A 2,4,4-trimethylthiazolidine derivative and a synthesis method thereof

Abstract

The present invention relates to the field of synthesis of thiazole compounds, and in particular to a 2,4,4-trimethylthiazole derivative and a synthesis method thereof. The present invention, in the presence of an alkali, uses calcium carbide, hydrogen sulfide and propargylamine compounds as main raw materials for reaction; calcium carbide is used as a solid alkyne source, acetylene gas is released by depolymerizing calcium carbide with hydrogen sulfide, and acetylene gas is reacted with propargylamine compounds, thereby synthesizing 2,4,4-trimethylthiazole derivatives. The present invention uses H2S to depolymerize calcium carbide to synthesize 2,4,4-trimethylthiazole derivatives, wherein safe, stable and easily available calcium carbide is used as a raw material, no transition metal catalysis and high-pressure resistant equipment are required, and toxic and harmful H2S gas is reasonably used. The synthesis method of the present invention has more prominent advantages in "atom economy" and "green chemistry".

Description

Technical Field

[0001] The present invention relates to the field of synthesis of thiazole compounds, and more particularly to a 2,4,4-trimethylthiazole derivative and a synthesis method thereof. Background Art

[0002] Thiazolidine (tetrahydrothiazole) is a multifunctional five-membered heterocyclic structure widely found in natural and biologically active compounds. The presence of sulfur significantly enhances the pharmacological properties of thiazolidine, making it an important carrier for the synthesis of valuable organic compounds. In addition, thiazolidine compounds are important intermediates for pesticides and medicines, and their synthesis research has been ongoing.

[0003] According to relevant literature reports, there are many methods for synthesizing thiazolidine heterocyclic compounds. Most of these methods use isothiocyanate, thiourea, carbon disulfide, and 1,4-dithio-2,5-diol as raw materials to synthesize thiazolidine compounds.

[0004] Methylthiazolidine derivatives are a class of thiazolidine compounds. Currently, there are relatively few types of methylthiazolidine derivatives disclosed. Moreover, there are relatively few methods for synthesizing methylthiazolidine compounds. Currently, there is only one method disclosed: synthesis by reaction of cysteamine hydrochloride with aldehydes or ketones. Among them, the product synthesized by reaction with aldehydes, such as acetaldehyde, is 2-methylthiazolidine, and the product synthesized by reaction with ketones, such as acetone, is 2,2-dimethylthiazolidine. The scope of the substrate cysteamine hydrochloride in this synthesis method is relatively limited. References: Tetrahedron 64 (2008) 3691-3700; Tetrahedron Letters 41 (2000) 3381–3384; Bulletin de la Societe Chimique de France (1967), 10, 3637-3639). Summary of the invention

[0005] In order to enrich the types of methylthiazolidine compounds, the present invention synthesizes 2,4,4-trimethylthiazolidine derivatives and provides a synthesis method of the 2,4,4-trimethylthiazolidine derivatives.

[0006] The present invention uses calcium carbide (CaC2), hydrogen sulfide (H2S) and propargylamine compounds as main raw materials to react in the presence of an alkali; uses calcium carbide as a solid acetylene source, depolymerizes calcium carbide with hydrogen sulfide to release acetylene gas, and uses acetylene gas to react with propargylamine compounds, thereby synthesizing 2,4,4-trimethylthiazole derivatives.

[0007] One of the purposes of the present invention is to provide a 2,4,4-trimethylthiazolidine derivative.

[0008] The 2,4,4-trimethylthiazolidine derivative refers to a derivative containing 2,4,4-trimethylthiazolidine The structural formula of the 2,4,4-trimethylthiazolidine derivative is shown in formula (I).

[0009] (I)

[0010] In formula (I), R1 is selected from thienyl, pyridyl, naphthyl, phenyl, substituted phenyl;

[0011] The substituted phenyl group is selected from halogen, trifluoromethyl, hydroxyl, C 1-8 Hydrocarbon, C 1-8 In one or more alkoxy groups, the number of substituents is one or more, and the position of the substituents is arbitrary. When the number of substituents is two, the position of the substituents can be ortho, meta or para.

[0012] R1, C 1-8 Hydrocarbyl groups include but are not limited to C 1-8 Alkyl, phenyl, alkyl-substituted phenyl, and the like.

[0013] R1, C 1-8 Alkyloxy includes but is not limited to C 1-8 Alkoxy, C 6-8 Aromatic alkyloxy.

[0014] The C 1-8 Alkyl, C 1-8 The alkyl involved in the alkoxy group is an alkyl group having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, and can be a straight-chain alkyl group or a branched-chain alkyl group; the present invention has no particular limitation.

[0015] According to the embodiments disclosed in the present invention, the 2,4,4-trimethylthiazolidine derivative may be:

[0016] 5-benzylidene-2,4,4-trimethylthiazolidine, whose structural formula is ,

[0017] 2,4,4-trimethyl-5-(4-methylbenzylidene)thiazolidine, whose structural formula is ,

[0018] 2,4,4-trimethyl-5-(4-methoxybenzylidene)thiazolidine, whose structural formula is ,

[0019] 2,4,4-trimethyl-5-(4-chlorobenzylidene)thiazolidine, whose structural formula is ,

[0020] 2,4,4-trimethyl-5-(4-iodobenzylidene)thiazolidine, whose structural formula is ,

[0021] 2,4,4-trimethyl-5-(4-trifluoromethylbenzylidene)thiazolidine, whose structural formula is ,

[0022] 2,4,4-trimethyl-5-(1-naphthylmethylene)thiazolidine, whose structural formula is ,

[0023] 2,4,4-trimethyl-5-(2-pyridylmethylene)thiazolidine, whose structural formula is ,

[0024] 2,4,4-trimethyl-5-(3-thienylmethylene)thiazolidine, whose structural formula is .

[0025] The second object of the present invention is to provide a method for synthesizing the 2,4,4-trimethylthiazolidine derivatives described in the first object of the invention.

[0026] A method for synthesizing 2,4,4-trimethylthiazolidine derivatives comprises: in a closed environment, in the presence of a base, calcium carbide, hydrogen sulfide and a propargylamine compound react in an organic solvent.

[0027] The propargylamine compound refers to a compound containing propargylamine The structural formula of the propargylamine compound is shown in formula (II).

[0028] (II)

[0029] In formula (II), R1 is selected from thienyl, pyridyl, naphthyl, phenyl, substituted phenyl;

[0030] The substituted phenyl group is selected from halogen, trifluoromethyl, hydroxyl, C 1-8 Hydrocarbon, C 1-8 In one or more alkoxy groups, the number of substituents is one or more, and the position of the substituents is arbitrary. When the number of substituents is two, the position of the substituents can be ortho, meta or para.

[0031] R1, C 1-8 Hydrocarbyl groups include but are not limited to C 1-8 Alkyl, phenyl, alkyl substituted phenyl, and the like.

[0032] R1, C 1-8 Alkyloxy includes but is not limited to C 1-8 Alkoxy, C 6-8 Aromatic alkyloxy.

[0033] The C 1-8 Alkyl, C 1-8 The alkyl involved in the alkoxy group is an alkyl group having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, and can be a straight-chain alkyl group or a branched-chain alkyl group; the present invention has no particular limitation.

[0034] R1 in formula (II) is the same as R1 in formula (I), and R1 in formula (I) is derived from R1 in formula (II). That is, different propargylamine compounds are selected, and different 2,4,4-trimethylthiazolidine derivatives are obtained; and the 2,4,4-trimethylthiazolidine derivative is determined by the propargylamine compound selected. Therefore, those skilled in the art can select a suitable propargylamine compound according to the 2,4,4-trimethylthiazolidine derivative to be prepared.

[0035] According to the embodiments disclosed in the present invention, the propargylamine compound is selected from:

[0036] 2-methyl-4-phenyl-3-butyn-2-amine, the structural formula of which is ;

[0037] 4-(4-methylphenyl)-2-methyl-3-butyn-2-amine, whose structural formula is ;

[0038] 4-(4-methoxyphenyl)-2-methyl-3-butyn-2-amine, whose structural formula is ;

[0039] 4-(4-chlorophenyl)-2-methyl-3-butyn-2-amine, whose structural formula is ;

[0040] 4-(4-iodophenyl)-2-methyl-3-butyn-2-amine, whose structural formula is ;

[0041] 4-(4-trifluoromethylphenyl)-2-methyl-3-butyn-2-amine, whose structural formula is ;

[0042] 2-methyl-4-naphthyl-3-butyn-2-amine, whose structural formula is ;

[0043] 2-methyl-4-(2-pyridyl)-3-butyn-2-amine, whose structural formula is ;

[0044] 2-methyl-4-(3-thienyl)-3-butyn-2-amine, whose structural formula is .

[0045] At this time, the prepared 2,4,4-trimethylthiazolidine derivatives are corresponding to 5-benzylidene-2,4,4-trimethylthiazolidine, 2,4,4-trimethyl-5-(4-methylbenzylidene)thiazolidine, 2,4,4-trimethyl-5-(4-methoxybenzylidene)thiazolidine), 2,4,4-trimethyl-5-(4-chlorobenzylidene)thiazolidine, 2,4,4-trimethyl-5-(4-iodobenzylidene)thiazolidine, 2,4,4-trimethyl-5-(4-trifluoromethylbenzylidene)thiazolidine, 2,4,4-trimethyl-5-(1-naphthylmethylene)thiazolidine, 2,4,4-trimethyl-5-(2-pyridylmethylene)thiazolidine, and 2,4,4-trimethyl-5-(3-thienylmethylene)thiazolidine.

[0046] The propargyl amine compound can be prepared by an existing method. For example, reference can be made to the literature: OrgLett. 2014, 16, 2430−2433.; ACS Sustainable Chem. Eng. 2022, 10, 3, 1214–1219). According to an embodiment disclosed in the present invention, one of the preparation methods of the propargyl amine compound comprises: adding CuI (0.20 mmol), PdCl2(PPh3)2 (0.10 mmol) and an aryl iodide compound to a THF / Et3N solution (5 mL, the volume ratio of THF to Et3N is 4:1) under nitrogen. (5.5 mmol), then 2-methyl-3-butyn-2-amine (5.0 mmol) was added, and the mixture was stirred at room temperature overnight. After the reaction was completed, saturated NH4Cl aqueous solution was added to the reaction mixture, and then extracted three times with Et2O. The combined organic layer was washed with saturated brine, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (PE / EA / Et3N=2 / 1 / 1%) to obtain the corresponding propargylamine compounds.

[0047] The role of the base is to promote the reaction and improve the yield. The base can be selected from a wide range. As a preferred embodiment, the base can be selected from 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), cesium carbonate (Cs2CO3), potassium tert-butoxide ( t -BuOK), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tetramethylguanidine (TMG), sodium hydroxide (NaOH), triethylamine (Et3N), more preferably TBD, Cs2CO3, t -At least one of BuOK.

[0048] The organic solvent can be selected in a wide range without particular limitation. The organic solvent commonly used in the field of organic synthesis can be selected. Specifically, the organic solvent can be a polar aprotic solvent. As a preferred embodiment, the organic solvent is selected from at least one of N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N, N-dimethylacetamide, dimethyl sulfoxide (DMSO), and 1,4-dioxane, and more preferably at least one of N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO).

[0049] The amount of the organic solvent can be selected in a wide range. As a preferred embodiment, the ratio of the organic solvent to the propargylamine compound is 0.5-15 mL:1 mmol; that is, relative to 0.2 mmol of the propargylamine compound, the amount of the organic solvent can be 0.1-3 mL.

[0050] The molar ratio of the propargylamine compound to calcium carbide and H2S can be selected in a wide range. As a preferred embodiment, the molar ratio of the propargylamine compound to calcium carbide and H2S can be 1:(1-6):(2-9), more preferably 1:(2-4):(2-6).

[0051] The molar ratio of the propargylamine compound to the base can be selected in a wide range. As a preferred embodiment, the molar ratio of the propargylamine compound to the base is 1:(0.25-2), preferably 1:(0.5-1), for example, it can be 1:0.3, 0.4, 0.5, and the ratio of any two values ​​or any interval between any two values.

[0052] The reaction temperature can be selected in a wide range. As a preferred embodiment, the reaction temperature is 80-150°C, preferably 110-120°C.

[0053] The reaction time can be selected in a wide range. As a preferred embodiment, the reaction time is 1-6 hours, preferably 3-5 hours.

[0054] The synthesis method of the 2,4,4-trimethylthiazolidine derivative may further include adding copper salt.

[0055] A method for synthesizing 2,4,4-trimethylthiazolidine derivatives comprises: in a closed environment, in the presence of a base and a copper salt, calcium carbide, hydrogen sulfide and a propargylamine compound react in an organic solvent.

[0056] The copper salt comprises +1-valent copper salt or +2-valent copper salt copper. The copper salt can be selected in a wide range. As a preferred embodiment, the copper salt is selected from at least one of CuI, CuCl, CuBr, Cu2O, CuCl2, and CuO, such as CuI.

[0057] The molar ratio of the propargylamine compound to the copper salt can be selected in a wide range. As a preferred embodiment, the molar ratio of the propargylamine compound to the copper salt can be 1:(0.1-3), preferably 1:(1-3), for example 1:1.

[0058] The synthesis method of the 2,4,4-trimethylthiazolidine derivative may include the following steps:

[0059] Add propargylamine compounds, alkali, solvent, ground calcium carbide, and optionally copper salt into a reaction kettle, seal the reaction kettle, introduce H2S gas, heat to the reaction temperature, and react under stirring conditions. After the reaction is completed, cool to room temperature, extract, wash, dry the organic layer, and remove the solvent under reduced pressure to obtain a crude product. The crude product is separated by column chromatography to obtain a 2,4,4-trimethylthiazole derivative.

[0060] According to an embodiment disclosed in the present invention, a method for synthesizing a 2,4,4-trimethylthiazolidine derivative shown in formula (I) comprises: adding a propargylamine compound shown in formula (II), a base, a solvent, and ground calcium carbide into a reaction kettle, optionally adding a copper salt, closing the reaction kettle, introducing H2S gas, heating to 100-120°C, reacting for 3-5 hours under stirring conditions, and after the reaction is completed, cooling to room temperature, extracting with ethyl acetate, washing with saturated brine, drying the organic layer, and removing the solvent under reduced pressure to obtain a crude product, and separating the crude product by column chromatography to obtain a 2,4,4-trimethylthiazolidine derivative shown in formula (I); the molar ratio of the propargylamine compound to calcium carbide, H2S, base, and copper salt is 1:(1-6):(2-9):(0.25-2):(0.1-3), preferably 1:(2-4):(2-6):(0.5-1):(1-3).

[0061] Compared with the prior art, the present invention has the following beneficial effects:

[0062] 1. The synthesis method of the present invention uses safe, stable and readily available calcium carbide as a reaction raw material; using H2S to depolymerize calcium carbide can not only solve the environmental pollution caused by H2S, but also reasonably utilize H2S to avoid the waste of sulfur resources.

[0063] 2. The synthesis method of the present invention is carried out in a closed environment. Except for the pressure generated by the introduction of hydrogen sulfide and the pressure generated by the gas generated during the reaction, no additional pressurization is required, and no high-pressure resistant equipment is required, which effectively reduces the risk of explosion and can synthesize 2,4,4-trimethylthiazolidine derivatives under relatively mild conditions.

[0064] 3. The synthesis method of the present invention is simple. In addition to the reaction raw materials, no transition metal catalysis is required. The target compound can be synthesized in high yield only under the action of a base.

[0065] 4. The synthesis method of the present invention has strong substrate applicability for synthesizing 2,4,4-trimethylthiazolidine derivatives and has a high yield.

[0066] 5. The synthesis method of the present invention can adjust the yield of 2,4,4-trimethylthiazolidine derivatives by adjusting specific reaction conditions (dosage, molar ratio, temperature, time).

[0067] In summary, the present invention uses H2S to depolymerize calcium carbide to synthesize 2,4,4-trimethylthiazole derivatives, wherein safe, stable and readily available calcium carbide is used as a raw material, no transition metal catalysis and high-pressure resistant equipment are required, and toxic and harmful H2S gas is used reasonably. The synthesis method of the present invention has more prominent advantages in "atom economy" and "green chemistry". DETAILED DESCRIPTION

[0068] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0069] The reaction reagents involved in the examples are all commonly used commercial products. The model of the nuclear magnetic resonance spectrometer used in the examples is Agilent 500 MHz DD2.

[0070] Examples 1 to 20

[0071] Synthesis of propargyl amine compounds:

[0072] CuI (0.20 mmol), PdCl2(PPh3)2 (0.10 mmol) and aryl iodide compounds were added to THF / Et3N solution (5 mL, volume ratio of THF to Et3N was 4:1) under nitrogen. (5.5 mmol), then 2-methyl-3-butyn-2-amine (5.0 mmol) was added, and the mixture was stirred at room temperature overnight. After the reaction was completed, saturated NH4Cl aqueous solution was added to the reaction mixture, and then extracted three times with Et2O. The combined organic layer was washed with saturated brine, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (PE / EA / Et3N=2 / 1 / 1%). Finally, the corresponding propargylamine compounds were obtained. The general reaction formula is as follows:

[0073]

[0074] The aryl iodide compounds and the corresponding propargyl amine compounds prepared and their NMR characterization data are shown in Table 1.

[0075] Table 1

[0076]

[0077] Synthesis of 5-benzylidene-2,4,4-trimethylthiazolidine:

[0078] (1) Add 0.2 mmol of propargylamine compounds (2-methyl-4-phenyl-3-butyn-2-amine ), CaC2, alkali and 2mL of solvent, optionally add copper salt, then close the reactor and pass H2S gas. The agitator speed of the reactor is adjusted to 800 rpm, and the reactor is reacted in a sand bath at a temperature of T℃ for a reaction time of t. After stopping the reaction, the reactor is taken out of the sand bath, cooled at room temperature, the residual gas is released in the fume hood, and the reactor is unscrewed. Extract with ethyl acetate, wash with saturated brine, dry the organic layer, and remove the solvent under reduced pressure to obtain a crude product. The crude product is separated by column chromatography (200-300 mesh silica gel) to obtain a light yellow oily substance with a purity greater than 99%.

[0079] (2) NMR characterization data of the light yellow oily substance obtained in step (1): 1 H NMR (500 MHz, CDCl3): δ 7.45 (d, J = 8.0 Hz, 2H), 7.34 (t, J = 7.5 Hz, 2H), 7.17 (t, J = 8.0 Hz, 1H), 6.32 (s, 1H), 4.83 (q, J = 6.0 Hz, 1H), 1.75 (br, 1H), 1.66 (d, J = 6.0Hz, 3H), 1.58 (s, 3H), 1.34 (s, 3H). 13 C NMR (126 MHz, CDCl3): δ 151.86,137.72, 128.27, 127.80, 125.99, 114.32, 70.74, 64.26, 27.63, 27.33, 20.59.

[0080] (3) The light yellow oily substance obtained in step (1) is 5-benzylidene-2,4,4-trimethylthiazolidine, and its structural formula is .

[0081] In step (1), the molar ratio of propargylamine compound, calcium carbide and H2S (hereinafter referred to as feed ratio), solvent, base, copper salt and their amounts, reaction temperature and reaction time are shown in Table 2; the yield of the prepared 5-benzylidene-2,4,4-trimethylthiazolidine is shown in Table 2.

[0082] Table 2

[0083]

[0084] According to Table 2, it can be concluded that under the conditions of 2-methyl-4-phenyl-3-butyn-2-amine: CaC2: H2S feed ratio of 0.2:0.6:0.9, 1 equivalent of TBD as base catalyst, reaction temperature of 110°C, reaction time of 4 h, and DMSO as solvent, the yield of 5-benzylidene-2,4,4-trimethylthiazolidine is 99%.

[0085] Examples 21 to 28

[0086] Synthesis of 2,4,4-trimethylthiazolidine derivatives:

[0087] The synthesis method is carried out according to Examples 1-20, and the feed ratio, solvent, base, reaction temperature and reaction time are the same as those of Example 19. The structural formula of the reaction substrate propargylamine compound is shown in Table 3. The structural formula, NMR characterization data and yield of the obtained product 2,4,4-trimethylthiazolidine derivative are shown in Table 3.

[0088] The general reaction formula of Examples 21-28 is as follows:

[0089] .

[0090] Among them, the product R1 in the reaction comes from the substrate R 1。 Reaction substrate The type and position of the substituent R1 in the product The uniform one-to-one correspondence.

[0091] Table 3

[0092]

[0093] In Table 2-3, the yield is calculated based on propargyl amine compounds, and the calculation formula is: Yield = target product mass / theoretical mass) × %.

Claims

1. A method for synthesizing a 2,4,4-trimethylthiazolidine derivative, characterized in that: The synthesis method comprises: in a closed environment, in the presence of a base, calcium carbide, hydrogen sulfide and a propargylamine compound react in an organic solvent; The structural formula of the 2,4,4-trimethylthiazolidine derivative is shown in formula (I); （Ⅰ） The structural formula of the propargylamine compound is shown in formula (II); （Ⅱ） In formula (I) and formula (II), R1 is selected from thienyl, pyridyl, naphthyl, phenyl, and substituted phenyl; The substituted phenyl group is selected from halogen, trifluoromethyl, hydroxyl, C 1-8 Hydrocarbon, C 1-8 One or more types of the hydrocarbyloxy groups may have one or more substituents, and the positions of the substituents may be arbitrary.

2. The synthesis method according to claim 1, characterized in that The C 1-8 Hydrocarbon groups include C 1-8 Alkyl; or / and, The C 1-8 Hydroxyl groups include C 1-8 Alkoxy.

3. The synthesis method according to claim 1, characterized in that The propargylamine compound is selected from 2-methyl-4-phenyl-3-butyn-2-amine, 4-(4-methylphenyl)-2-methyl-3-butyn-2-amine, 4-(4-methoxyphenyl)-2-methyl-3-butyn-2-amine, 4-(4-chlorophenyl)-2-methyl-3-butyn-2-amine, 4-(4-iodophenyl)-2-methyl-3-butyn-2-amine, 4-(4-trifluoromethylphenyl)-2-methyl-3-butyn-2-amine, 2-methyl-4-naphthyl-3-butyn-2-amine, 2-methyl-4-(2-pyridyl)-3-butyn-2-amine, 2-methyl-4-(3-thienyl)-3-butyn-2-amine; or / and, The base is selected from at least one of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, cesium carbonate, potassium tert-butoxide, 1,8-diazabicyclo[5.4.0]undec-7-ene, tetramethylguanidine, sodium hydroxide and triethylamine; or / and, The organic solvent is selected from at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and 1,4-dioxane.

4. The synthesis method according to claim 1, characterized in that The 2,4,4-trimethylthiazolidine derivative is: 5-benzylidene-2,4,4-trimethylthiazolidine, whose structural formula is ; 2,4,4-trimethyl-5-(4-methylbenzylidene)thiazolidine, whose structural formula is ; 2,4,4-trimethyl-5-(4-methoxybenzylidene)thiazolidine, whose structural formula is ; 2,4,4-trimethyl-5-(4-chlorobenzylidene)thiazolidine, whose structural formula is ; 2,4,4-trimethyl-5-(4-iodobenzylidene)thiazolidine, whose structural formula is ; 2,4,4-trimethyl-5-(4-trifluoromethylbenzylidene)thiazolidine, whose structural formula is ; 2,4,4-trimethyl-5-(1-naphthylmethylene)thiazolidine, whose structural formula is ; 2,4,4-trimethyl-5-(2-pyridylmethylene)thiazolidine, whose structural formula is ; 2,4,4-trimethyl-5-(3-thienylmethylene)thiazolidine, whose structural formula is .

5. The synthesis method according to claim 1, characterized in that The ratio of the organic solvent to the propargylamine compound is 0.5-15 mL: 1 mmol; or / and, The molar ratio of the propargylamine compound to calcium carbide and H2S is 1:(1-6):(2-9); or / and, The molar ratio of the propargylamine compound to the base is 1:(0.25-2); or / and, The reaction temperature is 80-150°C; or / and, The reaction time is 1-6h.

6. The synthesis method according to claim 1, characterized in that The molar ratio of the propargylamine compound to calcium carbide and H2S is 1:(2-4):(2-6); or / and, The molar ratio of the propargylamine compound to the base is 1:(0.5-1); or / and, The reaction temperature is 110-120°C; or / and, The reaction time is 3-5h.

7. The synthesis method according to claim 1, characterized in that Carry out the reaction in the presence of copper salt, Cu2O or CuO; The copper salt is selected from at least one of CuI, CuCl, CuBr and CuCl2; The molar ratio of the propylamine compound to the copper salt, Cu2O or CuO is 1:(0.1-3).

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