CN115260134A - Synthetic method of perfume intermediate 2-methyl-3-furanthiol acetate - Google Patents
Synthetic method of perfume intermediate 2-methyl-3-furanthiol acetate Download PDFInfo
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- CN115260134A CN115260134A CN202211039029.1A CN202211039029A CN115260134A CN 115260134 A CN115260134 A CN 115260134A CN 202211039029 A CN202211039029 A CN 202211039029A CN 115260134 A CN115260134 A CN 115260134A
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 ring carbon atoms
- C07D307/64—Sulfur atoms
Abstract
The invention discloses a synthetic method of a perfume intermediate 2-methyl-3-furanthiol acetate, which comprises the following steps: firstly, acetaldehyde and methylglyoxal are subjected to the catalytic action of prolinol and derivatives thereof through an aldol condensation process to obtain 3-hydroxy-4-oxo-valeraldehyde; adding organic alkali and methanesulfonyl chloride into the 3-hydroxy-4-oxo-valeraldehyde solution at low temperature, then heating to 20-40 ℃ to carry out substitution reaction of methanesulfonyl and hydrogen in hydroxyl to obtain a compound 2; dissolving the compound 2 in an organic solvent, adding potassium thioacetate and a phase transfer catalyst, and replacing an-OMS group in the compound 2 with a-SAC group to prepare 1,4-pentadecanyl-3-yl-ethanesulfate; 5363 and cyclizing the vinyl acetate solution of 1,4-pentadecanyl-3-yl-ethanesulfate under the catalysis of concentrated sulfuric acid to obtain 2-methyl-3-furanthiol acetate. The synthesis method has the advantages of simpler operation, less three wastes, high selectivity, and guaranteed yield and product quality, and is more suitable for industrial scale-up production.
Description
Technical Field
The invention belongs to the technical field of synthesis of perfume intermediates, and particularly relates to a synthesis method of a perfume intermediate 2-methyl-3-furanthiol acetate.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
2-methyl-3-mercapto furan is an important edible spice and is mainly applied to the field of food spices at present. The meat flavor enhancer exists in meat products, is a main flavor and taste substance, and is used in beef, pork, chicken and flavoring essence at present.
The 2-methyl-3-furanthiol acetate (e) is a key intermediate for synthesizing 2-methyl-3-mercaptofuran, and the 2-methyl-3-furanthiol acetate (e) is prepared by using 2-methylfuran (a) as a raw material, carrying out methoxylation and hydrolysis to obtain 4-carbonyl-2-pentenal (c), then carrying out nucleophilic addition with thioacetic acid to obtain 3-acetylthio-4-oxopentanal (d), and cyclizing the 3-acetylthio-4-oxopentanal (d) under the action of acid catalysis to obtain the 2-methyl-3-furanthiol acetate (e). The synthetic route is as follows:
in the method, the nucleophilic addition reaction of the 4-carbonyl-2-pentenal (c) and the thioacetic acid easily produces an isomer 2-acetylthio-4-oxopentanal (d ', and the structural formula of the d' is as follows:
) Resulting in lower yield and difficult purification, which severely restricts the wide application of 2-methyl-3-mercaptofuran.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a synthetic method of a perfume intermediate 2-methyl-3-furanthiol acetate, which has the advantages of simpler operation, less three wastes, high selectivity, guaranteed yield and product quality and is more suitable for industrial large-scale production.
In order to realize the purpose, the invention is realized by the following technical scheme:
a synthetic method of a perfume intermediate 2-methyl-3-furanthiol acetate comprises the following steps:
carrying out aldol condensation on acetaldehyde and methylglyoxal under the catalytic action of prolinol and derivatives thereof to obtain a compound 1, namely 3-hydroxy-4-oxo valeraldehyde;
adding organic base and methanesulfonyl chloride into the 3-hydroxy-4-oxo-valeraldehyde solution at low temperature, then heating to 20-40 ℃ to carry out substitution reaction of methanesulfonyl and hydrogen in hydroxy to obtain a compound 2;
dissolving the compound 2 in an organic solvent, adding potassium thioacetate and a phase transfer catalyst into the organic solvent, and substituting a-OMS group in the compound 2 by a-SAC group to prepare 1,4-pentadecanyl-3-yl-ethanesulfate;
5363 and cyclizing the vinyl acetate solution of 1,4-pentadecanyl-3-yl-ethanesulfate under the catalysis of concentrated sulfuric acid to obtain 2-methyl-3-furanthiol acetate.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
firstly, replacing hydroxy hydrogen in 3-hydroxy-4-oxo-valeraldehyde with methylsulfonyl, and then replacing-OMS group with-SAC, compared with the prior art, the thiosubstituted intermediate has no isomer d', good selectivity and high yield.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a nuclear magnetic hydrogen spectrum of 2-methyl-3-furanthiol acetate prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic carbon spectrum of 2-methyl-3-furanthiol acetate prepared in example 1 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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.
A synthetic method of a perfume intermediate 2-methyl-3-furanthiol acetate comprises the following steps:
performing aldol condensation on acetaldehyde and methylglyoxal under the catalytic action of prolinol and derivatives thereof to obtain a compound 1, namely 3-hydroxy-4-oxo valeraldehyde;
adding organic base and methanesulfonyl chloride into the 3-hydroxy-4-oxo-valeraldehyde solution at low temperature, then heating to 20-40 ℃ to carry out substitution reaction of methanesulfonyl and hydrogen in hydroxy to obtain a compound 2;
dissolving the compound 2 in an organic solvent, adding potassium thioacetate and a phase transfer catalyst into the organic solvent, and substituting a-OMS group in the compound 2 by a-SAC group to prepare 1,4-pentadecanyl-3-yl-ethanesulfate;
5363 and cyclizing the vinyl acetate solution of 1,4-pentadecanyl-3-yl-ethanesulfate under the catalysis of concentrated sulfuric acid to obtain 2-methyl-3-furanthiol acetate.
Acetaldehyde and methylglyoxal undergo aldol condensation under the catalytic action of prolinol and derivatives thereof to obtain a compound 1, namely 3-hydroxy-4-oxo-valeraldehyde, which is also the most critical step of the synthesis method and ensures the position single selectivity of a thiointermediate.
The low temperature is used to prevent local overheating. The organic base is used for neutralizing the generated hydrochloric acid, so that the reaction is more complete.
The phase transfer catalyst functions to promote the dissolution of potassium thioacetate in the organic solvent.
In some embodiments, the low temperature is from-5 to 5 ℃, preferably from-1 to 1 ℃, such as may be 0 ℃.
In some embodiments, the organic base is triethylamine, piperidine, or potassium carbonate.
In some embodiments, the phase transfer catalyst is tetrabutylammonium bromide or 18-crown-6.
In some embodiments, the solvent for the solution of 3-hydroxy-4-oxopentanal is dichloromethane, chloroform, acetonitrile or ethyl acetate.
In some embodiments, the temperature of the substitution reaction is from 25 ℃ to 35 ℃ for 5 to 7 hours.
Preferably, in the reaction system, the molar ratio of the 3-hydroxy-4-oxo-valeraldehyde to the organic base to the methanesulfonyl chloride is 1.0 to 2.5.
In some embodiments, the molar ratio of compound 2, potassium thioacetate, and phase transfer catalyst during the preparation of 1,4-pentadecan-3-yl-ethanesulfate is 1: 1.0-3.0: 0.001 to 0.1.
Preferably, the organic solvent is acetone, tetrahydrofuran, acetonitrile or chloroform.
Preferably, the catalytic reaction temperature of the compound 2 and the potassium thioacetate is 20-40 ℃ and the time is 20-30h.
Preferably, potassium thioacetate and 18-crown-6 are added to the compound 2 solution under stirring. The stirring function is to ensure that the reaction substrates are fully contacted, so that the reaction is more thorough and the side reaction is avoided.
In some embodiments, the preparation method of the 3-hydroxy-4-oxo-valeraldehyde comprises the steps of taking methylglyoxal and acetaldehyde as raw materials, taking tetrahydrofuran as a solvent, and reacting for 10-14h at 25-35 ℃ under the catalysis of L-prolinol.
The present invention will be further described with reference to the following examples.
Example 1
The synthetic route for methyl-3-furanthiol acetate is shown below:
the synthetic method of the 2-methyl-3-furanthiol acetate comprises the following steps:
a: to 50mL of tetrahydrofuran solvent containing methylglyoxal (40% aqueous solution, 10.4g, 47.2mmol), aqueous acetaldehyde (40% aqueous solution, 10.4g, 94.4mmol) and L-prolinol (0.24g, 2.36mmol) were added at 25 ℃ to react at room temperature for 12 hours, aldol condensation reaction was carried out, the solvent was removed under reduced pressure, and 3-hydroxy-4-oxopentanal 1 (4) was obtained by extractive separation with ethyl acetate and water, drying and distillation under reduced pressure.3g, 36.81mmol), yield 78%. 1 H NMR(500MHz,CDCl 3 )δ9.97(s,1H),4.57-4.32(m,1H),3.71(s,1H),2.95(dd,1H,J＝16Hz,4Hz),2.82(dd,1H,J＝16Hz,4Hz),2.15(s,3H). 13 C NMR(125MHz,CDCl 3 )δ210.5,198.4,73.2,43.8,26.4.
B: dissolving all of the 3-hydroxy-4-oxopentanal (4.3 g, 36.81mmol) prepared in step A in 50mL of dichloromethane, adding triethylamine (5.58g, 55.22mmol) at 0 ℃, dropwise adding methanesulfonyl chloride (4.23g, 36.81mmol) while maintaining at 0 ℃, stirring for 30 minutes after dropwise addition, raising the temperature to room temperature, stirring for 6 hours, diluting with dichloromethane and water, extracting and separating, drying, and distilling under reduced pressure to obtain methanesulfonate compound 2 (6.0g, 30.92mmol), with a yield of 84%.
C: dissolving the whole mesylate compound 2 (6.0g, 30.92mmol) prepared in the step B in 40mL of acetone, adding potassium thioacetate (3.52g, 30.92mmol) and a catalytic amount of 18-crown-6 (82mg, 0.31mmol) respectively under the stirring condition, stirring at room temperature for 24 hours, distilling under reduced pressure to remove acetone, diluting with ethyl acetate, adding deionized water, extracting and separating, drying, distilling under reduced pressure to obtain an intermediate 1,4-pentadecanyl-3-yl-ethanesulfate d (4.36g, 25.05mmol), wherein the yield is 81%. 1 H NMR(500MHz,CDCl 3 )δ9.83(s,1H),4.11-3.87(m,1H),3.44-3.29(m,1H),3.18-3.03(m,1H),2.41(s,3H),2.10(s,1H). 13 C NMR(125MHz,CDCl 3 )δ201.5,199.4,192.4,49.8,41.5,31.8,28.6.
D: adding a catalytic amount of concentrated sulfuric acid (0.2 mL) into 40mL of vinyl acetate solution, heating to reflux, dropwise adding a vinyl acetate (15 mL) solution of all the compounds 1,4-pentamethylene dicarbonyl-3-yl-ethyl sulfate d (4.36g, 25.05mmol) prepared in the step C, continuously refluxing for 2 hours after dropwise adding is finished, cooling to room temperature, removing the solvent under reduced pressure to obtain yellow oily liquid, diluting with ethyl acetate, adding water for extraction and separation, drying, and performing column chromatography to obtain 2-methyl-3-furanthiol acetate e (3.36g, 21.54mmol), wherein the yield is 86%.
1 H NMR(500MHz,CDCl 3 )δ7.38(d,J＝1.9Hz,1H),6.34(d,J＝1.9Hz,1H),2.40(s,4H),2.28(s,3H). 13 C NMR(126MHz,CDCl 3 )δ194.1,156.1,141.1,114.8,104.4,29.7,11.9.
Example 2
The synthetic method of the 2-methyl-3-furanthiol acetate comprises the following steps:
a: aqueous acetaldehyde (40% aqueous solution, 10.4g,94.4 mmol) and then (R) -diphenylprolinol (0.60g, 2.36mmol) were added to 50mL of tetrahydrofuran solvent at 25 ℃ to react at room temperature for 12 hours, aldol reaction was carried out, the solvent was removed under reduced pressure, and 3-hydroxy-4-oxopentanal 1 (3.9g, 33.98mmol) was obtained by extractive separation with ethyl acetate and water, drying and distillation under reduced pressure with a yield of 72%. 1 H NMR(500MHz,CDCl 3 )δ9.97(s,1H),4.57-4.32(m,1H),3.71(s,1H),2.95(dd,1H,J＝16Hz,4Hz),2.82(dd,1H,J＝16Hz,4Hz),2.15(s,3H). 13 C NMR(125MHz,CDCl 3 )δ210.5,198.4,73.2,43.8,26.4.
B: all of the 3-hydroxy-4-oxopentanal (3.9g, 33.98mmol) prepared in step A was dissolved in 50mL of dichloromethane, piperidine (4.33g, 50.97mmol) was added at 0 ℃, methanesulfonyl chloride (3.89g, 33.98mmol) was added dropwise while maintaining at 0 ℃, after stirring for 30 minutes, the temperature was raised to room temperature, stirring was carried out for 6 hours, the mixture was diluted with dichloromethane and water and then extracted and separated, and after drying, it was distilled under reduced pressure to give methanesulfonate compound 2 (5.27g, 27.18mmol) in a yield of 80%.
C: all of the methanesulfonate compound 2 (5.27g, 27.18mmol) prepared in step B was dissolved in 40mL of acetonitrile, and potassium thioacetate (3.1g, 27.18mmol) and a catalytic amount of 18-crown-6 (71mg, 0.27mmol) were added thereto under stirring, and the mixture was stirred at room temperature for 24 hours, then acetone was distilled off under reduced pressure, diluted with ethyl acetate, then deionized water was added thereto, followed by extraction separation, drying and distillation under reduced pressure to give an intermediate 1,4-pentadecan-3-yl-ethanesulfate d (3.5g, 20.11mmol) with a yield of 74%. 1 H NMR(500MHz,CDCl 3 )δ9.83(s,1H),4.11-3.87(m,1H),3.44-3.29(m,1H),3.18-3.03(m,1H),2.41(s,3H),2.10(s,1H). 13 C NMR(125MHz,CDCl 3 )δ201.5,199.4,192.4,49.8,41.5,31.8,28.6.
D: adding a catalytic amount of concentrated sulfuric acid (0.2 mL) into 40mL of vinyl acetate solution, heating to reflux, dropwise adding a vinyl acetate (15 mL) solution of all the compounds 1,4-pentadecan-3-yl-ethanesulfate d (3.5g, 20.111mmol) prepared in the step C, continuously refluxing for 2 hours after dropwise adding, cooling to room temperature, removing the solvent under reduced pressure to obtain yellow oily liquid, diluting with ethyl acetate, adding water for extraction and separation, drying, and performing column chromatography to obtain 2-methyl-3-furanthiol acetate e (2.64g, 16.89mmol), wherein the yield is 84%.
1 H NMR(500MHz,CDCl 3 )δ7.38(d,J＝1.9Hz,1H),6.34(d,J＝1.9Hz,1H),2.40(s,4H),2.28(s,3H). 13 C NMR(126MHz,CDCl 3 )δ194.1,156.1,141.1,114.8,104.4,29.7,11.9.
Example 3
The difference from example 1 is that: triethylamine was replaced with potassium carbonate, the number of moles of potassium carbonate being the same as the number of moles of triethylamine in example 1. Other parameters were the same as in example 1. The yield of 2-methyl-3-furanthiol acetate e was 85%.
Example 4
The difference from the embodiment 1 is that: "18-crown-6" in step C was replaced with "tetrabutylammonium bromide", the same number of moles of tetrabutylammonium bromide as the number of moles of 18-crown-6 in example 1. Other parameters were the same as in example 1. The yield of 2-methyl-3-furanthiol acetate e was 83%.
Example 5
The difference from example 1 is that: "3-hydroxy-4-oxopentanal (4.3g, 36.81mmol)" dissolved in 50mL of dichloromethane in step B "was replaced by" 3-hydroxy-4-oxopentanal (4.3g, 36.81mmol) dissolved in 50mL of acetonitrile ". Other parameters were the same as in example 1. The yield of 2-methyl-3-furanthiol acetate e was 84%.
Comparative example 1
The difference from the embodiment 1 is that: the "addition of triethylamine (5.58g, 55.22mmol) at 0 ℃ in step B" was omitted, and the other parameters were the same as in example 1. The yield of 2-methyl-3-furanthiol acetate e was 0%.
Comparative example 2
The difference from the embodiment 1 is that: "Add Triethylamine (5.58g, 55.22mmol) at 0 ℃ and methanesulfonyl chloride (4.23g, 36.81mmol) dropwise while maintaining 0 ℃ in step B" was replaced with "add triethylamine (5.58g, 55.22mmol) at 10 ℃ and methanesulfonyl chloride (4.23g, 36.81mmol) dropwise while maintaining 10 ℃ in step B", and the other parameters were the same as in example 1. The yield of 2-methyl-3-furanthiol acetate e was 45%.
Comparative example 3
The difference from example 1 is that: the catalyst "L-prolinol" in step A was changed to piperidine of the same molar mass, and the other parameters were the same as in example 1. The yield of 2-methyl-3-furanthiol acetate e was 10%.
Comparative example 4
The difference from the embodiment 1 is that: the catalyst "L-prolinol" in step A was changed to triethylamine of the same molar mass, and the other parameters were the same as in example 1. The yield of 2-methyl-3-furanthiol acetate e was 0.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A synthetic method of a perfume intermediate 2-methyl-3-furanthiol acetate is characterized in that: the method comprises the following steps:
carrying out aldol condensation on acetaldehyde and methylglyoxal under the catalytic action of prolinol and derivatives thereof to obtain a compound 1, namely 3-hydroxy-4-oxo valeraldehyde;
adding organic alkali and methanesulfonyl chloride into the 3-hydroxy-4-oxo-valeraldehyde solution at low temperature, then heating to 20-40 ℃ to carry out substitution reaction of methanesulfonyl and hydrogen in hydroxyl to obtain a compound 2;
dissolving the compound 2 in an organic solvent, adding potassium thioacetate and a phase transfer catalyst into the organic solvent, and substituting a-OMS group in the compound 2 by a-SAC group to prepare 1,4-pentadecanyl-3-yl-ethanesulfate;
5363 and cyclizing the vinyl acetate solution of 1,4-pentadecanyl-3-yl-ethanesulfate under the catalysis of concentrated sulfuric acid to obtain 2-methyl-3-furanthiol acetate.
2. The method for synthesizing 2-methyl-3-furanthiol acetate as an intermediate of perfume according to claim 1, wherein: the low temperature is-5 to 5 ℃.
3. The process for the synthesis of 2-methyl-3-furanthiol acetate, a flavor intermediate, according to claim 1, characterized in that: the organic base is triethylamine, piperidine or potassium carbonate;
or, the phase transfer catalyst is tetrabutylammonium bromide or 18-crown-6;
or the solvent of the 3-hydroxy-4-oxo-valeraldehyde solution is dichloromethane, trichloromethane, acetonitrile or ethyl acetate.
4. The process for the synthesis of 2-methyl-3-furanthiol acetate, a flavor intermediate, according to claim 1, characterized in that: the temperature of the substitution reaction is 25-35 ℃ and the time is 5-7h.
5. The process for the synthesis of 2-methyl-3-furanthiol acetate, a flavor intermediate, according to claim 1, characterized in that: in the reaction system, the molar ratio of the 3-hydroxy-4-oxo-valeraldehyde to the triethylamine to the methanesulfonyl chloride is 1.0-2.5.
6. The process for the synthesis of 2-methyl-3-furanthiol acetate, a flavor intermediate, according to claim 1, characterized in that: 5363 in the preparation of 1,4-pentadecanyl-3-yl-ethanesulfate, the molar ratio of compound 2, potassium thioacetate and phase transfer catalyst is 1:1.0 to 3.0:0.001 to 0.1.
7. The process for the synthesis of 2-methyl-3-furanthiol acetate, a flavor intermediate, according to claim 1, characterized in that: the organic solvent is acetone, tetrahydrofuran, acetonitrile or trichloromethane.
8. The process for the synthesis of 2-methyl-3-furanthiol acetate, a flavor intermediate, according to claim 1, characterized in that: the catalytic reaction temperature of the compound 2 and the potassium thioacetate is 20-40 ℃, and the time is 20-30h.
9. The method for synthesizing 2-methyl-3-furanthiol acetate as an intermediate of perfume according to claim 1, wherein: to the compound 2 solution was added potassium thioacetate and a phase transfer catalyst with stirring.
10. The process for the synthesis of 2-methyl-3-furanthiol acetate, a flavor intermediate, according to claim 1, characterized in that: the preparation method of the 3-hydroxy-4-oxo-valeraldehyde takes methylglyoxal and acetaldehyde as raw materials, tetrahydrofuran as a solvent, and the reaction is carried out for 10-14h at the temperature of 25-35 ℃ under the catalysis of L-prolinol.
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