CN114716356B - Method for synthesizing isothiocyanate compounds by rhodium catalysis - Google Patents
Method for synthesizing isothiocyanate compounds by rhodium catalysis Download PDFInfo
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- CN114716356B CN114716356B CN202210231448.9A CN202210231448A CN114716356B CN 114716356 B CN114716356 B CN 114716356B CN 202210231448 A CN202210231448 A CN 202210231448A CN 114716356 B CN114716356 B CN 114716356B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/28—Isothiocyanates having isothiocyanate groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
- C07C331/22—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for synthesizing isothiocyanate compounds by rhodium catalysis, which uses rhodium acetylacetonate Rh (acac) 3 In the presence of silver salt, halogenated hydrocarbon and thiocyanate are dissolved in DMF as a catalyst to react, and the isothiocyanate compound as a target product is obtained after separation and purification. Compared with the prior art, the synthesis method is simple and green, and the isothiocyanate compound is directly synthesized by using the halogenated hydrocarbon and the stable inorganic salt thiocyanide which are cheap and easy to obtain.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and relates to a method for synthesizing isothiocyanate compounds by rhodium catalysis.
Background
Isothiocyanate and its derivative are important raw materials for synthesizing nitrogen-containing or sulfur-containing heterocyclic compounds, and many natural and artificially synthesized isothiocyanate have strong biological activities, such as antibacterial, anti-inflammatory, antioxidant, anticancer, insecticidal, herbicidal and other activities, and have been widely used in the preparation of industrial products such as medicines, pesticides, dyes and the like. The traditional synthesis method of the compound is to take primary amine as a raw material and react the primary amine with thiophosgene or carbon disulfide or phenyl thiochloroformate to obtain isothiocyanate, but the reactions generally use reagents with higher toxicity as raw materials, have higher requirements on production equipment, have higher danger in the production process, have more severe reaction conditions and have higher requirements on high temperature and longer reaction time (Agrochemicals 2009,48,322;Synthesis 2013,1667;Chin.J.Org.Chem.2015,35,1999). In addition, a method for synthesizing an alkenyl thiocyanate derivative is disclosed in patent CN106167459 a. The method comprises the following steps: adding alkyne halogen and thiocyanate as raw materials into a reaction container, heating for reaction under the condition that silver salt is used as a catalyst and an organic solvent is used as a solvent, cooling the obtained reaction liquid to room temperature after the reaction is finished, and purifying to obtain the alkenyl thiocyanate derivative. The method uses alkyne halogen as a raw material, and the synthesis of the compound is extremely difficult, the synthesis method is rare, the yield is low, and the application range is narrow, so that the application of the method is greatly limited.
Therefore, in general, a new synthetic route is developed, the coupling of cheap halohydrocarbon and stable thiocyanate serving as raw materials is realized by using a transition metal catalysis method, and the direct synthesis of isothiocyanate compounds has very important research significance.
Disclosure of Invention
The invention aims to provide a method for synthesizing isothiocyanate compounds by rhodium catalysis.
The aim of the invention can be achieved by the following technical scheme:
rhodium catalyzed synthesis of isothiocyanate compounds with rhodium acetylacetonate Rh (acac) 3 In the presence of silver salt, halogenated hydrocarbon and thiocyanate are dissolved in DMF as a catalyst to react, and the isothiocyanate compound as a target product is obtained after separation and purification.
Further, the molar ratio of the rhodium acetylacetonate, the silver salt, the halogenated hydrocarbon and the thiocyanate is (0.02-0.05): (0.06-0.10): 1.0: (1.2-1.5).
Further, the halogenated hydrocarbon is at least one of bromobenzene, 4-methyl chlorobenzene, 2-methyl chlorobenzene, 3-methyl iodobenzene, 4-dimethylamino bromobenzene, 4-nitro bromobenzene, allyl chloride and p-fluoro iodobenzene.
Further, the silver salt is silver triflate AgOTf and silver nitrate AgNO 3 At least one of them.
Further, the thiocyanate is at least one of NaSCN and KSCN.
Further, the reaction temperature is 50 to 80 ℃.
Further, the reaction time is 5-10 h.
Further, column chromatography separation is adopted for separation and purification.
Compared with the prior art, the invention has the following advantages:
(1) The synthesis method is simple and green, and the isothiocyanate compound is directly synthesized by using the halogenated hydrocarbon and the stable inorganic salt thiocyanide which are cheap and easy to obtain.
(2) The invention has mild reaction condition and high yield.
(3) The invention uses rhodium acetylacetonate Rh (acac) which is cheap and easy to obtain and has stable property 3 Is a catalyst, green and economical.
(4) The invention has good substrate universality, thereby being better convenient for application.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise indicated, the starting materials or processing techniques are all conventional commercially available in the art.
Example 1:
bromobenzene (1.0 mmol), naSCN (1.2 mmol) and Rh (acac) catalyst were sequentially added to the reaction tube 3 (0.03 mmol) and AgOTf (0.06 mmol), and then adding DMF 2mL of solvent, reacting for 6 hours at 60 ℃, concentrating the reaction liquid after the reaction, and separating by column chromatography to obtain the corresponding product, wherein the separation yield is 90%. 1 H NMR(400MHz,CDCl 3 ) Delta 7.37 (t, j=7.0 hz,2 h), 7.30 (d, j=7.5 hz,1 h), 7.25 (d, j=7.5 hz,2 h). Theoretical value of HRMS C 7 H 5 NS(M) + :135.0143, actual measurement: 135.0149.
example 2:
4-methyl-chlorobenzene (1.0 mmol), naSCN (1.3 mmol), and catalyst Rh (acac) were successively introduced into a reaction tube 3 (0.02 mmol) and AgOTf (0.06 mmol), and then adding DMF 2mL of solvent, reacting for 10 hours at 80 ℃, concentrating the reaction solution after the reaction, and separating by column chromatography to obtain the corresponding product, wherein the separation yield is 92%. 1 H NMR(400MHz,CDCl 3 ) Delta 7.12 (d, j=8.5 hz, 2H), 7.08 (d, j=8.5 hz, 2H), 2.37 (s, 3H). Theoretical value of HRMS C 8 H 7 NS(M) + :149.0299, actual measurement: 149.0302.
example 3:
2-methyl-chlorobenzene (1.0 mmol), KSCN (1.5 mmol), and catalyst Rh (acac) were successively introduced into a reaction tube 3 (0.05 mmol) and AgOTf (0.10 mmol), and then adding DMF 2mL of solvent, reacting for 5 hours at 70 ℃, concentrating the reaction solution after the reaction, and separating by column chromatography to obtain the corresponding product, wherein the separation yield is 88%. 1 H NMR(400MHz,CDCl 3 ) Delta 7.27 (d, j=8.0 hz, 1H), 7.15 (d, j=8.0 hz, 1H), 7.09-7.03 (m, 2H), 2.39 (s, 3H). Theoretical value of HRMS C 8 H 7 NS(M) + :149.0299, actual measurement: 149.0303.
example 4:
3-methyl iodobenzene (1.0 mmol), KSCN (1.3 mmol) and catalyst Rh (acac) were successively introduced into a reaction tube 3 (0.05mmol)、AgNO 3 (0.08 mmol) and 2mL of DMF as solvent were added and reacted at 50℃for 10 hours, and after the completion of the reaction, the reaction mixture was concentrated and separated by column chromatography to give the corresponding product in a yield of 91%. 1 H NMR(400MHz,CDCl 3 ) Delta 7.33-7.25 (m, 3H), 7.07 (s, 1H), 2.32 (s, 3H). Theoretical value of HRMS C 8 H 7 NS(M) + :149.0299, actual measurement: 149.0294.
example 5:
4-dimethylaminobromobenzene (1.0 mmol), KSCN (1.4 mmol) and Rh (acac) as catalysts were added sequentially to the reaction tube 3 (0.04mmol)、AgNO 3 (0.08 mmol) and DMF 2mL were added and reacted at 60℃for 9 hours, after the reaction was completed, the reaction mixture was concentrated, and the corresponding product was isolated by column chromatography in 93% yield. 1 H NMR(400MHz,CDCl 3 ) Delta 7.12 (d, j=8.0 hz, 2H), 6.65 (d, j=8.0 hz, 2H), 2.92 (s, 6H). Theoretical value of HRMS C 9 H 10 N 2 S(M) + :178.0565, actual measurement: 178.0561.
example 6:
4-Nitrobromobenzene (1.0 mmol), KSCN (1.2 mmol) and Rh (acac) as catalysts were added sequentially to the reaction tube 3 (0.02mmol)、AgNO 3 (0.07 mmol) was further added with 2mL of DMF and reacted at 50℃for 8 hours, and after the completion of the reaction, the reaction mixture was concentrated and separated by column chromatography to give the corresponding product in a yield of 91%. 1 H NMR(400MHz,CDCl 3 ) Delta 8.29 (d, j=8.0 hz,2 h), 7.41 (d, j=8.0 hz,2 h). Theoretical value of HRMS C 7 H 4 N 2 O 2 S(M) + :179.9993, actual measurement: 179.9995.
example 7:
allyl chloride (1.0 mmol), KSCN (1.3 mmol), and catalyst Rh (acac) were added sequentially to the reaction tube 3 (0.04 mmol) and AgOTf (0.10 mmol), and then adding DMF 2mL of solvent, reacting at 60 ℃ for 6 hours, concentrating the reaction liquid after the reaction, and separating by column chromatography to obtain the corresponding product, wherein the separation yield is 87%. 1 H NMR(400MHz,CDCl 3 ) Delta 5.34 (s, 2H), 5.12 (s, 1H), 3.22 (d, j=7.5 hz, 2H). Theoretical value of HRMS C 4 H 5 NS(M) + :99.0143, actual measurement: 99.0141.
example 8:
parafluoroiodobenzene (1.0 mmol), naSCN (1.4 mmol) and Rh (acac) as catalysts were sequentially added to the reaction tube 3 (0.02mmol)、AgNO 3 (0.06 mmol) and 2mL of DMF as solvent were added and reacted at 50℃for 7 hours, the reaction mixture was concentrated after the completion of the reaction, and the corresponding product was isolated by column chromatography in a yield of 95%. 1 H NMR(400MHz,CDCl 3 ) δ 7.230-7.24 (m, 2H), 7.09 (d J =8.0hz, 2H). Theoretical value of HRMS C 7 H 4 FNS(M) + :153.0048, actual measurement: 153.0052.
the previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (7)
1. A method for synthesizing isothiocyanate compounds by rhodium catalysis is characterized in that rhodium acetylacetonate Rh (acac) is used 3 In the presence of silver salt, halogenated hydrocarbon and thiocyanate are dissolved in DMF as a catalyst to react, and the isothiocyanate compound serving as a target product is obtained after separation and purification;
the halohydrocarbon is at least one of bromobenzene, 4-methyl chlorobenzene, 2-methyl chlorobenzene, 3-methyl iodobenzene, 4-dimethylamino bromobenzene, 4-nitro bromobenzene, allyl chloride and p-fluoro iodobenzene;
the silver salt is at least one of silver triflate and silver nitrate;
the thiocyanate is at least one of sodium thiocyanate and potassium thiocyanate.
2. The method for synthesizing isothiocyanate compounds by rhodium catalysis according to claim 1, wherein the molar ratio of rhodium acetylacetonate, silver salt, halogenated hydrocarbon and thiocyanate is (0.02-0.05): (0.06-0.10): 1.0: (1.2-1.5).
3. The method for synthesizing isothiocyanate compounds by rhodium catalysis according to claim 1, wherein the molar ratio of the rhodium acetylacetonate, the silver salt, the halogenated hydrocarbon and the thiocyanate is 0.03:0.06:1.0:1.2.
4. the method for synthesizing isothiocyanate compounds by rhodium catalysis according to claim 1, wherein the molar ratio of the rhodium acetylacetonate, the silver salt, the halogenated hydrocarbon and the thiocyanate is 0.02:0.06:1.0:1.3.
5. the method for synthesizing isothiocyanate compounds by rhodium catalysis according to claim 1, wherein the reaction temperature is 50-80 ℃.
6. The method for synthesizing the isothiocyanate compound under the catalysis of rhodium according to claim 1, wherein the reaction time is 5-10 h.
7. The method for synthesizing isothiocyanate compounds by rhodium catalysis according to claim 1, wherein the separation and purification are carried out by column chromatography.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6812348B1 (en) * | 1999-11-15 | 2004-11-02 | Dsm Fine Chemicals Austria Nfg Gmbh & Co Kg | Method for producing 2-chloro-5-chloromethyl-1,3-thiazol |
| CN109734641A (en) * | 2019-01-15 | 2019-05-10 | 华东师范大学 | The synthetic method of a kind of isocyanate derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6812348B1 (en) * | 1999-11-15 | 2004-11-02 | Dsm Fine Chemicals Austria Nfg Gmbh & Co Kg | Method for producing 2-chloro-5-chloromethyl-1,3-thiazol |
| CN109734641A (en) * | 2019-01-15 | 2019-05-10 | 华东师范大学 | The synthetic method of a kind of isocyanate derivative |
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