APCI) m/z calculated value C₁₀H₁₂NS[M+H]⁺It was 178.0685 and the experimental value was 178.0678. According to the four results, the final product is 1, 3-dimethyl-5- (thiocyanomethyl) benzene.

(2) The mass of 1, 3-dimethyl-5- (thiocyanomethyl) benzene obtained in this example was 35mg, and the yield was 99%.

(3) The purity of the 1, 3-dimethyl-5- (thiocyanomethyl) benzene is more than 95 percent through nuclear magnetic hydrogen spectrum test.

Example 15

One-step synthesis method of 1-methyl-4- (1-thiocyanoethyl) benzeneThe method of (1), the method steps are as follows:

dissolving 1-methyl-4-ethylbenzene (120mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance by a silica gel column, wherein an eluent for purification consists of petroleum ether and ethyl acetate in a volume ratio of 10:1, and obtaining a final product after the purification is finished, wherein the final product is colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃)δ:7.28(d,J＝8.0Hz,2H),7.20(d,J＝8.0Hz,2H),4.60(q,J＝7.2Hz,1H),2.36(s,3H)1.87(d, J ═ 7.2Hz, 3H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 138.9,136.0,129.7,126.9,111.9,48.4,22.0 and 21.1. Comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1-methyl-4- (1-thiocyanoethyl) benzene, the final product is 1-methyl-4- (1-thiocyanoethyl) benzene.

(2) The mass of 1-methyl-4- (1-thiocyanoethyl) benzene obtained in this example was 31mg, and the yield was 88%.

(3) The purity of the 1-methyl-4- (1-thiocyanoethyl) benzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 16

One-step method for synthesizing 2- (thiocyanomethyl) naphthaleneThe method of (1), the method steps are as follows:

dissolving 2-methylnaphthalene (142mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance by a silica gel column, wherein an eluent for purification consists of petroleum ether and ethyl acetate according to a volume ratio of 10:1, and obtaining a final product after the purification is finished, wherein the final product is a white solid and has a melting point of 96-98 ℃ by using a digital micro melting point apparatus.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) δ 7.89-7.82 (m,4H), 7.55-7.52 (m,2H),7.45(dd, J ═ 8.4,1.6Hz,1H),4.32(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 133.1,133.1,131.5,129.2,128.3,128.0,127.7,126.8,126.7,126.0,111.9, 38.7. The two results are compared with the nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of the disclosed 2- (thiocyanomethyl) naphthalene, and the final product is the 2- (thiocyanomethyl) naphthalene。

(2) The mass of 2- (thiocyanomethyl) naphthalene obtained in this example was 30mg, and the yield was 75%.

(3) The purity of the 2- (thiocyanomethyl) naphthalene is more than 95 percent through nuclear magnetic hydrogen spectrum test.

Example 17

One-step synthesis of 1- (thiocyanomethyl) naphthaleneThe method of (1), the method steps are as follows:

dissolving 1-methylnaphthalene (142mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) in benzene (1.0mL) under air conditions, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance by a silica gel column, using an eluent for purification consisting of petroleum ether and ethyl acetate in a volume ratio of 10:1 to obtain a final product after purification, wherein the final product is a white solid, and the melting point of the final product is 81-83 ℃ by using a digital micro melting point apparatus.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) Delta 7.98-7.88 (m,3H), 7.65-7.45 (m,4H),4.66(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 134.0,130.6,130.2,129.4,129.2,128.6,127.0,126.3,125.3,122.7,112.0.36.4. Comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 1- (thiocyanomethyl) naphthalene, the final product is 1- (thiocyanomethyl) naphthalene.

(2) The mass of 1- (thiocyanomethyl) naphthalene obtained in this example was 33mg, and the yield was 83%.

(3) The purity of the 1- (thiocyanomethyl) naphthalene is more than 95 percent through nuclear magnetic hydrogen spectrum test.

Example 18

One-step synthesis of (thiocyano ethylene)Methyl) diphenylThe method of (1), the method steps are as follows:

diphenylmethane (178mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) were dissolved in benzene (1.0mL) under air conditions, and after 4h of reaction under reflux at 80 ℃, benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, an eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1, and the final product was obtained after the purification was completed and was a colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) Delta 7.43-7.33 (m,10H,5.83(s, 1H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(175MHz,CDCl₃) 137.5,129.1,128.8,128.2,111.7, 57.4. The two results are compared with the nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of the (thiocyanomethylene) diphenyl which are already disclosed, and the final product is the (thiocyanomethylene) diphenyl.

(2) The mass of (thiocyanomethylene) diphenyl obtained in this example was 36mg, and the yield was 80%.

(3) The purity of the (thiocyanomethylene) diphenyl is more than 95 percent through nuclear magnetic hydrogen spectrum test.

Example 19

One-step method for synthesizing 1-thiocyano-1, 2,3, 4-tetrahydronaphthaleneThe method of (1), the method steps are as follows:

dissolving 1,2,3, 4-tetrahydronaphthalene (132mg, 1.00mmol), azodiisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyanatosaccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, removing benzene by rotary evaporation under reduced pressure, purifying the remaining residue with a silica gel column, wherein an eluent for purification consists of petroleum ether and ethyl acetate in a volume ratio of 10:1, and obtaining the final product after the purification is finished, wherein the final product is colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum, infrared spectrum and High Resolution Mass Spectrum (HRMS) tests¹H NMR(400MHz,CDCl₃) δ 7.33(d, J ═ 7.6Hz,1H),7, 25-7.18 (m,2H),7.12(d, J ═ 8.4Hz,1H),4.91(t, J ═ 3.6Hz,1H), 2.92-2.75 (m,2H), 2.43-1.91 (m, 4H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) Delta 137.9,131.5,130.3,129.7,128.8,126.4,112.4,49.7,29.7,28.6, 18.2; the infrared spectrum result is that the IR (KBr) is 2931,2145,1489,1450,1265cm^-1，2145cm^-1The peak at (A) is a characteristic peak of thiocyano (-SCN); the result of high resolution mass spectrometry is HRMS (APCI) m/z calculated value C₁₁H₁₂NS[M+H]⁺It was 190.0685 and the experimental value was 190.0676. According to the four results, the final product is 1-thiocyano-1, 2,3, 4-tetrahydronaphthalene.

(2) The mass of 1-thiocyano-1, 2,3, 4-tetrahydronaphthalene obtained in this example was 37mg, and the yield was 98%.

(3) The purity of the 1-thiocyano-1, 2,3, 4-tetrahydronaphthalene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 20

One-step synthesis method of 1-thiocyano-2, 3-indaneThe method of (1), the method steps are as follows:

dissolving 2, 3-indane (118mg, 1.00mmol), azodiisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyanatosaccharin (48mg, 0.20mmol) in benzene (1.0mL) under air conditions, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual residue by a silica gel column, and obtaining the final product after purification, wherein the final product is colorless oily liquid after purification, and the eluent for purification consists of petroleum ether and ethyl acetate according to a volume ratio of 10: 1.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum, infrared spectrum and High Resolution Mass Spectrum (HRMS) tests¹H NMR(400MHz,CDCl₃) δ 7.43(d, J ═ 7.2Hz,1H), 7.31-7.25 (m,3H),4.93(dd, J ═ 7.2,2.8Hz,1H), 3.24-3.16 (m,1H), 3.00-2.93 (m,1H), 2.71-2.62 (m,1H), 2.43-2.36 (m, 1H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) 143.8,139.4,129.4,127.2,125.1,124.9,112.2,53.3,34.1, 30.4; the infrared spectrum result is that the IR (KBr) is 2939,2144,1465,1319cm^-1，2144cm^-1The peak at (A) is a characteristic peak of thiocyano (-SCN); the result of high resolution mass spectrometry is HRMS (APCI) m/z calculated value C₁₀H₁₀NS[M+H]⁺It was 176.0528 and the experimental value was 176.0524. According to the four results, the final product is 1-thiocyano-2, 3-dihydroindene.

(2) The mass of 1-thiocyano-2, 3-indane prepared in this example was 32mg, and the yield was 91%.

(3) The purity of the 1-thiocyano-2, 3-indane is more than 95 percent through nuclear magnetic hydrogen spectrum test.

Example 21

One-step method for synthesizing 2- (thiocyanomethyl) thiopheneThe method of (1), the method steps are as follows:

dissolving 2-methylthiophene (98mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyanatosaccharin (48mg, 0.20mmol) in benzene (1.0mL) under air conditions, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the remaining residue by a silica gel column, using an eluent for purification consisting of petroleum ether and ethyl acetate in a volume ratio of 10:1, and obtaining the final product after the purification is finished, wherein the final product is a yellow oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) δ 7.34(dd, J ═ 5.2,0.8Hz,1H),7.14(d, J ═ 3.2Hz,1H),6.99(dd, J ═ 5.2,3.2Hz,1H),4.42(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) 136.0,128.7,127.4,127.3,111.6, 33.2. The two results are compared with the published nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of 2- (thiocyanomethyl) thiophene, and the final product is 2- (thiocyanomethyl) thiophene.

(2) The mass of 2- (thiocyanomethyl) thiophene prepared in this example was 29mg, and the yield was 94%.

(3) The purity of the 2- (thiocyanomethyl) thiophene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 22

One-step synthesis of 2-methyl-5- (thiocyanomethyl) thiopheneThe method of (1), the method steps are as follows:

dissolving 2, 5-dimethylthiophene (112mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) in benzene (1.0mL) under air, refluxing and stirring at 80 ℃ for 4h, performing rotary evaporation under reduced pressure to remove benzene, purifying the residual substance by a silica gel column, and obtaining a final product after purification, wherein the final product is a yellow liquid after purification, and the eluent for purification consists of petroleum ether and ethyl acetate according to a volume ratio of 10: 1.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum, infrared spectrum and High Resolution Mass Spectrum (HRMS) tests¹H NMR(400MHz,CDCl₃) δ 6.91(d, J ═ 3.2Hz,1H),6.62(d, J ═ 3.2Hz,1H),4.35(s,2H),2.47(s, 3H); nuclear magnetic carbon spectrum resultsIs composed of¹³C{¹H}NMR(100MHz,CDCl₃) Delta 142.3,133.5,128.8,125.4,111.8,33.8,15.4 infrared spectrum result is IR (KBr) 2973,2912,2152,1666,1427,1249cm^-1，2152cm^-1The peak at (A) is a characteristic peak of thiocyano (-SCN); the result of high resolution mass spectrometry is HRMS (APCI) m/z calculated value C₇H₈NS₂[M+H]⁺It was 170.0093 and the experimental value was 170.0085. According to the four results, the final product is 2-methyl-5- (thiocyanomethyl) thiophene.

(2) The mass of 2-methyl-5- (thiocyanomethyl) thiophene prepared in this example was 33mg, and the yield was 98%.

(3) The purity of the 2-methyl-5- (thiocyanomethyl) thiophene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 23

One-step synthesis of 3- (thiocyanomethyl) thiopheneThe method of (1), the method steps are as follows:

3-methylthiophene (98mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyanatosaccharin (48mg, 0.20mmol) were dissolved in benzene (1.0mL) under air conditions, and after 4h of reaction under reflux at 80 ℃, the benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, and an eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1 to give the final product as a yellow oily liquid after the purification was completed.

The final product obtained in this example was tested as follows:

(1) the results of the nuclear magnetic resonance hydrogen spectrum, nuclear magnetic resonance carbon spectrum, infrared spectrum and High Resolution Mass Spectrum (HRMS) tests are shown in figures 3 and 4, so that the nuclear magnetic hydrogen spectrum result of the final product is shown as¹H NMR(400MHz,CDCl₃) δ: 7.38-7.33 (m,2H),7.11(dd, J ═ 4.8,1.2Hz,1H),4.22(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) 134.4,127.4,127.3,125.1,112.0, 32.9; infrared spectrum result is IR(KBr):2970,2923,2154,1667,1521,1420,1250cm^-1，2154cm^-1The peak at (A) is a characteristic peak of thiocyano (-SCN); the result of high resolution mass spectrometry is HRMS (APCI) m/z calculated value C₆H₆NS₂[M+H]⁺It was 155.9936 and the experimental value was 155.9932. According to the four results, the final product is 3- (thiocyanomethyl) thiophene.

(2) The mass of 3- (thiocyanomethyl) thiophene obtained in this example was 28mg, and the yield was 90%.

(3) The purity of the 3- (thiocyanomethyl) thiophene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 24

One-step synthesis of (E) - (3-thiocyano propenyl) benzeneThe method of (1), the method steps are as follows:

allyl benzene (118mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) were dissolved in benzene (1.0mL) under air conditions, and after 4h of reaction under reflux at 80 ℃, benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, an eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1, and the final product was obtained after the purification was completed and was a yellow oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) δ 7.42-7.30 (m,5H),6.70(d, J ═ 15.6Hz,1H), 6.30-6.25 (m,1H),3.76(d, J ═ 7.2Hz, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) 136.5,135.4,128.7,12.6,126.8,121.2,111.8 and 36.9. The above two results are compared with the published results of nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of (E) - (3-thiocyano propenyl) benzene, and the final product is (E) - (3-thiocyano propenyl) benzene.

(2) The mass of (E) - (3-thiocyanopropenyl) benzene obtained in this example was 24mg, and the yield was 69%.

(3) The purity of the (E) - (3-thiocyano propenyl) benzene is more than 95 percent as can be seen by nuclear magnetic hydrogen spectrum test.

Example 25

One-step method for synthesizing 2- (4- (2-methyl-1-thiocyano propyl) phenyl) propionic acidThe method of (1), the method steps are as follows:

ibuprofen (206mg, 1.00mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano saccharin (48mg, 0.20mmol) were dissolved in benzene (1.0mL) under air conditions, and after 4h of reaction under reflux at 80 ℃, benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, the eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 2:1, and the final product was obtained after the purification was finished, and was a colorless oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum, infrared spectrum and High Resolution Mass Spectrum (HRMS) tests¹H NMR(400MHz,CDCl₃) δ:7.33(d, J ═ 8.4Hz,2H),7.26(d, J ═ 8.4Hz,2H),4.06(d, J ═ 9.2Hz,1H),3.75(q, J ═ 7.2Hz,1H), 2.38-2.30 (m,1H),1.52(d, J ═ 7.2Hz,3H),1.17(d, J ═ 7.2Hz,3H),0.89(d, J ═ 6.4Hz, 3H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) Delta 180.1,140.0,137.6,128.1,128.0,111.9,61.4,44.9,33.5,21.0,20.5, 18.0; the infrared spectrum result is that the IR (KBr) is 2970,2931,2152,1705,1512,1458,1226cm^-1，2152cm^-1The peak at (A) is a characteristic peak of thiocyano (-SCN); the result of high resolution mass spectrometry is HRMS (APCI) m/z calculated value C₁₄H₁₆NO₂S[M–H]^–It was 262.0907 and the experimental value was 262.0915. According to the four results, the final product is 2- (4- (2-methyl-1-thiocyanatopropyl) phenyl) propionic acid.

(2) The mass of 2- (4- (2-methyl-1-thiocyanopropyl) phenyl) propionic acid obtained in this example was 46mg, and the yield was 87%.

(3) The purity of the 2- (4- (2-methyl-1-thiocyanatopropyl) phenyl) propionic acid is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 26

One-step synthesis of thiocyanomethylbenzeneThe method of (1), the method steps are as follows:

toluene (18mg, 0.20mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano succinimide (27mg, 0.24mmol) were dissolved in 1, 4-dioxane (1.0mL) under air, and after 2h of reaction under reflux at 100 ℃, benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, the eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1, and the final product was obtained after the purification was completed as a yellow oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) Delta 7.40-7.36 (m,5H),4.17(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) Delta 134.3,129.1,128.9,128.9,111.9, 38.3; comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of thiocyanomethylbenzene, the final product is thiocyanomethylbenzene.

(2) The thiocyanomethylbenzene obtained in this example had a mass of 9mg and a yield of 30%.

(3) The purity of the thiocyanomethylbenzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 27

One-step synthesis of thiocyanomethylbenzeneThe method of (1), the method steps are as follows:

toluene (18mg, 0.20mmol), azobisisobutyronitrile (6.6mg,0.04mmol) and nitrogen-thiocyano phthalimide (49mg, 0.24mmol) were dissolved in benzene (1.0mL) under air, and after 2h of reaction under reflux at 80 ℃, benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, an eluent for purification consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1, and after the purification was completed, the final product was obtained as a yellow oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) Delta 7.40-7.36 (m,5H),4.17(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) Delta 134.3,129.1,128.9,128.9,111.9, 38.3; comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of thiocyanomethylbenzene, the final product is thiocyanomethylbenzene.

(2) The thiocyanomethylbenzene obtained in this example had a mass of 3mg and a yield of 10%.

(3) The purity of the thiocyanomethylbenzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

Example 28

One-step synthesis of thiocyanomethylbenzeneThe method of (1), the method steps are as follows:

toluene (18mg, 0.20mmol), azobisisobutyronitrile (13.2mg, 0.08mmol) and nitrogen-thiocyanobenzenesulfonylimide (85mg, 0.24mmol) were dissolved in benzene (1.0mL) under air conditions, the mixture was stirred under reflux at 80 ℃ for 2 hours, then the benzene was removed by rotary evaporation under reduced pressure, the remaining residue was purified by a silica gel column, an eluent for purification was composed of petroleum ether and ethyl acetate in a volume ratio of 10:1, and the final product was obtained after the purification was completed and was a yellow oily liquid.

The final product obtained in this example was tested as follows:

(1) the nuclear magnetic hydrogen spectrum result of the final product is shown by the nuclear magnetic hydrogen spectrum test and the nuclear magnetic carbon spectrum test¹H NMR(400MHz,CDCl₃) Delta 7.40-7.36 (m,5H),4.17(s, 2H); the result of nuclear magnetic carbon spectrum is¹³C{¹H}NMR(100MHz,CDCl₃) Delta 134.3,129.1,128.9,128.9,111.9, 38.3; comparing the two results with the disclosed nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum results of thiocyanomethylbenzene, the final product is thiocyanomethylbenzene.

(2) The thiocyanomethylbenzene obtained in this example had a mass of 8mg and a yield of 27%.

(3) The purity of the thiocyanomethylbenzene is more than 95 percent as shown by nuclear magnetic hydrogen spectrum test.

The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention should be considered as being within the scope of the present invention.