CN110652027B - Synthesis method of release type xylose ester perfume for perfuming tobacco - Google Patents

Synthesis method of release type xylose ester perfume for perfuming tobacco Download PDF

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CN110652027B
CN110652027B CN201911099517.XA CN201911099517A CN110652027B CN 110652027 B CN110652027 B CN 110652027B CN 201911099517 A CN201911099517 A CN 201911099517A CN 110652027 B CN110652027 B CN 110652027B
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dimethyltetrahydrofuran
ethyl acetate
etoac
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CN110652027A (en
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张凤侠
彭军仓
师金鸽
杨芳
何媛
张萌萌
吕娟
康世平
王瑶
赵敏
孙赵麟
樊亚玲
何育萍
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China Tobacco Shaanxi Industrial Co Ltd
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    • 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
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/24—Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts
    • A24B15/26—Use of organic solvents for extraction
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom

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Abstract

Provides a synthesis method of a release type xylose ester spice for flavoring tobacco, which takes glucose as a raw material, adopts the principle of esterification of carboxylic acid and alcohol to prepare ester, and obtains a common parent carboxylic acid capable of being esterified with various alcohol compounds (see a product 6): (3aR,5S, 6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d ] [1,3] dioxolane-5-carboxylic acid; thus, the synthesis of the xylose ester with better quality and wider scope by combining with various alcohols (see a product 8): the (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (hydroxy) -2, 2-dimethyltetrahydrofuran [2,3-d ] [1,3] dioxolane-5-carboxylic ester is used for the perfuming production of release type perfumes of tobaccos, so that the fragrance quality and the fragrance quantity of cigarette smoke are improved, the self-production addition requirements of the release type perfume for tobaccos in China can be met, the fragrance characteristics of isovaleric acid, ethyl myrcene, 4-methylphenol and the like in the cigarette smoke are endowed, the cigarette smoke is softer and finer, the harmonicity is increased, and the aftertaste is purified.

Description

Synthesis method of release type xylose ester perfume for perfuming tobacco
Technical Field
The invention belongs to the technical field of chemical saccharide derivative preparation, and particularly relates to a synthesis method of a release type xylose ester perfume for perfuming tobacco.
Background
At present, in the tobacco flavoring technology: in the design of the novel release type tobacco flavor which replaces low-grade fatty acid, high-grade fatty acid, alcohols, phenols and the like and is easy to volatilize and lose in the tobacco flavoring and storing process, the release type tobacco flavor developed by taking the xylose as the target flavor is characterized in that: the release type tobacco flavor has a very small taste at normal temperature and normal pressure, and has smaller volatility in the adding period compared with the conventional sugar ester tobacco flavor, and the retention rate of the flavor after the tobacco leaves are flavored is higher; after the cigarette is burnt and smoked, the flavor can be more uniformly released after the cigarette is thermally cracked; meanwhile, the cigarette filter tip can effectively reduce the irritant miscellaneous gas during cigarette smoking, improve the quality of aroma, further improve the comprehensive advantages of various aspects such as aroma, taste and the like, and is gradually paid attention. In the prior art, xylitol and carboxylic acid are mostly adopted for synthesizing the xylose ester spice as ester, and the defects are that: in the synthetic route, the more extensive compounds of the xylose ester perfume cannot be obtained due to the limitation of the types of carboxylic acids. Besides, in addition to the synthetic products disclosed in the journal of tobacco science and technology, which is published in 2010 at 6/20 th, with the title of 1, 2-O-isopropylidene-3, 5-O-di (phenylethoxycarbonyl succinyl) xylofuranose and the application thereof in cigarettes, the development of a synthetic method of xylose ester with other characteristic aroma different from the synthetic route and process is urgently needed, and the following technical scheme is proposed.
Disclosure of Invention
The technical problems solved by the invention are as follows: the synthesis method of the release type xylose ester spice for flavoring the tobacco adopts the principle that carboxylic acid and alcohol are esterified to prepare the xylose ester through the obtained common parent carboxylic acid which can be esterified with various alcohol compounds, endows the cigarette smoke with the aroma characteristics of isovaleric acid, ethyl myrcene, 4-methylphenol and the like, and is used for flavoring production of the release type spice for the tobacco, so that the aroma quality and the aroma quantity of the cigarette smoke are improved, and the production requirement of the preparation of the release type spice for the cigarette is met.
The technical scheme adopted by the invention is as follows: the synthesis method of the release type xylose ester spice for flavoring the tobacco is characterized by comprising the following steps of: the method comprises the following steps:
step 1: 15-20 g (D +) glucose, 150-180-200 mL of anhydrous acetone, 1.25-1.82 g of anhydrous copper sulfate (CuSO)4) 0.75-2.25 g of concentrated sulfuric acid (H)2SO4) Placing the mixture into a 500mL single-neck flask, stirring the mixture for 48 hours at an internal temperature, concentrating the mixture in vacuum, and using 80-120 mL of saturated sodium bicarbonate (NaHCO) to obtain crude oil3) Washing, extraction 2 times with 50-95 mL ethyl acetate (EtOAc), combining the organic phases and adding anhydrous sodium sulfate (Na)2SO4) Drying and finally vacuum concentrating to obtain 18.95-28 g of white solid product 2: (3aR,5S,6S,6aR) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolan-6-ol; and the yield of product 2 is 95.3%; structural characterization of product 2: HR-MS M/z 260.2, [ M + H]+。
Step 2: putting 3.5-7.2 g of the product 2 and 40-70 mL of anhydrous N, N-Dimethylformamide (DMF) into a 200-300 mL four-neck flask, uniformly stirring, and introducing nitrogen for protection; cooling to 0 deg.C in ice bath, adding 0.85-1 g 60% sodium hydride (NaH) in portionsIn the solution, bubbles are generated and the solution is continuously stirred for 15-20 minutes at the temperature of 0 ℃; then slowly dropwise adding 2.8-4.05 g (20mmol) of benzyl bromide (BnBr) into the reaction bottle, and continuously stirring for 2 hours at the room temperature of 20-25 ℃ until the reaction is finished: the reaction solution after the completion of the reaction was extracted with ethyl acetate several times, and then anhydrous sodium sulfate (Na) was added2SO4) Drying and elution with 1:4 ethyl acetate (EtOAc) and Petroleum Ether (PE) afforded 5.25-8.2 g of product 3: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane; structural characterization of product 3: HR-MS M/z 351.1, [ M + H]+。
And step 3: placing 5.25-8.2 g of the product 3 and 95% of 50-90 mL of acetic acid (AcOH) aqueous solution in a 250mL single-neck flask, and stirring at room temperature for 24 hours; after vacuum concentration, washing extraction and drying, 3.1-7.2 g of a product 4 is obtained: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-5-yl) ethane-1, 2-diol; structural characterization of product 4: HR-MS M/z 311.1, [ M + H]+。
And 4, step 4: dissolving 3.1-7.2 g of product 4 in 100mL of Dichloromethane (DCM), and then dissolving 5.32-8.2 g (25mmoL) of sodium periodate (NaIO)4) Adding the mixture into the solution in batches, stirring the mixture at room temperature for 1 hour, filtering reaction liquid, collecting filtrate, and concentrating the filtrate in vacuum until the filtrate is dried to obtain 2.78-4.5 g of a product 5: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolane-5-aldehyde; and the yield of product 5 is 98%; structural characterization of product 5: HR-MS M/z 279.1, [ M + H]+。
And 5: 2.78-4.5 g of the product 5, 5.6-9.2g (100mmol) of potassium hydroxide (KOH) and 20-40 mL of water are placed in a 100mL three-neck flask, fully stirred at the room temperature of 20-25 ℃, and added with 3.36-5.56 g (20mmol) of silver nitrate (AgNO)3) Continuously stirring for 2 hours at room temperature; the reaction solution was filtered through a Buchner funnel with celite and the filtrate was collected, the pH of the filtrate was adjusted to 3 with 6N hydrochloric acid, extracted 3 times with 50-65 mL ethyl acetate (EtOAc), the organic phase was collected and washed with 10-20 g anhydrous sodium sulfate (Na)2SO4) Drying, and vacuum concentrating to dryness to obtain 2.1-4.2 g white solidAnd (3) a product 6: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolane-5-carboxylic acid; product 6 can be esterified with a variety of alcohols, it is a common parent carboxylic acid, and the yield of product 6 is 71%; structural characterization of product 6: HR-MS M/z 295.1, [ M + H]+。
Step 6: weighing 0.294-0.4 g of the product 6, 0.156-0.192 g (1mmol) of menthol, 0.0246-0.032 g (0.2mmol) of DMAP, 0.228-0.288 g (1.2mmol) of EDC, 0.202-0.282 g (2mmol) of Triethylamine (TEA) and 4-6 mL of Dichloromethane (DCM) into an 8-10 mL reaction bottle, and stirring at room temperature for 4 hours; washing the reaction solution with 10-20 mL of water, extracting with 5-10 mL of dichloromethane, and extracting with anhydrous sodium sulfate (Na)2SO4) The organic phase was dried, concentrated to dryness in vacuo and chromatographed on silica gel, eluting with ethyl acetate and petroleum ether to ethyl acetate EtOAc, petroleum ether PE ═ 1:1, to give 0.19 to 0.36g of product 7 in the colourless viscous oily state: (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolane-5-carboxylic acid menthyl ester; and yield of product 7 was 44%; structural characterization of product 7: HR-MS M/z 433.2, [ M + H]+。
And 7: placing 0.19-0.36 g of the product 7 and 5-15mL of methanol (MeOH) and 10% of 0.02-0.038 g of palladium carbon in a 25mL hydrogenation bottle, replacing the system with hydrogen for 3 times, stirring at room temperature under the hydrogen pressure of 20atm for 6 hours, filtering the reaction solution, collecting the filtrate, performing vacuum concentration on the filtrate, performing flash silica gel column chromatography, and eluting with dichloromethane and methanol according to DCM (MeOH: 20: 1) to finally obtain 0.095-0.18 g of a white solid product 8: (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (hydroxy) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolane-5-carboxylic acid menthyl ester; and the yield of product 8 was 63%; structural characterization of product 8: HR-MS M/z 432.5, [ M + H]+。1H NMR(300MHz,DMSO-d6)δ5.94(d,J＝3.5Hz,1H),5.66(d,J＝5.7Hz,1H),4.74–4.60(m,2H),4.43(d,J＝3.6Hz,1H),4.21(dd,J＝5.8,3.4Hz,1H),1.98–1.80(m,2H),1.71–1.57(m,2H),1.32(d,J＝45.5Hz,9H),1.15–0.94(m,2H),0.87(t,J＝6.5Hz,7H),0.72(d,J＝6.9Hz,3H)。
In the above technical scheme, there areThe yield of the product 3 in the step 2 is improved, and further: in the step 2, the reaction solution after the reaction further comprises the following processing steps: the first step is as follows: after the reaction, the reaction solution was carefully poured into 100mL of ice water, and extracted 3 times with 100mL of ethyl acetate (EtOAc); the second step is that: the extracted organic phases were combined and washed with 8-15 g of anhydrous sodium sulfate (Na)2SO4) Drying; the third step: concentrating the dried organic phase to dryness in vacuum, and performing silica gel column chromatography; elution with ethyl acetate (EtOAc) and Petroleum Ether (PE) at 1:4 gave product 3 as a colorless clear oil: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane; and the yield of product 3 was 98.8%.
In the above technical solution, to quantitatively determine whether the reaction of step 2 is completed, further: in the step 2, when the reaction solution after the completion of the reaction is checked for ethyl acetate (EtOAc)/Petroleum Ether (PE), i.e., EtOAc/PE, by thin layer chromatography, it is indicated that the reaction is completed when the ratio of EtOAc/PE is 1: 4.
In the above technical scheme, in order to maximize the yield of the product 4 in the step 3, further: in the step 3, the product after stirring for 24 hours at room temperature further comprises the following processing steps: the first step is as follows: vacuum concentration of acetic acid; the second step is that: 200mL of ethyl acetate were added, and 100mL of saturated sodium bicarbonate (NaHCO) were used3) Washing the aqueous solution, extracting, separating and collecting an organic phase; the third step: the organic phase was washed once with 100ml of saturated aqueous sodium chloride solution and with anhydrous sodium sulfate (Na)2SO4) Drying and vacuum concentration to dryness gave product 4 in a colorless viscous oily state: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-5-yl) ethane-1, 2-diol; and the yield of product 4 was 100%.
Wherein the chemical molecular structural formula of the product 6 is shown in the specification
Figure GDA0003183865370000051
Wherein the chemical molecular structural formula of the product 8 is shown as
Figure GDA0003183865370000061
The synthesis principle is as follows: the technical scheme adopts a new synthesis method to synthesize the xylose ester, and overcomes the technical problem that the prior art adopts xylitol and carboxylic acid as ester and the synthesis of the xylose ester is limited by the type of the carboxylic acid; alternatively, xylitol derivative xylose carboxylic acid and alcohol are used as ester; thereby being beneficial to synthesizing more extensive and better xylonate spice compounds; namely, the parent carboxylic acid of the product 6 obtained in the reaction route is used, and various alcohol compounds can be selected to perform esterification reaction with the product 6 by using the parent carboxylic acid of the product 6, so that a wider range of higher-quality xylose ester spice compounds can be obtained, and the xylose ester spice compounds can be used for perfuming cigarette release type perfuming spices.
Compared with the prior art, the invention can realize the following effects:
1. the product 8-xylose ester obtained by the scheme is a release type tobacco flavor, and the release type tobacco flavor has very small taste at normal temperature and normal pressure after being added and applied to flavoring of tobacco leaves; the volatility of the perfume in the adding period is lower, and the perfuming retention rate is higher; but after the cigarette is burnt and thermally cracked, the fragrance can be more uniformly released; can be used as a flavoring additive for a high-quality release type xylose ester cigarette flavor;
2. after the xylose ester product 8 obtained by the scheme is added into tobacco leaves with the same adding content, GC/MS analysis is carried out on the relative content heat components of the smoke components at the cracking temperature of 300 ℃, 600 ℃ and 900 ℃ after the product 8 with the same adding content is added into the tobacco leaves, and not less than fifty odorous aldehyde, ketone, acid and ester compounds can be obtained in total; when the addition amount of the compound in tobacco is 0.01%, the cigarette aroma quality can be obviously improved; the obtained smoke is soft and exquisite, the quality of aroma is improved, the aroma amount is obviously increased, the harmony is better, the aftertaste is purer and richer, the irritation is lower, and the tobacco aroma is more harmonious and lingering in smoking result evaluation;
3. the product 8 xylan ester synthesized by the scheme is used for perfuming cigarettes, and compared with the published documents: liuyun is the first author, research and development personnel of our prescription participate in Liuyun, and in the published title of 1, 2-O-isopropylidene-3, 5-O-di (phenylethoxycarbonyl succinyl) xylofuranose which is published in the journal of tobacco science and technology in 2010 at 6-20 days, and the final product (1, 2-O-isopropylidene-3, 5-O-di (phenylethoxycarbonyl succinyl) xylofuranose) mentioned in the published journal literature of tobacco science and application thereof in cigarettes, the final product xylose ester can endow the cigarette smoke with the aroma characteristics of isovaleric acid, ethyl myrcene, 4-methylphenol and the like, so that the cigarette smoke is softer and finer, the harmonious property is increased, and the aftertaste becomes pure.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is the nuclear magnetic resonance hydrogen spectrum of xylose ester containing a certain alcohol compound group of the product 8 xylose ester of the invention.
Detailed Description
Specific embodiments of the present invention are described below with reference to fig. 1-2. It is to be understood that the following description of the embodiments is merely exemplary and not intended to limit the invention in any way.
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were either commercially available, analytically pure or chemically pure, unless otherwise specified.
Example 1:
the synthesis method of the release type xylose ester spice for flavoring the tobacco is characterized by comprising the following steps of: the method comprises the following steps:
step 1: 15g (D +) of glucose, 150mL of anhydrous acetone, 1.25g of anhydrous copper sulfate (CuSO)4) 0.75g of concentrated sulfuric acid (H)2SO4) The mixture was stirred in a 500mL single-neck flask at room temperature for 48h with a stirrer, concentrated in vacuo, and the resulting crude oil was taken up in 80mL of saturated sodium bicarbonate (NaHCO)3) Washing, 50mL ethyl acetate (EtOAc) extraction 2 times, organic phase combined, and anhydrous sodium sulfate (Na)2SO4) Drying and final concentration in vacuo gave 18.95g of product 2 as a white solid: (3aR,5S,6S,6aR) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolan-6-ol; and the yield of product 2 is 95.3%; structural characterization of product 2: HR-MS m/z:260.2,[M+H]+。
Step 2: 3.5g of the product 2 and 40mL of anhydrous N, N-Dimethylformamide (DMF) are put into a 200mL four-neck flask to be uniformly stirred, and nitrogen is introduced for protection; cooling to 0 ℃ in an ice bath, adding 0.85g of 60% sodium hydride (NaH) into the solution in batches, and continuing stirring for 15-20 minutes at the temperature of 0 ℃ while generating bubbles; then slowly dripping 2.8g (20mmol) of benzyl bromide (BnBr) into the reaction bottle, and continuously stirring for 2 hours at the room temperature of 20-25 ℃ until the reaction is finished: the reaction solution after the completion of the reaction was extracted with ethyl acetate several times, and then anhydrous sodium sulfate (Na) was added2SO4) Drying and elution with 1:4 ethyl acetate (EtOAc) and Petroleum Ether (PE) gave 5.25g of product 3: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane; and structural characterization of product 3: HR-MS M/z 351.1, [ M + H]+。
And step 3: 5.25g of product 3 was placed in a 250mL single-neck flask with 95% 50mL of aqueous acetic acid (AcOH) and stirred at room temperature for 24 hours; after vacuum concentration, washing extraction and drying, 3.1g of product 4 is obtained: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-5-yl) ethane-1, 2-diol; structural characterization of product 4: HR-MS M/z 311.1, [ M + H]+。
And 4, step 4: 3.1g of product 4 are dissolved in 100mL of Dichloromethane (DCM), and 5.32g (25mmoL) of sodium periodate (NaIO)4) The reaction mixture was added to the above solution in portions, stirred at room temperature for 1 hour, filtered and the filtrate collected, concentrated to dryness in vacuo to give 2.78g of product 5: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolane-5-aldehyde; structural characterization of product 5: HR-MS M/z 279.1, [ M + H]+。
And 5: 2.78g of product 5, 5.6g (100mmol) of potassium hydroxide (KOH) and 20mL of water were placed in a 100mL three-necked flask, and thoroughly stirred at room temperature of 20-25 ℃, and 3.36g (20mmol) of silver nitrate (AgNO) was added3) Continuously stirring for 2 hours at room temperature; filtering the reaction solution with a Buchner funnel containing diatomaceous earth, collecting the filtrate, adjusting pH of the filtrate to 3 with 6N hydrochloric acid, and adding50mL ethyl acetate (EtOAc) were extracted 3 times, the organic phase was collected and over 10g anhydrous sodium sulfate (Na)2SO4) Drying and vacuum concentration to dryness gave 2.1g of product 6 as a white solid: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolane-5-carboxylic acid; and product 6 has a common parent carboxylic acid that can be esterified with a variety of alcohols; structural characterization of product 6: HR-MS M/z 295.1, [ M + H]+(ii) a And the yield of product 6 was 71%.
Step 6: 0.294g of product 6 was weighed out into an 8mL reaction flask with 0.156g (1mmol) of menthol, 0.0246g (0.2mmol) of DMAP, 0.228g (1.2mmol) of EDC,0.202g (2mmol) of Triethylamine (TEA) and 4mL of Dichloromethane (DCM) and stirred at room temperature for 4 hours. The reaction mixture was washed with 10mL of water, extracted with 5mL of dichloromethane, and dried over anhydrous sodium sulfate (Na)2SO4) The organic phase was dried, concentrated to dryness in vacuo and, after column chromatography on silica, eluted with ethyl acetate and petroleum ether (ethyl acetate EtOAc: petroleum ether PE ═ 1:1) to give 0.19g of product 7 in the colourless viscous oil state: (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolane-5-carboxylic acid menthyl ester; and yield of product 7 was 44%; structural characterization of product 7: HR-MS M/z 433.2, [ M + H]+。
And 7: after 0.19g of product 7 and 5mL of methanol (MeOH), 10% of 0.02g of palladium on charcoal are placed in a 25mL hydrogenation flask, the system is replaced with hydrogen for 3 times, the pressure of hydrogen is 20atm, and the mixture is stirred at room temperature for 6 hours, the reaction solution is filtered, the filtrate is collected, after vacuum concentration of the filtrate, flash silica gel column chromatography is performed, and the filtrate is eluted with dichloromethane and methanol according to DCM: MeOH ═ 20:1, so that 0.095 to 0.1 to 0.18g of white solid product 8 is finally obtained: (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (hydroxy) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolane-5-carboxylic acid menthyl ester; and the yield of product 8 was 63%. Structural characterization of product 8: HR-MS M/z 432.5, [ M + H]+。1H NMR(300MHz,DMSO-d6)δ5.94(d,J＝3.5Hz,1H),5.66(d,J＝5.7Hz,1H),4.74–4.60(m,2H),4.43(d,J＝3.6Hz,1H),4.21(dd,J＝5.8,3.4Hz,1H),1.98–1.80(m,2H),1.71–1.57(m,2H),1.32(d,J＝45.5Hz,9H),1.15–0.94(m,2H),0.87(t,J＝6.5Hz,7H),0.72(d,J＝6.9Hz,3H)。
In example 1, to advantageously increase the yield of product 3 of step 2, further: in the step 2, the reaction solution after the reaction further comprises the following processing steps: the first step is as follows: after the reaction, the reaction solution was carefully poured into 100mL of ice water, and extracted 3 times with 100mL of ethyl acetate (EtOAc); the second step is that: the extracted organic phases were combined and washed with 8g of anhydrous sodium sulfate (Na)2SO4) Drying; the third step: concentrating the dried organic phase to dryness in vacuum, and performing silica gel column chromatography; elution with ethyl acetate (EtOAc) and Petroleum Ether (PE) at 1:4 gave product 3 as a colorless clear oil: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane; and the yield of product 3 was 98.8%.
In example 1, to quantitatively determine whether the reaction of step 2 is complete, further: in the step 2, when the reaction solution after the completion of the reaction is checked for ethyl acetate (EtOAc)/Petroleum Ether (PE), i.e., EtOAc/PE, by thin layer chromatography, it is indicated that the reaction is completed when the ratio of EtOAc/PE is 1: 4. Or more intuitively, if the spot fluorescence of the starting material disappears, it indicates that the reaction is complete.
In example 1, to maximize the yield of product 4 from step 3, further: in the step 3, the product after stirring for 24 hours at room temperature further comprises the following processing steps: the first step is as follows: vacuum concentration of acetic acid; the second step is that: 200mL of ethyl acetate were added, and 100mL of saturated sodium bicarbonate (NaHCO) were used3) Washing the aqueous solution, extracting, separating and collecting an organic phase; the third step: the organic phase was washed once with 100ml of saturated aqueous sodium chloride solution and with anhydrous sodium sulfate (Na)2SO4) Drying and vacuum concentration to dryness gave product 4 in a colorless viscous oily state: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-5-yl) ethane-1, 2-diol; and the yield of product 4 was 100%.
The chemical molecular structural formula of the product 6 in example 1 is
Figure GDA0003183865370000111
The chemical molecular structural formula of the product 8 is
Figure GDA0003183865370000112
It should be noted that: the R-group represents different alcohol compounds.
Example 2:
the synthesis method of the release type xylose ester spice for flavoring the tobacco is characterized by comprising the following steps of: the method comprises the following steps:
step 1: 18g (D +) of glucose, 180mL of anhydrous acetone, 1.58g of anhydrous copper sulfate (CuSO)4) 0.98g of concentrated sulfuric acid (H)2SO4) The mixture was stirred in a 500mL single-neck flask at room temperature for 48h with a stirrer, concentrated in vacuo, and the resulting crude oil was purified with 100mL of saturated sodium bicarbonate (NaHCO)3) Washing, 70mL ethyl acetate (EtOAc) extraction 2 times, organic phase combined, and anhydrous sodium sulfate (Na)2SO4) Drying and final concentration in vacuo gave 24.8g of product 2 as a white solid: (3aR,5S,6S,6aR) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolan-6-ol; and the yield of product 2 is 95.3%; and the yield of product 2 is 95.3%; structural characterization: HR-MS M/z 260.2, [ M + H]+。
Step 2: 5.2g of the product 2 and 52mL of anhydrous N, N-Dimethylformamide (DMF) are put into a 250mL four-neck flask to be uniformly stirred, and nitrogen is introduced for protection; cooling to 0 ℃ in an ice bath, adding 0.96g of 60% sodium hydride (NaH) into the solution in batches, and continuing stirring for 15-20 minutes at the temperature of 0 ℃ while generating bubbles; then 3.42g (20mmol) of benzyl bromide (BnBr) is slowly dripped into the reaction bottle, and the stirring is continued for 2 hours at the room temperature of 20-25 ℃ until the reaction is finished: the reaction solution after the completion of the reaction was extracted with ethyl acetate several times, and then anhydrous sodium sulfate (Na) was added2SO4) Drying and elution with 1:4 ethyl acetate (EtOAc) and Petroleum Ether (PE) afforded 6.92g of product 3: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane; and structural characterization of product 3: HR-MS M/z 351.1, [ M + H]+。
And step 3: 7.32g of product 3 are mixed with 95%70mL of an acetic acid (AcOH) aqueous solution was placed in a 250mL single-neck flask and stirred at room temperature for 24 hours; after vacuum concentration, washing extraction and drying, 5.9g of product 4 is obtained: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-5-yl) ethane-1, 2-diol; structural characterization of product 4: HR-MS M/z 311.1, [ M + H]+。
And 4, step 4: 5.9g of product 4 are dissolved in 100mL of Dichloromethane (DCM), and 7.3g (25mmoL) of sodium periodate (NaIO)4) The reaction mixture was added to the above solution in portions, stirred at room temperature for 1 hour, filtered and the filtrate collected, concentrated to dryness in vacuo to give 3.25g of product 5: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolane-5-aldehyde; and the yield of product 5 is 98%; structural characterization of product 5: HR-MS M/z 279.1, [ M + H]+。
And 5: 3.25g of product 5, 6.6g (100mmol) of potassium hydroxide (KOH) and 20mL of water were placed in a 100mL three-necked flask, and thoroughly stirred at room temperature of 20-25 ℃, and 4.42g (20mmol) of silver nitrate (AgNO) was added3) Continuously stirring for 2 hours at room temperature; the reaction solution was filtered through a Buchner funnel with Celite and the filtrate was collected, the pH of the filtrate was adjusted to 3 with 6N hydrochloric acid, extracted 3 times with 50mL of ethyl acetate (EtOAc), the organic phase was collected and washed with 10g of anhydrous sodium sulfate (Na)2SO4) Dried and concentrated to dryness in vacuo to give 3.5g of product 6 as a white solid: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolane-5-carboxylic acid; the product 6 can be esterified with various alcohols, which is a common parent carboxylic acid, and the yield of the product 6 is 71 percent; structural characterization of product 6: HR-MS M/z 295.1, [ M + H]+。
Step 6: 0.3g of product 6 was weighed out into a 10mL reaction flask with 0.148g (1mmol) of menthol, 0.0247g (0.2mmol) of DMAP, 0.223g (1.2mmol) of EDC,0.219g (2mmol) of Triethylamine (TEA) and 4mL of Dichloromethane (DCM) and stirred at room temperature for 4 hours. The reaction mixture was washed with 10mL of water, extracted with 5mL of dichloromethane, and dried over anhydrous sodium sulfate (Na)2SO4) Drying the organic phase, vacuum concentrating to dryness, performing silica gel column chromatography, eluting with ethyl acetate and petroleum ether (ethyl acetate EtOAc: petroleum ether PE ═ 1:1) to obtainTo 0.2g of product 7 in the colorless viscous oil state: (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolane-5-carboxylic acid menthyl ester; and yield of product 7 was 44%; structural characterization of product 7: HR-MS M/z 433.2, [ M + H]+＝
And 7: after 0.2g of the product 7 was mixed with 10mL of methanol (MeOH), 0.021g (10%) of palladium on charcoal, and the mixture was placed in a 25mL hydrogenation flask, and the system was replaced with hydrogen gas 3 times, and the pressure of hydrogen gas was 20atm, and stirred at room temperature for 6 hours, the reaction solution was filtered, and the filtrate was collected, and after vacuum concentration of the filtrate by flash silica gel column chromatography, the filtrate was eluted with dichloromethane and methanol in DCM: MeOH ═ 20:1, to obtain 0.1g of a white solid product 8: menthyl (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (hydroxy) -2, 2-dimethyltetrahydrofuran [2,3-d ] [1,3] dioxolane-5-carboxylate; and the yield of product 8 was 63%.
In example 2, to advantageously increase the yield of product 3 of step 2, further: in the step 2, the reaction solution after the reaction further comprises the following processing steps: the first step is as follows: after the reaction, the reaction solution was carefully poured into 100mL of ice water, and extracted 3 times with 100mL of ethyl acetate (EtOAc); the second step is that: the extracted organic phases were combined and washed with 10g of anhydrous sodium sulfate (Na)2SO4) Drying; the third step: concentrating the dried organic phase to dryness in vacuum, and performing silica gel column chromatography; elution with ethyl acetate (EtOAc) and Petroleum Ether (PE) at 1:4 gave product 3 as a colorless clear oil: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane; and the yield of product 3 is 98.8%; structural characterization of product 8: HR-MS M/z 432.5, [ M + H]+。1H NMR(300MHz,DMSO-d6)δ5.94(d,J＝3.5Hz,1H),5.66(d,J＝5.7Hz,1H),4.74–4.60(m,2H),4.43(d,J＝3.6Hz,1H),4.21(dd,J＝5.8,3.4Hz,1H),1.98–1.80(m,2H),1.71–1.57(m,2H),1.32(d,J＝45.5Hz,9H),1.15–0.94(m,2H),0.87(t,J＝6.5Hz,7H),0.72(d,J＝6.9Hz,3H)。
In example 2, to quantitatively determine whether the reaction of step 2 was completed, further: in the step 2, when the reaction solution after the completion of the reaction is checked for ethyl acetate (EtOAc)/Petroleum Ether (PE), i.e., EtOAc/PE, by thin layer chromatography, it is indicated that the reaction is completed when the ratio of EtOAc/PE is 1: 4. Or more intuitively, if the spot fluorescence of the starting material disappears, it indicates that the reaction is complete.
In example 2, to maximize the yield of product 4 from step 3, further: in the step 3, the product after stirring for 24 hours at room temperature further comprises the following processing steps: the first step is as follows: vacuum concentration of acetic acid; the second step is that: 200mL of ethyl acetate were added, and 100mL of saturated sodium bicarbonate (NaHCO) were used3) Washing the aqueous solution, extracting, separating and collecting an organic phase; the third step: the organic phase was washed once with 100ml of saturated aqueous sodium chloride solution and with anhydrous sodium sulfate (Na)2SO4) Drying and vacuum concentration to dryness gave product 4 in a colorless viscous oily state: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-5-yl) ethane-1, 2-diol; and the yield of product 4 was 100%.
The chemical molecular structural formula of the product 6 in example 2 is
Figure GDA0003183865370000151
The chemical molecular structural formula of the product 8 is
Figure GDA0003183865370000152
It should be noted that: the R-group represents different alcohol compounds.
Example 3:
the synthesis method of the release type xylose ester spice for flavoring the tobacco is characterized by comprising the following steps of: the method comprises the following steps:
step 1: 20g (D +) of glucose, 200mL of anhydrous acetone, 1.82g of anhydrous copper sulfate (CuSO)4) 2.25g of concentrated sulfuric acid (H)2SO4) The mixture was stirred in a 500mL single-neck flask with a stirrer at room temperature for 48h, concentrated in vacuo, and the crude oil obtained was purified with 120mL of saturated sodium bicarbonate (NaHCO)3) Washing, 95mL ethyl acetate (EtOAc) extraction 2 times, combined organic phase, and anhydrous sodium sulfate (Na)2SO4) Drying and final concentration in vacuo afforded 28g of product 2 as a white solid: (3aR,5S,6S,6aR) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-6-ol; and the yield of product 2 is 95.3%; structural characterization: HR-MS M/z 260.2, [ M + H]+。
Step 2: putting 7.2g of the product 2 and 70mL of anhydrous N, N-Dimethylformamide (DMF) into a 300mL four-neck flask, uniformly stirring, and introducing nitrogen for protection; cooling to 0 ℃ in an ice bath, adding 1g of 60% sodium hydride (NaH) into the solution in batches, and continuing stirring for 15-20 minutes at the temperature of 0 ℃ while generating bubbles; then 4.05g (20mmol) of benzyl bromide (BnBr) is slowly dripped into the reaction bottle, and the mixture is continuously stirred for 2 hours at the room temperature of 20-25 ℃ until the reaction is finished: the reaction solution after the completion of the reaction was extracted with ethyl acetate several times, and then anhydrous sodium sulfate (Na) was added2SO4) Drying and elution with 1:4 ethyl acetate (EtOAc) and Petroleum Ether (PE) gave 8.2g of product 3: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane; and structural characterization of product 3: HR-MS M/z 351.1, [ M + H]+。
And step 3: placing 8.2g of product 3 and 95% of 90mL of acetic acid (AcOH) aqueous solution in a 250mL single-neck flask, and stirring at room temperature for 24 hours; after vacuum concentration, washing extraction and drying, 7.2g of product 4 is obtained: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-5-yl) ethane-1, 2-diol; structural characterization of product 4: HR-MS M/z 311.1, [ M + H]+。
And 4, step 4: 7.2g of product 4 are dissolved in 100mL of Dichloromethane (DCM), and then 8.2g (25mmoL) of sodium periodate (NaIO)4) The reaction mixture was added to the above solution in portions, stirred at room temperature for 1 hour, filtered and the filtrate collected, concentrated to dryness in vacuo to give 4.5g of product 5: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolane-5-aldehyde; and the yield of product 5 is 98%; structural characterization of product 5: HR-MS M/z 279.1, [ M + H]+。
And 5: 4.5g of the product 5, 9.2g (100mmol) of potassium hydroxide (KOH) and 40mL of water were placed in a 100mL three-necked flask, and sufficiently stirred at 20-25 ℃ at room temperature,5.56g (20mmol) of silver nitrate (AgNO) are added3) Continuously stirring for 2 hours at room temperature; the reaction solution was filtered through a Buchner funnel with Celite and the filtrate was collected, the pH of the filtrate was adjusted to 3 with 6N hydrochloric acid, extracted 3 times with 65mL ethyl acetate (EtOAc), the organic phase was collected and washed with 20g anhydrous sodium sulfate (Na)2SO4) Drying and vacuum concentration to dryness gave 4.2g of product 6 as a white solid: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolane-5-carboxylic acid; the product 6 can be esterified with various alcohols, which is a common parent carboxylic acid, and the yield of the product 6 is 71 percent; structural characterization of product 6: HR-MS M/z 295.1, [ M + H]+。
Step 6: 0.4g of product 6 was weighed out with 0.192g (1mmol) of menthol, 0.032g (0.2mmol) of DMAP, 0.288g (1.2mmol) of EDC,0.282g (2mmol) of Triethylamine (TEA) and 6mL of Dichloromethane (DCM) into a 10mL reaction flask and stirred at room temperature for 4 hours. The reaction mixture was washed with 20mL of water, extracted with 10mL of dichloromethane, and dried over anhydrous sodium sulfate (Na)2SO4) The organic phase was dried, concentrated to dryness in vacuo and, after column chromatography on silica, eluted with ethyl acetate and petroleum ether (ethyl acetate EtOAc: petroleum ether PE ═ 1:1) to give 0.36g of product 7 in the colourless viscous oil state: (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolane-5-carboxylic acid menthyl ester; and yield of product 7 was 44%; structural characterization of product 7: HR-MS M/z 433.2, [ M + H]+。
And 7: after 0.36g of the product 7 was mixed with 15mL of methanol (MeOH), 10% of 0.038g of palladium on charcoal, and the mixture was placed in a 25mL hydrogenation flask, and the system was replaced with hydrogen gas 3 times, and the pressure of hydrogen was 20atm, and stirred at room temperature for 6 hours, the reaction solution was filtered, and the filtrate was collected, and after vacuum concentration of the filtrate by flash silica gel column chromatography, the filtrate was eluted with dichloromethane and methanol in DCM: MeOH ═ 20:1, to finally obtain 0.18g of a white solid product 8: (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (hydroxy) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolane-5-carboxylic acid menthyl ester; and the yield of product 8 was 63%; structural characterization of product 8: HR-MS M/z 432.5, [ M + H]+。1H NMR(300MHz,DMSO-d6)δ5.94(d,J＝3.5Hz,1H),5.66(d,J＝5.7Hz,1H),4.74–4.60(m,2H),4.43(d,J＝3.6Hz,1H),4.21(dd,J＝5.8,3.4Hz,1H),1.98–1.80(m,2H),1.71–1.57(m,2H),1.32(d,J＝45.5Hz,9H),1.15–0.94(m,2H),0.87(t,J＝6.5Hz,7H),0.72(d,J＝6.9Hz,3H)。
In example 3, to advantageously increase the yield of product 3 of step 2, further: in the step 2, the reaction solution after the reaction further comprises the following processing steps: the first step is as follows: after the reaction, the reaction solution was carefully poured into 100mL of ice water, and extracted 3 times with 100mL of ethyl acetate (EtOAc); the second step is that: the extracted organic phases were combined and washed with 15g of anhydrous sodium sulfate (Na)2SO4) Drying; the third step: concentrating the dried organic phase to dryness in vacuum, and performing silica gel column chromatography; elution with ethyl acetate (EtOAc) and Petroleum Ether (PE) at 1:4 gave product 3 as a colorless clear oil: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane; and the yield of product 3 was 98.8%.
In example 3, to quantitatively determine whether the reaction of step 2 was completed, further: in step 2, the reaction solution after the reaction is finished is detected by a thin layer chromatograph, and the ethyl acetate (EtOAc)/Petroleum Ether (PE), i.e. EtOAc/PE, is 1:4, or more intuitively, the reaction is finished if the fluorescence of the raw material point disappears.
In example 3, to maximize the yield of product 4 from step 3, further: in the step 3, the product after stirring for 24 hours at room temperature further comprises the following processing steps: the first step is as follows: vacuum concentration of acetic acid; the second step is that: 200mL of ethyl acetate were added, and 100mL of saturated sodium bicarbonate (NaHCO) were used3) Washing the aqueous solution, extracting, separating and collecting an organic phase; the third step: the organic phase was washed once with 100ml of saturated aqueous sodium chloride solution and with anhydrous sodium sulfate (Na)2SO4) Drying and vacuum concentration to dryness gave product 4 in a colorless viscous oily state: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-5-yl) ethane-1, 2-diol; and the yield of product 4 was 100%.
The chemical molecular structural formula of the product 6 in example 3 is
Figure GDA0003183865370000181
The chemical molecular structural formula of the product 8 is
Figure GDA0003183865370000191
It should be noted that: the R-group represents different alcohol compounds.
In any of the foregoing embodiments (embodiment 1, embodiment 2, and embodiment 3), it should be noted that:
the reaction formula of the step 1 is as follows:
Figure GDA0003183865370000192
the related reactant a in the reaction formula comprises: anhydrous acetone (CH)3COCH3) Anhydrous copper sulfate (CuSO)4) Concentrated sulfuric acid (H)2SO4)。
The reaction formula of the step 2 is as follows:
Figure GDA0003183865370000193
the reaction formula of the step 3 is as follows:
Figure GDA0003183865370000194
the reaction formula of the step 4 is as follows:
Figure GDA0003183865370000195
the reaction formula of the step 5 is as follows:
Figure GDA0003183865370000201
the reaction formula of the step 6 is as follows:
Figure GDA0003183865370000202
the reaction formula of step 7 is:
Figure GDA0003183865370000203
with respect to the xylose ester synthesized in step 7, it is to be noted that: the R-group represents different alcohol compounds. Specifically, referring to the example of FIG. 2, the NMR spectrum of the product 8 of the present invention is a hydrogen nuclear magnetic resonance spectrum of a xylose ester containing a group R-of an alcohol compound. In combination with the embodiment, it should be noted that the synthesis principle of the present invention is as follows: the invention adopts a new synthesis method to synthesize the xylose ester, and overcomes the technical problem that the prior art adopts xylitol and carboxylic acid as ester and is limited by the types of carboxylic acid to synthesize the xylose ester; alternatively, xylitol derivative xylose carboxylic acid and alcohol are used as ester; thereby being beneficial to synthesizing more extensive and better xylonate spice compounds; namely, the parent carboxylic acid of the product 6 obtained in the step 5 in the reaction route is used, and various alcohol compounds can be selected to perform esterification reaction with the product 6 by using the parent carboxylic acid of the product 6 in the step 5, so that a more extensive and better xylose ester spice compound can be obtained, and the xylose ester spice compound can be used for perfuming cigarette release type perfuming spices.
After the synthetic product 8 of the invention is applied to flavoring tobacco leaves with the same addition content, the relative content of smoke is respectively detected at the cracking temperatures of 300 ℃, 600 ℃ and 900 ℃, and the GC/MS analysis result of the thermal cracking product of the detection of the relative content of smoke is shown as the following (see Table 1):
table 1: GC/MS analysis results of thermal cracking products of the synthetic product 8 at 30 ℃, 600 ℃ and 900 DEG C
Figure GDA0003183865370000211
Figure GDA0003183865370000221
Figure GDA0003183865370000231
Figure GDA0003183865370000241
Note: normalized peak area
As can be seen from table 1:
after the product 8 is added with 0.01 percent of perfume and applied to tobacco leaves, the relative content of smoke is in TIC at 300 ℃, and as the cracking temperature is mild, the cracking degree of the compound is not severe, and the components are few. As can be seen from table 1, 23 components, which account for 97.97% of the volatile component, were cleaved at 300 ℃, most of the cleaved components were various odorous esters, acids, ketones, alcohols, alkenes, and aldehydes, the highest peak (retention time 28.503) was acetylfuran, and the relative content was 61.38%; the secondary peak (retention time 10.143) was furfural with a relative content of 32.07%.
After the product 8 is added with 0.01 percent of perfume and applied to tobacco leaves, in TIC at 600 ℃, the main components are obviously increased compared with 300 ℃, the cracking products are 34, which account for 98.48 percent of the total volatile components, and are mainly ketones, aldehydes, various esters, various acids, alkenes, saccharides and the like. Compared with 300 ℃, alkynes and acid anhydrides appear, the cracking degree is complete at the temperature, the component with the highest content is still the acetylfuran, and the relative content is 60.17%; and the second is furfural with a relative content of 30.45%.
After the product 8 is added with 0.01 percent of perfume and applied to tobacco leaves, more cracking products are generated at the temperature of 900 ℃, which indicates that the cracking is more sufficient, 56 products are generated by cracking, and the products account for 99.72 percent of total volatile components. The highest peak is 2-furancarboxylic acid with relative content of 59.54%, the second highest peak is furfural with relative content of 30.97%, compared with the cracking product at the previous temperature, the content of benzene such as toluene, ethylbenzene and the like is larger, besides useful volatile components such as ketones, alkenes, ester aldehydes, alcohols, phenols, saccharides and the like, toxic substances such as indenol, indene, biphenyl, acenaphthylene, phenanthrene, fluoranthene and the like are obviously increased.
This fully indicates that the temperature has a great influence on the relative content of flue gas cracking products of the product 8 after the tobacco leaves are added and applied, and the cracking degree is more and more intense along with the increase of the cracking temperature. At 300 deg.C, it is mainly the breaking and hydroxyl-removing of ester bond and single bond, while at 600 deg.C and 900 deg.C, it is not only the cracking process, but also may be accompanied by the reaction processes of rearrangement, cyclization, aromatization, polymerization, etc.
Concerning the cigarette perfuming effect of product 8: see table 2:
table 2: smoking results in cigarette tobacco with addition of synthetic product 8
Figure GDA0003183865370000251
Figure GDA0003183865370000261
With regard to the evaluation of the results operation in table 2, it should be noted that: 50g of single C3F cut tobacco balanced at the temperature of 22 +/-1 ℃ and the relative humidity of 60 +/-2 percent is weighed, the synthesized compound product 8 is respectively weighed according to the mass of 0.002 percent, 0.004 percent, 0.01 percent, 0.02 percent and 0.03 percent, the product 8 is dissolved by 8ml of ethanol with the volume fraction of 95 percent and then is uniformly sprayed on the cut tobacco by a throat sprayer, the flavored and unflavored cut tobacco samples are put in a constant temperature and humidity box with the temperature of 22 +/-1 ℃ and the relative humidity of 60 +/-2 percent for balancing for 48 hours, the flavored and unflavored cut tobacco is respectively made into cigarettes by a cigarette filler, and the cigarettes are continuously put in the constant temperature and humidity box for balancing for 48 hours, and comprehensive evaluation and comparison are carried out by a smoke panel.
As can be seen from Table 2, with the change of the concentration gradient of the added spice, the smoking result changes, the amount of the spice added with a proper amount of the compound spice product 8 (0.01%) can be obviously increased, the aroma quality of the cigarette is improved, the cigarette aroma is more coordinated, the smoke is soft and delicate, the irritation and the offensive odor are reduced, the aftertaste is more comfortable, the taste of the cigarette with too small addition amount is not obviously improved, and the taste is deteriorated due to too large addition amount, so that the fragrance is excessively exposed.
For comparison experiments with the prior art:
the product of the invention 8 is now compared with the open literature: liuyun was the first author, and research and development personnel of our formulation participated in it, and the final product (1, 2-O-isopropylidene-3, 5-O-bis (phenethyloxycarbonyl succinyl) xylofuranose) mentioned in publication of published journal of "tobacco science" and application thereof in cigarettes (1, 2-O-isopropylidene-3, 5-O-bis (phenethyloxy carbonyl succinyl) xylofuranose) was repeatedly operated according to the aforementioned perfuming and smoking assessment manner at 20/6/2010 and the results after the control and smoking assessment experiments were performed are shown in Table 3.
Table 3: cigarette evaluation results of product 8 and 1, 2-O-isopropylidene-3, 5-O-di (phenethyloxy carbonyl succinyl) xylofuranose
Figure GDA0003183865370000271
Note: the scoring of the results of the panel in table 3 was performed with reference to the following criteria (table 4):
table 4: cigarette smoking standard in tobacco industry
Figure GDA0003183865370000272
From the above description it can be found that: the product 8 xylose ester obtained by the invention has the advantages that: firstly, the product 8 is release type tobacco flavor, and the release type tobacco flavor has small taste at normal temperature and normal pressure; the volatility of the perfume in the adding period is lower, and the perfuming retention rate is higher; but after the cigarette is burnt and thermally cracked, the fragrance can be more uniformly released; can be used as a flavoring additive for the high-quality release type xylose ester cigarette flavor.
Secondly, when the addition amount of the xylose ester product 8 obtained by the synthesis method in tobacco leaves is 0.01%, the relative content of smoke pyrolysis components of the product 8 after the application in the tobacco leaves is respectively subjected to GC/MS analysis under the conditions of thermal pyrolysis at 300 ℃, 600 ℃ and 900 ℃, and the relative content of smoke is measured to show that not less than fifty odorous aldehyde, ketone, acid and ester compounds can be obtained comprehensively; when the addition amount of the compound is 0.01%, the cigarette aroma quality can be obviously improved; the obtained smoke is soft and exquisite, the quality of the aroma is improved, the aroma amount is obviously increased, the harmony is better, the aftertaste is purer and richer, the irritation is lower, and the tobacco aroma is more harmonious and lingering in smoking result evaluation.
Most importantly: as can be seen from tables 3 and 4, the 8-xylose ester synthesized by the method can endow cigarette smoke with aroma characteristics of isovaleric acid, ethyl myrcene, 4-methylphenol and the like after being used for perfuming the cigarette, so that the cigarette smoke is softer and finer, the harmony is increased, and the aftertaste is purified.
The apparatus used in connection with the present invention comprises: the nuclear magnetic resonance spectrum is measured by a Bruker ABX-600 nuclear magnetic resonance instrument (TMS is an internal standard), and the mass spectrum is measured by Bruker maXis 4G Q-TOF high resolution; HPLC was performed using Dionex UltiMate 3000HPLC LC-2 HPLC, an angiolent Eclipse XDB-C18 column (46 mm. about.250 mm,5# m), mobile phase A was 0.5% TFA, mobile phase B was acetonitrile, detection wavelength was 220nm, flow rate was 1mL min-1, column temperature was 30 ℃, reaction monitoring used GF254 silica gel plates, all reagents were commercially available either analytically pure or chemically pure. And used at the same time: DPX-400 nuclear magnetic resonance spectrometer (400MHz, Bruker, Sweden); Pirkin-Elmer model 341 Infrared Spectrophotometer (Sammer Feishel technologies Co.); model 2400 element analyzer (Perkin-Elmer, USA); ZAB-HS mass spectrometer (VG, UK); agilent6890N/5975 GC (Agilent Corp.); CDSPyrobe5000 thermal cracker (CDS corporation, usa).
In addition, for the Py-GC/MS analysis method of the present invention, it should be noted that: 0.1g of the synthesized product 8 was weighed, placed in a solid sample injector (Pelletiser), and then placed in a pyrolysis furnace adjusted to a predetermined temperature, and subjected to instantaneous pyrolysis at a series of temperatures, respectively, and the pyrolysis product was directly introduced into a GC/MS by a carrier gas for separation and identification. And using NIST and WILEY standard mass spectrum library to search and qualify.
Wherein the thermal cracking and GC/MS conditions are respectively as follows:
1) thermal cracking conditions are as follows: cracking temperature: 300, 600 and 900 ℃; cracking furnace pressure: 1.03M Pa (above gas chromatography column head pressure); temperature of the cracking probe: 50 ℃ 5 ℃/ms 300, 600, 900 ℃ (20 s); the interface temperature was 280 ℃.
2) GC/MS conditions: a chromatographic column: an HP-FFAP elastomeric quartz capillary column (30m X250 mm i.d.. times.0.25 μm d.f.); sample inlet temperature: 250 ℃; carrier gas: he (purity 99.999%), flow rate 0.6mL/min (column head pressure 72.4 kPa); temperature rising procedure: 50 deg.C (1min) at 5 deg.C/min 300 deg.C (30 min); the split ratio is as follows: 10:1.
3) Transmission line temperature: 280 ℃; an ion source: EI; ionization energy: 70 eV; temperature of the quadrupole rods: 150 ℃; electron multiplier voltage: 1106V; ion source temperature: 230 ℃; solvent retardation: 2 min; scanning range: 29-550 amu.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and therefore, all equivalent changes made by the contents of the claims of the present invention should be included in the claims of the present invention.

Claims (5)

1. The synthesis method of the release type xylose ester spice for flavoring the tobacco is characterized by comprising the following steps of: the method comprises the following steps:
step 1: mixing 15-20 g glucose, 150-200 mL anhydrous acetone, 1.25-1.82 g anhydrous cupric sulfate (CuSO)4) 0.75-2.25 g of concentrated sulfuric acid (H)2SO4) Placing the mixture into a 500mL single-neck flask, stirring the mixture for 48 hours at an internal temperature, concentrating the mixture in vacuum, and using 80-120 mL of saturated sodium bicarbonate (NaHCO) to obtain crude oil3) Washing, extraction 2 times with 50-95 mL ethyl acetate (EtOAc), combining the organic phases and adding anhydrous sodium sulfate (Na)2SO4) Drying and finally vacuum concentrating to obtain 18.95-28 g of white solid product 2: (3aR,5S,6S,6aR) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]Dioxolan-6-ol; and the yield of product 2 is 95.3%;
step 2: putting 3.5-7.2 g of the product 2 and 40-70 mL of anhydrous N, N-Dimethylformamide (DMF) into a 200-300 mL four-neck flask, uniformly stirring, and introducing nitrogen for protection; cooling to 0 ℃ in an ice bath, adding 0.85-1 g of 60% sodium hydride (NaH) into the solution in batches, and continuing stirring for 15-20 minutes at the temperature of 0 ℃ while generating bubbles; then slowly dripping 2.8-4.05 g of benzyl bromide (BnBr) into the reaction bottle, and continuously stirring for 2 hours at the room temperature of 20-25 ℃ until the reaction is finished: the reaction solution after the completion of the reaction was extracted with ethyl acetate several times, and then anhydrous sodium sulfate (Na) was added2SO4) Drying and elution with 1:4 ethyl acetate (EtOAc) and Petroleum Ether (PE) afforded 5.25-8.2 g of product 3: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane;
and step 3: placing 5.25-8.2 g of the product 3 and 95% of 50-90 mL of acetic acid (AcOH) aqueous solution in a 250mL single-neck flask, and stirring at room temperature for 24 hours; after vacuum concentration, washing extraction and drying, 3.1-7.2 g of a product 4 is obtained: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d ] [1,3] dioxolan-5-yl) ethane-1, 2-diol;
and 4, step 4: 3.1-7.2 g of product 4 was dissolved in 100mL of Dichloromethane (DCM), and 5.32-8.2 g of sodium periodate (NaIO)4) Adding the mixture into the solution in batches, stirring the mixture at room temperature for 1 hour, filtering reaction liquid, collecting filtrate, and concentrating the filtrate in vacuum until the filtrate is dried to obtain 2.78-4.5 g of a product 5: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran[2,3-d][1,3]Dioxolane-5-aldehyde; and the yield of product 5 is 98%;
and 5: placing 2.78-4.5 g of the product 5, 5.6-9.2g of potassium hydroxide (KOH) and 20-40 mL of water in a 100mL three-neck flask, fully stirring at the room temperature of 20-25 ℃, and adding 3.36-5.56 g of silver nitrate (AgNO)3) Continuously stirring for 2 hours at room temperature; the reaction solution was filtered through a Buchner funnel with celite and the filtrate was collected, the pH of the filtrate was adjusted to 3 with 6N hydrochloric acid, extracted 3 times with 50-65 mL ethyl acetate (EtOAc), the organic phase was collected and over 10-20 g anhydrous sodium sulfate (Na)2SO4) Drying and vacuum concentrating to dryness to obtain 2.1-4.2 g of a white solid product 6: (3aR,5S,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolane-5-carboxylic acid; the product 6 can be esterified with various alcohols, which is a common parent carboxylic acid, and the yield of the product 6 is 71 percent;
step 6: weighing 0.294-0.4 g of product 6, 0.156-0.192 g of menthol, 0.0246-0.032 g of DMAP, 0.228-0.288 g of EDC, 0.202-0.282 g of Triethylamine (TEA) and 4-6 mL of Dichloromethane (DCM) into an 8-10 mL reaction bottle, and stirring at room temperature for 4 hours; washing the reaction solution with 10-20 mL of water, extracting with 5-10 mL of dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating to dryness in vacuum, performing silica gel column chromatography, eluting with ethyl acetate and petroleum ether until ethyl acetate EtOAc (petroleum ether PE) ═ 1:1, and obtaining 0.19-0.36 g of a colorless viscous oil product 7: menthyl (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d ] [1,3] dioxolane-5-carboxylate; and yield of product 7 was 44%;
and 7: placing 0.19-0.36 g of the product 7 and 5-15mL of methanol (MeOH) and 0.02-0.038 g of 10% palladium-carbon (Pd/C) in a 25mL hydrogenation bottle, replacing the system with hydrogen for 3 times, stirring at room temperature under 20atm of hydrogen pressure for 6 hours, filtering the reaction solution, collecting the filtrate, performing vacuum concentration on the filtrate by using a flash silica gel column chromatography, and eluting with dichloromethane and methanol according to DCM (MeOH) ═ 20:1 to finally obtain 0.095-0.18 g of a white solid product 8: menthyl (1R,2S,5R) -2-isopropyl-5-methylcyclohexyl- (3aR,5S,6R,6aR) -6- (hydroxy) -2, 2-dimethyltetrahydrofuran [2,3-d ] [1,3] dioxolane-5-carboxylate; and the yield of product 8 was 63%;
the chemical molecular structural formula of the product 8 is shown in the specification
Figure FDA0003220352180000031
(ii) a Structural characterization of product 8: HR-MSm/z 432.5, [ M + H]+。
2. The method for synthesizing a release type xylonate spice for flavoring tobacco according to claim 1, wherein the method comprises the following steps: in the step 2, the reaction solution after the reaction further comprises the following processing steps: the first step is as follows: after the reaction, the reaction solution was carefully poured into 100mL of ice water, and extracted 3 times with 100mL of ethyl acetate (EtOAc); the second step is that: the extracted organic phases were combined and washed with 8-15 g of anhydrous sodium sulfate (Na)2SO4) Drying; the third step: concentrating the dried organic phase to dryness in vacuum, and performing silica gel column chromatography; elution with ethyl acetate (EtOAc) and Petroleum Ether (PE) at 1:4 gave product 3 as a colorless clear oil: (3aR,5R,6S,6aR) -6- (benzyloxy) -5- ((S) -2, 2-dimethyl-1, 3-dioxolan-4-yl) -2, 2-dimethyltetrahydrofuran [2,3-d ]][1,3]A dioxolane; and the yield of product 3 was 98.8%.
3. The synthesis method of a release-type xylonate perfume for perfuming tobacco according to claim 1 or 2, characterized in that: in the step 2, when the reaction solution after the completion of the reaction is checked for ethyl acetate (EtOAc)/Petroleum Ether (PE), i.e., EtOAc/PE, by thin layer chromatography, it is indicated that the reaction is completed when the ratio of EtOAc/PE is 1: 4.
4. The method for synthesizing a release type xylonate spice for flavoring tobacco according to claim 1, wherein the method comprises the following steps: in the step 3, the product after stirring for 24 hours at room temperature further comprises the following processing steps: the first step is as follows: vacuum concentration of acetic acid; the second step is that: 200mL of ethyl acetate were added, and 100mL of saturated sodium bicarbonate (NaHCO) were used3) Washing the aqueous solution, extracting, separating and collecting an organic phase; the third step: the organic phase was washed once with 100ml of saturated aqueous sodium chloride solution and with anhydrous sodium sulfate (Na)2SO4) Drying and vacuum concentration to dryness gave product 4 in a colorless viscous oily state: (S) -1- ((3aR,5R,6S,6aR) -6- (benzyloxy) -2, 2-dimethyltetrahydrofuran [2,3-d][1,3]Dioxolan-5-yl) ethane-1, 2-diol; and the yield of product 4 was 100%.
5. The method for synthesizing a release type xylonate spice for flavoring tobacco according to claim 1, wherein the method comprises the following steps: the chemical molecular structural formula of the product 6 is
Figure FDA0003220352180000041
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