CN111393298B - Green pepper flavor compound, preparation method thereof, food additive and green pepper flavor food - Google Patents
Green pepper flavor compound, preparation method thereof, food additive and green pepper flavor food Download PDFInfo
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- 235000008534 Capsicum annuum var annuum Nutrition 0.000 title claims abstract description 86
- 240000008384 Capsicum annuum var. annuum Species 0.000 title claims abstract description 86
- 239000000796 flavoring agent Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 235000019634 flavors Nutrition 0.000 title claims abstract description 22
- 235000013373 food additive Nutrition 0.000 title claims abstract description 14
- 239000002778 food additive Substances 0.000 title claims abstract description 14
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- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 claims abstract description 54
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- 238000006243 chemical reaction Methods 0.000 claims description 60
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- LTMHNWPUDSTBKD-UHFFFAOYSA-N diethyl 2-(ethoxymethylidene)propanedioate Chemical compound CCOC=C(C(=O)OCC)C(=O)OCC LTMHNWPUDSTBKD-UHFFFAOYSA-N 0.000 claims description 33
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 28
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- 238000010438 heat treatment Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 18
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- 238000000034 method Methods 0.000 claims description 13
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Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/29—Fruit flavours
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Seasonings (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention relates to a green pepper flavor compound, a preparation method thereof, a food additive and a green pepper flavor food. The green pepper flavor compound has the following structural formula:
the green pepper flavor compound is a leaf alcohol ester compound, has a strong faint scent of fresh grass leaves different from leaf alcohol, is different from the grease gas of the traditional long-chain leaf alcohol ester compound, has a green pepper flavor different from leaf alcohol obviously, has an obvious fragrance, and provides a new idea for developing the leaf alcohol ester compound.
Description
Technical Field
The invention relates to the field of spices, in particular to a green pepper flavor compound, a preparation method thereof, a food additive and a green pepper flavor food.
Background
The leaf alcohol has strong faint scent of fresh grass leaves, new tea fragrance and strong diffusion, belongs to faint scent type rare spice, and can be used in essence formula, cosmetics and food spice or used for preparing series leaf alcohol ester. The geraniol ester prepared from the geraniol is mainly used as a foreagent of various floral essences and is used for blending clove, geranium oil, oak moss, lavender, mint and other flower essential oils to provide fresh top aroma. Researchers have developed various leaf alcohol ester compounds with edible flavor characteristics, but the aroma of the short-carbon-chain leaf alcohol ester is obviously homogenized with leaf alcohol, and the aroma of the long-carbon-chain leaf alcohol ester is weak and has grease gas.
Disclosure of Invention
Based on the above, the invention provides the green pepper flavor compound, which is a leaf alcohol ester compound, but has green pepper fragrance obviously different from leaf alcohol and obvious fragrance characteristics, and the fragrance range of the leaf alcohol ester compound is widened.
In addition, a preparation method of the green pepper flavor compound, a food additive and a green pepper flavor food are also needed to be provided.
A green pepper flavor compound having the following structural formula:
a preparation method of green pepper flavor compounds comprises the following steps: performing ester exchange reaction on ethoxymethylene diethyl malonate and cis-3-hexenol under the conditions of catalysis and heating to prepare the green pepper flavor compound, wherein the structural formula of the ethoxymethylene diethyl malonate is shown in the specification
The structural formula of the cis-3-hexenol is shown as
The green pepper flavor compound has the structural formula
In one embodiment, the molar ratio of the diethyl ethoxymethylenemalonate to the cis-3-hexenol is 1: 0.8-1: 1
In one embodiment, in the step of performing the transesterification reaction between diethyl ethoxymethylenemalonate and cis-3-hexenol under the catalytic and heating conditions, the reaction temperature is 110-135 ℃, and the reaction time is 7-12 h.
In one embodiment, the step of subjecting diethyl ethoxymethylenemalonate and cis-3-hexenol to transesterification reaction under catalytic and heating conditions further comprises: adding saturated salt solution into the reaction solution after the reaction for water washing, standing for layering, carrying out reduced pressure distillation on an upper layer organic phase, collecting fractions at 148-175 ℃ under the pressure of 260-580 Pa to obtain the purified green pepper flavor compound,
in one embodiment, the catalyst used in the step of performing transesterification reaction between diethyl ethoxymethylenemalonate and cis-3-hexenol under the catalysis and heating conditions is sodium hydroxide, potassium hydroxide or potassium carbonate.
In one embodiment, the method further comprises a step of preparing the diethyl ethoxymethylenemalonate, wherein the step of preparing the diethyl ethoxymethylenemalonate comprises: reacting diethyl malonate and triethyl orthoformate under the conditions of catalysis and heating to prepare the ethoxymethylene diethyl malonate.
In one embodiment, in the step of reacting diethyl malonate and triethyl orthoformate under the conditions of catalysis and heating, the catalyst used is acetic anhydride, the heating temperature is 110-130 ℃, and the reaction time is 6-8 hours.
In one embodiment, the step of reacting diethyl malonate and triethyl orthoformate under catalytic and heating conditions is specifically as follows: and mixing the diethyl malonate and the triethyl orthoformate, adding part of acetic anhydride, heating to 120 ℃ for reaction for 4 hours, then continuously dropwise adding the rest acetic anhydride, continuing the reaction for 2 hours after the dropwise adding is finished, and carrying out reduced pressure distillation after the reaction is finished to obtain the diethyl ethoxymethylenemalonate.
A food additive comprises the green pepper flavor compound or the green pepper flavor compound prepared by the preparation method of the green pepper flavor compound.
A food with green pepper flavor comprises the food additive.
The green pepper flavor compound is a leaf alcohol ester compound, has a strong faint scent of fresh grass leaves different from leaf alcohol, and is different from the grease gas of the traditional long-chain leaf alcohol ester compound.
Drawings
FIG. 1 is a process flow diagram of one embodiment of a method for producing green pepper flavor compounds;
FIG. 2 is a NMR spectrum of a green pepper flavor compound prepared in example 1.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. Preferred embodiments of the present invention are given in the detailed description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
An embodiment of a green pepper flavor compound has the following structural formula:
the green pepper flavor compound has a molecular formula of C14H22O5Molecular weight 270 and can be named as 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonic acid 1-ethyl ester. The green pepper flavor compound is a colorless to pale yellow liquid compound.
Traditional leaf alcohol ester compounds such as leaf alcohol butyrate have fruit fragrance and faint scent, leaf alcohol acetate has strong banana fragrance, leaf alcohol benzoate has fresh green grass fragrance, and leaf alcohol salicylate has fresh green flower fragrance. The traditional leaf alcohol ester compound has obvious fragrance homogenization with leaf alcohol.
The green pepper flavor compound of the embodiment is also a leaf alcohol ester compound, has a strong fresh grass leaf fragrance different from leaf alcohol, and also has a fat smell different from that of a conventional long-chain leaf alcohol ester compound, has a green pepper flavor obviously different from leaf alcohol, has an obvious fragrance characteristic, and provides a new idea for developing the leaf alcohol ester compound.
Referring to fig. 1, a method for preparing green pepper flavor compounds according to an embodiment includes the following steps:
step S110: the esterification reaction is carried out on malonic acid and ethanol under the conditions of catalysis and heating to prepare the diethyl malonate.
In one embodiment, the catalyst used in step S110 is p-toluenesulfonic acid. It is understood that in other embodiments, the catalyst in step S110 may also be other catalysts, such as an acidic catalyst like concentrated sulfuric acid or a basic catalyst like sodium hydroxide. In one embodiment, in the step of esterification, the reaction temperature is 78 ℃ and the reaction time is 4 h.
Specifically, the reaction process of step S110 is as follows:
in one embodiment, step S110 is: heating malonic acid and ethanol at 78 ℃ and carrying out esterification reaction for 4 hours under the condition of p-toluenesulfonic acid catalysis, and carrying out reduced pressure distillation after the reaction is finished to obtain diethyl malonate. It should be noted that the preparation process of diethyl malonate is not limited to the process in step S110, and may be other preparation methods commonly used in the art. Alternatively, diethyl malonate may be purchased directly, and step S110 may be omitted.
Step S120: diethyl malonate and triethyl orthoformate are reacted under the conditions of catalysis and heating to prepare the ethoxymethylene diethyl malonate.
Wherein the structural formulas of the diethyl malonate, the triethyl orthoformate and the ethoxymethylene diethyl malonate are respectively shown in the specification
In step S120, the molar ratio of diethyl malonate to triethyl orthoformate is 1: 3-1: 5. the dosage of the catalyst is 3-5% of the total weight of the diethyl malonate and the triethyl orthoformate.
Specifically, the catalyst used in step S120 is acetic anhydride, and the reaction temperature is 110 ℃ to 130 ℃. The reaction time is 6-8 h.
In one embodiment, step S120 specifically includes: mixing diethyl malonate and triethyl orthoformate, adding part of acetic anhydride, heating to 120 ℃, and reacting for 4 h. And then continuously dropwise adding the rest acetic anhydride, continuously reacting for 2 hours after dropwise adding is finished, and carrying out reduced pressure distillation after the reaction is finished to obtain the diethyl ethoxymethylenemalonate. Under the high temperature condition, the acetic anhydride and ethanol generated by the reaction are distilled off azeotropically and reduced, so the subsequent addition of the acetic anhydride is needed.
Specifically, the reaction process in step S120 is as follows:
it should be noted that the process for preparing ethoxymethylenediethyl malonate is not limited to the above step S120, and may be a method commonly used in the art, such as synthesizing ethoxymethylenediethyl malonate from diethyl malonate and triethyl orthoformate as raw materials, using activated clay as a carrier, carrying Zn as a catalyst, and using a small amount of acetic acid or acetic anhydride as a condensation medium. Alternatively, diethyl ethoxydimethylmalonate may be purchased directly, and in this case, step S110 and step S120 may be omitted.
Step S130: and (2) carrying out ester exchange reaction on diethyl ethoxymethylenemalonate and cis-3-hexenol under the conditions of catalysis and heating to prepare the green pepper flavor compound.
Wherein the structural formula of cis-3-hexenol (also called leaf alcohol) is shown as
The molar ratio of diethyl ethoxymethylenemalonate to cis-3-hexenol is 1: 0.8-1: 1. controlling the molar ratio of the diethyl ethoxymethylenemalonate to the cis-3-hexenol to ensure that the diethyl ethoxymethylenemalonate and the cis-3-hexenol only carry out unilateral ester exchange reaction to obtain the compound with the structural formula of
The compound of (1). If the cis-3-hexenol content is high, both ester groups on both sides of the ethoxymethylenediethyl malonate will undergo transesterification with the cis-3-hexenol, and the resulting compound will have no green pepper flavor due to its high molecular weight, insignificant odor, and substantial absence of odor. Therefore, in the present embodiment, it is necessary to control the molar ratio of diethyl ethoxymethylenemalonate to cis-3-hexenol to be 1: 0.8-1: 1 to obtain a compound of formula
The green pepper flavor compound of (1).
Specifically, the catalyst used in step S130 is an alkaline catalyst such as sodium hydroxide, potassium hydroxide, or potassium carbonate. Compared with the acid catalyst such as p-toluenesulfonic acid, concentrated sulfuric acid and the like, the alkaline catalyst has better reaction effect. Further, the cost of potassium hydroxide and potassium carbonate is higher than that of sodium hydroxide, and from the perspective of saving cost, the catalyst is sodium hydroxide.
Specifically, the temperature of the ester exchange reaction in step S130 is 110-135 ℃, and the reaction time is 7-12 h.
Further, the step of transesterification is followed by a purification step. Specifically, the purification steps are: and (2) adding saturated salt water into the reaction solution after the reaction for washing, standing for layering, carrying out reduced pressure distillation on an upper organic phase, and collecting fractions at 148-175 ℃ under the pressure of 260-580 Pa to obtain a purified green pepper flavor compound, namely 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonic acid 1-ethyl ester.
Specifically, the reaction process of step S130 is as follows:
through the step S130, the compound with the green pepper flavor is obtained by using ethoxymethylene diethyl malonate and cis-3-hexenol as raw materials through unilateral ester exchange reaction. The green pepper flavor compound has a molecular formula of C14H22O5Molecular weight 270 and can be named as 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonic acid 1-ethyl ester. The green pepper flavor compound is a colorless to pale yellow liquid compound.
Traditional leaf alcohol ester compounds such as leaf alcohol butyrate have fruit fragrance and faint scent, leaf alcohol acetate has strong banana fragrance, leaf alcohol benzoate has fresh green grass fragrance, and leaf alcohol salicylate has fresh green flower fragrance. The traditional leaf alcohol ester compound has obvious fragrance homogenization with leaf alcohol.
The green pepper flavor compound prepared by the embodiment is also a leaf alcohol ester compound, has a strong fresh grass leaf faint scent different from leaf alcohol, and is different from a traditional long-chain leaf alcohol ester compound in oil gas, the green pepper flavor compound has a green pepper flavor different from leaf alcohol, and the fragrance is obvious, so that a new idea is provided for development of the leaf alcohol ester compound.
Experiments have shown that if trans-3-hexenol and diethyl ethoxymethylenemalonate are subjected to transesterification in this embodiment, the resulting compound has a strong greasy smell and a rotten leaf-like aroma, and does not have a green pepper flavor. If diethyl malonate is directly used as a raw material and cis-3-hexenol is used as a raw material to carry out ester exchange reaction, the prepared compound has faint scent of violet leaves and does not have the flavor of green pepper.
In addition, diethyl ethoxymethylenemalonate is an important organic raw material containing various active groups, can be subjected to condensation polymerization and cyclization condensation with various substances, is an important intermediate for preparing heterocyclic compounds, is used for preparing norfloxacin and the like, and is widely used in the fields of medicines, dye synthesis and the like. However, it has not been found that a fragrant compound can be obtained by using diethyl ethoxymethylenemalonate in the field of perfumery. In this embodiment, the inventors found that when diethyl ethoxymethylenemalonate and cis-3-hexenol are used as raw materials to perform an ester exchange reaction, the obtained leaf alcohol ester compound has a distinct green pepper flavor and can be used as a food additive.
The method for preparing the green pepper flavor compound of the embodiment at least has the following advantages:
(1) the preparation method of the green pepper flavor compound can prepare the compound with obvious green pepper aroma, has the aroma obviously different from leaf alcohol, and can be used in food additives.
(2) The preparation method of the green pepper flavor compound is simple in steps and easy for industrial production.
A food additive according to an embodiment includes the green pepper flavor compound according to the above embodiment or the green pepper flavor compound produced by the method for producing a green pepper flavor compound according to the above embodiment. The food additive has obvious green pepper fragrance, and can be used for preparing food with green pepper flavor.
An embodiment of a green pepper-flavored food product comprises the food additive of the above embodiment.
The following are specific examples:
example 1
The preparation process of the green pepper flavor compound of this example is specifically as follows:
(1) preparation of diethyl malonate:
malonic acid (250g), absolute ethanol (570g) and p-toluenesulfonic acid (2g) were added to a 1L reaction vessel, the temperature was raised to 78 ℃, the reaction was stirred for 4 hours, and after the reaction was completed, distillation under reduced pressure was carried out to obtain diethyl malonate (245 g).
(2) Preparation of diethyl ethoxymethylenemalonate:
diethyl malonate (240g), triethyl orthoformate (296g, commercially available from dennay chemical company ltd.) and acetic anhydride (10mL) were sequentially charged into a 1L reaction vessel, and the temperature was raised to 120 ℃ to react for 4 hours. Then, acetic anhydride (20mL) was added dropwise over 2 hours, and the reaction was continued for 2 hours. After completion of the reaction, the mixture was distilled under reduced pressure to obtain ethoxymethylenemalonic acid diethyl ester (236 g).
(3) Preparation of 1-ethyl 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonate:
diethyl ethoxymethylenemalonate (216g, 1mol), cis-3-hexenol (100g, 1mol) and sodium hydroxide (2g) were sequentially added to a 1L reaction vessel, followed by heating to 120 ℃ and reaction for 8 hours. After the reaction is finished, cooling to room temperature, adding 500mL of saturated saline solution into the reaction kettle, washing for 5 minutes, and standing for layering to obtain an upper organic phase and a lower aqueous phase. The upper organic phase was distilled under reduced pressure, and the fraction having a boiling point of 148 to 155 ℃ was collected under 260Pa to obtain 1-ethyl 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonate (238g), which was the green pepper flavor compound of this example.
The structural characteristics of the 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonic acid 1-ethyl ester of the green pepper flavor compound prepared in example 1 were subjected to characterization tests, and the following data were obtained:
(1) NMR spectral characteristics:
1H NMR(400MHz,CD3Cl):7.95(s,1H),5.50(m,2H),4.49(m,2H),4.20(m,4H),2.28(m,2H),2.00(m,2H),1.29(t,6H),1.06(t,3H)。
the hydrogen nuclear magnetic spectrum is shown in FIG. 2.
13C NMR(100MHz,CD3Cl):179.5,165.4,165.4,132.9,125.7,96.9,67.8,65.3,61.4,42.6,26.5,15.3,14.2,14.1。
(2) Mass spectrum characteristics: MS (ESI, m/z): 293.1(M + Na)+) (ii) a The theoretical calculation data of the high-resolution electrospray ionization mass spectrum is [ C ]14H22NaO5]+(M+Na+): 293.1365, the actual measured value was 293.1306.
As can be seen from the above experimental data, 1-ethyl ester of the green pepper flavor compound 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonate was successfully prepared in example 1.
Example 2
The preparation process of the green pepper flavor compound of this example is specifically as follows:
(1) preparation of diethyl malonate:
malonic acid (250g), absolute ethanol (570g) and p-toluenesulfonic acid (2g) were added to a 1L reaction vessel, the temperature was raised to 78 ℃, the reaction was stirred for 4 hours, and after the reaction was completed, distillation under reduced pressure was carried out to obtain diethyl malonate (245 g).
(2) Preparation of ethoxymethylenemalonic acid diethyl ester:
diethyl malonate (240g), triethyl orthoformate (296g, commercially available from denamoniate chemical co., ltd.) and acetic anhydride (10mL) were sequentially added to a 1L reaction vessel, and the reaction was carried out at 120 ℃ for 4 hours. Then, acetic anhydride (20mL) was added dropwise over 2 hours, and the reaction was continued for 2 hours. After completion of the reaction, the mixture was distilled under reduced pressure to obtain ethoxymethylenemalonic acid diethyl ester (236 g).
(3) Preparation of 1-ethyl 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonate:
diethyl ethoxymethylenemalonate (216g, 1mol), cis-3-hexenol (80g, 0.8mol) and sodium hydroxide (2g) were added in this order to a 1L reaction vessel, heated to 130 ℃ and reacted for 7 hours. After the reaction is finished, cooling to room temperature, adding 500mL of saturated saline solution into the reaction kettle, washing for 5 minutes, and standing for layering to obtain an upper organic phase and a lower aqueous phase. The upper organic phase was distilled under reduced pressure, and the fraction having a boiling point of 152 to 164 ℃ was collected under 480Pa to obtain 1-ethyl 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonate (182.6g), which was the green pepper flavor compound of this example.
Experiments prove that the green pepper flavor compound prepared in example 2 is the same as the green pepper flavor compound prepared in example 1, and the description is omitted.
Example 3
The preparation process of the green pepper flavor compound of this example is specifically as follows:
(1) preparation of diethyl malonate:
malonic acid (250g), absolute ethanol (570g) and p-toluenesulfonic acid (2g) were added to a 1L reaction vessel, the temperature was raised to 78 ℃, the reaction was stirred for 4 hours, and after the reaction was completed, distillation under reduced pressure was carried out to obtain diethyl malonate (245 g).
(2) Preparation of ethoxymethylenemalonic acid diethyl ester:
diethyl malonate (240g), triethyl orthoformate (296g, commercially available from denamoniate chemical company, ltd.) and acetic anhydride (10mL) were sequentially added to a 1L reaction vessel, and the reaction was carried out at 120 ℃ for 4 hours. Then, acetic anhydride (20mL) was added dropwise over 2 hours, and the reaction was continued for 2 hours. After completion of the reaction, the mixture was distilled under reduced pressure to obtain ethoxymethylenemalonic acid diethyl ester (236 g).
(3) Preparation of 1-ethyl 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonate:
diethyl ethoxymethylenemalonate (216g, 1mol), cis-3-hexenol (90g, 0.9mol) and sodium hydroxide (1g) were sequentially added to a 1L reaction vessel, heated to 110 ℃ and reacted for 12 hours. After the reaction is finished, cooling to room temperature, adding 500mL of saturated saline solution into the reaction kettle, washing for 5 minutes, and standing for layering to obtain an upper organic phase and a lower aqueous phase. The upper organic phase was distilled under reduced pressure, and the fraction having a boiling point of 160 to 175 ℃ was collected under 580Pa to give 1-ethyl 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonate (191.8g), which was the green pepper flavor compound of this example.
Experiments prove that the green pepper flavor compound prepared in example 3 is the same as the green pepper flavor compound prepared in example 1, and the description is omitted.
The following are test sections:
1. the green pepper flavor compound 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) propanedioic acid 1-ethyl ester prepared in example 1 and the commercially available hexyl octanoate were each diluted to a mass concentration of 1% with propylene glycol and subjected to a double blind test. In a test of 100, 87 of them considered that 1-ethyl 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonate had a more pronounced green pepper flavor and the aroma was more characteristic.
2. A perfumer working over 5 years at 10 sites evaluated the 1-ethyl ester of the green pepper flavor compound 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonate prepared in example 1 simultaneously with the conventional leaf alcohol ester compounds, namely, leaf alcohol acetate and cis-3-hexenol, according to the following specific evaluation methods: the aroma properties of the above compounds were evaluated using (i) aroma intensities from 0 to 10 (where 0 is none, 1 is very weak, 5 is moderate, and 10 is very strong) and (ii) complexity levels (where 0 is none, 1 is very low, 5 is moderate, and 10 is very high) to give the data shown in table 1 below. The data in table 1 are the average scores of fragrance evaluations by 10 perfumers who have been experienced at 5 years or more.
TABLE 1 aroma evaluation data
| Compound (I) | Aroma characteristics | Intensity of fragrance | Complexity of |
| Example 1 | Green fragrance, green pepper fragrance | 8.7 | 8.5 |
| Acetic acid leaf alcohol ester | Fragrance of banana | 7.5 | 7.8 |
| Cis-3-hexenol | Green, herbal and green fragrance | 8.5 | 8.1 |
As can be seen from Table 1, the 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonic acid 1-ethyl ester prepared in example 1 has strong fragrance intensity, obviously changes fragrance compared with leaf alcohol, has no irritation fragrance of leaf alcohol, is softer and has rich fragrance.
The above experimental data show that the green pepper flavor compound 3- (3E) -hex-3-en-1-yl (2E) -2- (ethoxymethylene) malonic acid 1-ethyl ester prepared in example 1 has obvious green pepper fragrance, which is different from the fragrance of leaf alcohol and the conventional leaf alcohol ester compounds.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A green pepper flavor compound, having the following structural formula:
2. the preparation method of the green pepper flavor compound is characterized by comprising the following steps of:
reacting diethyl ethoxymethylenemalonate and cis-3-hexenol in the presence of catalystPerforming ester exchange reaction under heating condition to prepare green pepper flavor compound, wherein the structural formula of the ethoxymethylene diethyl malonate is shown in the specification
The structural formula of the cis-3-hexenol is shown as
The green pepper flavor compound has the structural formula
3. The method of producing a green pepper flavor compound according to claim 2, wherein the molar ratio of the diethyl ethoxymethylenemalonate to the cis-3-hexenol is 1: 0.8-1: 1.
4. the method for preparing green pepper flavor compound according to claim 2, wherein in the step of subjecting diethyl ethoxymethylenemalonate and cis-3-hexenol to transesterification reaction under catalytic and heating conditions, the reaction temperature is 110 ℃ to 135 ℃, and the reaction time is 7h to 12 h.
5. The method of claim 2, wherein the step of transesterifying diethyl ethoxymethylenemalonate and cis-3-hexenol under catalytic and heating conditions is followed by the step of: and adding saturated salt water into the reaction solution after the reaction for washing, standing for layering, carrying out reduced pressure distillation on an upper organic phase, and collecting fractions at 148-175 ℃ under the pressure of 260-580 Pa to obtain the purified green pepper flavor compound.
6. The method of claim 2, wherein the catalyst used in the step of transesterifying diethyl ethoxymethylenemalonate and cis-3-hexenol under catalytic and heating conditions is sodium hydroxide, potassium hydroxide or potassium carbonate.
7. The method of producing a green pepper flavor compound according to claim 2, further comprising the step of producing the diethyl ethoxymethylenemalonate comprising: reacting diethyl malonate and triethyl orthoformate under the conditions of catalysis and heating to prepare the ethoxymethylene diethyl malonate.
8. The method for preparing green pepper flavor compounds according to claim 7, wherein the step of reacting diethyl malonate and triethyl orthoformate under the catalysis and heating conditions uses acetic anhydride as a catalyst, the heating temperature is 110 ℃ to 130 ℃, and the reaction time is 6h to 8 h.
9. The method for preparing green pepper flavor compounds according to claim 8, wherein the step of reacting diethyl malonate and triethyl orthoformate under catalytic and heating conditions comprises: mixing the diethyl malonate and the triethyl orthoformate, adding part of acetic anhydride, heating to 120 ℃ for reaction for 4 hours, then continuing to dropwise add the rest acetic anhydride, continuing to react for 2 hours after dropwise adding, and performing reduced pressure distillation after the reaction is finished to prepare the diethyl ethoxymethylenemalonate.
10. A food additive comprising the green pepper flavor compound according to claim 1 or the green pepper flavor compound produced by the method for producing a green pepper flavor compound according to any one of claims 2 to 9.
11. A green pepper-flavored food product comprising the food additive according to claim 10.
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