CN108794426B - Heterocyclic dithiocarbamate compound and preparation method thereof - Google Patents
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- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention relates to a heterocyclic dithiocarbamate compound and a preparation method thereof. The heterocyclic dithiocarbamate compound has a structure shown as a formula (1) or a formula (2). The heterocyclic dithiocarbamate compound provided by the invention takes benzothiazole or furan as a mother ring to obtain a corresponding heterocyclic dithiocarbamate compound, the type of the dithiocarbamate compound is further enriched, and related products have wide application prospects in the fields of antibacterial agents, insecticides, pharmaceutical intermediates, fragrance precursor compounds and the like.
Description
Technical Field
The invention belongs to the field of synthesis of dithiocarbamate compounds, and particularly relates to a heterocyclic dithiocarbamate compound and a preparation method thereof.
Background
Dithiocarbamates are an important class of compounds with a variety of uses. Because of their important biological and physiological activities (e.g., antibacterial activity, antiviral activity, enzyme inhibitory activity, etc.), dithiocarbamates have important applications in pesticides (e.g., insecticides, herbicides) and pharmaceuticals (e.g., bactericides, antiviral agents). Dithiocarbamates can also be used as vulcanization accelerators in rubber synthesis. In addition, dithiocarbamates are important synthetic intermediates and chemical raw materials, and have various applications in organic synthesis. Due to its importance, the research on the synthesis of related compounds has been receiving much attention.
The patent application with publication number CN104844491A discloses a method for synthesizing dithiocarbamate, which comprises the steps of taking phenylboronic acid, amine and carbon disulfide as raw materials and copper salt and alkali as promoters in an organic solvent, stirring and reacting for 10-24h at 60-120 ℃, and then carrying out post-treatment to obtain the dithiocarbamate. The substrate applicable to the method is of a benzene ring structure, and the type and the application range of the obtained dithiocarbamate are all required to be improved.
Disclosure of Invention
The present invention aims to provide a heterocyclic dithiocarbamate compound. The invention also provides a preparation method of the heterocyclic dithiocarbamate compound.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a heterocyclic dithiocarbamate compound has a structure represented by formula (1) or formula (2):
in the formulae (1) and (2), R1Selected from H, alkyl, alkoxy, R2Selected from alkyl groups.
The alkyl and alkoxy are preferably C1-C5 alkyl and C1-C5 alkoxy.
The heterocyclic dithiocarbamate compound provided by the invention takes benzothiazole or furan as a mother ring to obtain a corresponding heterocyclic dithiocarbamate compound, the type of the dithiocarbamate compound is further enriched, and related products have wide application prospects in the fields of antibacterial agents, insecticides, pharmaceutical intermediates, fragrance precursor compounds and the like.
The method for producing the heterocyclic dithiocarbamate compound comprises the step of subjecting a heterocyclic compound and thiuram disulfide to a coupling reaction in a solvent in the presence of a base;
the heterocyclic compound has a structure as shown in formula (3) or formula (4):
the thiuram disulfide has the structure shown in formula (5):
in the formulae (3), (4) and (5), R1Selected from H, alkyl, alkoxy, R2Selected from alkyl groups and X is selected from halogen.
The preparation method of the heterocyclic dithio carbamate compound provided by the invention adopts a one-pot method, takes an economical and easily obtained heterocyclic compound and thiuram disulfide as raw materials, takes alkali as a catalyst, and directly generates a coupling reaction in the air to generate a corresponding product. The preparation method has the advantages of wide application range, simple process, convenient operation, mild reaction conditions and higher yield, and is very suitable for industrial popularization and application.
In order to obtain a higher yield, it is preferable that the molar ratio of the heterocyclic compound and the thiuram disulfide is not less than 1:1, more preferably (1-2):1, and still more preferably 1: 1. The molar ratio of the base to thiuram disulfide is greater than 1:1, more preferably (1.5-3):1, and still more preferably 2: 1.
The base is preferably at least one of an alkali metal carbonate, sodium hydrogen carbonate, potassium phosphate, sodium acetate, potassium acetate, sodium alkoxide, potassium alkoxide, lithium hydroxide, sodium hydroxide, and potassium hydroxide, from the viewpoints of cost and catalytic effect. The alkali metal carbonate is preferably at least one of sodium carbonate, potassium carbonate and cesium carbonate. The sodium alkoxide is preferably sodium ethoxide and/or sodium n-butoxide.
In order to improve the efficiency of the coupling reaction and reduce the occurrence of side reactions, the temperature of the coupling reaction is preferably 70-120 ℃ and the time is preferably 36-72 h.
The selection of the solvent is not particularly limited, and it does not affect the normal progress of the coupling reaction, and it is preferable from the viewpoint of the cost of the solvent and the reaction yield that the solvent is dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), toluene (tolumene), acetonitrile (CH) (dimethyl sulfoxide (DMF)), or a mixture thereof3CN).
After the coupling reaction, the separation of the target product can be realized by using conventional separation and purification means, such as column chromatography, thin-layer chromatography and the like. The invention herein provides a means for post-treatment using thin layer chromatography. Preferably, the coupling reaction is carried out to obtain a reaction solution, the reaction solution is concentrated to prepare a concentrated solution, and the concentrated solution is subjected to thin-layer chromatography separation to obtain the target product.
From the aspect of separation effect, the developing solvent used for the thin-layer chromatography is preferably a mixed solvent composed of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is (1-10): 1-10. Or the developing solvent is a mixed solvent consisting of dichloromethane and ethyl acetate, and the volume ratio of the dichloromethane to the ethyl acetate is (5-20): 1.
Detailed Description
The invention mainly realizes the convenient and efficient synthesis of the heterocyclic dithiocarbamate compound by using a one-pot method through the optimization of reaction raw materials, taking benzothiazole heterocyclic compounds as an example, the reaction route is shown as follows:
R1、R2see the description for a selection of (1).
The following examples are provided to further illustrate the practice of the invention.
Example 1
The heterocyclic dithiocarbamate compound of this example has the formula:
the heterocyclic dithiocarbamate compound of this example was prepared by the following steps:
1) taking 0.2mmol of 2-bromo-1, 3-benzothiazole, 0.2mmol of tetramethylthiuram disulfide and 0.4mmol of cesium carbonate, adding 1.0mL of dimethyl sulfoxide (DMSO) to prepare a mixture, placing the mixture in a 5mL Schlenk tube, heating the mixture in an oil bath at the temperature of 110 ℃ for reaction for 48 hours, and cooling the mixture to room temperature to obtain a reaction solution;
2) directly concentrating the reaction solution to obtain a concentrate, and carrying out thin-layer chromatography separation on the concentrate by taking ethyl acetate/petroleum ether (1/5 (v/v)) as a developing agent to obtain the target product, wherein the separation yield is 68%.
The target product benzothiazole-2-dimethyldithiocarbamate (5a) is a colorless solid, and the nuclear magnetism is characterized as follows:
1H NMR(400MHz,CDCl3)ppm:8.12(d,J＝7.9Hz,1H),7.91(d,J＝7.7Hz,1H),7.54-7.50(m,1H),7.48-7.44(m,1H),3.54(s,3H),3.52(s,3H)；
13C NMR(100MHz,CDCl3):191.5,159.0,152.8,138.4,126.4,126.1,124.0,121.5,45.4,42.5；
IR(KBr):3426,2922,1511,1454,1408,1380,1313,1246,1156,1079,1001,958,761,728cm-1；
HRMS(ESI)calcd.for C10H11N2S3:[M+H]+:255.0084,found:255.0082.
examples 2 to 14
The heterocyclic dithiocarbamate compounds of examples 2 to 14 are the same as in example 1, and the differences in the specific reaction conditions from example 1 and the corresponding yields are shown in Table 1.
TABLE 1 reaction conditions and yields of examples 2-14
Examples 15 to 17
The heterocyclic dithiocarbamate compounds of examples 15 to 17 were prepared in the same manner as in example 1 except that the reaction temperature was 100 ℃, 120 ℃ and 80 ℃ and the isolation yield was 84%, 63% and 70%, respectively.
Example 18
The heterocyclic dithiocarbamate compound of this example has the formula:
in the method for producing a heterocyclic dithiocarbamate compound of this example, 2-bromo-1, 3-benzothiazole and tetraethylthiuram disulfide are used as starting materials, and other reaction conditions are the same as in example 15.
The target product benzothiazole-2-diethylaminodithioformate (5b) is a yellow liquid, the isolation yield is 71%, and the nuclear magnetism is characterized as follows:
1H NMR(400MHz,CDCl3)ppm:8.12(d,J＝7.9Hz,1H),7.90(d,J＝7.5Hz,1H),7.51(td,J＝7.3,1.2Hz,1H),7.44(td,J＝8.1,1.2Hz,1H),4.01(q,J＝7.0Hz,2H),3.84(q,J＝7.0Hz,2H),1.42(t,J＝7.0Hz,3H),1.30(t,J＝7.0Hz,3H)；
13C NMR(100MHz,CDCl3):189.8,159.1,152.9,138.5,126.3,126.1,124.0,121.5,49.7,48.0,13.0,11.4；
IR(KBr):3443,2978,2929,1697,1494,1271,1202,1146,1076,994,965,915,824,725cm-1；
HRMS(ESI)calcd.for C12H15N2S3:[M+H]+:283.0397,found:283.0396.
example 19
The heterocyclic dithiocarbamate compound of this example has the formula:
in the method for producing a heterocyclic dithiocarbamate compound of this example, 2-bromo-1, 3-benzothiazole and tetrabutylthiuram disulfide are used as starting materials, and other reaction conditions are the same as in example 15.
The target product benzothiazole-2-dibutylaminodithiocarbamate (5c) is a yellow liquid, the isolation yield is 53%, and the nuclear magnetism is characterized as follows:
1H NMR(400MHz,CDCl3)ppm:8.11(d,J＝7.9Hz,1H),7.90(d,J＝7.6Hz,1H),7.50(td,J＝7.4,1.2Hz,1H),7.44(td,J＝8.1,1.2Hz,1H),3.93(t,J＝7.7Hz,2H),3.75(t,J＝7.8Hz,2H),1.84-1.78(m,2H),1.76-1.70(m,2H),1.46-1.41(m,2H),1.39-1.31(m,2H),1.01(t,J＝7.3Hz,3H),0.95(t,J＝7.3Hz,3H)；
13C NMR(100MHz,CDCl3):190.0,159.5,152.8,138.3,126.3,126.0,123.9,121.4,55.1,53.8,29.9,28.2,20.1,13.8,13.7；
IR(KBr):2958,2871,1670,1412,1367,1220,1092,976,939,759cm-1；
HRMS(ESI)calcd.for C16H23N2S3:[M+H]+:339.1023,found:339.1021.
example 20
The heterocyclic dithiocarbamate compound of this example has the formula:
in the method for producing a heterocyclic dithiocarbamate compound of this example, 2-bromo-6-methoxy-1, 3-benzothiazole and tetramethylthiuram disulfide are used as starting materials, and other reaction conditions are the same as in example 15.
The target product 6-methoxy-benzothiazole-2-dimethyldithiocarbamate (5d) is a white solid with an isolation yield of 53%, and the nuclear magnetism is characterized as follows:
1H NMR(400MHz,CDCl3)ppm:8.00(d,J＝9.0Hz,1H),7.34(d,J＝2.5Hz,1H),7.11(dd,J＝9.0,2.5Hz,1H),3.89(s,3H),3.54(s,3H),3.52(s,3H)；
13C NMR(100MHz,CDCl3):192.3,158.5,155.2,147.7,140.3,124.7,116.4,103.4,55.8,42.4；
IR(KBr):3442,2922,2851,1601,1504,1475,1378,1256,1224,1023,965,838cm-1；
HRMS(ESI)calcd.for C11H13N2OS3:[M+H]+:285.0190,found:285.0192.
example 21
The heterocyclic dithiocarbamate compound of this example has the formula:
in the method for producing a heterocyclic dithiocarbamate compound of this example, 2-bromo-6-methoxy-1, 3 benzothiazole and tetraethylthiuram disulfide are used as starting materials, and other reaction conditions are the same as in example 15.
The target product 6-methoxy-benzothiazole-2-diethyl dithiocarbamate (5e) is a yellow liquid, the isolation yield is 69%, and nuclear magnetism is characterized as follows:
1H NMR(400MHz,CDCl3)ppm:8.01(d,J＝9.0Hz,1H),7.33(d,J＝2.4Hz,1H),7.51(dd,J＝9.0,2.5Hz,1H),4.00(q,J＝6.9Hz,2H),3.88(s,3H),3.83(q,J＝7.2Hz,2H),1.42(t,J＝7.0Hz,3H),1.30(t,J＝7.0Hz,3H)；
13C NMR(100MHz,CDCl3):190.7,158.5,155.3,147.8,140.4,124.7,116.4,103.4,55.9,49.8,47.9,13.0,11.5；
IR(KBr):3424,3059,2928,1601,1550,1487,1421,1353,1277,1198,1142,1024,910,672cm-1；
HRMS(ESI)calcd.for C13H17N2OS3:[M+H]+:313.0503,found:313.0504.
example 22
The heterocyclic dithiocarbamate compound of this example has the formula:
in the process for producing a heterocyclic dithiocarbamate compound of this example, 2-bromo-6-methoxy-1, 3-benzothiazole and tetrabutylthiuram disulfide are used as starting materials, and the other reaction conditions are the same as in example 15.
The target product 6-methoxy-benzothiazole-2-dibutylamino dithio-formate (5f) is a yellow liquid, the isolation yield is 63%, and the nuclear magnetic characterization is as follows:
1H NMR(400MHz,CDCl3)ppm:8.00(d,J＝9.0Hz,1H),7.33(d,J＝2.4Hz,1H),7.10(dd,J＝9.0,2.5Hz,1H),3.92(t,J＝7.8Hz,2H),3.88(s,3H),3.74(t,J＝7.8Hz,2H),1.84-1.78(m,2H),1.77-1.71(m,2H),1.43(q,J＝7.4Hz,2H),1.35(q,J＝7.5Hz,2H),1.01(t,J＝7.3Hz,3H),0.94(t,J＝7.3Hz,3H)；
13C NMR(100MHz,CDCl3):190.8,158.4,155.6,147.7,140.4,124.6,116.3,103.4,55.8,55.2,53.7,29.8,28.2,20.1,13.8,13.7；
IR(KBr):3423,2958,2871,1602,1477,1416,1367,1259,1181,1027,819cm-1；
HRMS(ESI)calcd.for C17H25N2OS3:[M+H]+:369.1129,found:369.1130.
example 23
The heterocyclic dithiocarbamate compound of this example has the formula:
in the method for producing a heterocyclic dithiocarbamate compound of this example, 5-bromo-2-furancarbaldehyde and tetramethylthiuram disulfide were used as starting materials, and the other reaction conditions were the same as in example 15.
The target product, 5-formyl-furan-2-dimethyldithiocarbamate (5g), was a yellow solid with an isolated yield of 88%, and was characterized by nuclear magnetism as follows:
1H NMR(400MHz,CDCl3)ppm:9.73(s,1H),7.32(d,J＝3.6Hz,1H),6.95(d,J＝3.6Hz,1H),3.52(s,3H),3.48(s,3H)；
13C NMR(100MHz,CDCl3):192.3,178.2,156.0,147.6,124.8,120.5,45.6,42.4；
IR(KBr):3135,2925,1673,1518,1463,1385,1248,1022,966,936,829,762cm-1；
HRMS(ESI)calcd.for C8H10NO2S2:[M+H]+:216.0153,found:216.0150.
comparative example 1
Comparative example 1 in the preparation of the desired product of example 1, 0.02mmol of Cu was also added2O, otherwise the conditions were the same as in example 1, and the expected product was not finally obtained.
Comparative example 2
Comparative example 2 in the preparation of the objective product of example 1, cesium carbonate was not added and only 0.02mmol of Cu was added2O, otherwise the conditions were the same as in example 1, and the expected product was not finally obtained.
In other embodiments of the heterocyclic dithiocarbamate compounds of the invention, R1In the case of C1-C5 alkyl, a dithiocarbamate compound having a benzothiazole or furan parent ring and a C1-C5 alkyl group as a substituent can be synthesized by the method of example 15 using the corresponding starting materials. According to the previous research on dithiocarbamate compounds (refer to the related content of CN 104844491A), the compound containing a dithiocarbamate structure has various applications in the fields of pesticides, antiviral agents and other medicines, vulcanization accelerators, and synthetic intermediates and chemical raw materials, and the successful synthesis of dithiocarbamate compounds using benzothiazole or furan as a mother ring can provide more possibilities for the selection of raw materials or the optimization of properties in the related fields.
Claims (8)
1. A method for producing a heterocyclic dithiocarbamate compound, which comprises the step of subjecting a heterocyclic compound and thiuram disulfide to a coupling reaction in a solvent in the presence of a base;
the heterocyclic compound has a structure as shown in formula (3) or formula (4):
the thiuram disulfide has the structure shown in formula (5):
in the formulae (3), (4) and (5), R1Selected from H, alkyl, alkoxy, R2Selected from alkyl, X is selected from halogen;
the heterocyclic dithiocarbamate compound has a structure as shown in formula (1) or formula (2):
in the formulae (1) and (2), R1Selected from H, alkyl, alkoxy, R2Selected from alkyl groups.
2. The method for producing a heterocyclic dithiocarbamate compound according to claim 1, wherein the molar ratio of the heterocyclic compound to the thiuram disulfide is not less than 1: 1.
3. A method of preparing a heterocyclic dithiocarbamate compound according to claim 1 wherein the molar ratio of base to thiuram disulfide is greater than 1: 1.
4. The method for producing a heterocyclic dithiocarbamate compound according to any one of claims 1 to 3, wherein the base is at least one of alkali metal carbonate, sodium bicarbonate, potassium phosphate, sodium acetate, potassium acetate, sodium alkoxide, potassium alkoxide, lithium hydroxide, sodium hydroxide, and potassium hydroxide.
5. The method for preparing a heterocyclic dithiocarbamate compound according to claim 1, wherein the temperature of the coupling reaction is 70 to 120 ℃ and the time is 36 to 72 hours.
6. The method for producing a heterocyclic dithiocarbamate compound according to claim 1, wherein the solvent is at least one of dimethylsulfoxide, N-dimethylformamide, toluene and acetonitrile.
7. The method for producing a heterocyclic dithiocarbamate compound according to claim 1, wherein the target product is obtained by obtaining a reaction solution after the coupling reaction, concentrating the reaction solution to obtain a concentrated solution, and subjecting the concentrated solution to thin layer chromatography.
8. The method for preparing a heterocyclic dithiocarbamate compound according to claim 7, wherein the developing solvent used in the thin layer chromatography is a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of (1-10) to (1-10).
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| US2524082A (en) * | 1949-04-06 | 1950-10-03 | Sharples Chemicals Inc | Preparation of thiazolyl and thiazolinyl dithiocarbamates |
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| "A new synthesis of aromatic thiols";Jen Kwan-Yue;《Tetrahedron Letters》;19821231;第23卷(第19期);第2001-4页 * |
| "Copper-Catalyzed C(sp2)−S Coupling Reactions for the Synthesis of Aryl Dithiocarbamates with Thiuram Disulfide Reagents";Zhi-Bing Dong;《Org. Lett.》;20171016;第19卷;第5916-5919页 * |
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