CN111087375B - Preparation method of 2H-chromene derivative - Google Patents
Preparation method of 2H-chromene derivative Download PDFInfo
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Abstract
The invention discloses a method for preparing a compound with brensted acid
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a 2H-chromene derivative.
Background
2H-chromene derivatives, in particular 3-substituted 2H-chromene derivatives, have been found to be widely present in bioactive molecules and in natural product structures (see formula below):
although many impressive synthetic methods have been established over the last decades, these synthetic methods still suffer from drawbacks such as multi-step synthesis, limited substrate range, harsh reaction conditions and low yields. Therefore, there is still an urgent need to develop new strategies for constructing 2H-chromene frameworks, in particular synthetic methods with good universality and high efficiency.
In recent years, ortho-Quinone methides (o-QMs), an intermediate with high reactivity, can be easily obtained from the corresponding o-hydroxybenzyl alcohol compounds, and have been proven to be an important structural unit for constructing oxygen-containing heterocycles. These intermediates participate as electron deficient oxobutadienes in various forms [4+2 ] in the presence of organic or transition metal catalysts]And (3) carrying out cyclization reaction. Despite these significant achievements, these [4+2 ]]Cyclization reactions are generally limited to electron-rich olefins such as vinyl ethers, vinyl sulfides, enaminones, styrene, and the like. The prior art based on acetylenic compounds participating in the above reaction has been very limited to date. Based on the above conclusion and the research results of the present group of subjects of the inventors on the development of hetero-substituted acetylenic compounds to synthesize heterocycles, we assume that the catalysis of ortho-hydroxybenzyl alcohol compounds and electron-rich acetylenic thioether compounds may be similar to [4+2 ]]Cyclization reaction to produce 2H-chromene compound. In the present invention, the inventors have unexpectedly employed brensted acid(s) ((R))
acid) -catalysis alkynyl o-hydroxy benzyl alcohol compound and alkynyl thioether compound rich in electrons to be [4+2 ]]Cyclization reaction to prepare 2H-chromene compound.
Disclosure of Invention
The invention aims to enrich the synthesis strategy for preparing 2H-chromene compounds and provides a new method for preparing 2H-chromene compounds by using brensted acid (brensted acid)
acid) -catalysis o-hydroxy benzyl alcohol compound and alkynyl thioether compound rich in electrons to obtain alpha-hydroxy benzyl alcohol compound [4+2 ]]A novel method for preparing 2H-chromene compounds by cyclization reaction. The method can be carried out under mild reaction conditions without using a metal catalyst, can synthesize valuable various polysubstituted 2H-chromene compounds in a very practical manner, has excellent yield, and has a wide substrate adaptation range and excellent functional group tolerance.
The invention provides a preparation method of a 2H-chromene derivative, which comprises the following steps: and (2) sequentially adding an alkynyl thioether compound shown in a formula I, an o-hydroxy benzyl alcohol compound shown in a formula II, an acid catalyst and an organic solvent into a Schlenk tube-sealed reactor, replacing the reactor with an inert atmosphere, stirring at room temperature for reaction, monitoring the reaction by TLC (thin layer chromatography), concentrating the reaction solution, and separating the obtained residue by silica gel column chromatography to obtain the 2H-chromene derivative shown in a formula III. The reaction formula is as follows:
in the above reaction formula, R 1 Is selected from C 1-6 Alkyl radical, C 3-8 Cycloalkyl, substituted or unsubstituted C 6-14 Aryl radical, C 6-14 One of an arylvinyl group; wherein said "substituted or unsubstituted C 6-14 The substituents in aryl "are selected from halogen, C 1-6 Alkyl radical, C 1-6 Alkoxy, halogen substituted C 1-6 An alkyl group.
R 2 Is selected from C 1-6 Alkyl radical, C 6-14 Aryl radical, C 6-14 aryl-C 1-6 An alkyl group.
R 3 Selected from substituted or unsubstituted C 6-14 An aryl group; wherein said "substituted or unsubstituted C 6-14 The substituents in aryl "are selected from halogen, C 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 6-14 Aryl, halogen substituted C 1-6 An alkyl group.
R 4 Represents one or more substituents on the attached phenyl ring, each R 3 The substituents are independently selected from hydrogen, halogen, C 1-6 Alkyl radical, C 1-6 An alkoxy group.
Preferably, in the above reaction formula, R 1 One selected from cyclopropyl, substituted or unsubstituted phenyl and styryl; wherein the substituents in said "substituted or unsubstituted benzene" are selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, methoxy, trifluoromethyl.
R 2 Selected from methyl, ethyl, phenyl, benzyl.
R 3 Selected from substituted or unsubstituted phenyl; wherein the substituents in said "substituted or unsubstituted phenyl" are selected from the group consisting of fluoro, chloro, bromo, iodo, methyl, methoxy, phenyl.
R 4 Represents one or more substituents on the attached phenyl ring, each R 3 The substituents are selected independently of one another from hydrogen, fluorine, chlorine, bromine, iodine, methyl, methoxy.
The aforementioned method according to the present invention, wherein the acid catalyst is selected from the group consisting of MsOH (methanesulfonic acid), HOTf (trifluoromethanesulfonic acid), HNTf 2 (bis (trifluoromethanesulfonyl) imide), cu (OTf) 2 、Zn(OTf) 2 、Sc(OTf) 2 、FeCl 3 Any one of them. Preferably, the acid catalyst is selected from HNTf 2 (bis (trifluoromethanesulfonylimide)).
According to the aforementioned preparation method of the present invention, the organic solvent is any one selected from DCE (dichloroethane), THF (tetrahydrofuran), and toluene. Preferably, said organic solvent is selected from DCE (dichloroethane).
According to the preparation method of the invention, the inert atmosphere refers to a nitrogen atmosphere or an argon atmosphere, and is preferably a nitrogen atmosphere.
According to the preparation method of the invention, the reaction time of the stirring reaction is 5 min-24 h, preferably 15min, and the reaction can be completed.
According to the preparation method, the feeding molar ratio of the alkynyl thioether compound shown in the formula I, the o-hydroxy benzyl alcohol compound shown in the formula II and the acid catalyst is 1 (1-2) to 0.01-0.2; preferably, the feeding molar ratio of the alkynyl thioether compound shown in the formula I, the o-hydroxybenzyl alcohol compound shown in the formula II and the acid catalyst is 1.
According to the preparation method of the invention, the reaction mechanism is as follows (scheme one):
compared with the prior art, the method of the invention has the following beneficial effects: the method of the invention uses brensted acid (A)
acid, preferably bis (trifluoromethanesulfonyl) imide) -catalyzes o-hydroxybenzyl alcohol compounds and electron-rich alkynyl thioether compounds to generate [4+2 ]]The preparation of the 2H-chromene compound by cyclization reaction is a brand-new synthesis strategy for preparing the 2H-chromene compound and has remarkable innovation. The method can be carried out at room temperature without using a metal catalyst, has the advantages of reaction time of only 15 minutes, high efficiency, excellent yield, wide substrate application range and excellent functional group tolerance, and can be used for synthesizing various valuable polysubstituted 2H-chromene compounds in a very practical way.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Hereinafter, unless otherwise specified, the methods are all conventional in the art, and the reagents used are commercially available in a conventional manner. Each reaction substrate can be prepared according to the preparation method known in the prior art and the existing synthesis conditions.
Reaction conditions optimization examples
The influence of different synthesis process conditions on the yield of the target product is discussed by using the phenylethynyl ethyl sulfide shown in the formula I-1 and the alpha-phenyl o-hydroxy benzyl alcohol shown in the formula II-1 as templates. The reaction formula is as follows:
example 1
A Schlenk closed-tube reactor was charged with phenylethynyl ethyl sulfide (0.2 mmol) represented by formula I-1, α -phenylphthalyl alcohol (0.24 mmol) represented by formula II-1, acid catalyst TsOH (0.2M in DCE, 0.1mL) and DCE (dichloroethane, 4.0 mL) in this order, the atmosphere in the reactor was replaced with nitrogen, the reaction was stirred at room temperature for 24 hours, 0.02mol of 1,3, 5-trimethoxybenzene was added to the reaction solution as an internal standard, the reaction solution was concentrated, and the yield was calculated to be less than 5% by sampling and nuclear magnetic resonance detection.
Example 2
Acid catalyst substituted for MsOH (0.2M in DCE, 0.1mL) and the conditions were the same as in example 1 with a nuclear magnetic yield of 30%.
Example 3
The acid catalyst was replaced with HOTf (0.2M in DCE, 0.1mL) for a reaction time of 15min, the rest of the conditions were the same as in example 1, in a NMR yield of 73%.
Example 4
Acid catalyst replacement to HNTf 2 (0.2M in DCE, 0.1mL), reaction time 15min, rest conditions as in example 1, nuclear magnetic yield 92%
Example 5
Acid catalyst replacement is Cu (OTf) 2 (0.02 mmol) and a reaction time of 18h, the same conditions as in example 1, NMR yield of 75%.
Example 6
Acid catalyst replacement by Zn (OTf) 2 (0.02 mmol), reaction time 12h, remainderThe conditions were the same as in example 1, and the nuclear magnetic yield was 83%.
Example 7
Acid catalyst replacement is Sc (OTf) 2 (0.02 mmol) and a reaction time of 12h, the other conditions were the same as in example 1, and the nuclear magnetic yield was 79%.
Example 8
Replacement of acid catalyst with FeCl 3 (0.02 mmol) and a reaction time of 15min, the other conditions were the same as in example 1, with a NMR yield of 76%.
Example 9
The solvent was replaced by THF, the reaction time was 24h, the other conditions were the same as in example 4, and the nuclear magnetic yield was 83%.
Example 10
The solvent was replaced by toluene, the reaction time was 3h, the other conditions were the same as in example 4, and the nuclear magnetic yield was 53%.
Substrate development examples
Based on the determination of the optimal conditions (example 4), the reaction conditions of example 4 are used as templates, the separation yield is calculated, the adaptability of different types of substrates to the reaction system is studied, and a series of 2H-chromene derivatives are prepared, and the reaction formula and the result are as follows:
EXAMPLE 11 Synthesis of the target product III-1
Phenylethynyl ethyl sulfide (0.2 mmol) shown in formula I-1, alpha-phenyl o-hydroxybenzyl alcohol (0.24 mmol) shown in formula II-1 and acid catalyst HNTf are sequentially added into a Schlenk tube-sealed reactor 2 (0.2M in DCE, 0.1mL) and DCE (dichloroethane, 4.0 mL), the atmosphere in the reactor was replaced with nitrogen, the reaction was stirred at room temperature for 15min, completion of the reaction was monitored by TLC, the reaction solution was concentrated, and the obtained residue was chromatographed on a silica gel column (elution solvent n-hexane/ethyl acetate) to give a 2H-chromene derivative represented by the formula III-1. Separation ofThe yield was 87%. Pale yellow solid (mp 111-113 ℃ C.). 1 H NMR(400MHz,CDCl 3 )δ7.80–7.77(m,1H),7.33–7.23(m,7H),7.20–7.16(m,3H),7.13–7.07(m,1H),6.98–6.93(m,1H),6.80(d,J＝8.0Hz,1H),6.04(s,1H),2.61–2.51(m,1H),2.47–2.37(m,1H),1.02(t,J＝7.6Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ152.4,141.4,138.6,137.7,129.4,129.3,128.4,128.3,127.9(3),127.8(6),127.7,126.5,126.3,122.6,121.4,117.0,81.0,28.0,14.5；IR(neat):3061,2962,2924,1598,1476,1451,1263,962,761,698；HRESIMS Calcd for[C 23 H 20 NaOS] + (M+Na + )367.1127,found 367.1138。
EXAMPLE 12 Synthesis of the target product III-2
EXAMPLE 13 Synthesis of the target product III-3
EXAMPLE 14 Synthesis of the target product III-4
EXAMPLE 15 Synthesis of the target product III-5
EXAMPLE 16 Synthesis of the target product III-6
EXAMPLE 17 Synthesis of the target product III-7
EXAMPLE 18 Synthesis of the target product III-8
EXAMPLE 19 Synthesis of the target product III-9
EXAMPLE 20 Synthesis of the target product III-10
EXAMPLE 21 Synthesis of the target product III-11
EXAMPLE 22 Synthesis of the target product III-12
EXAMPLE 23 Synthesis of the target product III-13
EXAMPLE 24 Synthesis of the target product III-14
EXAMPLE 25 Synthesis of the target product III-15
EXAMPLE 26 Synthesis of the target product III-16
EXAMPLE 27 Synthesis of the desired product III-17
EXAMPLE 28 Synthesis of the target product III-18
EXAMPLE 29 Synthesis of the target product III-19
EXAMPLE 30 Synthesis of the target product III-20
EXAMPLE 31 Synthesis of the target product III-21
The embodiments described above are only preferred embodiments of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (7)
1. A method for preparing a 2H-chromene derivative, comprising the steps of: sequentially adding an alkynyl thioether compound shown in a formula I, an o-hydroxy benzyl alcohol compound shown in a formula II, an acid catalyst and an organic solvent into a Schlenk tube-sealed reactor, replacing the reactor with an inert atmosphere, stirring at room temperature for reaction, monitoring by TLC (thin layer chromatography), concentrating reaction liquid, and performing chromatographic separation on obtained residues through a silica gel column to obtain a 2H-chromene derivative shown in a formula III; the reaction formula is as follows:
in the reaction formula, R1 is selected from one of C1-6 alkyl, C3-8 cycloalkyl, substituted or unsubstituted C6-14 aryl and C6-14 arylethenyl; wherein the substituent in said "substituted or unsubstituted C6-14 aryl" is selected from the group consisting of halogen, C1-6 alkyl, C1-6 alkoxy, halogen-substituted C1-6 alkyl;
r2 is selected from C1-6 alkyl, C6-14 aryl-C1-6 alkyl;
r3 is selected from substituted or unsubstituted C6-14 aryl; wherein the substituent in the "substituted or unsubstituted C6-14 aryl" is selected from the group consisting of halogen, C1-6 alkyl, C1-6 alkoxy, C6-14 aryl, halogen-substituted C1-6 alkyl;
r4 represents one or more substituents on the attached phenyl ring, each R3 substituent being selected independently from each other from hydrogen, halogen, C1-6 alkyl, C1-6 alkoxy;
the acid catalyst is selected from any one of MsOH (methanesulfonic acid), HOTf (trifluoromethanesulfonic acid), HNTf 2 (bis (trifluoromethanesulfonimide)), cu (OTf) 2, zn (OTf) 2, sc (OTf) 2 and FeCl 3;
the feeding molar ratio of the alkynyl thioether compound shown in the formula I, the o-hydroxy benzyl alcohol compound shown in the formula II and the acid catalyst is 1 (1-2) to 0.01-0.2.
2. The preparation method according to claim 1, wherein R1 is selected from one of cyclopropyl, substituted or unsubstituted phenyl, styryl; wherein the substituents in said "substituted or unsubstituted benzene" are selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, methoxy, trifluoromethyl;
r2 is selected from methyl, ethyl, phenyl and benzyl;
r3 is selected from substituted or unsubstituted phenyl; wherein the substituents in said "substituted or unsubstituted phenyl" are selected from the group consisting of fluoro, chloro, bromo, iodo, methyl, methoxy, phenyl;
r4 represents one or more substituents on the attached phenyl ring, each R3 substituent being selected independently from each other from hydrogen, fluoro, chloro, bromo, iodo, methyl, methoxy.
3. The process of claim 1 wherein the acid catalyst is selected from the group consisting of HNTf 2 (bis-trifluoromethanesulfonimide).
4. The method according to claim 1, wherein the organic solvent is selected from the group consisting of DCE (dichloroethane), THF (tetrahydrofuran), and toluene.
5. The method according to claim 1, wherein the inert gas atmosphere is a nitrogen gas atmosphere or an argon gas atmosphere.
6. The method according to claim 1, wherein the stirring reaction is carried out for a reaction time of 5min to 24 hours.
7. The method according to claim 1, wherein the molar ratio of the alkynyl thioether compound represented by formula I, the ortho-hydroxybenzyl alcohol compound represented by formula II, and the acid catalyst is 1.2.
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