CN115010634A - A kind of dithiooxamide compound and preparation method thereof - Google Patents

A kind of dithiooxamide compound and preparation method thereof Download PDF

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CN115010634A
CN115010634A CN202210813896.XA CN202210813896A CN115010634A CN 115010634 A CN115010634 A CN 115010634A CN 202210813896 A CN202210813896 A CN 202210813896A CN 115010634 A CN115010634 A CN 115010634A
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aliphatic hydrocarbon
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dithiooxamide
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唐本忠
胡蓉蓉
黎丰霆
马世荣
王壮
秦安军
赵祖金
王志明
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South China University of Technology SCUT
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Abstract

本发明提供了一种二硫代草酰胺化合物及其制备方法,属于有机化合物制备技术领域。本发明将单质硫磺、四氯乙烷以及胺类单体混合,于溶剂中或于无溶剂条件下进行加热搅拌反应,并在反应结束后对其进行提纯,得到N,N‑二取代二硫代草酰胺化合物。本发明实现了对少有报道的N,N‑二脂肪基取代二硫代草酰胺化合物以及N,N‑二芳香基取代二硫代草酰胺化合物的高效低成本制备,且该发明的制备方法具有反应条件温和且操作简单,产物结构多样等特点。

Figure 202210813896

The invention provides a dithiooxamide compound and a preparation method thereof, belonging to the technical field of organic compound preparation. In the present invention, elemental sulfur, tetrachloroethane and amine monomers are mixed, heated and stirred in a solvent or under solvent-free conditions, and purified after the reaction to obtain N,N-disubstituted disulfide Oxamide compound. The invention realizes the high-efficiency and low-cost preparation of rarely reported N,N-dialiphatic substituted dithiooxamide compounds and N,N-diaryl substituted dithiooxamide compounds, and the preparation method of the invention It has the characteristics of mild reaction conditions, simple operation and diverse product structures.

Figure 202210813896

Description

一种二硫代草酰胺化合物及其制备方法A kind of dithiooxamide compound and preparation method thereof

技术领域technical field

本发明涉及有机化合物制备技术领域,尤其涉及一种二硫代草酰胺化合物及其制备方法。The invention relates to the technical field of organic compound preparation, in particular to a dithiooxamide compound and a preparation method thereof.

背景技术Background technique

目前,同时含有氮原子与硫原子的化合物,如硫脲化合物、硫代酰胺化合物、硫代氨基甲酸酯化合物、苯并噻二唑化合物等在生物医药领域、有机合成化学、配位化学、太阳能电池、农药以及其他领域有着广泛的应用,对其合成及应用的研究具有重要意义。与之结构类似的二硫代草酰胺化合物也被发现在有机合成化学、配位化学等领域有着重要的应用,但相比上述的数类化合物,二硫代草酰胺化合物的合成方法相对较少,因此对二硫代草酰胺化合物在前述领域的应用的研究也受到限制。At present, compounds containing both nitrogen and sulfur atoms, such as thiourea compounds, thioamide compounds, thiocarbamate compounds, and benzothiadiazole compounds, are widely used in the field of biomedicine, organic synthesis chemistry, coordination chemistry, Solar cells, pesticides and other fields have a wide range of applications, and the research on their synthesis and application is of great significance. Dithiooxamide compounds with similar structures have also been found to have important applications in organic synthesis chemistry, coordination chemistry and other fields, but compared with the above-mentioned compounds, there are relatively few synthetic methods for dithiooxamide compounds. , so the research on the application of dithiooxamide compounds in the aforementioned fields is also limited.

目前已报道的二硫代草酰胺化合物的制备方法可以归类为两类:1、使用具有难闻味道的劳森试剂或五硫化二磷来处理草酰胺化合物,并得到相应的二硫代草酰胺化合物;2、使用胺基未取代的二硫代草酰胺与胺类化合物进行反应,并得到相应的二硫代草酰胺化合物。劳森试剂或五硫化二磷难闻、成本较高且可能仅取代草酰胺化合物中的一个氧原子并生成单硫代草酰胺化合物,而胺基未取代的二硫代草酰胺成本也较高,且反应放出氨气,这使得二硫代草酰胺化合物的生产成本较高。因此,开发一种利用廉价易得的单体的低成本制备方法来制备二硫代草酰胺类化合物具有重大意义。具有反应条件温和且操作简单,产物结构多样等特点的多组分反应(Multicomponent Reaction,MCR)已被证明可以令廉价易得或储量丰富的化合物,如水、二氧化碳等有效地参与到反应中并参与构筑结构复杂的功能分子。石油工业的发展使单质硫磺的产量与储存量增加,然而单质硫易氧化成硫氧化物的性质使得对硫的储存引发一定的安全问题与潜在的环境问题。一些多组分反应,如胺化合物、醛化合物与单质硫参与的Willgerodt-Kindler反应可以将低成本的单质硫磺高效地转化为硫代酰胺化合物,使得含氮元素与硫元素的化合物的合成成本降低,且更为绿色环保。被证明可以将低成本的单质硫磺高效地转化为硫代酰胺化合物等各种含硫化合物的多组分反应也被期望用于合成二硫代草酰胺化合物。The reported preparation methods of dithiooxamide compounds can be classified into two categories: 1. Use Lawson's reagent with unpleasant taste or phosphorus pentasulfide to process oxamide compounds, and obtain the corresponding dithiooxamide compounds; 2. Use an unsubstituted dithiooxamide with an amine group to react with an amine compound to obtain a corresponding dithiooxamide compound. Lawson's reagent or phosphorus pentasulfide is unpleasant, expensive, and may replace only one oxygen atom in the oxamide compound and generate a monothiooxamide compound, while the unsubstituted amine group dithiooxamide is also more expensive, and the reaction Ammonia gas is released, which makes the production cost of the dithioxamide compound higher. Therefore, it is of great significance to develop a low-cost preparation method using inexpensive and readily available monomers to prepare dithiooxamides. Multicomponent reactions (MCRs), which have the characteristics of mild reaction conditions, simple operation, and diverse product structures, have been proven to allow cheap and readily available or abundant compounds, such as water and carbon dioxide, to effectively participate in the reaction and participate in the reaction. Construct functional molecules with complex structures. The development of the petroleum industry has increased the production and storage of elemental sulfur. However, the easy oxidation of elemental sulfur into sulfur oxides makes the storage of sulfur cause certain safety and potential environmental problems. Some multi-component reactions, such as the Willgerodt-Kindler reaction involving amine compounds, aldehyde compounds and elemental sulfur, can efficiently convert low-cost elemental sulfur into thioamide compounds, which reduces the synthesis cost of compounds containing nitrogen and sulfur elements. , and more green. Multi-component reactions, which have been shown to efficiently convert low-cost elemental sulfur into various sulfur-containing compounds such as thioamide compounds, are also expected to be used for the synthesis of dithioxamide compounds.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于提供一种二硫代草酰胺化合物及一种成本低、条件温和、反应效率高的二硫代草酰胺化合物的制备方法。The purpose of the present invention is to provide a dithiooxamide compound and a preparation method of the dithiooxamide compound with low cost, mild conditions and high reaction efficiency.

为了实现上述发明目的,本发明提供以下技术方案:In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

本发明提供了一种二硫代草酰胺化合物,所述二硫代草酰胺化合物包含如下结构通式中的一种:The present invention provides a dithiooxamide compound, the dithiooxamide compound comprises one of the following general structural formulas:

Figure BDA0003741467540000021
Figure BDA0003741467540000021

其中,R1和R2独立的为脂肪烃基、氧代脂肪烃基、带芳香取代基的脂肪烃基、带芳香取代基的氧代脂肪烃基、带卤代物取代基的脂肪烃基或带卤代物取代基的氧代脂肪烃基;Wherein, R 1 and R 2 are independently aliphatic hydrocarbon groups, oxo aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents, oxo aliphatic hydrocarbon groups with aromatic substituents, aliphatic hydrocarbon groups with halogenated substituents or halogenated substituents oxo aliphatic hydrocarbon group;

R3和R4独立的为氢原子、烃基、烷氧基、卤素、羟基、酯基、羰基、芳基或氰基; R3 and R4 are independently a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group;

R5和R6独立的为两侧同时与氮原子相连的烃基、带有芳香取代基的烃基或带卤代物取代基的烃基;R 5 and R 6 are independently a hydrocarbon group connected to nitrogen atoms on both sides at the same time, a hydrocarbon group with an aromatic substituent or a hydrocarbon group with a halogen substituent;

R7和R8独立的为脂肪烃基、带有芳香取代基的脂肪烃基或带卤代物取代基的脂肪烃基。R 7 and R 8 are independently aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents or aliphatic hydrocarbon groups with halogen substituents.

进一步的,所述二硫代草酰胺化合物具体包含以下结构式中的一种:Further, the dithiooxamide compound specifically includes one of the following structural formulas:

Figure BDA0003741467540000022
Figure BDA0003741467540000022

Figure BDA0003741467540000031
Figure BDA0003741467540000031

本发明提供了一种二硫代草酰胺化合物的制备方法,包括以下步骤:The invention provides a preparation method of a dithiooxamide compound, comprising the following steps:

硫磺、四氯乙烷和胺类化合物进行反应得到的产物即为二硫代草酰胺化合物。The product obtained by the reaction of sulfur, tetrachloroethane and amine compounds is the dithiooxamide compound.

进一步的,所述硫磺、四氯甲烷和胺类化合物的摩尔比为0.25~10.0:0.17~4.0:1.0~10.0。Further, the molar ratio of the sulfur, tetrachloromethane and the amine compound is 0.25-10.0:0.17-4.0:1.0-10.0.

进一步的,所述胺类化合物包含以下结构通式中的一种:Further, the amine compound comprises one of the following general structural formulas:

Figure BDA0003741467540000032
Figure BDA0003741467540000032

其中,R1和R2独立的为脂肪烃基、氧代脂肪烃基、带芳香取代基的脂肪烃基、带芳香取代基的氧代脂肪烃基、带卤代物取代基的脂肪烃基或带卤代物取代基的氧代脂肪烃基;Wherein, R 1 and R 2 are independently aliphatic hydrocarbon groups, oxo aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents, oxo aliphatic hydrocarbon groups with aromatic substituents, aliphatic hydrocarbon groups with halogenated substituents or halogenated substituents oxo aliphatic hydrocarbon group;

R3和R4独立的为氢原子、烃基、烷氧基、卤素、羟基、酯基、羰基、芳基或氰基; R3 and R4 are independently a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group;

R5和R6独立的为两侧同时与氮原子相连的烃基、带有芳香取代基的烃基或带卤代物取代基的烃基;R 5 and R 6 are independently a hydrocarbon group connected to nitrogen atoms on both sides at the same time, a hydrocarbon group with an aromatic substituent or a hydrocarbon group with a halogen substituent;

R7和R8独立的为脂肪烃基、带有芳香取代基的脂肪烃基或带卤代物取代基的脂肪烃基。R 7 and R 8 are independently aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents or aliphatic hydrocarbon groups with halogen substituents.

进一步的,所述胺类化合物具体包含以下结构式中的一种:Further, the amine compound specifically comprises one of the following structural formulas:

Figure BDA0003741467540000041
Figure BDA0003741467540000041

其中,n和k独立的为1~30的整数。Here, n and k are independently an integer of 1-30.

进一步的,所述反应在溶剂中进行,所述胺类化合物与溶剂的摩尔体积比为0.01~5mol:1L;Further, the reaction is carried out in a solvent, and the molar volume ratio of the amine compound to the solvent is 0.01-5mol:1L;

所述溶剂包含N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和二甲基亚砜中的一种或几种。The solvent contains one or more of N,N-dimethylformamide, N,N-dimethylacetamide and dimethylsulfoxide.

进一步的,所述反应在保护气氛下进行,所述保护气氛包含氮气和/或氩气。Further, the reaction is carried out under a protective atmosphere, and the protective atmosphere contains nitrogen and/or argon.

进一步的,所述反应的温度为20~120℃,反应的时间为2~48h。Further, the temperature of the reaction is 20~120°C, and the reaction time is 2~48h.

进一步的,所述反应在催化剂的作用下进行,所述催化剂为碱性化合物,所述碱性化合物包含N,N-二异丙基乙胺、三乙胺、氟化钾和碳酸钾中的一种或几种;所述催化剂的用量为10~40:1~10。Further, the reaction is carried out under the action of a catalyst, and the catalyst is a basic compound, and the basic compound comprises N,N-diisopropylethylamine, triethylamine, potassium fluoride and potassium carbonate. One or more; the dosage of the catalyst is 10-40:1-10.

本发明的有益效果:Beneficial effects of the present invention:

(1)本发明可提供芳香基取代的二硫代草酰胺化合物,而不限制于其他方法制备的脂肪基取代的二硫代草酰胺化合物。(1) The present invention can provide aromatic-substituted dithiooxamide compounds, but is not limited to aliphatic-substituted dithiooxamide compounds prepared by other methods.

(2)本发明的制备方法反应原料廉价且可通过商业渠道购买而不需要额外的合成步骤,且有机反应的条件温和、工艺简单、反应效率高。同时,本发明可以实现之前较少的由单质硫到二硫代草酰胺化合物的一步转化。(2) In the preparation method of the present invention, the reaction raw materials are cheap and can be purchased through commercial channels without additional synthesis steps, and the organic reaction conditions are mild, the process is simple, and the reaction efficiency is high. At the same time, the present invention can realize less one-step conversion from elemental sulfur to dithiooxamide compound.

(3)本发明中的制备方法具有良好的反应物普适性,兼容脂肪基伯胺,脂肪基仲胺以及芳香基伯胺,并且可以合成结构范围较广的二硫代草酰胺化合物。(3) The preparation method of the present invention has good universality of reactants, is compatible with aliphatic primary amines, aliphatic secondary amines and aromatic primary amines, and can synthesize dithioxamide compounds with a wide range of structures.

(4)本发明中的制备方法可以单次制备克级规模的二硫代草酰胺化合物。(4) The preparation method of the present invention can prepare a gram-scale dithiooxamide compound at a time.

(5)本发明制备的二硫代草酰胺化合物被发现具有与金属离子进行配位的能力,表明该二硫代草酰胺化合物可应用于配位化学的领域。(5) The dithiooxamide compound prepared by the present invention is found to have the ability to coordinate with metal ions, indicating that the dithiooxamide compound can be applied in the field of coordination chemistry.

附图说明Description of drawings

图1为本发明实施例2制备的二硫代草酰胺化合物在二氯甲烷-正己烷溶剂体系中培养的单晶的单晶X射线衍射解析图;1 is a single crystal X-ray diffraction analysis diagram of the single crystal of the dithiooxamide compound prepared in Example 2 of the present invention grown in a dichloromethane-n-hexane solvent system;

图2为本发明实施例1制备的二硫代草酰胺化合物在氘代二甲基亚砜中核磁共振氢谱图;Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the dithiooxamide compound prepared in the embodiment of the present invention 1 in deuterated dimethyl sulfoxide;

图3为本发明实施例1制备的二硫代草酰胺化合物在氘代二甲基亚砜中核磁共振碳谱图。Fig. 3 is the carbon nuclear magnetic resonance spectrum of the dithiooxamide compound prepared in Example 1 of the present invention in deuterated dimethyl sulfoxide.

具体实施方式Detailed ways

本发明提供了一种二硫代草酰胺化合物,所述二硫代草酰胺化合物包含如下结构通式中的一种:The present invention provides a dithiooxamide compound, the dithiooxamide compound comprises one of the following general structural formulas:

Figure BDA0003741467540000051
Figure BDA0003741467540000051

其中,R1和R2独立的为脂肪烃基、氧代脂肪烃基、带芳香取代基的脂肪烃基、带芳香取代基的氧代脂肪烃基、带卤代物取代基的脂肪烃基或带卤代物取代基的氧代脂肪烃基;Wherein, R 1 and R 2 are independently aliphatic hydrocarbon groups, oxo aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents, oxo aliphatic hydrocarbon groups with aromatic substituents, aliphatic hydrocarbon groups with halogenated substituents or halogenated substituents oxo aliphatic hydrocarbon group;

R3和R4独立的为氢原子、烃基、烷氧基、卤素、羟基、酯基、羰基、芳基或氰基; R3 and R4 are independently a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group;

R5和R6独立的为两侧同时与氮原子相连的烃基、带有芳香取代基的烃基或带卤代物取代基的烃基;R 5 and R 6 are independently a hydrocarbon group connected to nitrogen atoms on both sides at the same time, a hydrocarbon group with an aromatic substituent or a hydrocarbon group with a halogen substituent;

R7和R8独立的为脂肪烃基、带有芳香取代基的脂肪烃基或带卤代物取代基的脂肪烃基。R 7 and R 8 are independently aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents or aliphatic hydrocarbon groups with halogen substituents.

在本发明中,R1和R2独立的优选为环己基、环戊基、苯甲基或苯乙基。In the present invention, R 1 and R 2 are independently preferably cyclohexyl, cyclopentyl, benzyl or phenethyl.

在本发明中,R3和R4独立的优选为氢原子、甲基或溴。In the present invention, R 3 and R 4 are independently preferably a hydrogen atom, a methyl group or a bromine.

在本发明中,R5和R6独立的优选为4~8个碳原子的环状烷烃。In the present invention, R 5 and R 6 are independently preferably cyclic alkanes having 4 to 8 carbon atoms.

在本发明中,R7和R8独立的优选为4~8个碳原子的链状烷烃。In the present invention, R 7 and R 8 are independently preferably chain alkanes having 4 to 8 carbon atoms.

在本发明中,所述二硫代草酰胺化合物优选为以下结构式中的一种:In the present invention, the dithiooxamide compound is preferably one of the following structural formulas:

Figure BDA0003741467540000061
Figure BDA0003741467540000061

本发明提供了一种二硫代草酰胺化合物的制备方法,包括以下步骤:The invention provides a preparation method of a dithiooxamide compound, comprising the following steps:

硫磺、四氯乙烷和胺类化合物进行反应得到的产物即为二硫代草酰胺化合物。The product obtained by the reaction of sulfur, tetrachloroethane and amine compounds is the dithiooxamide compound.

在本发明中,所述二硫代草酰胺化合物的反应方程式如下式(Ⅰ):In the present invention, the reaction equation of the dithiooxamide compound is the following formula (I):

Figure BDA0003741467540000062
Figure BDA0003741467540000062

其中,R9和R10独立的为R1~R8中的任一种。Here, R 9 and R 10 are independently any one of R 1 to R 8 .

在本发明中,所述硫磺、四氯甲烷和胺类化合物的摩尔比为0.25~10.0:0.17~4.0:1.0~10.0,优选为0.5~8.0:0.3~3.0:2.0~8.0,进一步优选为1.0~6.0:1.0~2.0:8.0。In the present invention, the molar ratio of the sulfur, tetrachloromethane and amine compounds is 0.25-10.0: 0.17-4.0: 1.0-10.0, preferably 0.5-8.0: 0.3-3.0: 2.0-8.0, more preferably 1.0 ~6.0: 1.0 ~ 2.0: 8.0.

在本发明中,所述胺类化合物包含以下结构通式中的一种:In the present invention, the amine compound comprises one of the following general structural formulas:

Figure BDA0003741467540000063
Figure BDA0003741467540000063

Figure BDA0003741467540000071
Figure BDA0003741467540000071

其中,R1和R2独立的为脂肪烃基、氧代脂肪烃基、带芳香取代基的脂肪烃基、带芳香取代基的氧代脂肪烃基、带卤代物取代基的脂肪烃基或带卤代物取代基的氧代脂肪烃基;Wherein, R 1 and R 2 are independently aliphatic hydrocarbon groups, oxo aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents, oxo aliphatic hydrocarbon groups with aromatic substituents, aliphatic hydrocarbon groups with halogenated substituents or halogenated substituents oxo aliphatic hydrocarbon group;

R3和R4独立的为氢原子、烃基、烷氧基、卤素、羟基、酯基、羰基、芳基或氰基; R3 and R4 are independently a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group;

R5和R6独立的为两侧同时与氮原子相连的烃基、带有芳香取代基的烃基或带卤代物取代基的烃基;R 5 and R 6 are independently a hydrocarbon group connected to nitrogen atoms on both sides at the same time, a hydrocarbon group with an aromatic substituent or a hydrocarbon group with a halogen substituent;

R7和R8独立的为脂肪烃基、带有芳香取代基的脂肪烃基或带卤代物取代基的脂肪烃基。R 7 and R 8 are independently aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents or aliphatic hydrocarbon groups with halogen substituents.

在本发明中,所述R1优选为环己基、环戊基、苯甲基或苯乙基。In the present invention, the R 1 is preferably cyclohexyl, cyclopentyl, benzyl or phenethyl.

在本发明中,R3优选为氢原子、甲基或溴。In the present invention, R 3 is preferably a hydrogen atom, methyl or bromine.

在本发明中,R5优选为4~8个碳原子的环状烷烃。In the present invention, R 5 is preferably a cyclic alkane having 4 to 8 carbon atoms.

在本发明中,R7和R8独立的优选为4~8个碳原子的链状烷烃。In the present invention, R 7 and R 8 are independently preferably chain alkanes having 4 to 8 carbon atoms.

在本发明中,所述胺类化合物进一步优选为以下结构式中的一种:In the present invention, the amine compound is further preferably one of the following structural formulas:

Figure BDA0003741467540000072
Figure BDA0003741467540000072

其中,n和k独立的为1~30的整数。Here, n and k are independently an integer of 1-30.

在本发明中,n和k独立的优选为5~20的整数,进一步优选为10~15的整数。In the present invention, n and k are independently preferably an integer of 5-20, more preferably an integer of 10-15.

在本发明中,所述反应在溶剂中进行,所述胺类化合物与溶剂的摩尔体积比为0.01~5mol:1L,优选为0.5~4mol:1L,进一步优选为1~3mol:1L。In the present invention, the reaction is carried out in a solvent, and the molar volume ratio of the amine compound to the solvent is 0.01-5mol:1L, preferably 0.5-4mol:1L, more preferably 1-3mol:1L.

在本发明中,所述溶剂包含N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和二甲基亚砜中的一种或几种,优选为二甲基亚砜。In the present invention, the solvent comprises one or more of N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide, preferably dimethyl sulfoxide.

在本发明中,所述反应在保护气氛下进行,所述保护气氛包含氮气和/或氩气,优选为氮气。In the present invention, the reaction is carried out under a protective atmosphere containing nitrogen and/or argon, preferably nitrogen.

在本发明中,所述反应的温度为20~120℃,反应的时间为2~48h;优选的,反应的温度为50~100℃,反应的时间为5~40h;进一步优选为,反应的温度为60~80℃,反应的时间为10~30h。In the present invention, the reaction temperature is 20-120 °C, and the reaction time is 2-48 h; preferably, the reaction temperature is 50-100 °C, and the reaction time is 5-40 h; more preferably, the reaction time is 5-40 h. The temperature is 60~80℃, and the reaction time is 10~30h.

在本发明中,通过搅拌加速反应的进行,所述搅拌的转速为300~800rpm,优选为500rpm。In the present invention, the reaction is accelerated by stirring, and the rotational speed of the stirring is 300-800 rpm, preferably 500 rpm.

在本发明中,所述反应在催化剂的作用下进行,所述催化剂为碱性化合物,所述碱性化合物包含N,N-二异丙基乙胺、三乙胺、氟化钾和碳酸钾中的一种或几种,优选为N,N-二异丙基乙胺。In the present invention, the reaction is carried out under the action of a catalyst, and the catalyst is a basic compound, and the basic compound includes N,N-diisopropylethylamine, triethylamine, potassium fluoride and potassium carbonate One or more of them, preferably N,N-diisopropylethylamine.

在本发明中,所述催化剂和胺类化合物的摩尔比为10~40:1~10,优选为40:10。In the present invention, the molar ratio of the catalyst and the amine compound is 10-40:1-10, preferably 40:10.

在本发明中,反应结束后需要对反应产物进行提纯处理,所述提纯处理为:用乙酸乙酯稀释反应液,过滤除去固体物质并对剩余液体顺次进行萃取处理、洗脱处理、干燥即得提纯后的产物。In the present invention, the reaction product needs to be purified after the reaction, and the purification treatment is as follows: diluting the reaction solution with ethyl acetate, filtering to remove the solid matter, and sequentially performing extraction treatment, elution treatment, and drying on the remaining liquid. The purified product was obtained.

在本发明中,所述萃取处理的水相为饱和氯化铵水溶液、油相为乙酸乙酯;所述洗脱处理用到的溶剂为体积比为3~5:1的石油醚和乙酸乙酯,优选为4:1。In the present invention, the water phase of the extraction treatment is saturated aqueous ammonium chloride solution, and the oil phase is ethyl acetate; the solvent used in the elution treatment is petroleum ether and ethyl acetate with a volume ratio of 3-5:1 Esters, preferably 4:1.

在本发明中,所述干燥的温度为50~70℃,干燥的时间为10~30min;优选的,干燥的温度为60℃,干燥的时间为20min。In the present invention, the drying temperature is 50-70 °C, and the drying time is 10-30 min; preferably, the drying temperature is 60 °C, and the drying time is 20 min.

在本发明中,使用的化学药品均可自化学试剂公司购得,其中,环己胺、四氯乙烷、N,N-二甲基乙酰胺、N,N-二异丙基乙胺与2-苯乙胺购自安耐吉公司,对甲氧基苯甲胺购自TCI公司,哌啶购自凯信化学,硫磺(升华硫)购自阿法埃沙公司,十二胺购自阿拉丁公司。In the present invention, the chemicals used can be purchased from chemical reagent companies, wherein cyclohexylamine, tetrachloroethane, N,N-dimethylacetamide, N,N-diisopropylethylamine and 2-Phenylethylamine was purchased from Anaiji Company, p-methoxybenzylamine was purchased from TCI Company, piperidine was purchased from Kaixin Chemical, sulfur (sublimated sulfur) was purchased from Alfa Esa Company, and dodecylamine was purchased from Aladdin Co.

下面结合实施例对本发明提供的技术方案进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the protection scope of the present invention.

实施例1Example 1

利用单质硫磺、四氯乙烷和胺化合物制备二硫代草酰胺化合物的多组分反应制备环己基取代的二硫代草酰胺,反应方程式如式(Ⅱ):Cyclohexyl-substituted dithiooxamides are prepared by a multi-component reaction using elemental sulfur, tetrachloroethane and amine compounds to prepare dithiooxamide compounds. The reaction equation is as formula (II):

Figure BDA0003741467540000091
Figure BDA0003741467540000091

该合成方法步骤如下所示:The synthetic method steps are as follows:

在灌注氮气的反应器内,将8mLN,N-二甲基乙酰胺加入8mmol的环己胺、2mmol的四氯乙烷与10mmol的硫磺中,使其溶解,并加热到100摄氏度500rpm下搅拌8小时。In a reactor filled with nitrogen, 8 mL of N,N-dimethylacetamide was added to 8 mmol of cyclohexylamine, 2 mmol of tetrachloroethane and 10 mmol of sulfur to dissolve it, and heated to 100 degrees Celsius and stirred at 500 rpm for 8 Hour.

反应结束后,停止加热并加入100mL乙酸乙酯淬灭并稀释反应液,而后通过过滤去除反应液中析出的固体。使用饱和氯化铵水溶液作为水相,乙酸乙酯作为有机相,对去除固体后的反应液进行萃取,而后将所得到的有机相进行合并。通过加热减压蒸发将合并后的有机相的溶剂去除并得到粗产物。而后,通过硅胶柱层析法并使用石油醚与乙酸乙酯体积比为4:1的混合溶剂作为洗脱剂,将提纯产物从体系中分离出来并在60℃下干燥20min,最后以59%的产率得到橙红色固体产物,即环己基取代的二硫代草酰胺化合物。After the reaction, the heating was stopped and 100 mL of ethyl acetate was added to quench and dilute the reaction solution, and then the solid precipitated in the reaction solution was removed by filtration. Using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, the solid-removed reaction solution was extracted, and the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, the purified product was separated from the system by silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 4:1 as the eluent and dried at 60 °C for 20 min. The yield of 3000 gave the product as an orange-red solid, the cyclohexyl-substituted dithiooxamide compound.

本实施例中所得的二硫代草酰胺化合物如Compound 1所示。The dithiooxamide compound obtained in this example is shown in Compound 1.

Figure BDA0003741467540000092
Figure BDA0003741467540000092

本实施例制备的二硫代草酰胺化合物的表征数据如下所示:The characterization data of the dithiooxamide compounds prepared in this example are as follows:

二硫代草酰胺化合物,橙红色固体,产率为59%。核磁数据如下:1H NMR(400MHz,CDCl3-d),δ(TMS,ppm):10.35(d,1H,-NH-),4.25(m,1H),2.05(m,2H),1.79(m,2H),1.66(m,1H),1.44(m,4H),1.33(m,1H).13C NMR(100MHz,CDCl3-d),δ(TMS,ppm):183.09(C=S),55.82,30.64,25.45,24.35。Dithioxamide compound, orange-red solid, yield 59%. The nuclear magnetic data are as follows: 1 H NMR (400MHz, CDCl 3 -d), δ (TMS, ppm): 10.35 (d, 1H, -NH-), 4.25 (m, 1H), 2.05 (m, 2H), 1.79 ( m, 2H), 1.66 (m, 1H), 1.44 (m, 4H), 1.33 (m, 1H). 13 C NMR (100 MHz, CDCl 3 -d), δ (TMS, ppm): 183.09 (C=S ), 55.82, 30.64, 25.45, 24.35.

实施例2Example 2

利用单质硫磺、四氯乙烷和胺化合物制备二硫代草酰胺化合物的多组分反应制备对甲氧基苯甲基取代的二硫代草酰胺,反应方程式如式(Ⅲ):Utilize the multi-component reaction of elemental sulfur, tetrachloroethane and amine compound to prepare dithiooxamide compound to prepare p-methoxybenzyl substituted dithiooxamide, the reaction equation is as formula (III):

Figure BDA0003741467540000101
Figure BDA0003741467540000101

该合成方法步骤如下所示:The synthetic method steps are as follows:

将8mmol的对甲氧基苯甲胺、2mmol的四氯乙烷与10mmol的硫磺加入反应器内中并灌注氮气,加热到100摄氏度500rpm下搅拌8小时。8 mmol of p-methoxybenzylamine, 2 mmol of tetrachloroethane and 10 mmol of sulfur were added to the reactor and nitrogen gas was injected into the reactor, and the reactor was heated to 100 degrees Celsius and stirred at 500 rpm for 8 hours.

反应结束后,停止加热并加入60mL乙酸乙酯与50ml纯净水淬灭并稀释反应液,而后通过过滤去除反应液中析出的固体。使用饱和氯化铵水溶液作为水相,乙酸乙酯作为有机相,对去除固体后的反应液进行萃取,而后将所得到的有机相进行合并。通过加热减压蒸发将合并后的有机相的溶剂去除并得到粗产物。而后,通过硅胶柱层析法并使用石油醚与乙酸乙酯体积比为4:1的混合溶剂作为洗脱剂,将提纯产物从体系中分离出来并在60℃下干燥20min,最后以47%的产率得到黄色固体产物,即对甲氧基苯甲基取代的二硫代草酰胺化合物。After the reaction was completed, the heating was stopped and 60 mL of ethyl acetate and 50 mL of purified water were added to quench and dilute the reaction solution, and then the solid precipitated in the reaction solution was removed by filtration. Using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, the solid-removed reaction solution was extracted, and the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, the purified product was separated from the system by silica gel column chromatography using a mixed solvent with a volume ratio of petroleum ether and ethyl acetate of 4:1 as the eluent, and dried at 60 °C for 20 min. A yield of 100% yields a yellow solid product, a p-methoxybenzyl-substituted dithiooxamide compound.

本实施例中所得的二硫代草酰胺化合物如Compound 2所示。The dithiooxamide compound obtained in this example is shown in Compound 2.

Figure BDA0003741467540000102
Figure BDA0003741467540000102

作为对实施例2中得到的二硫代草酰胺化合物的结构证明手段,以体积比为1:1的二氯甲烷与正己烷为混合溶剂培养了该化合物的条状单晶,并对单晶进行了单晶X射线衍射的测试,测试结果证明了该二硫代草酰胺化合物的结构,单晶X射线衍射分析显示的化合物结构如图1所示。As a means of proving the structure of the dithiooxamide compound obtained in Example 2, a strip-shaped single crystal of the compound was grown in a mixed solvent of dichloromethane and n-hexane with a volume ratio of 1:1, and the single crystal was analyzed. The single-crystal X-ray diffraction test was carried out, and the test results proved the structure of the dithiooxamide compound. The compound structure shown by the single-crystal X-ray diffraction analysis is shown in FIG. 1 .

实施例3Example 3

利用单质硫磺、四氯乙烷和胺化合物制备二硫代草酰胺化合物的多组分反应在加入碱试剂的情况下制备对甲基苯基取代的二硫代草酰胺,反应方程式如式(Ⅳ)所示:Utilize elemental sulfur, tetrachloroethane and amine compound to prepare the multi-component reaction of dithiooxamide compound to prepare p-methylphenyl substituted dithiooxamide under the condition of adding alkali reagent, the reaction equation is as formula (IV ) as shown:

Figure BDA0003741467540000111
Figure BDA0003741467540000111

该合成方法步骤如下所示:The synthetic method steps are as follows:

在灌注氩气的反应器内,将8mL的N,N-二甲基乙酰胺与5573.7μL的N,N-二异丙基乙胺(32.0mmol)加入8mmol的对甲基苯胺、6mmol的四氯乙烷与10mmol的升华硫中,使其溶解,并加热到100摄氏度400rpm下搅拌8小时。In a reactor filled with argon, 8 mL of N,N-dimethylacetamide and 5573.7 μL of N,N-diisopropylethylamine (32.0 mmol) were added to 8 mmol of p-methylaniline, 6 mmol of tetrakis Dissolve ethyl chloride with 10 mmol of sublimed sulfur and heat to 100 degrees Celsius with stirring at 400 rpm for 8 hours.

反应结束后,停止加热并加入100mL乙酸乙酯淬灭并稀释反应液,而后通过过滤去除反应液中析出的固体。使用饱和氯化铵水溶液作为水相,乙酸乙酯作为有机相,对去除固体后的反应液进行萃取,而后将所得到的有机相进行合并。通过加热减压蒸发将合并后的有机相的溶剂去除并得到粗产物。而后,通过硅胶柱层析法并使用石油醚与乙酸乙酯体积比为4:1的混合溶剂作为洗脱剂,将提纯产物从体系中分离出来并在50℃下干燥10min,最后以26%的产率得到橙红色固体产物,即对甲基苯基取代的二硫代草酰胺化合物。After the reaction, the heating was stopped and 100 mL of ethyl acetate was added to quench and dilute the reaction solution, and then the solid precipitated in the reaction solution was removed by filtration. Using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, the solid-removed reaction solution was extracted, and the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, the purified product was separated from the system by silica gel column chromatography and a mixed solvent with a volume ratio of petroleum ether and ethyl acetate of 4:1 was used as the eluent, and dried at 50 °C for 10 min. The yield of 3000 gave the product as an orange-red solid, the p-methylphenyl substituted dithiooxamide compound.

本实施例中所得的二硫代草酰胺化合物如Compound3所示。The dithiooxamide compound obtained in this example is shown in Compound 3.

Figure BDA0003741467540000112
Figure BDA0003741467540000112

实施例4Example 4

利用单质硫磺、四氯乙烷和胺化合物制备二硫代草酰胺化合物的多组分反应制备哌啶基取代的全取代二硫代草酰胺,反应方程式如式(Ⅴ)所示:The multi-component reaction of preparing dithiooxamide compound using elemental sulfur, tetrachloroethane and amine compound prepares piperidinyl-substituted fully substituted dithiooxamide, and the reaction equation is shown in formula (V):

Figure BDA0003741467540000121
Figure BDA0003741467540000121

该合成方法步骤如下所示:The synthetic method steps are as follows:

在灌注氩气的反应器内,将8mL的N,N-二甲基乙酰胺与加入8mmol的哌啶、2mmol的四氯乙烷与10mmol的硫磺中,使其溶解,并加热到100摄氏度800rpm下搅拌8小时。In a reactor filled with argon, 8 mL of N,N-dimethylacetamide was added to 8 mmol of piperidine, 2 mmol of tetrachloroethane and 10 mmol of sulfur to dissolve, and heated to 100 degrees Celsius at 800 rpm under stirring for 8 hours.

反应结束后,停止加热并加入100mL乙酸乙酯淬灭并稀释反应液,而后通过过滤去除反应液中析出的固体。使用饱和氯化铵水溶液作为水相,乙酸乙酯作为有机相,对去除固体后的反应液进行萃取,而后将所得到的有机相进行合并。通过加热减压蒸发将合并后的有机相的溶剂去除并得到粗产物。而后,通过硅胶柱层析法并使用石油醚与乙酸乙酯体积比为4:1的混合溶剂作为洗脱剂,将提纯产物从体系中分离出来并在60℃下干燥10min,最后以38%的产率得到黄色固体产物哌啶基取代的全取代二硫代草酰胺化合物。After the reaction, the heating was stopped and 100 mL of ethyl acetate was added to quench and dilute the reaction solution, and then the solid precipitated in the reaction solution was removed by filtration. Using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, the solid-removed reaction solution was extracted, and the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, the purified product was separated from the system by silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 4:1 as the eluent and dried at 60 °C for 10 min. The yield of yellow solid product piperidinyl substituted fully substituted dithiooxamide compound.

本实施例中所得的二硫代草酰胺化合物如Compound4所示。The dithiooxamide compound obtained in this example is shown in Compound 4.

Figure BDA0003741467540000122
Figure BDA0003741467540000122

实施例5Example 5

利用单质硫磺、四氯乙烷和胺化合物制备二硫代草酰胺化合物的多组分反应制备(2-苯乙基)取代的二硫代草酰胺,反应方程式如式(Ⅵ)所示:The multi-component reaction of preparing dithiooxamide compound using elemental sulfur, tetrachloroethane and amine compound prepares (2-phenethyl) substituted dithiooxamide, and the reaction equation is shown in formula (VI):

Figure BDA0003741467540000123
Figure BDA0003741467540000123

该合成方法步骤如下所示:The synthetic method steps are as follows:

在灌注氩气的反应器内,将8mL的N,N-二甲基乙酰胺与加入8mmol的2-苯乙胺、2mmol的四氯乙烷与10mmol的硫磺中,使其溶解,并加热到100摄氏度800rpm下搅拌8小时。In a reactor filled with argon, 8 mL of N,N-dimethylacetamide was added with 8 mmol of 2-phenylethylamine, 2 mmol of tetrachloroethane and 10 mmol of sulfur to dissolve, and heated to Stir at 800 rpm at 100 degrees Celsius for 8 hours.

反应结束后,停止加热并加入100mL乙酸乙酯淬灭并稀释反应液,而后通过过滤去除反应液中析出的固体。使用饱和氯化铵水溶液作为水相,乙酸乙酯作为有机相,对去除固体后的反应液进行萃取,而后将所得到的有机相进行合并。通过加热减压蒸发将合并后的有机相的溶剂去除并得到粗产物。而后,通过硅胶柱层析法并使用石油醚与乙酸乙酯体积比为4:1的混合溶剂作为洗脱剂,将提纯产物从体系中分离出来并在60℃下干燥10min,最后以25%的产率得到黄色固体产物(2-苯乙基)取代的全取代二硫代草酰胺化合物。After the reaction, the heating was stopped and 100 mL of ethyl acetate was added to quench and dilute the reaction solution, and then the solid precipitated in the reaction solution was removed by filtration. Using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, the solid-removed reaction solution was extracted, and the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, the purified product was separated from the system by silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 4:1 as the eluent and dried at 60 °C for 10 min. A yellow solid product (2-phenethyl) substituted fully substituted dithiooxamide compound was obtained in a yield of 100%.

本实施例中所得的二硫代草酰胺化合物如Compound5所示。The dithiooxamide compound obtained in this example is shown in Compound 5.

Figure BDA0003741467540000131
Figure BDA0003741467540000131

实施例6Example 6

利用单质硫磺、四氯乙烷和胺化合物制备二硫代草酰胺化合物的多组分反应制备十二烷基取代的二硫代草酰胺,反应方程式如式(Ⅶ)所示:Dodecyl-substituted dithiooxamide is prepared by the multi-component reaction of elemental sulfur, tetrachloroethane and amine compound to prepare dithiooxamide compound, and the reaction equation is shown in formula (VII):

Figure BDA0003741467540000132
Figure BDA0003741467540000132

该合成方法步骤如下所示:The synthetic method steps are as follows:

在灌注氩气的反应器内,将8mL的N,N-二甲基乙酰胺与加入8mmol的十二胺、2mmol的四氯乙烷与10mmol的硫磺中,使其溶解,并加热到100摄氏度800rpm下搅拌8小时。In a reactor filled with argon, 8 mL of N,N-dimethylacetamide was dissolved in 8 mmol of dodecylamine, 2 mmol of tetrachloroethane and 10 mmol of sulfur, and heated to 100 degrees Celsius. Stir at 800 rpm for 8 hours.

反应结束后,停止加热并加入100mL乙酸乙酯淬灭并稀释反应液,而后通过过滤去除反应液中析出的固体。使用饱和氯化铵水溶液作为水相,乙酸乙酯作为有机相,对去除固体后的反应液进行萃取,而后将所得到的有机相进行合并。通过加热减压蒸发将合并后的有机相的溶剂去除并得到粗产物。而后,通过硅胶柱层析法并使用石油醚与乙酸乙酯体积比为4:1的混合溶剂作为洗脱剂,将提纯产物从体系中分离出来并在60℃下干燥10min,最后以20%的产率得到黑色粘稠固体产物十二烷基取代的二硫代草酰胺化合物。After the reaction, the heating was stopped and 100 mL of ethyl acetate was added to quench and dilute the reaction solution, and then the solid precipitated in the reaction solution was removed by filtration. Using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, the solid-removed reaction solution was extracted, and the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, the purified product was separated from the system by silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 4:1 as the eluent and dried at 60 °C for 10 min. The yield of dodecyl-substituted dithiooxamide compound was obtained as a black viscous solid product.

本实施例中所得的二硫代草酰胺化合物如Compound6所示。The dithiooxamide compound obtained in this example is shown in Compound 6.

Figure BDA0003741467540000141
Figure BDA0003741467540000141

由以上实施例可知,本发明提供了一种二硫代草酰胺化合物及其制备方法,本发明实现了对少有报道的N,N-二脂肪基取代二硫代草酰胺化合物以及N,N-二芳香基取代二硫代草酰胺化合物的高效低成本制备,且该发明的制备方法具有反应条件温和且操作简单,产物结构多样等特点。It can be seen from the above examples that the present invention provides a dithiooxamide compound and a preparation method thereof, and the present invention realizes the N,N-dialiphatic group substituted dithiooxamide compound and N,N which are rarely reported. -The high-efficiency and low-cost preparation of diaryl-substituted dithiooxamide compounds, and the preparation method of the invention has the characteristics of mild reaction conditions, simple operation, diverse product structures, and the like.

以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1.一种二硫代草酰胺化合物,其特征在于,所述二硫代草酰胺化合物包含如下结构通式中的一种:1. a dithiooxamide compound, is characterized in that, described dithiooxamide compound comprises a kind of in following structural formula:
Figure FDA0003741467530000011
Figure FDA0003741467530000011
其中,R1和R2独立的为脂肪烃基、氧代脂肪烃基、带芳香取代基的脂肪烃基、带芳香取代基的氧代脂肪烃基、带卤代物取代基的脂肪烃基或带卤代物取代基的氧代脂肪烃基;Wherein, R 1 and R 2 are independently aliphatic hydrocarbon groups, oxo aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents, oxo aliphatic hydrocarbon groups with aromatic substituents, aliphatic hydrocarbon groups with halogenated substituents or halogenated substituents oxo aliphatic hydrocarbon group; R3和R4独立的为氢原子、烃基、烷氧基、卤素、羟基、酯基、羰基、芳基或氰基; R3 and R4 are independently a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group; R5和R6独立的为两侧同时与氮原子相连的烃基、带有芳香取代基的烃基或带卤代物取代基的烃基;R 5 and R 6 are independently a hydrocarbon group connected to nitrogen atoms on both sides at the same time, a hydrocarbon group with an aromatic substituent or a hydrocarbon group with a halogen substituent; R7和R8独立的为脂肪烃基、带有芳香取代基的脂肪烃基或带卤代物取代基的脂肪烃基。R 7 and R 8 are independently aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents or aliphatic hydrocarbon groups with halogen substituents.
2.根据权利要求1所述的二硫代草酰胺化合物,其特征在于,所述二硫代草酰胺化合物具体包含以下结构式中的一种:2. dithiooxamide compound according to claim 1, is characterized in that, described dithiooxamide compound specifically comprises a kind of in following structural formula:
Figure FDA0003741467530000012
Figure FDA0003741467530000012
3.权利要求1或2所述的二硫代草酰胺化合物的制备方法,其特征在于,包括以下步骤:3. the preparation method of the described dithiooxamide compound of claim 1 or 2, is characterized in that, comprises the following steps: 硫磺、四氯乙烷和胺类化合物进行反应得到的产物即为二硫代草酰胺化合物。The product obtained by the reaction of sulfur, tetrachloroethane and amine compounds is the dithiooxamide compound. 4.根据权利要求3所述的二硫代草酰胺化合物的制备方法,其特征在于,所述硫磺、四氯甲烷和胺类化合物的摩尔比为0.25~10.0:0.17~4.0:1.0~10.0。4 . The method for preparing a dithiooxamide compound according to claim 3 , wherein the molar ratio of the sulfur, tetrachloromethane and the amine compound is 0.25-10.0:0.17-4.0:1.0-10.0. 5 . 5.根据权利要求3或4所述的二硫代草酰胺化合物的制备方法,其特征在于,所述胺类化合物包含以下结构通式中的一种:5. the preparation method of the dithiooxamide compound according to claim 3 or 4, is characterized in that, described amine compound comprises a kind of in following structural formula:
Figure FDA0003741467530000021
Figure FDA0003741467530000021
其中,R1和R2独立的为脂肪烃基、氧代脂肪烃基、带芳香取代基的脂肪烃基、带芳香取代基的氧代脂肪烃基、带卤代物取代基的脂肪烃基或带卤代物取代基的氧代脂肪烃基;Wherein, R 1 and R 2 are independently aliphatic hydrocarbon groups, oxo aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents, oxo aliphatic hydrocarbon groups with aromatic substituents, aliphatic hydrocarbon groups with halogenated substituents or halogenated substituents oxo aliphatic hydrocarbon group; R3和R4独立的为氢原子、烃基、烷氧基、卤素、羟基、酯基、羰基、芳基或氰基; R3 and R4 are independently a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group; R5和R6独立的为两侧同时与氮原子相连的烃基、带有芳香取代基的烃基或带卤代物取代基的烃基;R 5 and R 6 are independently a hydrocarbon group connected to nitrogen atoms on both sides at the same time, a hydrocarbon group with an aromatic substituent or a hydrocarbon group with a halogen substituent; R7和R8独立的为脂肪烃基、带有芳香取代基的脂肪烃基或带卤代物取代基的脂肪烃基。R 7 and R 8 are independently aliphatic hydrocarbon groups, aliphatic hydrocarbon groups with aromatic substituents or aliphatic hydrocarbon groups with halogen substituents.
6.根据权利要求5所述的二硫代草酰胺化合物的制备方法,其特征在于,所述胺类化合物具体包含以下结构式中的一种:6. the preparation method of dithiooxamide compound according to claim 5, is characterized in that, described amine compound specifically comprises a kind of in following structural formula:
Figure FDA0003741467530000031
Figure FDA0003741467530000031
其中,n和k独立的为1~30的整数。Here, n and k are independently an integer of 1-30.
7.根据权利要求6所述的二硫代草酰胺化合物的制备方法,其特征在于,所述反应在溶剂中进行,所述胺类化合物与溶剂的摩尔体积比为0.01~5mol:1L;7 . The method for preparing a dithiooxamide compound according to claim 6 , wherein the reaction is carried out in a solvent, and the molar volume ratio of the amine compound to the solvent is 0.01 to 5 mol: 1 L; 7 . 所述溶剂包含N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和二甲基亚砜中的一种或几种。The solvent contains one or more of N,N-dimethylformamide, N,N-dimethylacetamide and dimethylsulfoxide. 8.根据权利要求4或6或7所述的二硫代草酰胺化合物的制备方法,其特征在于,所述反应在保护气氛下进行,所述保护气氛包含氮气和/或氩气。8 . The method for preparing a dithiooxamide compound according to claim 4 , wherein the reaction is carried out under a protective atmosphere, and the protective atmosphere contains nitrogen and/or argon. 9 . 9.根据权利要求8所述的二硫代草酰胺化合物的制备方法,其特征在于,所述反应的温度为20~120℃,反应的时间为2~48h。9 . The method for preparing a dithiooxamide compound according to claim 8 , wherein the reaction temperature is 20-120° C., and the reaction time is 2-48 h. 10 . 10.根据权利要求3或9所述的二硫代草酰胺化合物的制备方法,其特征在于,所述反应在催化剂的作用下进行,所述催化剂为碱性化合物,所述碱性化合物包含N,N-二异丙基乙胺、三乙胺、氟化钾和碳酸钾中的一种或几种;所述催化剂和胺类化合物的摩尔比为10~40:1~10。10. The method for preparing a dithiooxamide compound according to claim 3 or 9, wherein the reaction is carried out under the action of a catalyst, and the catalyst is a basic compound, and the basic compound comprises N , one or more of N-diisopropylethylamine, triethylamine, potassium fluoride and potassium carbonate; the molar ratio of the catalyst and the amine compound is 10-40:1-10.
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GB1219853A (en) * 1967-04-28 1971-01-20 Basf Ag Production or dithio-oxamides
DE2246025A1 (en) * 1972-09-20 1974-03-28 Akzo Gmbh Dithiooxamides derivs prepn - from amines and alkali cyanodithioformate
CN104151220A (en) * 2014-08-12 2014-11-19 湖南凯米尔生物科技有限公司 N,N'-dialkyl dithiooxamide as well as preparation method and application thereof

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