CN110105269B - 1,4-diionic sulfur-containing ylide derivative based on asymmetric alkyne and preparation method thereof - Google Patents
1,4-diionic sulfur-containing ylide derivative based on asymmetric alkyne and preparation method thereof Download PDFInfo
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Abstract
The invention mainly aims to provide a 1,4-diionic sulfur-containing ylide derivative based on asymmetric alkyne and a preparation method thereof, and the method realizes the one-step simple and efficient synthesis of the 1,4-diionic sulfur-containing ylide derivative based on asymmetric alkyne from pyridine, elemental sulfur and asymmetric internal alkyne with different substituents under the condition that dichloromethane is used as a reaction solvent, and also provides a preparation method of the compound.
Description
Technical Field
The invention relates to a novel 1,4-diionic sulfur-containing ylide derivative based on asymmetric alkyne and a synthesis method thereof.
Background
The organic sulfur-containing compounds are closely related to the life of people and have very important application in pesticides, medicines, materials and even foods. Thus, many reagents have been developed to introduce sulfur into organic molecules. For example: in the traditional method, sulfur atoms are introduced by adopting mercaptan and thioether, but the mercaptan and the thioether have unpleasant odor, so that the application of the mercaptan and the thioether is limited; sulfur powder, inorganic sulfur salts and some organic sulfur-containing small molecules are also developed as sulfur sources, but the development and application of the sulfur sources are limited; and these methods mostly adopt transition metal catalysis conditions. In the course of the deficiencies of current research (e.g. malodorous odour, harsh conditions, metal catalysis and ligand requirements, etc.) and the slow development, the development of new sulfur-containing synthons, a simple and easy-to-operate strategy for the synthesis of sulfur-containing compounds is highly desirable. In 2011, the Ayoob Bazgir subject group reported the Synthesis of 1,4-Diionic organic sulfur-containing onium salts (Moafi, L.; ahadi, S.; khavasi, H.R.; bazgir, A.three-Component diesel Synthesis of Stable 1,4-Diionic organic sulfur fuels, synthesis 2011, 1399), but the research thereof has great limitation, and only the reaction of symmetric butynedioic acid esters is researched, because the two same ester groups greatly limit the research value and the application range of the onium salts in the research.
In view of the above, it is important to study how to efficiently synthesize the 1,4-diionic organic sulfur-containing ylide derivatives based on asymmetric alkynes. Because two asymmetric groups can be introduced simultaneously during synthesis, subsequent functionalization can be facilitated without the need to distinguish between the selectivities of the same group. Especially, the fluorine-containing group can be simultaneously introduced into the synthon, and the method has important significance. Since trifluoromethyl can be introduced into the target molecule simultaneously with the Introduction of sulfur atoms, the Introduction of Fluorine can greatly alter the physical, chemical and metabolic stability of the molecule ((a) O 'Hagan, D.; rzepa, H.S. Some innovations of Fluorine in biological Chemistry. Chem. Commun.1997,645. (b) Hiyama, T.; kanie, K.; kusumoto, T.; morizawa, Y.; shimizu, M.Organofluorine Compounds: chemistry and Applications; springer: berlin,2000 (C) Unyama, K.Organofluorine Chemistry; blackwell: oxford,2006 (d) O' Hagan, D.Ursantan, and chemical 308. Soundrien.2008. C.. The present invention solves the above problems well.
Disclosure of Invention
The invention mainly aims to provide a preparation method of 1,4-diionic sulfur-containing ylide based on asymmetric alkyne. The method realizes the simple and efficient synthesis of the 1,4-diion organic sulfur-containing onium salt derivative based on asymmetric alkyne in one step by using pyridine, elemental sulfur and asymmetric internal alkyne with different substituents under the condition of taking dichloromethane as a reaction solvent, and also provides a preparation method of the compound.
The 1,4-diionic organic sulfur-containing ylide derivative based on asymmetric alkyne is a synthon for potentially introducing sulfur into organic molecules, particularly the synthon can simultaneously introduce trifluoromethyl, and the derivative has good application value and prospect in the fields of organic synthesis and pharmaceutical chemistry research.
The compounds described in the invention are compounds of formula I-1, 4-diionic sulfur-containing ylide derivatives based on asymmetric alkynes.
Wherein: r 1 The substituent on the pyridine ring can be hydrogen and 4-methoxy; r 2 Is methyl ester, ethyl ester, tert-butyl ester, trifluoromethyl and benzoyl; r 3 Is methyl ester, ethyl ester, benzoyl, 4-methoxybenzoyl, 4-methylbenzoyl, 4-bromobenzoyl, 4-nitrobenzoyl or furoyl.
The preparation process of the 1,4-diionic organic sulfonium salt derivatives based on asymmetric alkynes of the present invention is as follows:
wherein: r 1 Is a substituent on a pyridine ring, and can be 4-methoxyl; r 2 Methyl ester, ethyl ester, tert-butyl ester, trifluoromethyl and benzoyl; r 3 Is methyl ester, ethyl ester, benzoyl, 4-methoxybenzoyl, 4-methylbenzoyl, 4-bromobenzoyl, 4-nitrobenzoyl and furoyl.
Dissolving a compound shown as a general formula II and a compound shown as a general formula III in a dichloromethane solvent, adding the compound shown as the general formula IV into the reaction system at the temperature of-40 ℃, naturally heating the reaction system to room temperature, and reacting for 24 hours. After the reaction is finished, the target compound I can be obtained by suction filtration, and the target compound I is shown in a general formula II: r 1 Is a substituent on a pyridine ring, and can be 4-methoxy; in the compounds of formula IV: r 2 Is methyl ester, ethyl ester, tert-butyl ester, trifluoromethyl and benzoyl; r 3 Is methyl ester, ethyl ester, benzoyl, 4-methoxybenzoyl, 4-methylbenzoyl, 4-bromobenzoyl, 4-nitrobenzoyl and furoyl.
The preferred 1,4-diionic organic sulfonium salt derivatives based on asymmetric alkynes of the present invention are prepared by using methylene chloride as a solvent.
Further, the preferred preparation method of the invention is as follows: the molar ratio (namely equivalent ratio) of the compound II to the compound III to the compound IV is II: III: iv =1.0, and a dichloromethane solution concentration of 0.2M, i.e. 0.2 moles per liter.
Furthermore, the preferable preparation method of the invention does not need silica gel column chromatography elution, and the target compound I can be obtained by direct suction filtration after the reaction is finished.
The invention relates to a method for synthesizing 1,4-diionic sulfur-containing ylide derivatives based on asymmetric alkyne by using a chemical method for the first time, which greatly widens the variety and range of 1,4-diionic organic sulfur-containing ylides on the basis of the original research and increases the application value of the derivatives in various fields such as chemistry, medicine, materials, food and the like.
The method can easily prepare the 1,4-diionic organic sulfur-containing ylide derivative based on asymmetric alkyne, has easily obtained raw materials, does not use any noble metal reagent in the reaction, does not need to add other reagents except the three reactants, has simple reaction operation, convenient post-treatment and good yield, does not need inert gas protection in the preparation process, and is easy to amplify.
Drawings
FIGS. 1-2 are nuclear magnetic spectra (hydrogen and carbon spectra) of the product I-1 obtained in the examples of the present invention, respectively.
Detailed Description
The invention is illustrated below with reference to specific embodiments.
The preparation method comprises the steps of dissolving a compound II, a compound III and a compound IV in an organic solvent for reaction, and performing suction filtration after the reaction is finished to obtain the target compound. Experiments show that the preferred organic solvent in the invention is dichloromethane, and the best raw material molar ratio is compound II: compound iii: compound iv =1.0, and the optimal concentration of the solution is 0.2M. The following is a preferred example of the invention for preparing the compounds. In all the following examplesNuclear magnetic Spectroscopy measurements were performed in CDCl using a Varian 300, bruker 400, JEOL 400 and Varian 600MHz instrument 3 、(CD 3 ) 2 CO or d 6 -obtained in DMSO. Delta values are internal standard relative values (CDCl) 3 Scaling delta 7.26 1 H NMR and 77.00 13 C NMR；(CD 3 ) 2 CO scaling of delta 2.05 1 H NMR and 29.84 13 C NMR；d 6 -DMSOδ2.50 1 H NMR and 39.52 13 C NMR). High Resolution Mass Spectrometry (HRMS) was obtained using a 4G quadrupole time-of-flight (QTof) mass spectrometer.
Example 1
The reaction scheme of example 1, the structures of the compound IV-1 and compound V-1 and the product I-1 are as follows.
The specific experimental steps are as follows: 791mg (10mmol, 1.0 equivalent) of the compound II-1 and 320mg (10mmol, 1.0 equivalent) of the compound III were dissolved in 50mL of a methylene chloride solvent, 166mg (10mmol, 1.0 equivalent) of the compound IV-1 was added thereto at-40 ℃ and the mixture was allowed to naturally warm to room temperature, followed by reaction for 24 hours. After the reaction is finished, the target compound I-1 can be obtained by suction filtration.
The product I-1 is a yellow solid with a yield of 58%; melting point: 118-119 ℃. 1 H NMR(400MHz,d 6 -DMSO)δ9.00(d,J＝5.6Hz,2H),8.74(t,J＝7.6Hz,1H),8.24(t,J＝7.2Hz,2H),4.18(q,J＝7.2Hz,2H),1.23(t,J＝7.1Hz,3H)； 13 C NMR(100MHz,d 6 -DMSO)δ168.84,167.28,149.66,147.63,128.92,122.4(q,J＝267.3Hz),118.1(q,J＝36.2Hz),61.06,13.93；ESI-HRMS m/z calcd for C 11 H 10 F 3 NO 2 S+H + 278.0457,found 278.0453.
The procedures used in the examples for preparing the other compounds of the present invention (compound I-2 to compound I-10) were the same as in example 1, and the reaction conditions were as follows: dissolving a compound II and a compound III in a dichloromethane solvent in equal proportion, adding a compound IV in equal molar ratio into the reaction system at the temperature of-40 ℃, naturally heating the reaction system to room temperature, and reacting for 24 hours.
The resulting product structure and data are characterized as follows:
the product I-2 is a yellow solid with a yield of 55%; melting point: at the temperature of between 146 and 147 ℃. 1 H NMR(400MHz,CDCl 3 )δ8.83–8.76(m,2H),8.41–8.39(m,1H),8.11–8.04(m,2H),8.04–7.96(m,2H),7.54–7.49(m,1H),7.47–7.40(m,2H),3.51(s,3H)； 13 C NMR(100MHz,d 6 -DMSO)δ190.92,186.05,160.33,148.80,146.03,135.56,132.33,129.18,128.28,127.89,125.30,51.25；ESI-HRMS m/z calcd for C 16 H 13 NO 3 S+H + 300.0689,found 300.0686.
The product I-3 is a yellow solid with a yield of 58%; melting point: 120-121 ℃. 1 H NMR(300MHz,CDCl 3 )δ8.81–8.74(m,2H),8.44–8.37(m,1H),8.06–8.95(m,4H),6.96–6.89(m,2H),3.86(s,3H),3.52(s,3H)； 13 C NMR(100MHz,d 6 -DMSO)δ190.24,186.49,162.42,160.20,148.82,145.91,131.32,128.44,127.81,125.18,113.47,55.46,51.14；ESI-HRMS m/z calcd for C 17 H 15 NO 4 S+H + 330.0795,found 330.0791.
The product I-4 was a yellow solid with a yield of 57%; melting point: 166-167 ℃. 1 H NMR(400MHz,d 6 -DMSO)δ9.05(d,J＝5.6Hz,2H),8.68–8.61(m,1H),8.23–8.15(m,2H),7.86(d,J＝8.0Hz,2H),7.27(d,J＝7.6Hz,1H),3.39(s,3H),2.37(s,3H)； 13 C NMR(100MHz,d 6 -DMSO)δ190.70,186.31,160.19,148.74,145.85,142.33,133.06,129.20,128.73,127.75,125.15,51.09,21.18；ESI-HRMS m/z calcd for C 17 H 15 NO 3 S+H + 314.0845,found 314.0841.
The product I-5 is a yellow solid with a yield of 49%; the melting point is 149-150 ℃. 1 H NMR(400MHz,d 6 -DMSO)δ9.07(d,J＝5.6Hz,2H),8.70–8.63(m,1H),8.25–8.18(m,2H),7.92–7.86(m,2H),7.70–7.64(m,2H),3.41(s,3H)； 13 C NMR(100MHz,d 6 -DMSO)δ189.62,185.11,160.26,148.67,146.02,134.73,131.26,131.08,127.81,126.10,125.24,51.22；ESI-HRMS m/z calcd for C 16 H 12 BrNO 3 S+H + 377.9794,found 377.9792.
The product I-6 is a yellow solid with a yield of 76%; melting point:>200℃. 1 H NMR(400MHz,d 6 -DMSO)δ9.12(d,J＝4.8Hz,2H),8.68(t,J＝8.0Hz,1H),8.29(d,J＝8.8Hz,2H),8.27–8.19(m,4H),3.42(s,3H)； 13 C NMR(100MHz,d 6 -DMSO)δ188.56,184.22,160.54,149.54,148.70,146.32,140.77,130.46,128.02,125.46,123.59,51.53；ESI-HRMS m/z calcd for C 16 H 12 N 2 O 5 S+H + 345.0540,found345.0537.
the product I-7 is a yellow solid with a yield of 41%; melting point: 138-139 ℃. 1 H NMR(400MHz,d 6 -DMSO)δ9.03(d,J＝4.8Hz,2H),8.65(t,J＝7.2Hz,1H),8.19(t,J＝7.2Hz,2H),7.93(s,1H),7.26(d,J＝3.2Hz,1H),6.66(d,J＝1.6Hz,1H),3.43(s,3H)； 13 C NMR(100MHz,d 6 -DMSO)δ184.46,180.27,160.24,151.03,148.78,146.93,146.08,127.94,125.22,118.58,112.24,51.37；ESI-HRMS m/z calcd for C 14 H 11 NO 4 S+H + 290.0482,found 290.0480.
The product I-8 is a yellow solid with a yield of 61%; melting point: 137-138 ℃. 1 H NMR(400MHz,CDCl 3 )δ8.83(d,J＝5.6Hz,2H),8.41–8.36(m,1H),8.08–8.02(m,2H),8.00–7.93(m,2H),7.54–7.49(m,1H),7.47–7.40(m,2H),1.17(s,9H)； 13 C NMR(100MHz,d 6 -DMSO)δ190.08,183.52,159.61,148.83,145.72,135.73,132.31,129.36,128.13,127.62,127.05,81.02,27.60；ESI-HRMS m/z calcd for C 19 H 19 NO 3 S+H + 342.1158,found 342.1155.
The product I-9 was a yellow solid with a yield of 54%; melting point: 121-122 ℃. 1 H NMR(400MHz,d 6 -DMSO)δ8.70(d,J＝7.2Hz,2H),7.63(d,J＝7.2Hz,2H),4.20–4.10(m,5H),1.22(t,J＝7.2Hz,2H)； 13 C NMR(100MHz,d 6 -DMSO)δ171.8,168.6,167.5,150.8,122.6(q,J＝267.3Hz),116.8(q,J＝35.8Hz),114.1,60.9,58.4,14.0；ESI-HRMS m/z calcd for C 12 H 12 F 3 NO 3 S+H + 308.0563,found308.0560.
The product I-10 is a yellow solid with a yield of 48%; melting point: 169 to 170 ℃. 1 H NMR(400MHz,d 6 -DMSO)δ8.83(d,J＝3.6Hz,2H),8.00–7.92(m,2H),7.66–7.60(m,2H),7.58–7.52(m,1H),7.50–7.44(m,2H),4.14(s,3H),3.39(s,3H)； 13 C NMR(100MHz,d 6 -DMSO)δ191.0,185.9,170.7,160.8,150.1,135.6,132.2,129.2,128.2,123.9,113.0,58.1,51.10；ESI-HRMS m/z calcd for C 17 H 15 NO 4 S+H + 330.0795,found 330.0791.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, improvement and the like made within the content and principle of the present invention shall be included in the protection scope of the present invention.
Claims (4)
1. A preparation method of 1,4-diionic sulfur-containing ylide derivatives based on asymmetric alkyne is provided, the 1,4-diionic sulfur-containing ylide derivatives based on asymmetric alkyne has a structure shown as I, and R 2 ，R 3 Are different electron withdrawing groups;
wherein: r 1 The substituent on the pyridine ring can be hydrogen and 4-methoxy; r 2 Is methyl ester, ethyl ester, tert-butyl ester, trifluoromethyl and benzoyl; r 3 Is methyl ester, ethyl ester, benzoyl, 4-methoxybenzoyl or 4-methylbenzoyl4-bromobenzoyl, 4-nitrobenzoyl and furoyl;
the preparation method is characterized by comprising the following steps:
preparation of the target compound i: dissolving a compound shown as a general formula II and a compound shown as a general formula III in a dichloromethane solvent, adding the compound shown as a general formula IV into the reaction system at the temperature of minus 40 ℃, naturally heating the reaction system to room temperature, and reacting for 24 hours; after the reaction is finished, the target compound I can be obtained by suction filtration, and the target compound I is shown in a general formula II: r 1 The substituent on the pyridine ring can be hydrogen and 4-methoxy; r 2 Is methyl ester, ethyl ester, tert-butyl ester, trifluoromethyl and benzoyl; r 3 Is methyl ester, ethyl ester, benzoyl, 4-methoxybenzoyl, 4-methylbenzoyl, 4-bromobenzoyl, 4-nitrobenzoyl and furoyl.
2. The method for preparing asymmetric alkyne-based 1,4-diionic sulfur-containing ylide derivatives as claimed in claim 1, wherein no additional reagent is required other than the three reactants of the compound represented by the general formula II, the compound represented by the general formula III and the compound represented by the general formula IV; and (3) taking dichloromethane as a reaction solvent, and performing suction filtration after the reaction is finished to obtain the target compound I.
3. The process for the preparation of unsymmetrical alkyne-based 1,4-diionic sulfur-containing ylium salt derivatives as set forth in claim 1, wherein the molar ratio of compound ii, compound iii and compound iv is ii: III: iv = 1.0.
4. The preparation method of the asymmetric alkyne-based 1,4-diionic organic sulfur-containing ylide derivative as claimed in claim 1, wherein the target compound I can be obtained by directly suction filtering after the reaction without silica gel column chromatography elution.
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