CN117964458A - Preparation method of vicinal diol compound - Google Patents

Preparation method of vicinal diol compound Download PDF

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CN117964458A
CN117964458A CN202310743105.5A CN202310743105A CN117964458A CN 117964458 A CN117964458 A CN 117964458A CN 202310743105 A CN202310743105 A CN 202310743105A CN 117964458 A CN117964458 A CN 117964458A
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substituted
unsubstituted
diol compound
reaction
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李加洪
曹坤
申青
陈雪琴
张乃友
蒋合众
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Southwest Jiaotong University
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Southwest Jiaotong University
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Abstract

The invention relates to a preparation method of an o-diol compound, which comprises the following steps: in a nonaqueous solvent, reacting a compound shown in a formula (I) with a reducing agent under an illumination condition to obtain an vicinal diol compound shown in a formula (II); the reducing agent is formic acid or formate; the wavelength of the illumination is less than 390nm; the reaction formula is as follows. The preparation method of the invention does not need a transition metal catalyst, does not need other special catalysts and special additives, can obtain the corresponding o-diol compound through high-yield reaction of aldehyde ketone substrate and formic acid or formate in a solvent by the illumination of specific wavelength, has mild reaction condition and wide substrate applicability, is environment-friendly, has simple and practical operation method, and provides an effective synthesis strategy for synthesizing the pinacol compound.

Description

Preparation method of vicinal diol compound
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of an o-diol compound.
Background
The development of a gentle, efficient, economical method to build carbon-carbon bonds from inexpensive, readily available raw materials has been a hotspot for synthetic chemistry, with the traditional pinacol coupling reaction being one of the most important reactions to build carbon-carbon bonds. The pinacol coupling reaction is an organic reaction in which a radical reaction occurs through the carbonyl group of an aldehyde or ketone molecule in the presence of an electron donor to form a new carbon-carbon covalent bond, and the reaction product is an vicinal diol. The pinacol coupling reaction is usually mainly carried out by coupling with molecules, and can also occur by cross coupling reaction among different molecules, and the formed pinacol compound (o-diol) is a key intermediate for preparing medicines, pesticides and polyesters.
The conventional pinacol coupling process requires the use of a metal catalyst, a stoichiometric metal reducing agent Mg, al, zn, mn, etc., and the reaction conditions are severe, and these conventional methods all generate a large amount of metal waste during the production process. In recent years, the use of photocatalytic and electrochemical methods has become a research hotspot, and the use of them to obtain pinacol compounds has become a useful method. However, both photocatalytic and electrochemical methods require photocatalysts and reducing agents, as well as other specific additives.
Disclosure of Invention
Based on this, the present invention aims to provide a novel method for preparing an vicinal diol compound which is more green, efficient and simpler to operate.
In order to achieve the above purpose, the invention comprises the following technical scheme.
A process for the preparation of an vicinal diol compound comprising the steps of:
In a nonaqueous solvent, reacting a compound shown in a formula (I) with a reducing agent under an illumination condition to obtain an vicinal diol compound shown in a formula (II);
The reducing agent is formic acid or formate;
The wavelength of the illumination is less than 390nm;
the reaction formula is as follows:
Wherein R 1 is selected from: substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl;
R 2 is selected from: H. an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group; or the substituents in R 1 are linked to R 2 to form a carbocyclic or heterocyclic ring.
The preparation method of the o-diol compound has the following beneficial effects:
1. The method of the invention can obtain the corresponding o-diol compound in high yield by the reaction of aldehyde or ketone substrate and formic acid or formate in solvent through illumination with specific wavelength without adding transition metal catalyst or other special catalyst or special additive.
2. The method has very wide substrate applicability, and can prepare the corresponding o-diol compound with excellent yield or higher yield by taking various aryl ketone or aryl aldehyde as a substrate.
3. The method of the invention has the advantages of high yield, high product purity, easy purification and simple post-treatment process except carbon dioxide without other byproducts; the operation method is simple and practical, the reaction condition is mild, the batch large-scale reaction is facilitated, the pinacol compound can be generated in a large scale, and a high-efficiency and simple synthesis strategy is provided for synthesizing the pinacol compound.
4. The method of the invention uses formate (potassium formate, sodium formate, cesium formate and the like) which has wide sources, is cheap and easy to obtain, is easy to store and transport and is safe to operate as a reducing agent, has no other additives and has low preparation cost.
5. In the method, the green alcohol compound (such as ethanol) is preferably used as the solvent, and the solvent can be recycled, so that the method has the advantages of less three wastes and environmental protection.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
In the present invention, the term "plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In order to provide a novel method for preparing an o-diol compound which is green, efficient and easy to operate, in one embodiment of the present invention, there is provided a method for preparing an o-diol compound, comprising the steps of:
In a nonaqueous solvent, reacting a compound shown in a formula (I) with a reducing agent under an illumination condition to obtain an vicinal diol compound shown in a formula (II);
The reducing agent is formic acid or formate;
The wavelength of the illumination is less than 390nm;
the reaction formula is as follows:
Wherein R 1 is selected from: substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl;
R 2 is selected from: H. an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group; or the substituents in R 1 are linked to R 2 to form a carbocyclic or heterocyclic ring.
The method can obtain the corresponding o-diol compound through high-yield reaction of aldehyde ketone substrate and formic acid or formate in a solvent by means of illumination with specific wavelength without transition metal catalyst, other special catalysts and special additives, has mild reaction conditions and wide substrate applicability, is environment-friendly, has simple and practical operation method, and provides an effective synthesis strategy for synthesizing the pinacol compound.
In some embodiments of the invention, R 1 is selected from: 1 or more R 3 substituted or unsubstituted C 6-C10 aryl, 1 or more R 3 substituted or unsubstituted 5-10 membered heteroaryl;
Each R 3 is independently selected from: H. c 1-C8 alkyl, C 1-C8 alkoxy, C 1-C8 alkylthio, C 1-C8 alkoxycarbonyl, phenyl, naphthyl, phenoxy, naphthoxy, C 1-C8 haloalkyl, halogen, or R 3 is attached to R 2 to form a 5-7 membered carbocyclic or heterocyclic ring.
In some embodiments of the invention, R 1 is selected from: 1 or more R 3 substituted or unsubstituted phenyl, 1 or more R 3 substituted or unsubstituted naphthyl, 1 or more R 3 substituted or unsubstituted thienyl, 1 or more R 3 substituted or unsubstituted furyl.
In some embodiments of the invention, each R 3 is independently selected from: H. methyl, ethyl, isopropyl, isobutyl, tert-butyl, propyl, pentyl, hexyl, methoxy, phenoxy, methylthio, methoxyformyl, phenyl, trifluoromethyl, fluoro, chloro, bromo; or R 3 is linked to R 2 to form a 6 membered carbocyclic ring.
In some embodiments of the invention, R 2 is selected from: H. c 1-C6 alkyl, 1 or more R 3 substituted or unsubstituted C 6-C10 aryl, 1 or more R 3 substituted or unsubstituted 5-10 membered heteroaryl.
In some embodiments of the invention, R 2 is selected from: H. c 1-C3 alkyl, 1 or more R 3 substituted or unsubstituted phenyl.
In some embodiments of the invention, R 2 is selected from: H. methyl, ethyl, propyl, phenyl, fluorophenyl, chlorophenyl, methoxy substituted phenyl.
In some embodiments of the invention, the compound of formula (I) is selected from:
The corresponding vicinal diol compound of formula (II) is selected from:
The inventors found that the process for producing an vicinal diol compound of the present invention has very wide substrate applicability, and that a high or excellent vicinal diol product yield can be obtained with various aryl ketones or aldehydes and heteroaryl ketones or aldehydes as reaction substrates.
In some embodiments of the invention, the reducing agent is selected from at least one of formic acid, potassium formate, sodium formate, cesium formate, calcium formate, and ammonium formate.
In some embodiments of the invention, the reducing agent is selected from at least one of potassium formate, sodium formate, and cesium formate.
The inventor finds that a plurality of formates or formic acid can obtain good reaction effect, and can obtain the target product of the o-diol with high yield, especially potassium formate, sodium formate and cesium formate, so that the yield of the product can reach more than 99 percent, and the yield of ammonium formate is slightly lower than that of other formates.
In some embodiments of the invention, the wavelength of the illumination is less than 380nm.
In some embodiments of the invention, the wavelength of the illumination is less than 370nm.
In some embodiments of the invention, the illumination has a wavelength of 300-390nm.
In some embodiments of the invention, the illumination has a wavelength of 350nm to 380nm.
In some embodiments of the invention, the illumination has a wavelength of 360nm-370nm.
In some embodiments of the invention, the illumination has a wavelength of 363nm-367nm.
In some embodiments of the invention, the illumination has a wavelength of 365nm.
The inventor finds that the corresponding vicinal diol target product can be obtained efficiently under the irradiation of illumination with specific wavelength, and the vicinal diol target product can not be obtained without illumination or when the illumination wavelength is longer than 390 nm.
In some embodiments of the invention, the illumination power is 20W-40W, preferably 25W-35W.
In some embodiments of the invention, the solvent is dimethyl sulfoxide and/or an alcohol solvent.
In some embodiments of the invention, the solvent is selected from at least one of dimethyl sulfoxide, methanol, ethanol, isopropanol, n-propanol, and n-butanol.
The inventor finds that the reaction solvent has great influence on the reaction effect, and when DMSO and alcohol compounds (MeOH, etOH, i-PrOH, n-BuOH and the like) are used as the reaction solvent, the reaction effect is very good, and the expected pinacol product can be obtained in a high yield of 99%; however, the expected target product of the vicinal diol is not obtained when water is used as a solvent, and the yield of the product is greatly reduced when THF and DMF are used as reaction solvents.
In some embodiments of the invention, the molar ratio of the compound of formula (I) to the reducing agent is 1:1-3.
In some embodiments of the invention, the molar ratio of the compound of formula (I) to the reducing agent is 1:1.5-2.5.
In some embodiments of the invention, the temperature of the reaction is 15 ℃ to 40 ℃.
In some embodiments of the invention, the temperature of the reaction is from 20 ℃ to 30 ℃.
In some embodiments of the invention, the reaction time is from 2 hours to 86 hours.
In some embodiments of the invention, the reaction time is 8 hours to 72 hours.
The following are specific examples.
Example 1
The reaction steps are as follows: to a 15mL quartz tube equipped with a magnetic stirrer were added acetophenone (0.2 mmol), potassium formate (0.4 mmol), and ethanol (10 mL) in this order. Placing the assembled quartz tube above the 30W and 365nm LED lamp, and ensuring that the distance between the quartz tube and the lamp sheet is 8mm (avoiding contact with the lamp sheet); the reaction was stirred at room temperature (about 25 ℃) and was performed during the reaction using a TLC plate, after 12 hours of reaction, the reaction was stopped after the TLC plate detected that the substrate acetophenone was completely reacted.
Post-treatment: after the reaction was completed, the solvent was removed under reduced pressure, then 10mL of water was added, the reaction solution was extracted with ethyl acetate (10 ml×3), the organic phases were combined, dried with anhydrous sodium sulfate, suction filtered, and the filtrate was spin-dried at 40 ℃ to obtain a crude product, which was separated by column chromatography and spin-evaporated at 40 ℃ to give the desired product 2, 3-diphenyl-2, 3-butanediol as a white solid in 99% yield.
Example 2
The reaction steps are as follows: acetophenone (0.166 mol,1equiv,20 g), potassium formate (0.332 mol,2 equiv) and ethanol (160 mL) were added sequentially to a 250mL quartz round bottom flask equipped with a magnetic stirrer, and stirred at room temperature (about 25 ℃) under LED illumination conditions of 30W and 365nm to ensure that the distance between the quartz round bottom flask and the lamp chip is 8mm (avoid contact with the lamp chip); the reaction was performed using a TLC plate, and the reaction was stopped when the complete reaction of the starting acetophenone was detected by the TLC plate.
Post-treatment: after the reaction was completed, the solvent was removed under reduced pressure, then 100mL of water was added, the reaction mixture was extracted with ethyl acetate (100 ml×3), the organic phases were combined, dried over anhydrous sodium sulfate, suction filtered, and the filtrate was dried at 40 ℃ to obtain a crude product, which was dissolved by 100mL of ethyl acetate under heating and then crystallized with stirring, to obtain a pure 2, 3-diphenyl-2, 3-butanediol product with a yield of 99%.
Example 3
The reaction steps are as follows: a mixed solution containing 0.01mol of acetophenone and 0.02mol of potassium formate per milliliter was prepared by using ethanol as a solvent, and the mixed solution was passed through a continuous flow reactor having a tube length of 14m, a tube diameter of 2.0mm and a flow rate of 0.05mL/s under LED illumination of 30W and 365nm by a peristaltic pump at room temperature (about 25 ℃).
Post-treatment: the solvent is removed from the reaction liquid under reduced pressure, a proper amount of water is added, the reaction liquid is extracted by a proper amount of ethyl acetate, the organic phases are combined, the mixture is dried by anhydrous sodium sulfate, the suction filtration is carried out, the filtrate is dried by spin to obtain a crude product at 40 ℃, and the crude product is heated and dissolved by ethyl acetate and then stirred for crystallization, thus obtaining the pure 2, 3-diphenyl-2, 3-butanediol product with the yield of 99 percent.
Example 4
This embodiment differs from embodiment 1 in that: a different solvent was used (Table 1), and the procedure was the same as in example 1. Solvents used in this example include DMSO (dimethyl sulfoxide), H 2 O (water), THF (tetrahydrofuran), meOH (methanol), etOH (ethanol), DMF (dimethylformamide), i-PrOH (isopropanol), n-PrOH (n-propanol), n-BuOH (n-butanol).
Reaction conditions: at 25℃with acetophenone 1a (0.2 mmol) as the substrate and potassium formate (0.4 mmol,2 equiv) as the additive, 10mL of solvent were reacted with 30W, 365nm ultraviolet radiation in air for 12h.
The reaction results found that: with H 2 O as the reaction solvent, the expected product 3a (2 in table 1) was not obtained; with THF, DMF as reaction solvent, only a small amount of product 3a was produced (3-4 in table 1); using DMSO and alcohol compounds (MeOH, etOH, i-PrOH, n-BuOH) as reaction solvents, the reaction was excellent and the desired pinacol product 3a (1, 5-9 in Table 1) was obtained in 99% yield.
TABLE 1 influence of the reaction solvent on the reaction effect
Example 5
This embodiment differs from embodiment 1 in that: different formates and other bases were used as additives (Table 2), all other operations being identical to example 1. Formate salts used in this example included HCO 2Cs、HCO2Na、HCO2K、HCO2Ca、HCO2H、HCO2NH4, other bases including KOH, DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene), DABCO (triethylenediamine), et 3 N (triethylamine).
Reaction conditions: at 25℃with acetophenone 1a (0.2 mmol) as substrate, formate or base (0.4 mmol,2 equiv) as additive, 10mM DS O as solvent, and 30W, 365nm UV irradiation for 12h in air.
As a result, it was found that, after 12 hours of reaction under the reaction conditions, the intended pinacol product 3a (1 in Table 2) was successfully obtained in 99% yield with cesium formate as an additive; with other bases such as KOH, DBU, DABCO, et 3 N, etc. as additives, the yields were very low or no product 3a (2-6 in Table 2) could be obtained. The pinacol product 3a (7-10 in table 2) was also obtained in excellent yields after the cesium formate was replaced with other formate salts; when ammonium formate was used as an additive, the yield was lowered (11 in Table 2). It can be seen that various formates can be obtained in excellent yields to the desired product 3a, and in view of the cost, potassium formate, which is inexpensive, can be selected as a preferred additive for the reaction.
TABLE 2 influence of formate salts and different bases on the reaction effect
Example 6
This embodiment differs from embodiment 1 in that: a light source of a different wavelength (table 3) was used and the other operations were the same as in example 1. In this example, the reaction was carried out under four light sources of 30W ultraviolet light (365 nm), 30W violet light (395 nm), 30W blue light (410 nm), and 30W blue light (455 nm), respectively.
Reaction conditions: at 25 ℃, acetophenone 1a (0.2 mmol) is used as a reaction substrate, potassium formate (0.4 mmol,2 equiv) is used as an additive, 10mL of ethanol is used as a solvent, and ultraviolet light or blue light is irradiated for reaction for 12h under the air condition.
The results are shown in Table 3 below: the pinacol product 3a was obtained in 99% yield when irradiated with ultraviolet light (365 nm); whereas no pinacol product 3a was found when irradiated with violet light (395 nm), blue light (410 nm), and blue light (455 nm).
TABLE 3 influence of reaction light Source on reaction Effect
EXAMPLE 7 reaction of differently substituted ketones
This embodiment differs from embodiment 1 in that: the structure of the reaction substrate 1 was different, and the other operations were the same as in example 1.
Reaction conditions: at 25 ℃, ketone 1 (0.2 mmol) is used as a reaction substrate, potassium formate (0.4 mmol,2 equv) is used as an additive, 10mL of ethanol is used as a solvent, and the reaction is carried out under 30W and 365nm ultraviolet irradiation, and the reaction is carried out for 12h under the air condition.
Results show (table 4): aliphatic ketone compounds are used as reaction substrates, and pinacol products cannot be obtained; the aryl ketone compound is used as a reaction substrate, so that the pinacol product can be obtained in high yield. Aromatic ketones having electron donating groups such as methyl, isobutyl, t-butyl, propyl, hexyl, methoxy, phenoxy groups on the benzene ring all give pinacol compounds (3 b-3 o) in excellent yields. Aromatic ketones having electron withdrawing groups such as fluorine, chlorine, bromine, trifluoromethyl on the benzene ring also give pinacol compounds (3 p-3 t) in medium to high yields, wherein the electron withdrawing groups fluorine is reduced in yield at the ortho position (3 r) and the yields in substitution for chlorine and bromine are reduced (3 s-3 t). The pinacol product (3 u-3 v) can be obtained in higher yield when the benzene ring is provided with both an electron withdrawing group and an electron donating group. When the benzene ring is changed to naphthalene ring, the product 3w can be obtained in 70% yield. When methyl in acetophenone was changed to propyl, the product 3x was also obtained in excellent yield of 99%. In addition, substrate extension of the benzophenone compound is also carried out, and the benzophenones with electron donating groups or electron withdrawing groups such as methyl, methoxy, fluorine and chlorine can be substituted to obtain pinacol (3 z-3 ae) with higher or excellent yield.
TABLE 4 reaction substrate extension of acetophenone Compounds
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Wherein, the structural formula of the reaction substrate 1 is as follows:
EXAMPLE 8 reaction of various substituted aldehydes
This embodiment differs from embodiment 1 in that: the structure of the reaction substrate was different, and the other operations were the same as in example 1.
Reaction conditions: under the condition of 25 ℃, aldehyde 4 (0.2 mmol) is taken as a reaction substrate, potassium formate (0.4 mmol,2 equiv) is taken as an additive, 10mL of ethanol is taken as a solvent, and the reaction is carried out under the ultraviolet irradiation of 30W and 365nm, and the reaction is carried out for 12h under the air condition.
Results show (table 5): substrates with electron donating groups such as methyl, t-butyl, isobutyl, methoxy, phenoxy groups in the ortho-, meta-, and para-positions of aromatic aldehydes give pinacol products (5 b-5p, 5 u) in excellent yields. Substrates bearing electron withdrawing groups in the meta-and para-positions of aromatic aldehydes, such as substrates bearing fluorine, chlorine, bromine, trifluoromethyl, also give pinacol product (5 q-5t, 99%) in excellent yields, and substrates bearing methylthio groups also give pinacol product (5 v) in 90% yields.
TABLE 5 substrate extension of aldehydes
Wherein, the structural formula of the reaction substrate 4 is as follows:
Pinacol compounds prepared in examples 1-8 were characterized by the following structure:
127.25,127.16,127.09,127.07,127.00,126.91,78.91,78.66,25.11,24.94;HRMS(ESI,m/z):Calcd for C16H18O2Na[M+Na]+:265.125,Found:265.1195.
CDCl3):δ140.97,140.62,136.56,136.41,128.03,127.87,127.34,126.90,78.81,78.56,25.24,25.06,21.01,20.98;HRMS(ESI,m/z):Calcd for C18H22O2Na[[M+Na]+:293.1518,Found:293.1513./>
1.54(s,3H),1.45(s,4H).13C NMR(100 MHz,CDCl3):δ143.75,143.42,143.38,136.71,136.69,136.67,136.50,136.49,136.47,128.30,128.27,128.25,127.90,127.86,127.73,127.60,127.16,127.00,124.57,124.53,124.51,124.08,124.05,78.91,78.89,78.68,78.65,25.11,25.01,21.61,21.59;HRMS(ESI,m/z):Calcd for C18H22O2Na[[M+Na]+:293.1518,Found:293.1512.
CDCl3):(100MHz,CDCl3)δ147.54,147.44,141.35,141.00,127.31,126.90,125.33,125.22,78.79,78.51,33.65,33.64,25.19,25.12,24.07,24.03,23.99;HRMS(ESI,m/z):Calcd for C22H30O2Na[M+Na]+:349.2144,Found:349.2134.
140.66,127.03,126.62,124.20,124.12,78.71,78.43,34.42,34.38,31.44,31.42,25.16;HRMS(ESI,m/z):Calcd for C24H34O2Na[M+Na]+:354.5340,Found:354.5322.
6.2 Hz,4H),1.55(s,2H),1.47(s,4H),0.93(td,J＝7.4,5.7 Hz,6H);13C NMR(100 MHz,CDCl3):δ141.37,141.21,141.12,140.82,128.68,128.48,128.38,128.20,127.38,127.24,127.22,126.78,78.83,78.61,38.03,37.58,37.52,26.52,25.09,25.03,24.46,24.39,24.22,13.92,13.84,13.75;HRMS(ESI,m/z):Calcd for C22H30O2Na[M+Na]+:349.2144,Found:349.2134.
diol(3g);White solid(99％yield);1H NMR(400 MHz,CDCl3):δ7.10(dd,J＝12.7,8.1 Hz,4H),7.06–6.96(m,4H),2.57(q,J＝7.2 Hz,5H),2.29(d,J＝6.6 Hz,1H),1.58(dq,J＝12.9,6.1,5.4Hz,5H),1.53(s,2H),1.46(s,3H),1.39–1.24(m,13H),1.08–0.68(m,7H);13C NMR(100 MHz,CDCl3):δ141.62,141.59,141.46,141.43,141.12,140.83,128.53,127.31,127.26,127.17,126.85,126.81,78.85,78.63,35.53,35.48,31.81,31.78,31.42,31.39,31.36,29.04,28.97,25.08,25.03,25.01,22.68,14.14;HRMS(ESI,m/z):Calcd for C27H40O2Na[M+Na]+:419.2926,Found:419.2916.
1.56(s,2H),1.49(s,4H);13C NMR(100 MHz,CDCl3):δ141.39,141.05,135.29,135.16,135.08,135.04,128.74,128.64,128.44,128.34,124.91,124.42,78.75,78.50,25.29,25.19,19.93,19.90,19.35,19.31;HRMS(ESI,m/z):Calcd for C20H26O2Na[M+Na]+:321.1831,Found:321.1822.
1.53(d,J＝36.0 Hz,6H);13C NMR(100 MHz,CDCl3):δ158.54,158.45,136.10,135.77,128.57,128.14,112.56,112.41,78.72,78.50,77.36,77.25,77.05,76.73,55.21,25.18,25.01;HRMS(ESI,m/z):Calcd for C18H22O4Na[M+Na]+:325.1416,Found:325.1410.
1H),6.77(d,J＝7.6 Hz,5H),3.69(s,4H),3.65(s,3H),2.88(d,J＝1.1 Hz,2H),1.54(s,3H),1.47(s,3H);13C NMR(100 MHz,CDCl3):δ158.79,158.60,145.63,145.25,128.17,128.02,120.05,119.46,113.46,113.08,112.66,112.53,78.86,78.86,78.62,55.15,55.13,25.08,24.95;HRMS(ESI,m/z):Calcd for C18H22O4Na[M+Na]+:325.1416,Found:325.1410.
Hz,2H),5.41(s,2H),3.40(s,6H),1.57(s,6H);13C NMR(100 MHz,CDCl3):δ157.89,132.09,129.80,128.25,120.21,111.22,55.35,24.49;HRMS(ESI,m/z):Calcd for C18H22O4Na[M+Na]+:325.1416,Found:325.1413.
(100 MHz,CDCl3):δ166.98,148.36,129.03,128.56,128.46,127.43,127.08,78.83,52.11,24.75;HRMS(ESI,m/z):Calcd for C20H22O6Na[M+Na]+:381.1314,Found:381.1311./>
(100 MHz,DMSO-d6):δ146.63,140.21,138.50,128.90,127.21,126.57,126.36,125.93,67.84,25.88;HRMS(ESI,m/z):Calcd for C28H26O2Na[M+Na]+:417.1831,Found:417.1830.
(s,2H),1.58(d,J＝1.2 Hz,2H),1.48(d,J＝1.3 Hz,4H).13C NMR(100 MHz,CDCl3):δ147.93,147.42,136.20,119.89,111.32,109.66,78.83,55.83,55.71,55.69,24.93.HRMS(ESI,m/z):Calcd for C20H26O6Na[M+Na]+:385.1627,Found:385.1620.
(m,4H),2.62(s,1H),2.44(s,1H),1.59(s,2H),1.50(s,3H);13C NMR(100 MHz,CDCl3):δ157.32,157.15,156.31,156.09,138.82,138.40,129.79,129.76,128.86,128.47,123.33,123.21,118.93,118.90,118.87,118.73,117.66,117.38,117.33,78.75,78.54,25.10,25.00;HRMS(ESI,m/z):Calcd for C28H26O4Na[M+Na]+:449.1729,Found:449.1720.
1H),2.40(s,1H),1.55(s,3H),1.50(s,4H);13C NMR(100 MHz,CDCl3):δ147.71,147.15,147.13,130.03,129.71,129.51,129.38,129.19,129.06,127.75,127.47,125.55,125.51,124.28,124.24,124.20,124.19,124.15,124.11,122.84,122.80,78.61,78.29,25.10,24.72;HRMS(ESI,m/z):Calcd for C18H16F6O2Na[M+Na]+:401.0952,Found:401.0922.
2H),1.47(s,4H);13C NMR(100 MHz,CDCl3):δ163.24,163.15,160.80,160.70,139.50,139.47,139.12,139.09,129.11,129.03,128.72,128.64,114.08,114.01,113.87,113.80,78.59,78.34,25.15,24.89;HRMS(ESI,m/z):Calcd for C16H16F2O2Na[M+Na]+:301.1016,Found:301.1011.
3.08(s,1H),1.76(d,J＝2.2 Hz,3H),1.64(t,J＝2.2 Hz,4H).13C NMR(100 MHz,CDCl3):δ161.84,161.76,159.40,159.32,130.23,130.18,130.07,129.98,129.94,129.42,129.33,129.29,129.20,123.61,123.58,123.25,123.21,116.32,116.07,115.82,24.47,24.44,24.40,24.38,24.03,24.01,23.97,23.95;HRMS(ESI,m/z):Calcd for C16H16F2O2Na[M+Na]+:301.1016,Found:301.1011.
7.9,1.5 Hz,1H),2.34(s,2H),1.56(s,3H),1.50(s,3H);13C NMR(100 MHz,CDCl3):δ145.87,145.32,133.52,133.43,128.53,128.41,127.69,127.44,127.39,127.19,125.56,125.21,78.54,78.22,25.11,24.77;HRMS(ESI,m/z):Calcd for C16H16Cl2O2Na[M+Na]+:333.0425,Found:333.0422.
Hz,2H),6.97–6.92(m,2H),2.21(s,4H),1.59–1.20(m,12H);13C NMR(100 MHz,CDCl3):δ143.79,143.43,142.79,142.32,130.39,130.31,130.23,130.17,129.28,129.22,128.88,127.44,127.37,127.32,127.29,127.26,127.16,127.12,127.07,126.93,126.91,121.46,121.27,78.88,78.62,78.51,78.23,25.13,25.08,24.96,24.73;HRMS(ESI,m/z):Calcd for C16H16Br2O2Na[M+Na]+:422.9395,Found:422.9350.
3H),2.30(d,J＝6.2 Hz,3H),1.56–1.50(m,2H),1.48–1.42(m,3H).13C NMR(100 MHz,CDCl3):δ142.27,141.80,134.68,134.56,133.27,133.11,130.08,129.75,127.83,127.70,126.31,125.89,25.14,24.87,20.16,20.13.HRMS(ESI,m/z):Calcd for C18H20Cl2O2Na[M+Na]+:361.0738,Found:361.0730.
12.0,2.7 Hz,2H),6.34(dd,J＝14.5,2.6 Hz,1H),3.71(d,J＝0.9Hz,3H),3.67(d,J＝0.9 Hz,3H),2.95(s,2H),1.63(d,J＝2.3 Hz,3H),1.55–1.47(m,3H).13C NMR(100 MHz,CDCl3):δ162.21,162.16,160.26,160.14,160.01,159.77,159.72,130.71,130.65,130.51,130.45,122.26,122.22,122.15,122.11,109.33,109.31,109.00,108.98,102.04,101.75,101.46,79.47,79.43,79.37,79.33,55.50,55.46,24.50,24.48,24.44,24.42,24.08,24.01.HRMS(ESI,m/z):Calcd for C18H20F2O4Na[M+Na]+:361.1228,Found:361.1220./>
7.50–7.36(m,5H),7.27(dd,J＝8.7,1.9 Hz,1H),2.91–2.64(m,1H),2.37(s,1H),1.68(s,2H),1.62(s,4H);13C NMR(100 MHz,CDCl3):δ141.54,141.02,132.69,132.56,132.48,132.39,128.45,128.34,128.32,127.81,127.38,126.73,126.48,125.99,125.91,125.90,125.82,125.53,79.27,78.91,26.71,25.60,25.30;HRMS(ESI,m/z):Calcd for C24H22O2Na[M+Na]+:365.1518,Found:365.1515.
CDCl3):δ141.75,140.85,128.16,127.48,127.29,127.08,126.80,126.61,81.68,37.80,37.34,16.86,16.69,14.51,14.49;HRMS(ESI,m/z):Calcd for C20H26O2Na[M+Na]+:321.1831,Found:321.1830.
14.3,6.4,3.6 Hz,5H),1.57(q,J＝3.8,3.1 Hz,1H),1.26(ddd,J＝14.5,12.1,5.0 Hz,2H).13C NMR(100 MHz,CDCl3):δ140.56,138.39,129.09,129.06,128.87,127.22,126.41,36.47,31.16,20.10;HRMS(ESI,m/z):Calcd for C20H22O2Na[M+Na]+:317.1518,Found:317.1510.
83.10.HRMS(ESI,m/z):Calcd for C26H22O2Na[M+Na]+:389.1518,Found:389.1511.
128.59,128.54,128.50,128.48,128.22,128.06,128.03,127.23,127.20,126.80,126.73,82.96,20.97.HRMS(ESI,m/z):Calcd for C28H26O2Na[M+Na]+:417.1831,Found:417.1830./>
(s,1H).13C NMR(100 MHz,CDCl3):13C NMR(101 MHz,CDCl3)δ143.89,143.67,130.51,130.48,130.43,130.40,128.41,128.35,127.51,127.37,127.24,114.17,113.96,82.80.HRMS(ESI,m/z):Calcd for C26H20F2O2Na[M+Na]+:425.1329,Found:425.1321.
114.20,82.58.HRMS(ESI,m/z):Calcd for C26H18F4O2Na[M+Na]+:461.1141,Found:461.1131.
NMR(100 MHz,CDCl3):δ199.32,158.50,158.46,158.39,158.33,158.05,144.59,143.90,139.17,137.63,136.43,135.49,132.21,131.90,131.60,131.15,131.07,130.73,130.29,129.94,129.88,129.58,129.41,128.68,128.64,128.60,128.57,128.35,128.31,128.21,127.75,127.63,127.59,127.49,127.27,127.25,127.17,127.10,126.96,126.89,126.85,126.78,126.53,113.91,113.82,113.78,113.16,113.05,112.97,112.60,112.59,82.92,69.84,55.18,55.15,55.13;HRMS(ESI,m/z):Calcd for C28H26O4Na[M+Na]+:449.1729,Found:449.1722.
133.04,132.86,130.19,130.15,130.11,128.67,128.61,128.51,128.39,128.36,128.29,127.63,127.57,127.53,127.48,127.43,127.38,82.78,82.75;HRMS(ESI,m/z):Calcd for C26H20Cl2O2Na[M+Na]+:457.0738,Found:457.0735.
2.76–2.27(m,1H).13C NMR(100 MHz,CDCl3):δ139.93,139.76,128.43,128.16,128.10,128.01,128.00,127.88,127.14,127.01,79.10.HRMS(ESI,m/z):Calcd for C14H14O2Na[M+Na]+:237.0892,Found:237.0890.
NMR(100 MHz,CDCl3):δ137.79,137.48,137.05,137.03,128.99,128.83,127.07,126.89,78.79,21.18,21.15.HRMS(ESI,m/z):Calcd for C16H18O2Na[M+Na]+:265.2968,Found:265.2965.
(d,J＝2.0 Hz,1H),6.78(dt,J＝7.6,1.6 Hz,1H),4.59(s,1H),4.51(s,1H),2.82(s,2H),2.23(s,3H),2.18(s,3H);13C NMR(100 MHz,CDCl3):δ140.02,139.98,137.72,128.91,128.60,128.57,128.19,127.99,127.97,127.84,127.52,124.29,124.03,78.81,78.22,78.20,21.43,21.39.
NMR(100 MHz,CDCl3):13C NMR(101 MHz,CDCl3)δ151.21,150.75,137.34,130.07,126.93,126.50,125.44,125.36,125.08,34.59,34.51,31.37,31.35,26.94.
6.85–6.80(m,2H),5.07(s,1H),4.84(s,2H),3.01(s,2H),2.05(s,3H),1.56(s,6H);13C NMR(100 MHz,CDCl3):δ138.11,138.06,136.10,135.92,130.16,130.02,127.70,127.68,127.27,126.81,126.02,125.92,74.62,73.23,19.12,18.75.
1H),4.51(d,J＝1.9 Hz,1H),2.54(s,2H),2.16(s,6H),2.11(s,4H),2.10(s,4H);13C NMR(100MHz,CDCl3):δ137.80,137.70,136.65,136.58,136.32,136.03,129.67,129.37,128.39,127.99,124.69,124.36,78.40,78.21,19.81,19.76,19.51,19.46.
/>
NMR(100 MHz,CDCl3):δ138.14,137.79,135.62,135.28,133.27,132.60,130.13,130.09,128.57,128.43,127.62,127.19,74.38,73.80,21.11,21.07,18.86,18.34.
1H),2.91(s,1H),2.37(d,J＝7.2 Hz,2H),2.33(dd,J＝7.2,1.5 Hz,2H),2.29–2.09(m,1H),1.74(dhept,J＝16.5,6.8 Hz,2H),0.84–0.75(m,12H);13C NMR(100 MHz,CDCl3):δ141.59,141.28,137.30,137.18,128.98,128.79,126.87,126.67,79.09,78.03,45.14,45.08,30.21,30.20,22.34,22.31,22.22.
5.13(s,2H),4.93(s,4H),2.33(s,6H),2.28(s,12H),2.20(s,6H),1.71(s,12H);13C NMR(100MHz,CDCl3):δ137.33,137.19,136.10,135.67,135.44,135.18,130.92,127.08,126.87,126.65,126.57,77.36,77.04,76.73,74.43,73.57,21.04,20.99,19.18,18.80.
5.14(s,1H),4.91(d,J＝1.2 Hz,1H),3.00(s,2H),2.17(s,2H),2.01(d,J＝6.3 Hz,6H),1.45(s,4H).13C NMR(100 MHz,CDCl3):δ138.27,137.96,136.60,136.54,134.91,134.57,129.40,129.19,128.58,125.57,125.41,125.20,124.92,124.45,74.82,73.97,26.95,20.78,20.65,14.76,14.26.
2H),6.61–6.53(m,2H),4.65(d,J＝1.3 Hz,1H),4.52–4.45(m,1H),3.59(dt,J＝9.0,1.2 Hz,6H),2.83–2.71(m,2H).13C NMR(100 MHz,CDCl3):δ159.46,159.36,141.63,141.45,129.16,129.11,119.50,119.33,113.89,113.87,113.64,112.39,112.32,78.84,55.23,55.20,55.18.
7.17(m,8H),5.41(s,4H),4.71(d,J＝2.1 Hz,4H);13C NMR(100MHz,DMSO-d6):δ142.26,140.44,138.89,129.35,128.29,127.69,126.94,126.05,77.54./>
5.07(s,1H),5.02(s,1H),3.80–3.70(m,8H),3.70–3.65(m,4H),3.20(s,2H).13C NMR(100MHz,CDCl3):δ152.34,146.84,146.63,134.33,133.89,133.85,124.03,124.00,123.92,120.14,120.10,111.94,111.89,73.80,73.78,73.69,60.83,60.82,60.69,55.77,55.73,18.81.
6.86–6.76(m,1H),6.69(d,J＝8.3 Hz,1H),4.63(s,1H),4.61(s,1H),3.85(s,3H),3.81(s,3H),2.92(s,1H),2.24(s,3H),2.18(s,3H),2.08(s,1H);13C NMR(100 MHz,CDCl3):δ199.10,157.35,157.17,131.84,131.34,130.13,129.42,129.13,128.21,127.34,127.30,126.31,125.83,125.50,110.25,109.75,109.47,78.49,62.65,55.39,55.36,55.31,55.27,16.29,16.22,16.12.
(m,6H),6.81–6.77(m,2H),4.71(s,1H),4.56(s,1H),2.96(s,1H),2.34(s,1H).13C NMR(100MHz,CDCl3):13C NMR(101 MHz,DMSO)δ152.38,152.34,152.18,129.99,129.80,125.05,125.02,123.82,123.70,118.65,118.58,114.18,114.06,113.81,113.79,74.08,22.20.
1H),4.73(s,1H),4.49(d,J＝1.8 Hz,1H),2.97(s,2H);13C NMR(100 MHz,CDCl3):δ157.10,157.07,157.04,156.95,141.77,141.50,129.99,129.77,129.65,129.48,123.25,123.24,121.85,119.21,118.78,118.68,118.51,117.71,117.52,79.01.
3.1,1.5 Hz,1H),4.65–4.60(m,1H),4.58(dd,J＝3.2,1.3 Hz,1H);13C NMR(100 MHz,CDCl3):δ167.53,165.19,165.13,144.37,144.34,143.48,143.45,134.34,134.26,134.18,134.10,119.27,119.25,119.06,119.04,81.87,81.42.
4.85(q,J＝2.1 Hz,1H),4.66(q,J＝2.7 Hz,1H),2.68(s,2H).13C NMR(100 MHz,CDCl3):13C NMR(101 MHz,CDCl3)δ163.91,161.47,142.22,142.15,142.06,141.99,129.76,129.68,129.60,122.65,122.62,122.59,115.14,115.11,114.93,114.90,114.06,113.92,113.84,113.70,78.40.
4.68(d,J＝2.6 Hz,1H),4.61(d,J＝3.5 Hz,1H).
130.84,130.63,130.52,130.30,130.19,129.98,128.00,127.33,127.27,125.35,125.29,125.27,125.23,125.20,125.16,125.12,125.09,125.05,125.01,122.65,122.59,78.37.
2H),5.29(s,1H),5.07(s,1H),3.68(s,3H),3.66(s,3H),3.55(s,1H),3.20(s,1H).13C NMR(100MHz,CDCl3):13C NMR(100 MHz,CDCl3)δ156.97,156.92,128.66,128.56,128.50,128.44,128.27,128.24,120.46,110.25,110.22,74.35,73.42,73.41,55.27,55.23.HRMS(ESI,m/z):Calcd for C16H18O4Na[M+Na]+:297.1103,Found:297.1101.
2.44(d,J＝12.3 Hz,6H);13C NMR(100 MHz,DMSO-d6):δ140.53,139.53,136.53,136.38,128.47,128.39,128.31,125.67,125.61,125.54,77.50,77.04,15.45,15.29.
Hz,2H),6.75(dd,J＝3.6,1.2 Hz,2H),5.05(s,1H),4.97(s,2H),3.02(s,1H),2.50(s,1H);13C NMR(100MHz,CDCl3):δ142.91,142.54,126.64,126.61,126.03,125.86,125.65,125.42,74.96,74.44.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. A process for producing an vicinal diol compound, comprising the steps of:
In a nonaqueous solvent, reacting a compound shown in a formula (I) with a reducing agent under an illumination condition to obtain an vicinal diol compound shown in a formula (II);
The reducing agent is formic acid or formate;
The wavelength of the illumination is less than 390nm;
the reaction formula is as follows:
Wherein R 1 is selected from: substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl;
R 2 is selected from: H. an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group; or the substituents in R 1 are linked to R 2 to form a carbocyclic or heterocyclic ring.
2. The method for producing an vicinal diol compound according to claim 1, wherein R 1 is selected from: 1 or more R 3 substituted or unsubstituted C 6-C10 aryl, 1 or more R 3 substituted or unsubstituted 5-10 membered heteroaryl;
Each R 3 is independently selected from: H. c 1-C8 alkyl, C 1-C8 alkoxy, C 1-C8 alkylthio, C 1-C8 alkoxycarbonyl, phenyl, naphthyl, phenoxy, naphthoxy, C 1-C8 haloalkyl, halogen, or R 3 is attached to R 2 to form a 5-7 membered carbocyclic or heterocyclic ring.
3. The method for producing an vicinal diol compound according to claim 2, wherein R 1 is selected from: 1 or more R 3 substituted or unsubstituted phenyl, 1 or more R 3 substituted or unsubstituted naphthyl, 1 or more R 3 substituted or unsubstituted thienyl, 1 or more R 3 substituted or unsubstituted furyl.
4. The process for producing an vicinal diol compound according to claim 2, wherein each R 3 is independently selected from the group consisting of: H. methyl, ethyl, isopropyl, isobutyl, tert-butyl, propyl, pentyl, hexyl, methoxy, phenoxy, methylthio, methoxyformyl, phenyl, trifluoromethyl, fluoro, chloro, bromo; or R 3 is linked to R 2 to form a 6 membered carbocyclic ring.
5. The method for producing an vicinal diol compound according to any one of claims 1 to 4, wherein R 2 is selected from: H. c 1-C6 alkyl, 1 or more R 3 substituted or unsubstituted C 6-C10 aryl, 1 or more R 3 substituted or unsubstituted 5-10 membered heteroaryl.
6. The method for producing an vicinal diol compound according to claim 5, wherein R 2 is selected from the group consisting of: H. c 1-C3 alkyl, 1 or more R 3 substituted or unsubstituted phenyl.
7. The method for producing an vicinal diol compound according to claim 6, wherein R 2 is selected from the group consisting of: H. methyl, ethyl, propyl, phenyl, fluorophenyl, chlorophenyl, methoxy substituted phenyl.
8. The process for the preparation of vicinal diol compounds according to claim 1, characterized in that the compound of formula (I) is chosen from:
The corresponding vicinal diol compound of formula (II) is selected from:
9. The method for producing an vicinal diol compound according to any one of claims 1 to 4, wherein the reducing agent is at least one selected from formic acid, potassium formate, sodium formate, cesium formate, calcium formate and ammonium formate; and/or the number of the groups of groups,
The wavelength of the illumination is 350nm-380nm; and/or the number of the groups of groups,
The illumination power is 20W-40W; and/or the number of the groups of groups,
The solvent is dimethyl sulfoxide and/or an alcohol solvent; and/or the number of the groups of groups,
The molar ratio of the compound of formula (I) to the reducing agent is 1:1-3; and/or the number of the groups of groups,
The temperature of the reaction is 15-40 ℃.
10. The process for producing an vicinal diol compound according to claim 9, wherein,
The reducing agent is at least one of potassium formate, sodium formate and cesium formate; and/or the number of the groups of groups,
The wavelength of the illumination is 360nm-370nm; and/or the number of the groups of groups,
The illumination power is 25W-35W; and/or the number of the groups of groups,
The solvent is at least one selected from dimethyl sulfoxide, methanol, ethanol, isopropanol, n-propanol and n-butanol; and/or the molar ratio of the compound of formula (I) to the reducing agent is 1:1.5-2.5; and/or the number of the groups of groups,
The temperature of the reaction is 20-30 ℃.
CN202310743105.5A 2023-06-21 2023-06-21 Preparation method of vicinal diol compound Pending CN117964458A (en)

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