CN116162667A - Synthesis method and application of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone - Google Patents

Synthesis method and application of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone Download PDF

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CN116162667A
CN116162667A CN202310025597.4A CN202310025597A CN116162667A CN 116162667 A CN116162667 A CN 116162667A CN 202310025597 A CN202310025597 A CN 202310025597A CN 116162667 A CN116162667 A CN 116162667A
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furanone
dimethyl
dihydroxy
synthesizing
diacetoxy
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白冰
杨静
张改红
赵明林
张敏
何静
杨靖
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Zhengzhou University of Light Industry
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/02—Oxygen as only ring hetero atoms
    • C12P17/04—Oxygen as only ring hetero atoms containing a five-membered hetero ring, e.g. griseofulvin, vitamin C
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B3/00—Preparing tobacco in the factory
    • A24B3/12—Steaming, curing, or flavouring tobacco
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D307/62—Three oxygen atoms, e.g. ascorbic acid

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Abstract

The invention discloses a synthesis method and application of 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone (acetyl formolin), which comprises the steps of dissolving furanone in toluene, adding lead tetraacetate or manganese triacetate, reacting to obtain 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone, placing the 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone in phosphate buffer solution, adding ester hydrolase, reacting, extracting, purifying by LH-20 gel, and obtaining 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone.

Description

Synthesis method and application of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone
Technical Field
The invention belongs to the technical field of flavors, and particularly relates to a synthesis method of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone and application of the flavor in cigarettes.
Background
The Chinese style cigarette is mainly flue-cured tobacco type cigarette, and has the style characteristics of mellow taste, prominent burnt sweet and roasted sweet aroma, and serious aroma loss of the cigarette along with deep development of tar reduction and harm reduction, so that the aroma loss needs to be compensated by a flavoring technology, thereby strengthening the style characteristics of the Chinese style cigarette.
2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone (acetylformolin) belongs to enolone compounds, is one of Maillard reaction products, and exists two tautomers of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone (I-a) and 3, 4-dihydroxy-3-hexene-2, 5-dione (I-b), and is mainly composed of a cyclic (I-a) structure in a solid phase and a polar solvent, and is mainly composed of a (I-b) structure in a gas phase and a nonpolar solvent. Engel et al (Eur Food Res Technol,2001, 213:104-106) report that the compound has strong sweet aroma, the threshold value is 10 mug/L, which is far lower than common sweet aroma flavor maltol and furanone, and no report on application in cigarette flavoring, food and the like exists at present, so that the compound has wide application prospect as a novel characteristic flavor.
Synthetic method reported in literatureJ. Agric. Food Chem. 1998, 46,3918-3928）The method is realized by benzoin condensation reaction under the catalysis of potassium cyanide by taking methylglyoxal as a raw material, and the method has complicated separation and purification operation and only 10-16% of yield, and is not suitable for large-scale production and application because of using extremely toxic potassium cyanide.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a synthesis method of 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone and application of the furanone as a perfume in cigarettes, and the method takes the furanone which is cheap and easy to obtain as a raw material, can obtain the 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone with high yield through a two-step reaction, and has simple operation method.
In order to solve the problems, the invention adopts the following technical scheme:
the synthesis method of the 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone comprises the following steps:
(1) Dissolving furanone in anhydrous toluene, adding anhydrous lead tetraacetate or manganese triacetate, heating to 90 ℃ to react completely, cooling to room temperature, washing, drying, concentrating under reduced pressure to obtain 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone, wherein the structural formula is as follows:
Figure 900524DEST_PATH_IMAGE001
；
(2) Placing the 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone prepared in the step (1) in a phosphate buffer solution, adding ester hydrolase, reacting 5H, adding ethyl acetate for extraction after the reaction is finished, washing an organic layer with saturated NaCl, and carrying out anhydrous Na 2 SO 4 Drying, evaporating the solvent, purifying the residue by LH-20 gel to obtain the target product 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone, wherein the structural formula is as follows:
Figure 100002_DEST_PATH_IMAGE002
the synthetic route is as follows:
Figure 100002_DEST_PATH_IMAGE004
。
further, the ratio of the amount of furanone and lead tetraacetate in the step (1) is 1:3; the ratio of the amount of furanone to manganese triacetate is 1:5.
Further, the amount of the ester hydrolase in the step (2) is 2 to 20 percent of the mass of the substrate 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone.
Further, the ester hydrolase in the step (2) is Novozyme435 lipase, candida antarctica lipase immobilized enzyme or pig liver esterase.
Further, the reaction temperature in the step (2) is 25-40 ℃ and the reaction time is 8-16 h.
Further, the specific structure of the target product in the step (2) is any one of a ring structure and an open chain structure (I-a and I-b). Namely, the target product in the step (2) is any one of 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone (I-a) and a tautomer 3, 4-dihydroxyl-3-hexene-2, 5-dione (I-b) thereof.
The 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone synthesized by the method is mixed with a stabilizer or a diluent to be used as a spice in cigarettes.
The invention has the beneficial effects that: the method of the invention takes furanone as a raw material, can obtain 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone through two-step reaction, and has high yield and simple preparation operation method. The 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone is added into cigarettes, can be gasified, volatilized and migrated into main stream smoke and alcohol smoke during smoking of the cigarettes, and endows the cigarettes with obvious sweet and fragrant style.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations can be made by those skilled in the art in light of the foregoing disclosure.
Example 1
The synthesis method of this example 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone (I) is as follows:
(1) Synthesis of 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone (II)
Furanone (1.28 g,10 mmol) was dissolved in toluene, anhydrous lead tetraacetate (13.2 g,30 mmol) was added, the temperature was raised to 90℃and 4. 4 h to complete the reaction, cooled to room temperature, 50. 50 mL water was added, the organic layer was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was combined, washed with saturated NaCl solution, anhydrous Na 2 SO 4 Drying and concentrating under reduced pressure to obtain compound (II) 2.05 g.
Spectroscopic data for compound (ii):
1 H NMR (600 MHz, CDCl 3 ) δ 2.27 (s, 3H), 2.14 (s, 3H), 2.10 (s, 3H), 1.60 (s, 3H). 13 C NMR (150 MHz, CDCl 3 ) δ 191.07, 175.88, 167.58, 167.56, 128.59, 100.27, 21.38, 20.38, 20.19, 13.62.
(2) Synthesis of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone (I)
Compound (ii) (500 mg) was placed in a flask, phosphate buffer solution at ph=8.0 was added, then Novozyme435 lipase (50 mg) was added, reaction was performed at 40 ℃ for 12 h, the aqueous phase was extracted 3 times with ethyl acetate, and anhydrous Na 2 SO 4 Drying, concentrating under reduced pressure, subjecting the residue to LH-20 gel column chromatography, eluting with dichloromethane/methanol=1/1 to give compound (I) 250 mg.
Spectroscopic data for compound (i):
1 H NMR (600 MHz, CD 3 OD) δ 2.17 (s, 3H), 1.41 (s, 3H). 13 C NMR (150 MHz, CD 3 OD) δ 197.83, 175.02, 132.24, 101.89, 22.77, 13.45.
1 H NMR (600 MHz, CDCl 3 ) δ 2.49 (s, 6H). 13 C NMR (150 MHz, CDCl 3 ) δ 26.05, 139.58, 205.61.
example 2
The synthesis method of this example 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone (I) is as follows:
(1) Synthesis of 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone (II)
Furanone (1.28 g,10 mmol) was dissolved in benzene, manganese triacetate dihydrate (13.4 g,50 mmol) was added, reflux reaction 6 h to completion by warming to 90 ℃ with a water separator, cooling to room temperature, adding 50 mL water, separating out the organic layer, extracting the aqueous phase with ethyl acetate, combining the organic phases, washing with saturated NaCl solution, anhydrous Na 2 SO 4 Drying, concentrating under reduced pressure, subjecting the residue to silica gel column chromatography, eluting with petroleum ether/ethyl acetate=7/1 to give compound (ii) 1.48, g.
(2) Synthesis of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone (I)
Compound (II)500 mg) was placed in a flask, phosphate buffer solution at ph=7.5 was added, then pig liver esterase (10 mg) was added, reaction was performed at 25 ℃ for 8 h, the aqueous phase was extracted 3 times with ethyl acetate, anhydrous Na 2 SO 4 Drying, concentrating under reduced pressure, subjecting the residue to LH-20 gel column chromatography eluting with dichloromethane/methanol=1/1 to give compound (I) 266 mg.
Example 5
The synthesis method of this example 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone (I) is as follows:
(1) The synthesis of 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone (II) was carried out in the same manner as in example 1;
(2) Synthesis of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone (I)
Compound (ii) (500 mg) was placed in a flask, phosphate buffer solution at ph=7.8 was added, then candida antarctica lipase (100 mg) was added, reaction was performed at 38 ℃ for 16 h, the aqueous phase was extracted 3 times with ethyl acetate, anhydrous Na 2 SO 4 Drying, concentrating under reduced pressure, subjecting the residue to LH-20 gel column chromatography, eluting with dichloromethane/methanol=1/1 to give compound (I) 230 mg.
Example 6
Application of 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone in cigarette flavoring
2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone 100 mg was weighed, fixed to a volume of 2 mL with ethanol, and diluted sequentially. The prepared solutions with different concentrations are uniformly added into cigarettes by an essence and spice injector, the adding gradient of the cigarettes is 0.001%,0.002%,0.005% and 0.01% of the weight of tobacco shreds, and cigarette samples meeting the requirements are selected and placed in an environment with the temperature (22+/-1) DEG C and the relative humidity (60+/-3) percent to be balanced by more than 48 and h, and compared with blank samples for smoking, and the result is shown in table 1.
Table 1 control evaluation results
Figure 4615DEST_PATH_IMAGE005
From table 1, it can be seen that the effect of the compound 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone in cigarette flavoring is mainly to improve the burnt sweet flavor and improve the sweet taste and the oral comfort.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. The synthesis method of the 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone is characterized by comprising the following steps:
(1) Dissolving furanone in anhydrous toluene, adding anhydrous lead tetraacetate or manganese triacetate, heating to 90 ℃ to react completely, cooling to room temperature, washing, drying, concentrating under reduced pressure to obtain 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone, wherein the structural formula is as follows:
Figure DEST_PATH_IMAGE001
；
(2) Placing the 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone prepared in the step (1) into a phosphate buffer solution, adding ester hydrolase to react, adding ethyl acetate to extract after the reaction is finished, washing an organic layer with saturated NaCl, and using anhydrous Na 2 SO 4 Drying, evaporating the solvent, purifying the residue by LH-20 gel to obtain the target product 2, 4-dihydroxyl-2, 5-dimethyl-3 (2H) -furanone, wherein the structural formula is as follows:
Figure DEST_PATH_IMAGE002
。
2. the method for synthesizing 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone according to claim 1, wherein: the ratio of the amount of furanone to the amount of lead tetraacetate in the step (1) is 1:3; the ratio of the amount of furanone to manganese triacetate is 1:5.
3. The method for synthesizing 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone according to claim 1, wherein: the dosage of the ester hydrolase in the step (2) is 2-20% of the mass of the substrate 2, 4-diacetoxy-2, 5-dimethyl-3 (2H) -furanone.
4. The method for synthesizing 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone according to claim 1, wherein: the ester hydrolase in the step (2) is Novozyme435 lipase, candida antarctica lipase immobilized enzyme or pig liver esterase.
5. The method for synthesizing 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone according to claim 1, wherein: the reaction temperature in the step (2) is 25-40 ℃ and the reaction time is 8-16 h.
6. The method for synthesizing 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone according to claim 1, wherein the synthetic route is as follows:
Figure DEST_PATH_IMAGE004
；
the target product in the step (2) is any one of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone (I-a) and a tautomer 3, 4-dihydroxy-3-hexene-2, 5-dione (I-b).
7. Use of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone synthesized by the method of any one of claims 1-6 in combination with a stabilizer or diluent as a flavoring in cigarettes.
CN202310025597.4A 2023-01-09 2023-01-09 Synthesis method and application of 2, 4-dihydroxy-2, 5-dimethyl-3 (2H) -furanone Pending CN116162667A (en)

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