CN113387855A - Method for synthesizing disulfide compound by using visible light and titanocene complex under concerted catalysis - Google Patents
Method for synthesizing disulfide compound by using visible light and titanocene complex under concerted catalysis Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a disulfide compound by concerted catalysis of visible light and a titanocene complex, which utilizes visible light and a reduction quenching agent N, N-diisopropylethylamine or triethylamine to reduce a titanocene (IV) complex into a titanocene (III) complex, inhibit a cross coupling process of a sulfur free radical and an acyl free radical, and promote the self coupling of the sulfur free radical to generate the disulfide compound. The method is green and environment-friendly, has certain substrate applicability, is also beneficial to further exploring the selective coupling process of free radicals, and expands the application of cyclopentadienyl titanium in the field of photocatalysis.
Description
Technical Field
The invention belongs to the technical field of synthesis of disulfide compounds, and particularly relates to a method for selectively synthesizing a disulfide compound by using visible light and a cyclopentadienyl titanium complex to synergistically catalyze sodium sulfinate and benzoyl chloride.
Background
Polysulfide compounds are widely used in various fields. The S-S bond is used as a natural connecting bond and can determine the secondary and tertiary structures of partial polypeptide; the S-S bond also plays an important role in natural products, for example, Lissocliadin 5 has antiviral efficacy; epidithiodiketopiperazines (ETPs) as alkaloids are resistant against viruses, bacteria, malaria and the like. Disulfide compounds are also of widespread interest in anti-medical research: disulfiram (Disulfiam) can be used not only for alcohol withdrawal but also for cancer treatment; polycapamine (polycapamine) exhibits significant in vitro bacteriostatic activity against yeast and candida albicans; ajoene (ajoene) is used as an antithrombotic drug and can effectively prevent platelet aggregation. Polysulfide compounds generally have special odor, such as disulfide compounds having garlic flavor, and other compounds such as trithione and tetrasulfide having milk flavor and beef flavor, and can be used as food additive to play the role of essence and perfume.
The most common method for the synthesis of symmetrical disulfide compounds is the oxidation of thiols, with common oxidizing agents including O2、I2、Br2、H2O2Higher order sulfides, and the like. In addition to oxidizing thiols, a variety of sulfur-containing reagents can also be converted into symmetric disulfide compounds: by using S2Cl2Unsaturated hydrocarbons or reactive aromatic compounds can be converted into disulfide compounds; elemental sulfur can also convert alkyl or aryl halides to symmetrical disulfide compounds; in a heterogeneous phosphine reagent [ PCl3-n(SiO2)n]And the like, and symmetric disulfide compounds can also be synthesized by reducing sulfonyl compounds. The synthesis of disulfide compounds by photocatalytic oxidation of thiols has also received much attention from researchers, An2TeO、CdSe-QD、Eosin Y、TiO2The like can be used as a photocatalyst to realize the conversion of mercaptan under the condition of illumination. The harsh reaction conditions and great pollution are common problems in the synthesis method of the disulfide compound, and even under the green photocatalytic condition, the mercaptan with larger pungent odor is used as a reaction raw material, so that the development of a more green and efficient method for synthesizing the disulfide compound is necessary.
Disclosure of Invention
The invention aims to overcome the defects of the existing disulfide compound synthesis method and provide the disulfide compound synthesis method which is green in reaction process, mild in reaction condition, short in reaction time, safe, efficient and high in yield.
Aiming at the purposes, the invention adopts the scheme that: under the protection of inert gas, adding sodium sulfinate shown in a formula I and benzoyl chloride into an organic solvent, adding bis (pentamethylcyclopentadiene) titanium dichloride, 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester and organic alkali, reacting at room temperature under the irradiation of visible light, and separating and purifying a product after the reaction is finished to obtain a disulfide compound shown in a formula II; the reaction equation is as follows:
in the formula, Ar represents naphthyl, phenyl and C1～C6Alkyl-substituted phenyl, C1～C4Any one of alkoxy substituted phenyl, halogenated phenyl and trifluoromethyl substituted phenyl.
In the synthesis method, the molar ratio of the sodium sulfinate to the benzoyl chloride is preferably 1: 2.5-4.
In the above synthesis method, the amount of diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate added is preferably 2 to 3 times the molar amount of sodium sulfinate.
In the synthesis method, the organic base is N, N-diisopropylethylamine or triethylamine, and preferably, the addition amount of the organic base is 2.5-4 times of the molar amount of sodium sulfinate.
In the synthesis method, the organic solvent is any one of 1, 2-dichloroethane, dichloromethane, N-dimethylformamide, tetrahydrofuran and acetonitrile.
In the synthesis method, the reaction is preferably carried out for 5-8 hours at room temperature under the irradiation of visible light, and an LED lamp with the wavelength of 8-10W 440-470 nm is adopted for the irradiation of the visible light.
The invention has the following beneficial effects:
according to the invention, sodium sulfinate and benzoyl chloride are used as reaction substrates, bis (pentamethylcyclopentadiene) titanium dichloride is used as a catalyst, benzoyl chloride is used to drive 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester and organic base to form a photocatalyst, visible light and a titanocene complex are used for concerted catalysis to realize selective synthesis of a disulfide compound from the sodium sulfinate and the benzoyl chloride, the visible light and a reduction quencher N, N-diisopropylethylamine are used for reducing the titanocene (IV) complex into a titanocene (III) complex, a cross coupling process of a sulfur free radical and an acyl free radical is inhibited, and self coupling of the sulfur free radical is promoted to generate the disulfide compound. The method has the advantages of greenness, safety, easy operation, mild and efficient reaction conditions, short reaction time, high atom economy, higher yield of target products, wide applicability of substrates and wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
Synthesis of p-toluene disulfide of the formula
0.036g (0.2mmol) of sodium p-toluenesulfinate, 0.008g (0.02mmol) of bis (pentamethylcyclopentadienyl) titanium dichloride and (0.4mmol) of diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate were added successively to the reaction tube, gas displacement was carried out on a photocatalytic parallel reactor, then the reaction tube under protection of an argon atmosphere was placed in a glove box, 70. mu.L (0.6mmol) of benzoyl chloride, 100. mu.L (0.6mmol) of N, N-diisopropylethylamine and 2mL of 1, 2-dichloroethane after re-evaporation were added successively, the reaction mixture was stirred at room temperature and irradiated with a 10W 470nm blue LED lamp for 6 hours, and the reaction was detected by TLC. The reaction mixture was concentrated in vacuo to remove 1, 2-dichloroethane, and the residue was purified by flash column chromatography using petroleum ether as eluent to give p-toluene disulfide in 71% yield, and the product had the spectral data:1H NMR(600MHz,CDCl3)δ7.39(d,J＝8.2Hz,4H),7.11(d,J＝8.1Hz,4H),2.33(s,6H)；13C NMR(151MHz,CDCl3)δ139.61,134.12,129.97,128.77,21.22。
example 2
Synthesis of bis (4-methoxyphenyl) disulfide
In this example, the same procedure as in example 1 was repeated except for replacing the sodium p-toluenesulfinate used in example 1 by an equimolar amount of sodium p-methoxybenzenesulfinate to give bis (4-methoxyphenyl) disulfide in a yield of 25%, and the product had the following spectral data:1H NMR(600MHz,CDCl3)δ7.40(d,J＝8.8Hz,4H),6.84(d,J＝8.8Hz,4H),3.80(s,6H)；13C NMR(151MHz,CDCl3)δ161.59,132.85,124.77,116.55,55.15。
example 3
Synthesis of bis (4-fluorophenyl) disulfide having the formula
In this example, the same procedure as in example 1 was repeated except for replacing sodium p-toluenesulfinate used in example 1 by equimolar amount of sodium p-fluorobenzenesulfonate, to give bis (4-fluorophenyl) disulfide in a yield of 32%, the product having spectral data as follows:1H NMR(600MHz,CDCl3)δ7.37(dd,J＝8.6,5.1Hz,4H),6.94(m,4H)；13C NMR(151MHz,CDCl3)δ162.83(d,J＝249.2Hz),132.39(d,J＝4.5Hz),131.50(d,J＝9.1Hz),116.48(d,J＝22.6Hz)。
example 4
Synthesis of bis (4-chlorophenyl) disulfide having the formula
In this example, the p-toluenesulfinic acid used in example 1 was replaced by equimolar amounts of sodium p-chlorobenzenesulfinateSodium, otherwise the same procedure as in example 1 gave bis (4-chlorophenyl) disulfide in 41% yield and the product having the spectral data:1H NMR(600MHz,CDCl3)δ7.33(d,J＝8.6Hz,4H),7.20(d,J＝8.6Hz,4H)；13C NMR(151MHz,CDCl3)δ135.32,133.83,129.53,129.49。
example 5
Synthesis of bis (4-trifluoromethylphenyl) disulfide
In this example, the same procedure as in example 1 was repeated except for replacing the sodium p-toluenesulfinate used in example 1 by an equimolar amount of sodium p-trifluoromethylbenzenesulfinate, to give bis (4-trifluoromethylphenyl) disulfide in a yield of 53%, and the product had spectral data as follows:1H NMR(600MHz,CDCl3)δ7.59(d,J＝8.8Hz,4H),7.57(d,J＝8.6Hz,4H)；13C NMR(151MHz,CDCl3)δ140.99,129.62(q,J＝33.2Hz),126.76,126.32(q,J＝4.5Hz),123.12(q,J＝271.8Hz)。
example 6
Synthesis of bis (4-tert-butylphenyl) disulfide
In this example, the same procedure as in example 1 was repeated except for replacing the sodium p-toluenesulfinate used in example 1 by an equimolar amount of sodium p-tert-butylphenylsulfinate, to give bis (4-tert-butylphenyl) disulfide in a yield of 59%, and the product had spectral data as follows:1H NMR(600MHz,CDCl3)δ7.37(d,J＝8.5Hz,4H),7.26(d,J＝8.6Hz,4H),1.22(s,18H)；13C NMR(151MHz,CDCl3)δ155.28,134.76,127.93,126.31,36.83,31.45。
example 7
Synthesis of o-toluene disulfide of the formula
In this example, the same procedure as in example 1 was repeated except for replacing the sodium p-toluenesulfinate used in example 1 by an equimolar amount of sodium o-toluenesulfinate, to give o-toluenesulfandisulfide in a yield of 70%, and the product had spectral data as follows:1H NMR(600MHz,CDCl3)δ7.58-7.45(m,2H),7.15(ddd,J＝9.9,6.5,2.2Hz,6H),2.43(s,6H)；13C NMR(151MHz,CDCl3)δ137.94,135.04,130.49,128.78,127.49,126.87,19.33。
example 8
Synthesis of bis (2-chlorophenyl) disulfide having the formula
In this example, the same procedure as in example 1 was repeated except for replacing the sodium p-toluenesulfinate used in example 1 by equimolar amounts of sodium o-chlorobenzenesulfonate, to give bis (2-chlorophenyl) disulfide in 50% yield, the product having spectral data as follows:1H NMR(600MHz,CDCl3)δ7.56(dd,J＝7.9,1.6Hz,2H),7.37(dd,J＝7.9,1.4Hz,2H),7.22(td,J＝7.7,1.4Hz,2H),7.16(td,J＝7.6,1.6Hz,2H)；13C NMR(151MHz,CDCl3)δ134.03,131.08,129.38,127.99,127.76,127.38。
example 9
Synthesis of bis (3-chlorophenyl) disulfide having the formula
In this example, the same procedure as in example 1 was repeated except for replacing the sodium p-toluenesulfinate used in example 1 by an equimolar amount of sodium 3-chlorophenylsulfinate, to give bis (3-chlorophenyl) disulfide in a yield of 32%, and the spectral data of the product were:1H NMR(600MHz,CDCl3)δ7.40(t,J＝1.9Hz,2H),7.29-7.25(m,2H),7.18-7.12(m,4H)；13C NMR(151MHz,CDCl3)δ141.15,136.16,130.96,127.76,127.19,125.90。
example 10
Synthesis of bis (naphthalen-2-yl) disulfide of the formula
In this example, the same procedure as in example 1 was repeated except for replacing the sodium p-toluenesulfinate used in example 1 by the equimolar amount of sodium 2-naphthalenesulfinate to give bis (naphthalen-2-yl) disulfide in 51% yield, and the product had the spectral data:1H NMR(600MHz,CDCl3)δ7.90(s,2H),7.70(d,J＝8.7Hz,4H),7.65(d,J＝7.2Hz,2H),7.54(dd,J＝8.6,2.0Hz,2H),7.37(tt,J＝7.0,5.2Hz,4H)；13C NMR(151MHz,CDCl3)δ134.47,133.67,132.70,129.16,127.96,127.66,126.92,126.77,126.43,125.87。
example 11
Synthesis of Diphenyl disulfide of the formula
In this example, replacing the sodium p-toluenesulfinate used in example 1 by an equimolar amount of sodium benzenesulfinate and following the same procedure as in example 1, diphenyl disulfide was obtained in 41% yield and the product had the spectral data:1H NMR(600MHz,CDCl3)δ7.52-7.47(m,4H),7.30(t,J＝7.8Hz,4H),7.24-7.20(m,2H)；13C NMR(151MHz,CDCl3)δ137.22,128.87,127.70,127.34。
example 12
Synthesis of bis (2, 4-dichlorophenyl) disulfide
In this example, the same procedure as in example 1 was repeated except for replacing the sodium p-toluenesulfinate used in example 1 by an equimolar amount of sodium 2, 4-dichlorobenzenesulfinate, to give bis (2, 4-dichlorophenyl) disulfide in a yield of 75%, and the product had spectral data as follows:1H NMR(600MHz,CDCl3)δ7.38(d,J＝8.6Hz,2H),7.31(d,J＝2.2Hz,2H),7.13(dd,J＝8.6,2.2Hz,2H)；13C NMR(151MHz,CDCl3)δ133.75,133.01,132.98,129.80,128.76,127.69。
in example 1, no benzoyl chloride was added, the other steps were the same as in example 1, and no p-toluene disulfide was formed, indicating that benzoyl chloride is a necessary condition for forming a disulfide compound. 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester and organic base can form a photocatalyst for reaction under the drive of benzoyl chloride, and in-situ detection of a gas chromatograph-mass spectrometer shows that a compound 1, 2-diphenylethanedione can be obtained after a titanocene complex is added in the reaction, so that the titanocene complex is supposed to consume a part of benzoyl chloride, so that the cross coupling process of acyl free radicals and sulfur free radicals is inhibited, the self-coupling process of the sulfur free radicals and the free radicals is promoted, and more disulfide compounds are obtained.
Claims (7)
1. A method for synthesizing disulfide compound by the concerted catalysis of visible light and titanocene complex is characterized in that: under the protection of inert gas, adding sodium sulfinate shown in a formula I and benzoyl chloride into an organic solvent, adding bis (pentamethylcyclopentadiene) titanium dichloride, 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester and organic alkali, reacting at room temperature under the irradiation of visible light, and separating and purifying a product after the reaction is finished to obtain a disulfide compound shown in a formula II;
in the formula, Ar represents naphthyl, phenyl and C1～C6Alkyl-substituted phenyl, C1～C4Any of alkoxy-substituted phenyl, halogenophenyl and trifluoromethyl-substituted phenylOne kind of the material is selected;
the organic base is N, N-diisopropylethylamine or triethylamine.
2. The method for the concerted catalytic synthesis of disulfide compounds by visible light and titanocene complexes according to claim 1, characterized in that: the molar ratio of the sodium sulfinate to the benzoyl chloride is 1: 2.5-4.
3. The method for the concerted catalytic synthesis of disulfide compounds by visible light and titanocene complexes according to claim 1, characterized in that: the addition amount of the 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester is 2-3 times of the molar amount of sodium sulfinate.
4. The method for the concerted catalytic synthesis of disulfide compounds by visible light and titanocene complexes according to claim 1, characterized in that: the addition amount of the organic alkali is 2.5-4 times of the molar amount of the sodium sulfinate.
5. The method for the concerted catalytic synthesis of disulfide compounds by visible light and titanocene complexes according to claim 1, characterized in that: the organic solvent is any one of 1, 2-dichloroethane, dichloromethane, N-dimethylformamide, tetrahydrofuran and acetonitrile.
6. The method for the concerted catalytic synthesis of disulfide compounds by visible light and titanocene complexes according to claim 1, characterized in that: and reacting for 5-8 hours at room temperature under the irradiation of visible light.
7. The method for the concerted catalytic synthesis of disulfide compounds by visible light and titanocene complexes according to claim 1, characterized in that: the visible light irradiation adopts 8-10W 440-470 nm LED lamps.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114014790A (en) * | 2021-12-03 | 2022-02-08 | 西安交通大学 | Synthesis method of selenide/thioether compound and synthesized compound |
| CN114957515A (en) * | 2022-06-13 | 2022-08-30 | 北京化工大学 | Preparation method and application of disulfide compound with initiation, volume shrinkage reduction and degradation capabilities for LED photopolymerization |
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| CN109476946A (en) * | 2016-04-13 | 2019-03-15 | 西甘产业股份有限公司 | Optics fadout color-changing composition and its method made and used |
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| CN109476946A (en) * | 2016-04-13 | 2019-03-15 | 西甘产业股份有限公司 | Optics fadout color-changing composition and its method made and used |
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| CN114014790A (en) * | 2021-12-03 | 2022-02-08 | 西安交通大学 | Synthesis method of selenide/thioether compound and synthesized compound |
| CN114957515A (en) * | 2022-06-13 | 2022-08-30 | 北京化工大学 | Preparation method and application of disulfide compound with initiation, volume shrinkage reduction and degradation capabilities for LED photopolymerization |
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