CN113185376A - Synthesis method of (Z) -3-methylthio-2-bromoacrylate compound - Google Patents

Synthesis method of (Z) -3-methylthio-2-bromoacrylate compound Download PDF

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CN113185376A
CN113185376A CN202110467258.2A CN202110467258A CN113185376A CN 113185376 A CN113185376 A CN 113185376A CN 202110467258 A CN202110467258 A CN 202110467258A CN 113185376 A CN113185376 A CN 113185376A
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bromoacrylate
reaction
methylthio
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芦玲慧
吴超
彭村
周强
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Hunan University of Science and Engineering
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B45/00—Formation or introduction of functional groups containing sulfur
    • C07B45/06—Formation or introduction of functional groups containing sulfur of mercapto or sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

The invention discloses a method for synthesizing a (Z) -3-methylthio-2-bromoacrylate compound. The method comprises the step of carrying out multicomponent one-pot reaction on a propiolate compound, a bromization reagent and dimethyl sulfoxide to obtain a (Z) -3-methylthio-2-bromoacrylate compound. The method does not need to add a transition metal catalyst, obtains the (Z) -3-methylthio-2-bromoacrylate compound under mild conditions with high selectivity and high yield, has high reaction atom efficiency, low cost, environmental friendliness and simple separation and purification, and is beneficial to large-scale production.

Description

Synthesis method of (Z) -3-methylthio-2-bromoacrylate compound
Technical Field
The invention relates to a method for synthesizing a (Z) -3-methylthio-2-bromoacrylate compound. In particular to a method for synthesizing (Z) -3-methylthio-2-bromoacrylate compound by multi-component one-pot reaction of propiolate compound, bromization reagent and dimethyl sulfoxide under the condition of no additional transition metal catalyst, belonging to the technical field of organic intermediate synthesis.
Background
The (Z) -3-methylthio-2-bromoacrylate compound has a bioactive group and a modifiable group, and plays an important role in the field of drug development. According to literature and patent search, no relevant report on the preparation of (Z) -3-methylthio-2-bromoacrylate derivatives exists at present. Research on introduction of halogen atoms and thioether structures on multiple bonds through one-step alkyne bifunctional reaction is mainly limited to non-activated alkynes, such as Taniguchi 2009, which realizes the reaction of copper-catalyzed alkynes with tetrabutylammonium bromide and diaryl disulfide, and synthesizes (E) -2-arylthio-1-bromostyrene compounds (tetrahedron.2009,65, 2782-2790), as shown in the following reaction (a); in addition, in 2019, Sedrin et al reported that arylacetylene was reacted with dimethyl sulfoxide, 3 times the chemical equivalent of 1, 4-epoxy hexacyclic ring hydrochloride at 120 ℃ to give (E) -2-methylthio-1-chlorostyrene compound (Asian J.Org.Chem.2019,8, 479-one 481) as shown in reaction (b). These methods require the use of a transition metal catalyst or a large amount of 1, 4-epoxy-hexacyclic inorganic salt of hydrochloric acid, increase the reaction cost, and furthermore, the substrate structure of the reaction is relatively limited.
Figure BDA0003044660680000011
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for synthesizing a (Z) -3-methylthio-2-bromoacrylate compound by multi-component one-pot reaction from cheap raw materials such as propiolate compound, a bromization reagent, dimethyl sulfoxide and the like, the method does not need an additional transition metal catalyst, obtains the (Z) -3-methylthio-2-bromoacrylate compound in high selectivity and high yield under mild conditions, and has the advantages of high reaction atom efficiency, low cost, environmental friendliness, simple product separation and purification and contribution to large-scale production.
In order to realize the technical purpose, the invention provides a synthesis method of a (Z) -3-methylthio-2-bromoacrylate compound, which comprises the steps of carrying out multicomponent one-pot reaction on a propiolic acid ester compound, a bromization reagent and dimethyl sulfoxide to obtain the compound;
the propiolate compound has the structure of formula 1:
Figure BDA0003044660680000021
the (Z) -3-methylthio-2-bromoacrylate compound has the structure of formula 2:
Figure BDA0003044660680000022
wherein,
r is alkyl, alkyl containing hydroxyl substituent, aryl or alkyl containing aryl substituent.
In the (Z) -3-methylthio-2-bromoacrylate compound of the present invention, R is a substituent group introduced from a propiolate compound, and R may be an alkyl group, an alkyl group having a hydroxyl substituent, an aryl group or an alkyl group having an aryl substituent. The alkyl group is C1～C10The alkyl group of (2) may be a straight-chain alkyl group or a branched-chain alkyl group, and when the number of carbon atoms is more than 3, the alkyl group may be a cyclic structure, specifically, methyl group, ethyl group, butyl group, isobutyl group, hexyl group, cyclohexyl group, and the like. The alkyl containing the hydroxyl substituent is C containing the hydroxyl substituent1～C10The number and position of the hydroxyl group of the alkyl group (b) are not limited, and the hydroxyl group can be any carbon atom on the alkyl main chain, and is usually an alkyl group containing one terminal hydroxyl group. The aryl can be phenyl, naphthyl or phenyl containing substituent, wherein the phenyl containing substituent is the substituent derived from phenyl, the benzene ring contains common substituent, and can be halogen substituent, trifluoromethyl, trifluoromethoxy, nitro or C1～C5Alkyl of (C)1～C5Alkoxy group of (C)1～C4The phenyl group as at least one substituent of the alkoxyacyl group in (1), may be a benzo-heterocycle group or the like; halogen substituents such as fluoro, chloro, bromo or iodo substituents; c1～C5Alkyl groups such as methyl, ethyl, butyl, isobutyl, etc., C1～C5Alkoxy groups such as methoxy, ethoxy, butoxy and the like, C1～C4Alkoxyacyl such as methoxyacyl, ethoxyacyl and the likeThe phenyl group containing substituent(s) may contain one or more substituents, generally one substituent, and the position of the substituent(s) is not limited, and may be ortho, meta or para. The alkyl containing aryl substituent is C containing benzene ring substituent1～C5Most commonly, alkyl groups such as benzyl. The influence of R on the reaction for synthesizing the (Z) -3-methylthio-2-bromoacrylate compound by three components of propiolate compound, bromization reagent and dimethyl sulfoxide is not obvious, and the yield of the (Z) -3-methylthio-2-bromoacrylate compound is kept above 85% when R selects different substituents under optimized reaction conditions.
As a preferred scheme, the brominating agent is Br2NBS and DBDMH. The optimized brominating reagent can be used as a bromine source for synthesizing the (Z) -3-methylthio-2-bromoacrylate compound, higher yield of target products can be obtained, the best effect is NBS, and in addition, NH4The ionic bromine source such as Br can not react with propiolate compound and dimethyl sulfoxide to obtain the target product.
In a preferred embodiment, the amount of the brominating agent is 90 to 150% of the molar amount of the propiolic acid ester compound. When the relative amount of the brominating agent is more than 100% of the molar amount of the propiolic acid ester compound, the reaction effect is not obviously increased, and when the relative amount of the brominating agent is less than 100% of the molar amount of the propiolic acid ester compound, the yield of the target product has a tendency of decreasing, especially when the relative amount of the brominating agent is less than 90% of the molar amount of the propiolic acid ester compound, the yield of the target product is obviously decreased. The amount of the brominating agent is more preferably 100 to 110% by mole of the propiolic acid ester compound.
As a preferred embodiment, the reaction employs triethylamine and/or diisopropylethylamine as a catalyst. A large number of experiments show that the reaction can be smoothly carried out without adding a catalyst, but the yield is relatively low, the yield of the (Z) -3-methylthio-2-bromoacrylate compound can be increased by adding triethylamine or diisopropylethylamine as the catalyst, the effect is obvious particularly when the diisopropylethylamine is used as the catalyst, and the reaction effect is not obviously improved or is not beneficial to the reaction when other tetramethylethylenediamine or triethylenediamine and the like are used as the catalyst.
In a preferred embodiment, the amount of the catalyst is 5 to 30% by mole of the propiolic acid ester compound. The amount of the catalyst is preferably 5 to 15 mol%, most preferably 10 mol%, based on the amount of the propiolic acid ester compound. The amount of the catalyst is 10% or less by mole of the propiolic acid ester compound, and the yield of the target product is slightly reduced.
As a preferred embodiment, the reaction conditions are: reacting for 6-10 hours at 85-105 ℃. The reaction can be ensured to be carried out smoothly at the temperature of 85-105 ℃, the (Z) -3-methylthio-2-bromoacrylate compound target product can be obtained with high selectivity, the reaction can be ensured to obtain a relatively ideal target product yield at the temperature of 90-100 ℃, if the temperature is too high, the selectivity of the reaction is obviously reduced, the target product yield is also reduced, and if the temperature is too low, the reaction yield is correspondingly reduced.
The dimethyl sulfoxide of the invention is used as a benign solvent for reaction and also as a cheap reaction raw material, and the dosage proportion is relatively excessive and is common solvent addition amount, which can be understood by a person skilled in the art.
The route of the reaction of propiolate compound, bromization reagent and methyl sulfoxide is as follows:
Figure BDA0003044660680000041
the invention also provides a reaction mechanism for synthesizing the (Z) -3-methylthio-2-bromoacrylate compound: the reaction between ethyl propiolate, NBS and dimethyl sulfoxide is specifically described as an example. Firstly, N-bromosuccinimide as a bromization reagent and ethyl propiolate are subjected to Michael addition reaction, a (Z) -1, 2-dibromo ethyl acrylate intermediate is obtained with high stereoselectivity, dimethyl sulfoxide is heated to decompose to generate methyl mercaptan, and the dibromo ethyl acrylate intermediate is further subjected to nucleophilic substitution reaction with methyl mercaptan to generate (Z) -3-methylthio-2-bromoacrylate and release hydrogen bromide molecules.
Figure BDA0003044660680000042
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) the method adopts common bromization reagent and dimethyl sulfoxide as reaction raw materials, has low raw material cost, and the dimethyl sulfoxide is not only a reaction substrate but also a reaction medium, has high atom economy and does not need to additionally add an oxidant;
2) the propiolic acid ester compound adopted by the invention has wide selectivity and good functional group compatibility;
3) the invention does not use transition metal catalyst, has high reaction selectivity, easy separation and purification of the product and high yield;
4) the method has simple reaction steps, can be realized through one-pot reaction, has mild reaction conditions, and can be realized under the condition of lower temperature.
Drawings
FIG. 1 shows (Z) -3-methylthio-2-bromoacrylic acid ethyl ester1H NMR。
FIG. 2 shows (Z) -3-methylthio-2-bromoacrylic acid ethyl ester13C NMR。
Detailed Description
The following specific examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
The reaction raw materials referred to in the following examples are conventional commercial raw materials unless otherwise specified.
Taking the reaction of ethyl propiolate, dimethyl sulfoxide and N-bromosuccinimide under the optimal reaction condition as a standard reaction, the specific reaction formula is as follows:
Figure BDA0003044660680000051
the specific operation steps are as follows: in an 8mL reaction flask, ethyl propiolate (0.5mmol), diisopropylethylamine (0.05mmol), N-bromosuccinimide (0.5mmol), and DMSO (1.0mL) were sequentially added. The resulting mixture was stirred at 95 ℃ for reaction. The progress of the reaction was monitored by thin layer chromatography for 8 hours. After the reaction was completed, the reaction mixture was poured into 10ml of water and extracted with ethyl acetate (3 ml. times.2), the organic phases were combined and washed with saturated brine, the solvent was removed under reduced pressure, and the yield was analyzed by nuclear magnetic crude spectrum.
The following experimental groups 1 to 16 are illustrated by comparison with reference to the standard reaction:
Figure BDA0003044660680000052
in the table, experiment groups 1-4 investigate the influence of different tertiary amine catalysts on the reaction, and experiments show that the reaction can be smoothly carried out when no catalyst is added, but the reaction selectivity is low, and i-Pr is added2When NEt or triethylamine is used as catalyst, the yield and selectivity of target product are improved to a certain extent, and i-Pr is adopted in specific2When NEt is used as a catalyst, the yield and selectivity of the target product are highest, while when tetramethylethylenediamine or triethylenediamine is used as a catalyst for the reaction instead of diisopropylethylamine, the reaction yield is obviously reduced and the stereoselectivity is also deteriorated.
In the table, experiment groups 1 and 5-7 investigate the influence of the dosage of the diisopropylethylamine catalyst on the reaction, experiments show that the dosage of the catalyst is 0.1 equivalent of the substrate of the ethyl propiolate, the reaction is most facilitated, and the highest target product yield can be obtained, while when the dosage of the diisopropylethylamine is lower than 0.1 equivalent of the substrate of the ethyl propiolate, the reaction effect is obviously reduced, and when the dosage of the diisopropylethylamine is increased to be higher than 0.1 equivalent, the reaction yield is not obviously improved. If diisopropylethylamine is not used in the reaction, the reaction yield is remarkably reduced to 22%, which shows that the use of the catalyst can remarkably improve the reaction effect.
In the table, experiment groups 1 and 8-10 investigate the influence of different bromination reagents on the reaction, and experiments show that the bromine simple substance, the dibromohydantoin and the N-bromosuccinimide can be used as the bromination reagents for synthesizing the (Z) -1, 2-dibromo ethyl acrylate, but when the bromine simple substance and the dibromohydantoin are adopted, the reaction yield is respectively reduced to 61% and 87%, the effect is slightly inferior to that of the N-bromosuccinimide, and the reaction cannot be carried out when the ionic bromine sources such as ammonium bromide are used for replacing the N-bromosuccinimide.
In the table, experiment groups 1 and 11-13 investigate the influence of the usage amount of the N-bromosuccinimide on the reaction, experiments show that the usage amount of the N-bromosuccinimide is 90-150% of the molar amount of the ethyl propiolate substrate, the reaction can be smoothly carried out, the yield of the target product of more than 80% can be obtained, the usage amount of the N-bromosuccinimide is within 100-110% of the molar amount of the ethyl propiolate substrate, the yield of the target product of more than 90% can be obtained, the reaction effect is not obviously improved by the excessive N-bromosuccinimide, the bromo reagent is wasted, and the yield of the target product can be obviously reduced when the usage amount of the N-bromosuccinimide is too low.
In the table, the experiment groups 1 and 14-16 examine the influence of the reaction temperature on the reaction, and experiments show that when the reaction temperature is reduced to 85 ℃, the reaction yield is obviously reduced, the reaction effect is relatively poor, and when the reaction temperature is increased to 105 ℃ and 115 ℃, the reaction yield is reduced to a certain extent, and the stereoselectivity of the product is poor. Therefore, the optimal reaction temperature of the reaction is 90-100 ℃.
Examples 1 to 6
The following examples 1 to 6 all react under the optimal reaction conditions, and the specific reaction equation is as follows, mainly examining the yield conditions of different substrates reacting under the optimal conditions:
Figure BDA0003044660680000071
the specific operation steps are as follows: to an 8mL reaction flask, propiolate (1.0mmol), diisopropylethylamine (0.1mmol), N-bromosuccinimide (1.0mmol), and DMSO (1.5mL) were added in this order. The resulting mixture was stirred at 95 ℃ for reaction. The progress of the reaction was monitored by thin layer chromatography for 8 hours. After the reaction was completed, the reaction mixture was poured into 15ml of water and extracted with ethyl acetate (5ml × 2), and the organic phases were combined, washed with saturated brine, dried, concentrated in vacuo and purified by chromatography to give the objective compound.
Example 1
Compound 1: yield 92%, ethyl (Z) -2-bromo-3- (meththio) acrylate;
Figure BDA0003044660680000072
1H NMR(400MHz,CDCl3)δ8.11(s,1H),4.27(q,J＝7.2Hz,2H),2.52(s,3H),1.33(t,J＝7.2Hz,3H).
13C NMR(100MHz,CDCl3)δ161.1,149.0,107.7,62.2,17.12,14.2.
example 2
Compound 2: yield 90%, cyclohexyl (Z) -2-bromo-3- (methythio) acrylate;
Figure BDA0003044660680000073
1H NMR(400MHz,CDCl3)δ8.07(s,1H),4.92–4.83(m,1H),2.51(s,3H),1.87–1.85(m,2H),1.76–1.73(m,2H),1.57(s,3H),1.56–1.48(m,3H),1.42–1.30(m,3H).
13C NMR(100MHz,CDCl3)δ160.5,148.5,108.4,74.6,31.5,25.3,23.5,17.1.
example 3
Compound 3: yield 93%, 4-hydroxybutyl (Z) -2-bromo-3- (methythio) acrylate;
Figure BDA0003044660680000074
1H NMR(400MHz,CDCl3)δ8.11(s,1H),4.25(t,J＝6.4Hz,2H),3.71(q,J＝6.4Hz,2H),2.52(s,3H),1.84–1.77(m,2H),1.71–1.64(m,2H),1.26(s,1H).
13C NMR(100MHz,CDCl3)δ161.1,149.3 107.4,66.0,62.3,29.1,25.1,17.1.
example 4
Compound 4: yield 89%, benzyl (Z) -2-bromo-3- (methythio) acrylate;
Figure BDA0003044660680000081
1H NMR(400MHz,CDCl3)δ8.15(s,1H),7.40–7.35(m,5H),5.25(s,2H),2.50(s,3H).
13C NMR(100MHz,CDCl3)δ160.9,149.8,135.5,128.6,128.4,128.2,107.3,67.8,17.2.
example 5
Compound 5: yield 92%, benzod [1,3] dioxol-5-yl (Z) -2-bromo-3- (methythio) acrylate;
Figure BDA0003044660680000082
1H NMR(400MHz,CDCl3)δ8.34(s,1H),6.78(d,J＝8.8Hz,2H),6.64(s,1H),6.57(d,J＝9.6Hz,2H),6.00(s,2H),2.56(s,3H).
13C NMR(100MHz,CDCl3)δ159.8,151.7,148.0,145.5,145.1,113.9,107.9,106.3,103.6,101.7,17.3.
example 6
Compound 6: yield 85%, 4-bromophenyl (Z) -2-bromoo-3- (methythio) acrylate;
Figure BDA0003044660680000083
1H NMR(400MHz,CDCl3)δ8.38(s,1H),7.51(d,J＝8.8Hz,2H),7.03(d,J＝8.8Hz,2H),2.57(s,3H)；
13C NMR(100 MHz,CDCl3)δ159.2,152.3,149.8,132.5,123.2,119.1,105.9,17.3.

Claims (8)

1. a method for synthesizing (Z) -3-methylthio-2-bromoacrylate compound is characterized in that: carrying out multi-component one-pot reaction on the propiolate compound, the bromization reagent and dimethyl sulfoxide to obtain the compound;
the propiolate compound has the structure of formula 1:
Figure FDA0003044660670000011
the (Z) -3-methylthio-2-bromoacrylate compound has the structure of formula 2:
Figure FDA0003044660670000012
wherein,
r is alkyl, alkyl containing hydroxyl substituent, aryl or alkyl containing aryl substituent.
2. The method for synthesizing a (Z) -3-methylthio-2-bromoacrylate compound according to claim 1, wherein:
the alkyl group is C1～C10Alkyl groups of (a);
the alkyl containing the hydroxyl substituent is C containing the hydroxyl substituent1～C10Alkyl groups of (a);
the aryl is phenyl, naphthyl or phenyl containing substituent, and the phenyl containing substituent is halogen substituent, trifluoromethyl, trifluoromethoxy, nitro or C1～C5Alkyl of (C)1～C5Alkoxy group of (C)1～C4Phenyl group as at least one substituent of the alkoxyacyl group of (a);
the above-mentionedThe alkyl containing aryl substituent is C containing benzene ring substituent1～C5Alkyl group of (1).
3. The method for synthesizing a (Z) -3-methylthio-2-bromoacrylate compound according to claim 1, wherein: the brominating agent is Br2NBS and DBDMH.
4. The method for synthesizing a (Z) -3-methylsulfanyl-2-bromoacrylate compound according to claim 1 or 3, wherein: the dosage of the bromization reagent is 90-150% of the molar weight of the propiolic acid ester compound.
5. The method for synthesizing a (Z) -3-methylthio-2-bromoacrylate compound according to claim 1, wherein: the one-pot reaction adopts triethylamine and/or diisopropylethylamine as a catalyst.
6. The method for synthesizing a (Z) -3-methylsulfanyl-2-bromoacrylate compound according to claim 1 or 5, wherein: the dosage of the catalyst is 5-30% of the molar weight of the propiolic acid ester compound.
7. The method for synthesizing a (Z) -3-methylsulfanyl-2-bromoacrylate compound according to claim 1,2, 3 or 5, wherein: the conditions of the one-pot reaction are as follows: reacting for 6-10 hours at 85-105 ℃.
8. The method for synthesizing a (Z) -3-methylsulfanyl-2-bromoacrylate compound according to claim 7, wherein: the conditions of the one-pot reaction are as follows: reacting for 7-9 hours at the temperature of 90-100 ℃.
CN202110467258.2A 2021-04-28 2021-04-28 Synthesis method of (Z) -3-methylthio-2-bromoacrylate compound Pending CN113185376A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004178A (en) * 2021-03-12 2021-06-22 湖南科技学院 Synthesis method of (E) -3-methylthio-2-iodoacrylate compound
CN113045463A (en) * 2021-03-26 2021-06-29 湖南科技学院 Synthesis method of (E) -3-arylthio-2-iodoethyl acrylate compound

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004178A (en) * 2021-03-12 2021-06-22 湖南科技学院 Synthesis method of (E) -3-methylthio-2-iodoacrylate compound
CN113045463A (en) * 2021-03-26 2021-06-29 湖南科技学院 Synthesis method of (E) -3-arylthio-2-iodoethyl acrylate compound

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