CN110627693B - Allyl sulfone compound and preparation method and application thereof - Google Patents

Allyl sulfone compound and preparation method and application thereof Download PDF

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CN110627693B
CN110627693B CN201910983148.4A CN201910983148A CN110627693B CN 110627693 B CN110627693 B CN 110627693B CN 201910983148 A CN201910983148 A CN 201910983148A CN 110627693 B CN110627693 B CN 110627693B
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sulfinic acid
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解沛忠
孙作恋
罗德平
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Nanjing Tech University
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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Abstract

The invention discloses an allyl sulfone compound and a preparation method and application thereof. Sequentially adding allyl alcohol, sulfinic acid, palladium tetrakis (triphenylphosphine) and calcium bis (trifluoromethylsulfonyl) imide into a reaction solvent in an inert gas atmosphere, and stirring and reacting for 12-48 h at the temperature of 30 ℃; wherein the equivalent ratio of allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide is 1: (1.5-2): (1-3%): (5-10%); and removing the reaction solvent in the reaction liquid, and then purifying to obtain the allyl sulfone compound. The preparation method has high economy and wide applicable substrate range; in addition, the obtained allyl sulfone compound has potential pharmaceutical activity and biological activity and is an important skeleton widely existing in biological and pharmaceutical active molecules.

Description

Allyl sulfone compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to an allyl sulfone compound and a preparation method and application thereof.
Background
Sulfones play an important role in organic synthesis and are also widely found in many biologically active natural products and in some well-established drugs (e.g., eletriptan ([2H ] -SB-3CT) for the treatment of migraine, MMP-9 inhibitors for the treatment of prostate cancer).
Furthermore, the widespread distribution of the allylsulfone backbone in biologically and pharmaceutically active molecules (e.g. anticancer agents, cysteine protease inhibitors, antibacterial agents, herbicides) has also attracted considerable attention. Therefore, the development of synthetic methods for allyl sulfone has attracted considerable attention in the synthetic community. Existing synthetic methods include the use of transition metal catalyzed (oxidation) -cross-coupling reactions and hydrosulfiding by the use of highly reactive allylic substrates and sulfinyl nucleophiles. However, from an environmental and economic point of view, it is very attractive to develop an energy-saving and efficient green synthesis method using nontoxic, inexpensive, readily available and relatively harmless raw materials, and particularly to a method using allyl alcohol as a raw material and water as a byproduct.
Disclosure of Invention
The invention aims to provide an allyl sulfone compound.
The invention further aims to provide a preparation method of the allyl sulfone compound.
The invention further aims to provide application of the allyl sulfone compound.
The invention is realized by the following steps that the chemical structural formula of the compound is shown as the following formula (I):
Figure BDA0002235859010000021
in the above formula (I), R1Is aryl or alkyl; r2～R5Any of hydrogen radicals, aryl radicals and alkyl radicals.
The invention further discloses a preparation method of the allyl sulfone compound, which comprises the following steps:
(1) sequentially adding allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide into a reaction solvent in an inert gas atmosphere, and stirring and reacting for 12-48 h at the temperature of 30 ℃; wherein the equivalent ratio of allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide is 1: (1.5-2): (1-3%): (5-10%);
(2) and removing the reaction solvent in the reaction liquid, and then purifying to obtain the allyl sulfone compound.
Preferably, in step (1), the inert gas is argon;
the allyl alcohol comprises primary cinnamyl alcohol allyl alcohol, secondary allyl alcohol and tertiary allyl alcohol;
the sulfinic acid is any one of phenyl sulfinic acid, 3-methyl phenyl sulfinic acid, methyl sulfinic acid, cyclohexane sulfinic acid, camphor sulfinic acid and benzyl sulfinic acid;
the reaction solvent is any one of 1, 2-dichloroethane, tetrahydrofuran and N, N-dimethylacetamide.
Preferably, the allyl alcohol is any one of cinnamyl alcohol, p-methyl cinnamyl alcohol, p-fluoro cinnamyl alcohol, trans-2-octen-1-ol, 1-phenylprop-2-en-1-ol, 2-methyl-1-phenyl-2-propen-1-ol and 2-phenylbut-3-en-2-ol.
Preferably, the allyl alcohol is 1-phenylprop-2-en-1-ol.
Preferably, the synthesis method of the 1-phenylprop-2-en-1-ol comprises the following steps:
A. adding benzaldehyde into a tetrahydrofuran solvent at room temperature to obtain a solution 1; adding a vinyl Grignard reagent into the solution 1 at 0 ℃, and stirring for 2 hours to obtain a reaction mixture; wherein the ratio of the quantities of the benzaldehyde, the vinyl Grignard reagent and the tetrahydrofuran solvent is 10 mmol: (15-20) mmol: (10-20) mL;
B. the reaction mixture was quenched by addition to saturated ammonium chloride, extracted 3 times with ethyl acetate, the organic phases combined, dried over anhydrous magnesium sulfate, the solvent removed with a rotary evaporator, and the residue purified by column silica gel chromatography with petroleum ether and ethyl acetate (PE/EA ═ 50:1 to 10:1) to give 1-phenylpropan-2-en-1-ol as a pale yellow liquid.
Preferably, the sulfinic acid is phenyl sulfinic acid; the reaction solvent is N, N-dimethylacetamide.
Preferably, the method for synthesizing the phenylsulfinic acid comprises the following steps:
A. dissolving sodium benzene sulfinate in water, adding tert-butyl methyl ether, slowly adding hydrochloric acid with the mass fraction of 36-38% within 2 minutes, and stirring the mixture for 10 minutes; wherein the ratio of the quantities of the sodium benzene sulfinate, the hydrochloric acid, the water and the tert-butyl methyl ether is 17.5 mmol: (1-2) mL: (10-15) mL: (5-10) mL;
B. the mixture was transferred to a separatory funnel, the aqueous layer was removed, the organic layer was concentrated on a rotary evaporator until the solvent disappeared, and the obtained white solid was dried in vacuo to give benzenesulfinic acid.
Preferably, in step (2), the reaction solvent is removed by extraction with EA (50mL x 3 times) followed by vacuum rotary evaporation; the purification adopts a thin layer chromatography method, namely, a system mixture is uniformly coated on a silica gel plate, the silica gel plate is dried by a blower, the silica gel plate is placed in a spreading cylinder containing a developing agent PE/EA (2: 1-3: 1), when a solvent reaches the front edge of the solvent, silica gel powder at the position of a product is scraped off under the detection of an ultraviolet lamp, EA (60mL for 3 times) is washed off in a sand core funnel instrument to obtain the product, and the developing agent system is petroleum ether/ethyl acetate (PE/EA: 2: 1-3: 1).
The invention further discloses application of the allyl sulfone compound in serving as a skeleton of bioactive molecules and pharmaceutical active molecules.
The invention discloses a preparation method and application of an allyl sulfone compound. The allyl alcohol raw material, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide are sequentially added into a reaction solvent, stirred under the condition of argon and 30 ℃ for catalytic reaction, and the obtained reaction liquid is purified after the reaction solvent is removed to obtain the allyl sulfone compound. The synthesis method has high economy and wide applicable substrate range, and the obtained allyl sulfone compound has potential pharmaceutical activity and biological activity and is an important skeleton widely existing in biological and pharmaceutical active molecules.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) part of the raw materials used by the method is low-cost commercial cinnamyl alcohol raw materials, and the obtained by-product is only water, so that the method is high in atom economy, green and environment-friendly;
(2) the method of the invention needs not very harsh conditions, the substrate has wide application range, for example, allyl alcohol can be various substituted phenyl, heterocycle and alkyl;
(3) the process of the invention is applicable to different types of allyl alcohol;
(4) the allyl sulfone compound has wide application prospect in biologically and pharmaceutically active molecules (such as anticancer agents, cysteine protease inhibitors, antibacterial agents and herbicides).
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of (cinnamoylsulfonyl) benzene;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of (cinnamoylsulfonyl) benzene.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Adding 10mmol of benzaldehyde into 10mL of tetrahydrofuran solvent at room temperature to obtain a solution 1; slowly adding 15mmol of vinyl Grignard reagent into the solution 1 at the temperature of 0 ℃, and stirring for 2 hours to obtain a reaction mixture; the reaction equation is:
Figure BDA0002235859010000051
(2) the reaction mixture was quenched by addition to saturated ammonium chloride solution, extracted 3 times with ethyl acetate, the organic phases combined, dried over anhydrous magnesium sulfate, the solvent removed with a rotary evaporator, and the residue purified by column silica gel chromatography with petroleum ether and ethyl acetate (PE/EA ═ 50:1 to 10:1) to give 1-phenylpropan-2-en-1-ol as a pale yellow liquid.
Example 2
This example is substantially the same as example 1 above except that, in step (1), 10mmol of benzaldehyde was added to 20mL of tetrahydrofuran solvent to give a solution 1; at 0 deg.C, 20mmol of vinyl Grignard reagent was slowly added to solution 1.
Example 3
(1) Dissolving 17.5mmol of sodium benzene sulfinate in 10mL of water, adding 5mL of tert-butyl methyl ether, slowly adding 1.6mL of concentrated hydrochloric acid with the mass fraction of 36-38% within 2 minutes, and stirring the mixture for 30 minutes to obtain a reaction mixture; the reaction equation is:
Figure BDA0002235859010000052
(2) transferring the mixed solution to a separating funnel, and removing a water layer; the organic layer was concentrated on a rotary evaporator until the solvent disappeared and the white solid obtained was dried in vacuo to give the benzenesulfinic acid.
Example 4
This example is substantially the same as example 3 above, except that in step (1), 17.5mmol of sodium benzenesulfinate was dissolved in 15mL of water, 10mL of t-butyl methyl ether was added, 2mL of concentrated hydrochloric acid with a mass fraction of 36-38% was slowly added over 2 minutes, and the mixture was stirred for another 30 minutes to obtain a reaction mixture.
Example 5
(1) In a 10mL Schlenk tube, under argon atmosphere, 1-phenylprop-2-en-1-ol (0.3mmol), benzenesulfinic acid (0.45mmol), tetrakis (triphenylphosphine) palladium (1 mol%), calcium bis (trifluoromethylsulfonyl) imide (5 mol%) was added with N, N-dimethylacetamide (2mL) and stirred at 30 ℃ for reaction, the equation is:
Figure BDA0002235859010000061
(2) after completion of the reaction monitored by TLC, the reaction solution was extracted with EA extraction (50mL × 3 times), and the solvent was removed by vacuum rotary evaporator;
uniformly coating the system mixture on a silica gel plate, drying by using a blower, and putting the silica gel plate into a solution containing a developing agent PE/EA (2-3): 1, scraping silica gel powder at the product position under the detection of an ultraviolet lamp when the solvent reaches the front edge of the solvent, and washing the silica gel powder in a sand core funnel instrument by using EA (60mL for 3 times) to obtain a product, wherein a developing agent system is petroleum ether/ethyl acetate (PE/EA is 2: 1-3: 1), the product is white solid (cinnamyl sulfonyl) benzene, and the yield is 68%.
Example 6
(1) In a 10ml Schlenk tube, under argon atmosphere, cinnamyl alcohol (0.3mmol), benzene sulfinic acid (0.45mmol), tetrakis (triphenylphosphine) palladium (1 mol%), calcium bis (trifluoromethylsulfonyl) imide (5 mol%), N-dimethylacetamide (2ml) was added, and the reaction was stirred at 30 ℃ according to the equation:
Figure BDA0002235859010000062
(2) after TLC monitoring reaction, the reaction solution was extracted, the solvent was removed by vacuum rotary evaporator, and the product was isolated by thin layer chromatography with a white solid (cinnamyl sulfonyl) benzene as the developing agent in the petroleum ether/ethyl acetate system in 93% yield.
The product (cinnamoylsulfonyl) benzene obtained in this example was subjected to a nuclear magnetic resonance test, and as shown in fig. 1 to 2, fig. 1 is a nuclear magnetic resonance hydrogen spectrum of (cinnamoylsulfonyl) benzene, and fig. 2 is a nuclear magnetic resonance carbon spectrum of (cinnamoylsulfonyl) benzene.
Example 7
(1) The embodiment is different from embodiments 5 to 6 in that: the allyl alcohol starting material used was 1- (4- (trimethylsilyl) phenyl) prop-2-en-1-ol, the reaction equation is:
Figure BDA0002235859010000071
(2) after TLC monitoring reaction was complete, the reaction was extracted, solvent was removed by vacuum rotary evaporator and the product was isolated by thin layer chromatography using petroleum ether/ethyl acetate system as developing agent in 80% yield as white solid (E) -trimethyl (4- (3- (phenylsulfonyl) prop-1-en-1-yl) phenyl) silane.
In the technical scheme provided by the applicant, the (cinnamyl sulfonyl) benzene prepared by the method has potential pharmaceutical activity and biological activity.
Application example 1
This example is the same as example 6 above, except that cinnamyl alcohol (6mmol), 4-ethynylanisole (7.5mmol), tetrakis (triphenylphosphine) palladium (1 mol%), calcium bis (trifluoromethylsulfonyl) imide (5 mol%) were added to a 50mL reaction tube followed by addition of N, N-dimethylacetamide (10mL) to give (cinnamyl sulfonyl) benzene 1.3g, 85% yield.
Application example 2
The allyl sulfone compound prepared in the above example 7 of the present invention has potential pharmaceutical activity and biological activity, and is modified with the pharmaceutical raw material zidovudine having pharmaceutical activity to synthesize a macromolecular skeleton containing both sulfur and nitrogen heteroatoms.
(1) The product obtained in example 7 was subjected to desilylation reaction with TBAF reagent, and to a solution (1.5mL) of the terminal alkyne (0.2mmol) and zidovudine (0.22mmol) in t-butanol, copper sulfate pentahydrate (0.1mmol) and an aqueous solution (1.5mL) of sodium ascorbate (0.1mmol) were added, and the mixture was stirred at room temperature for 2 hours. The equation is:
Figure BDA0002235859010000081
(2) the reaction mixture was diluted with ethyl acetate, washed with water, and the organic phase was dried over anhydrous sodium sulfate. Filtration afforded a white solid in 85% yield.
Application example 3
The allyl sulfone compound prepared by the invention is an important skeleton widely existing in biological and pharmaceutical active molecules, such as a cysteine protease inhibitor, and has the following structural formula:
Figure BDA0002235859010000082
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. The preparation method of the allyl sulfone compound is characterized by comprising the following steps:
(1) sequentially adding allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide into a reaction solvent in an inert gas atmosphere, and stirring and reacting for 12-48 h at the temperature of 30 ℃; wherein the equivalent ratio of allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide is 1: (1.5-2): (1-3%): (5-10%);
(2) removing the reaction solvent in the reaction liquid and then purifying to obtain an allyl sulfone compound; the chemical structural formula of the compound is shown as the following formula (I):
Figure FDA0003028114320000011
in the above formula (I), R1Is aryl or alkyl; r2～R5Any of hydrogen radicals, aryl radicals and alkyl radicals.
2. The method for preparing an allylsulfone compound according to claim 1, wherein in the step (1), the inert gas is argon;
the allyl alcohol comprises primary cinnamyl alcohol allyl alcohol, secondary allyl alcohol and tertiary allyl alcohol;
the sulfinic acid is any one of phenyl sulfinic acid, 3-methyl phenyl sulfinic acid, methyl sulfinic acid, cyclohexane sulfinic acid, camphor sulfinic acid and benzyl sulfinic acid;
the reaction solvent is any one of 1, 2-dichloroethane, tetrahydrofuran and N, N-dimethylacetamide.
3. The method for producing an allylsulfone compound according to claim 2, wherein the allyl alcohol is any one of cinnamyl alcohol, p-methylcinnamyl alcohol, p-fluorocinnamyl alcohol, trans-2-octen-1-ol, 1-phenylpropan-2-en-1-ol, 2-methyl-1-phenyl-2-propen-1-ol, and 2-phenylbut-3-en-2-ol.
4. The method for preparing an allylsulfone compound according to claim 3, wherein the allyl alcohol is 1-phenylprop-2-en-1-ol.
5. The method for preparing the allyl sulfone compound as claimed in claim 4, wherein the method for synthesizing the 1-phenylprop-2-en-1-ol comprises the following steps:
A. adding benzaldehyde into a tetrahydrofuran solvent at room temperature to obtain a solution 1; adding a vinyl Grignard reagent into the solution 1 at 0 ℃, and stirring for 2 hours to obtain a reaction mixture; wherein the ratio of the quantities of the benzaldehyde, the vinyl Grignard reagent and the tetrahydrofuran solvent is 10 mmol: (15-20) mmol: (10-20) mL;
B. the reaction mixture was quenched by addition to saturated ammonium chloride, extracted 3 times with ethyl acetate, the organic phases combined, dried over anhydrous magnesium sulfate, the solvent removed with a rotary evaporator, and the residue purified by column silica gel chromatography with petroleum ether and ethyl acetate to give 1-phenylprop-2-en-1-ol as a pale yellow liquid.
6. The method for preparing an allylsulfone compound according to claim 2, wherein the sulfinic acid is phenyl sulfinic acid;
the reaction solvent is N, N-dimethylacetamide.
7. The method for preparing an allylsulfone compound of claim 6, wherein the method for synthesizing the phenylsulfinic acid comprises the following steps:
A. dissolving sodium benzene sulfinate in water, adding tert-butyl methyl ether, slowly adding hydrochloric acid with the mass fraction of 36-38% within 2 minutes, and stirring the mixture for 10 minutes; wherein the ratio of the quantities of the sodium benzene sulfinate, the hydrochloric acid, the water and the tert-butyl methyl ether is 17.5 mmol: (1-2) mL: (10-15) mL: (5-10) mL;
B. the mixture was transferred to a separatory funnel, the aqueous layer was removed, the organic layer was concentrated on a rotary evaporator until the solvent disappeared, and the obtained white solid was dried in vacuo to give benzenesulfinic acid.
8. The method for preparing an allylsulfone compound according to claim 1, wherein in the step (2), the reaction solvent is removed by extraction with EA and vacuum rotary evaporation; the purification adopts thin layer chromatography, and the developing agent system is petroleum ether/ethyl acetate.
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