阅读说明：本技术 一种利用茴香脑制备对甲氧基肉桂醛香料的方法 (Method for preparing p-methoxycinnamaldehyde spice by using anethole ) 是由 杨漓 潘英明 唐海涛 李桂珍 蒙秀金 谷瑶 于 2021-02-04 设计创作，主要内容包括：本发明公开了一种利用茴香脑制备对甲氧基肉桂醛香料的方法,是以质量比计,取POL-PPh-3@PdCl-2催化剂1份、茴香脑15-20份,加入2-14份水和300-500份甲苯,搅拌均匀,再加入DDQ45-65份,在常温下催化氧化反应0.5-1.5h；再通过吸附剂过滤,加入水萃取,脱水干燥,真空浓缩回收有机溶剂,提纯,干燥,得到的淡黄色固体即为对甲氧基肉桂醛。本发明方法还具有对甲氧基肉桂醛产率高、反应条件温和、生产效率高、工艺简单、生产成本低、原料易得、三废排放少等优点,具有良好的社会、生态和经济效益,为对甲氧基肉桂醛香料能够实现工业化生产提供了有效的途径。(The invention discloses a method for preparing p-methoxycinnamaldehyde spice by utilizing anethole, which takes POL-PPh in mass ratio 3 @PdCl 2 Adding 1 part of catalyst and 15-20 parts of anethole, adding 2-14 parts of water and 500 parts of toluene in 300-fold proportion, uniformly stirring, adding 45-65 parts of DDQ, and carrying out catalytic oxidation reaction for 0.5-1.5h at normal temperature; and filtering by using an adsorbent, adding water for extraction, dehydrating and drying, concentrating in vacuum to recover the organic solvent, purifying and drying to obtain a light yellow solid, namely the p-methoxycinnamaldehyde. The method also has the advantages of high yield of p-methoxycinnamaldehyde, mild reaction conditions, high production efficiency, simple process, low production cost, easily obtained raw materials, less discharge of three wastes and the like, has good social, ecological and economic benefits, and can realize industrialization of p-methoxycinnamaldehyde spiceProduction provides an efficient way.)

1. A method for preparing p-methoxycinnamaldehyde spice by using anethole is characterized by comprising the following steps:

(1) preparing a catalyst: POL-PPh₃、PdCl₂Adding anhydrous THF into a sealed container at a mass ratio of 100:5-10:1, reacting at 25-35 deg.C overnight, filtering, removing filtrate, washing filter residue with ethyl acetate and ethanol, and collecting solid to obtain POL-PPh₃@PdCl₂A catalyst;

(2) catalytic oxidation reaction: taking POL-PPh by mass ratio₃@PdCl₂1 part of catalyst and 15-30 parts of anethole, adding 7-10 parts of water and 500 parts of toluene in 300 parts of water, uniformly stirring, adding 35-55 parts of DDQ, and carrying out catalytic oxidation reaction for 0.5-1.5h at normal temperature;

(3) and (3) purification: and (3) filtering the reaction liquid obtained in the step (2) by using an adsorbent, adding water for extraction, dehydrating and drying, concentrating in vacuum to recover an organic solvent, purifying, and drying to obtain a light yellow solid, namely the p-methoxycinnamaldehyde.

2. The method for preparing p-methoxycinnamaldehyde flavor using anethole according to claim 1, wherein: the POL-PPh₃The preparation method comprises the following steps: 1.0g of 3V-PPh₃Dissolving in 10ml THF, adding 25mg azobisisobutyronitrile, mixing, transferring to a reaction kettle, reacting at 100 deg.C for 24 hr, filtering, removing filtrate, washing the filter residue with ethyl acetate and ethanol to obtain white powdered POL-PPh₃。

3. The method for preparing p-methoxycinnamaldehyde flavor using anethole according to claim 2, wherein: the 3V-PPh₃The preparation process is as follows: 22mmol of PPh₃Dissolving in 30ml THF, slowly dripping into prepared 4-vinyl magnesium bromide Grignard reagent at 0 deg.C, reacting at room temperature for 2 hr, and adding saturated NH₄Quenching reaction with Cl solution, extracting with excessive ethyl acetate, washing the organic phase with saturated salt water, drying with anhydrous magnesium sulfate, and purifying the product with silica gel column to obtain white 3V-PPh₃And (3) a solid.

4. The method for preparing p-methoxycinnamaldehyde flavor using anethole according to claim 1, wherein: the adsorbent is one or more of diatomite, zeolite molecular sieve, activated alumina, quartz sand and clay.

5. The method for preparing p-methoxycinnamaldehyde flavor using anethole according to claim 1, wherein: the dehydration and drying in the step (3) are carried out by using anhydrous Na₂SO₄And (5) drying.

6. The method for preparing p-methoxycinnamaldehyde flavor using anethole according to claim 1, wherein: the catalyst preparation in the step (1) is to carry out the reaction under a sealed container of inert gas.

7. The method for preparing p-methoxycinnamaldehyde flavor using anethole according to claim 1, wherein: the ethyl acetate and the ethanol in the step (1) are analytically pure.

8. The method for preparing p-methoxycinnamaldehyde flavor using anethole according to claim 1, wherein: and (3) purifying, namely adsorbing the crude product after the solvent is recovered by a silica gel column, eluting by using an organic solvent, collecting eluent, concentrating and recovering the organic solvent.

9. The method for preparing p-methoxycinnamaldehyde flavor using anethole according to claim 8, wherein: the elution is carried out by taking petroleum ether and ethyl acetate with the volume ratio of 10:1 as eluent.

10. The method for preparing p-methoxycinnamaldehyde flavor using anethole according to claim 8, wherein: the concentration is carried out at 40-50 ℃ in vacuum until the concentrate is dry.

Technical Field

The invention relates to the technical field of essences and flavors, in particular to a method for preparing a p-methoxycinnamaldehyde flavor by utilizing anethole.

Background

p-Methoxycinnamaldehyde (MCA), white to light yellow crystalline solid, is spice and flower fragrance, is insoluble in water, is dissolved in organic solvents such as ethanol, is one of the components of plant anise, and is a food-grade spice (No. 3567) accepted by China. However, the content of p-methoxycinnamaldehyde in plant raw materials such as plant spice anise and the like is very low, the extraction difficulty from the natural edible spice plant anise is very high, and the p-methoxycinnamaldehyde is still prepared by artificial synthesis in large yield. At present, documents about synthesizing p-methoxycinnamaldehyde are found, for example, in 2013, Mahyari and other people link graphene on ionic liquid, and after a gold nano-catalyst is loaded, 4-methoxycinnamyl alcohol can be efficiently catalyzed to be directly oxidized into p-methoxycinnamaldehyde, but in the method, expensive graphene oxide and gold salt are required to be used; zaks et al found that hydrogen peroxide can oxidize methyl styrene to cinnamaldehyde in water, but the yield of the reaction was only twenty-five percent.

The anethole is colorless or yellowish liquid or crystal with specific fennel fragrance and corresponding sweet taste, the anethole content in the anise oil mainly existing in the anise oil in nature exceeds 80%, and the anethole is mainly applied to products such as wines, candies, beverages, toothpaste, tooth powder, tobacco and the like, is used as a flavoring agent or a flavoring agent, has the effects of invigorating stomach, warming stomach, dispelling cold, diminishing inflammation, relieving pain and the like in the aspect of medicine, and has wide application in the fields of spice industry, chemical industry and medicine. The anethole is industrially produced at present and is cheap and environment-friendly, so that the invention utilizes the anethole as a raw material to synthesize the p-methoxycinnamaldehyde and provides an effective way for realizing the industrial production of the p-methoxycinnamaldehyde spice.

Disclosure of Invention

The invention aims to provide a method for utilizing fennelA method for preparing p-methoxycinnamaldehyde perfume from medulla Citri Junoris is provided. The method takes anethole as a raw material and adopts POL-PPh₃@PdCl₂Under the catalytic oxidation of DDQ, toluene and a small amount of water are used as solvents to synthesize the p-methoxycinnamaldehyde, and an effective way is provided for realizing the industrial production of the p-methoxycinnamaldehyde perfume. The synthetic method also has the advantages of high yield of p-methoxycinnamaldehyde, mild reaction conditions, high production efficiency, simple process, low production cost, easily obtained raw materials, less discharge of three wastes and the like, and has good social, ecological and economic benefits.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:

a method for preparing p-methoxycinnamaldehyde spice by using anethole comprises the following steps:

(1) preparing a catalyst: POL-PPh₃、PdCl₂Adding anhydrous THF into a sealed container at a mass ratio of 100:5-10:1, reacting at 25-35 deg.C overnight, filtering, removing filtrate, washing the filter residue with ethyl acetate and ethanol for 2 times respectively, and collecting solid to obtain POL-PPh₃@PdCl₂A catalyst;

(2) catalytic oxidation reaction: taking POL-PPh by mass ratio₃@PdCl₂Adding 1 part of catalyst and 15-20 parts of anethole, adding 2-14 parts of water and 500 parts of toluene in 300-fold proportion, uniformly stirring, adding 45-65 parts of DDQ, and carrying out catalytic oxidation reaction for 0.5-1.5h at normal temperature;

(3) and (3) purification: and (3) filtering the reaction liquid obtained in the step (2) by using an adsorbent, adding water for extraction, drying, concentrating in vacuum to recover an organic solvent, purifying, and drying to obtain a light yellow solid, namely the p-methoxycinnamaldehyde.

The reaction route for synthesizing the methoxycinnamaldehyde by utilizing the anethole is as follows:

further, the POL-PPh₃The preparation method comprises the following steps: 1.0g of 3V-PPh₃Dissolving in 10ml of THF, adding 25mg of azobisisobutyronitrile, mixing uniformly and transferringAdding into a reaction kettle, reacting for 24 hours at 100 ℃, and volatilizing the solvent in vacuum to obtain white powdered POL-PPh₃。

Further, the 3V-PPh₃The preparation process is as follows: 22mmol of PPh₃Dissolving in 30ml THF, slowly dripping 4-vinyl magnesium bromide Grignard reagent at 0 deg.C, reacting at room temperature for 2 hr, and adding saturated NH₄Quenching reaction with Cl solution, extracting with excessive ethyl acetate, washing the organic phase with saturated salt water, drying with anhydrous magnesium sulfate, and purifying the product with silica gel column to obtain white 3V-PPh₃And (3) a solid.

Further, the adsorbent is one or more of diatomite, zeolite molecular sieve, activated alumina, quartz sand and clay.

Further, the dehydration and drying in the step (3) are carried out by using anhydrous Na₂SO₄And (5) drying.

Further, the catalyst preparation in step (1) is carried out under a sealed vessel of an inert gas.

Further, both ethyl acetate and ethanol described in step (1) were analytically pure.

Further, the purification in the step (3) is to pass the crude product after the solvent is recovered through a silica gel column for adsorption, elute by an organic solvent, collect the eluent, concentrate and recover the organic solvent.

Further, the elution is performed by taking petroleum ether and ethyl acetate in a volume ratio of 10:1 as an eluent.

Further, the concentration is vacuum concentration to dryness at 40-50 ℃.

Furthermore, the anethole is natural anethole extracted from star anise oil, and the purity of the anethole is more than or equal to 80%.

Compared with the prior art, the invention has the advantages and beneficial effects that:

1. the method takes anethole as a raw material and adopts POL-PPh₃@PdCl₂Under the catalytic oxidation of DDQ, toluene and a small amount of water are used as solvents to synthesize the p-methoxycinnamaldehyde, and an effective way is provided for realizing the industrial production of the p-methoxycinnamaldehyde spice。

2. The method also has the advantages of high yield of p-methoxycinnamaldehyde, high product purity, mild reaction conditions, high production efficiency, simple process, low production cost, easily available raw materials, less discharge of three wastes and the like, and has good social, ecological and economic benefits.

3. The catalyst used in the method is a catalyst which is researched and synthesized by the inventor, has the advantages of reusability, high catalytic activity, high catalytic efficiency, high selectivity, no corrosion, no toxicity, simple preparation process, mild reaction conditions and the like, can efficiently catalyze anethole to synthesize the p-methoxycinnamaldehyde, and obviously improves the yield and the production efficiency of the p-methoxycinnamaldehyde.

Drawings

FIG. 1 is an HPLC chart of p-methoxycinnamaldehyde.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.

POL-PPh used in the present invention₃The preparation method comprises the following steps: 1.0g of 3V-PPh₃Dissolving in 10ml THF, adding 25mg azobisisobutyronitrile, mixing uniformly, transferring to a reaction kettle, reacting for 24 hours at 100 ℃, and volatilizing the solvent in vacuum to obtain white powder POL-PPh 3.

The 3V-PPh₃The preparation process is as follows: 22mmol of PPh₃Dissolving in 30ml THF, slowly dripping 4-vinyl magnesium bromide Grignard reagent at 0 deg.C, reacting at room temperature for 2 hr, and adding saturated NH₄Quenching reaction with Cl solution, extracting with excessive ethyl acetate, washing the organic phase with saturated salt water, drying with anhydrous magnesium sulfate, and purifying the product with silica gel column to obtain white 3V-PPh₃And (3) a solid.

Example 1

A method for preparing p-methoxycinnamaldehyde spice by using anethole comprises the following steps:

(1) preparing a catalyst: under argon atmosphere, 500 mgPOL-PPh₃、25 mg PdCl₂Adding into 25mL sealed tube, adding 5mL anhydrous THF, reacting at 25 deg.C overnight, filtering, removing filtrate, washing the residue with ethyl acetate and ethanol for 2 times, and collecting solid to obtain POL-PPh₃@PdCl₂518 mg of catalyst;

(2) catalytic oxidation reaction: 100 mg of POL-PPh was weighed into a 250 mL round bottom flask₃@PdCl_2，Adding 10 mmol (1.482 g) of anethole, 50 mmol (0.9 g) of water and 50mL of toluene, stirring uniformly, slowly adding 20mmol of DDQ (4.54 g) into a round-bottom flask, and carrying out catalytic oxidation reaction for 1h at normal temperature;

(3) and (3) purification: the reaction solution obtained in step (2) was filtered through celite, extracted with 20mL of water, and extracted with anhydrous Na₂SO₄Drying, vacuum concentrating to recover organic solvent, adsorbing with silica gel column, eluting with petroleum ether and ethyl acetate at volume ratio of 10:1, collecting eluate, vacuum concentrating at 40-50 deg.C to recover organic solvent, and vacuum drying to obtain 1.02 g pale yellow solid, i.e. p-methoxycinnamaldehyde.

The yield of p-methoxycinnamaldehyde in this example was calculated to be 69%, and the eluate collected on the silica gel column was subjected to HPLC under the conditions: flow rate: 1 mL/min; mobile phase: acetonitrile/water =85:15, the detection result is shown in fig. 1, and it is known from fig. 1 that the purity of the p-methoxycinnamaldehyde product prepared by the present invention reaches more than 99%.

Example 2

A method for preparing p-methoxycinnamaldehyde spice by using anethole comprises the following steps:

(4) preparing a catalyst: under the argon atmosphere, 500 mgPOL-PPh₃、40mg PdCl₂Adding into 25mL sealed tube, adding 5mL anhydrous THF, reacting at 30 deg.C overnight, filtering, removing filtrate, washing the residue with ethyl acetate and ethanol for 2 times, and collecting solid to obtain POL-PPh₃@PdCl₂532 mg of catalyst;

(5) catalytic oxidation reaction: 100 mg of POL-PPh was weighed into a 250 mL round bottom flask₃@PdCl_2，15 mmol (2.223 g) of anethole, 45mmol (0.81 g) of water and 50mL of formazan were addedBenzene is evenly stirred, then 30mmol of DDQ (6.81 g) is slowly added into the round-bottom flask, and the catalytic oxidation reaction is carried out for 1.5h at normal temperature;

(6) and (3) purification: the reaction solution obtained in step (2) was filtered through celite, extracted with 30mL of water, and extracted with anhydrous Na₂SO₄Drying, vacuum concentrating to recover organic solvent, adsorbing with silica gel column, eluting with petroleum ether and ethyl acetate at volume ratio of 10:1, collecting eluate, vacuum concentrating at 40-50 deg.C to recover organic solvent to obtain 1.40 g pale yellow solid, i.e. p-methoxycinnamaldehyde.

The yield of p-methoxycinnamaldehyde in this example was calculated to be 63%, and the purity of the product after silica gel column purification was 99% or more.

Example 3

A method for preparing p-methoxycinnamaldehyde spice by using anethole comprises the following steps:

(1) preparing a catalyst: under the nitrogen atmosphere, 500 mgPOL-PPh₃、50 mg PdCl₂Adding into 25mL sealed tube, adding 5mL anhydrous THF, reacting at 25 deg.C overnight, filtering, removing filtrate, washing the residue with ethyl acetate and ethanol for 2 times, and collecting solid to obtain POL-PPh₃@PdCl₂541 mg of catalyst;

(2) catalytic oxidation reaction: 100 mg of POL-PPh was weighed into a 250 mL round bottom flask₃@PdCl_2，Adding 10 mmol (1.482 g) of anethole, 80 mmol (1.44g) of water and 50mL of toluene, stirring uniformly, slowly adding 20mmol of DDQ (4.54 g) into a round-bottom flask, and carrying out catalytic oxidation reaction for 1h at normal temperature;

(3) and (3) purification: the reaction solution obtained in step (2) was filtered through celite, extracted with 50mL of water, and extracted with anhydrous Na₂SO₄Drying, vacuum concentrating to recover organic solvent, adsorbing with silica gel column, eluting with petroleum ether and ethyl acetate at volume ratio of 10:1, collecting eluate, vacuum concentrating at 40-50 deg.C to recover organic solvent to obtain 0.92g pale yellow solid, i.e. p-methoxycinnamaldehyde.

The yield of p-methoxycinnamaldehyde in this example was calculated to be 62%, and the purity of the product after silica gel column purification was 99% or more.

The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and such substitutions and modifications are to be considered as within the scope of the invention.