CN106631847B - A kind of synthesis technology of preservative intermediate sorbic acid phenylalanine ethyl ester - Google Patents
A kind of synthesis technology of preservative intermediate sorbic acid phenylalanine ethyl ester Download PDFInfo
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- CN106631847B CN106631847B CN201611216846.4A CN201611216846A CN106631847B CN 106631847 B CN106631847 B CN 106631847B CN 201611216846 A CN201611216846 A CN 201611216846A CN 106631847 B CN106631847 B CN 106631847B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
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- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention discloses a kind of synthesis technologies of preservative intermediate sorbic acid phenylalanine ethyl ester, with phenylalanine, thionyl chloride, sorbic acid, the raw materials such as the nanoscale Cu HMS catalyst that homemade yttrium is modified pass through rotary evaporation, ice salt bath, the operational means such as magnetic agitation prepare sorbic acid phenylalanine ethyl ester.
Description
Technical field
The present invention relates to a kind of synthesis technologies of preservative intermediate sorbic acid phenylalanine ethyl ester, belong to organic synthesis neck
Domain.
Background technology
Food is base substance for the survival of mankind, it is supplied to the required various nutrients of human lives and energy
Amount.By consuming the nutriment in food, bacterium, yeast and fungi etc. can breed rapidly, occur so as to cause food micro-
Biological infection.With the improvement of living standards, people increasingly focus on the quality problems of food.Therefore, enhance the safety of food
Property be very it is necessary to.Growth and the prevent food spoilage of microorganism are controlled using the chemical food preservations of synthesis,
It is one of most common method.Currently, domestic common food preservative presses ingredient and source difference, it is broadly divided into ester type anti-corrosion
Agent, four class of acidic preservative, biological preservative and inorganic corrosion inhibitor.The structure of food preservative imitate research shows that：α, β have antibacterial
One of active effective efficiency structure.Sorbic acid phenylalanine ethyl ester is that have good fungistatic effect, present invention one kind
The sorbic acid phenylalanine ethyl ester for the nanoscale Cu-HMS catalyst synthesis that the homemade yttrium of new technique is modified, the technological operation
Simply, raw material sources are convenient, and product purity is high in high yield.
Invention content
In view of the above existing problems in the prior art, the present invention provides a kind of preservative intermediate sorbic acid phenylalanine second
The synthesis technology of ester.
To achieve the goals above, the technical solution adopted by the present invention is：A kind of preservative intermediate sorbic acid phenylpropyl alcohol ammonia
The synthesis technology of acetoacetic ester, includes the following steps：
Absolute ethyl alcohol is added into the 250mL three-necked flasks equipped with low-reading thermometer in step 1, the phenylpropyl alcohol being added thereto
Propylhomoserin and thionyl chloride, then magnetic agitation 4h；
Step 2 and then the nanoscale Cu-HMS catalyst that homemade yttrium is modified is added, reacts, reheat back in ice salt bath
Stream continues magnetic agitation 4h；
Remaining ethyl alcohol and SOCl2 is removed under reduced pressure using Rotary Evaporators in step 3, obtains intermediate phenylalanine ethyl ester
Hydrochloride；
Sorbic acid and thionyl chloride are added into 250mL round-bottomed flasks for step 4, and magnetic agitation reacts 4h at normal temperatures.Profit
Remaining SOCl2 is removed under reduced pressure with Rotary Evaporators, while recycling the nanoscale Cu-HMS catalyst that homemade yttrium is modified, obtains
Sorbic acid after chloride；
Step 5, by the sorbic acid 1 after synthetic phenylalanine ethyl ester hydrochloride and chloride:1 (molar ratio) mixes,
Ice salt bath reacts 3h, reacts at room temperature 4h.Low-boiling point material is removed under reduced pressure using Rotary Evaporators, obtains sorbic acid phenylalanine second
Then ester crude product is recrystallized to give the sorbic acid phenylalanine ethyl ester of high-purity with absolute ethyl alcohol.
The nanoscale Cu-HMS catalyst synthesis that yttrium is modified
Step 1, by 5gCu (NO3) 23H2O, will be added in 100ml ethanol solutions, then ultrasonication 1h；
Step 2 and then addition 3ml tetraethyl orthosilicates, while opening 80 DEG C of reaction 4h of magnetic agitation water-bath；
Step 3 is then transferred into microwave treatment 2h in microwave reactor；
Step 4 and then 30ml is added contains the ethanol solutions of the 2ml lauryl amines magnetic agitation 3h at 50 DEG C；
Step 5, products therefrom centrifugation washing are then in 110 DEG C of dry 12h；
Step 6 and then the calcination processing in Muffle furnace：Under the atmosphere of nitrogen and carbon dioxide, 550 DEG C, under 0.1kpa
Calcine 4h；
Step 7 and then use infusion process introduce yttrium, and the solid after calcining is all in the yttrium sulfate of 0.1mol/L
8h in solution；
It is then washed with deionized after step 8, dipping, by moisture evaporation under rotary evaporator, finally obtains
The nanoscale Cu-HMS catalyst that yttrium is modified.
Advantageous effect:A kind of sorbic acid phenylpropyl alcohol for the nanoscale Cu-HMS catalyst synthesis being modified with homemade yttrium of the present invention
Propylhomoserin ethyl ester technique, the technological operation is simple, and catalyst is easy to be made, and raw material relatively easily obtains, by the way that homemade yttrium is added
Modified nanoscale Cu-HMS catalyst, effectively raises reaction rate, reduces the generation of side reaction, in the synthesis process
By processing such as magnetic agitations, activation can be played to reactant enables reaction to be more smoothed out, and makes reaction towards expection
Direction carry out, so that the yield of target product is improved.By carrying out rotary evaporation, ice salt bath, magnetic agitation recrystallizes energy
Access purer sorbic acid phenylalanine ethyl ester.Wherein embodiment 1 produces phenylalanine, and thionyl chloride is (for producing phenylpropyl alcohol
Thionyl chloride used in propylhomoserin carbethoxy hydrochloride), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：60:
1.2 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g,
The nanoscale Cu-HMS catalyst 1.2g that yttrium is modified, sorbic acid 11g, thionyl chloride (are used for the thionyl chloride used in chloride)
33g, absolute ethyl alcohol 100ml.And embodiment 2 produces phenylalanine, thionyl chloride is (for producing phenylalanine ethyl ester hydrochloride
Used thionyl chloride), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 30：65:1.1 sample.Phenylpropyl alcohol ammonia
Sour 30g, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 65g, the nanoscale that yttrium is modified
Cu-HMS catalyst 1.1g, sorbic acid 11g, thionyl chloride (being used for the thionyl chloride used in chloride) 33g, absolute ethyl alcohol
100ml.Sorbic acid phenylalanine ethyl ester purity and yield obtained is best under both techniques.
Specific implementation mode
Embodiment 1
The nanoscale Cu-HMS catalyst preparation process that homemade yttrium is modified is as follows：
Step 1, by 5gCu (NO3) 23H2O, will be added in 100ml ethanol solutions, then ultrasonication 1h；
Step 2 and then addition 3ml tetraethyl orthosilicates, while opening 80 DEG C of reaction 4h of magnetic agitation water-bath；
Step 3 is then transferred into microwave treatment 2h in microwave reactor；
Step 4 and then 30ml is added contains the ethanol solutions of the 2ml lauryl amines magnetic agitation 3h at 50 DEG C；
Step 5, products therefrom centrifugation washing are then in 110 DEG C of dry 12h；
Step 6 and then the calcination processing in Muffle furnace：In nitrogen and carbon dioxide (volume ratio 4:1) under atmosphere,
550 DEG C, 4h is calcined under 0.1kpa；
Step 7 and then use infusion process introduce yttrium, and the solid after calcining is all in the yttrium sulfate of 0.1mol/L
8h in solution；
It is then washed with deionized after step 8, dipping, by moisture evaporation under rotary evaporator, finally obtains
The nanoscale Cu-HMS catalyst that yttrium is modified.
Produce phenylalanine, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride), from
The nanoscale Cu-HMS catalyst qualities that the yttrium of system is modified are than 33：60:1.2 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride is (for making
Take the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, the nanoscale Cu-HMS catalyst 1.2g that yttrium is modified, sorb
Sour 11g, thionyl chloride (being used for the thionyl chloride used in chloride) 33g, absolute ethyl alcohol 100ml.
100ml absolute ethyl alcohols are added into the 250mL three-necked flasks equipped with low-reading thermometer for step 1, are added thereto
33g phenylalanines and 60g thionyl chlorides, then magnetic agitation 4h；
Step 2 and then the nanoscale Cu-HMS catalyst that the homemade yttriums of 1.2g are modified is added, is reacted in ice salt bath, then add
Heat reflux, continues magnetic agitation 4h；
Remaining ethyl alcohol and SOCl2 is removed under reduced pressure using Rotary Evaporators in step 3, while recycling what homemade yttrium was modified
Nanoscale Cu-HMS catalyst obtains intermediate phenylalanine ethyl ester hydrochloride；
11g sorbic acids and 33g thionyl chlorides are added into 250mL round-bottomed flasks for step 4, and magnetic agitation is anti-at normal temperatures
Answer 4h.Remaining SOCl2 is removed under reduced pressure using Rotary Evaporators, obtains the sorbic acid after chloride；
Step 5, by the sorbic acid 1 after synthetic phenylalanine ethyl ester hydrochloride and chloride:1 (molar ratio) mixes,
Ice salt bath reacts 3h, reacts at room temperature 4h.Low-boiling point material is removed under reduced pressure using Rotary Evaporators, obtains sorbic acid phenylalanine second
Then ester crude product is recrystallized to give the sorbic acid phenylalanine ethyl ester of high-purity with absolute ethyl alcohol.
Embodiment 2 produces phenylalanine, and thionyl chloride is (for producing the protochloride used in phenylalanine ethyl ester hydrochloride
Sulfone), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 30：65:1.1 sample.Phenylalanine-3,4-quinone 0g, thionyl chloride
(for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 65g, the nanoscale Cu-HMS catalyst that yttrium is modified
1.1g, other raw material dosages, operating procedure is as embodiment 1.Embodiment 3 produces phenylalanine, and thionyl chloride is (for producing
Thionyl chloride used in phenylalanine ethyl ester hydrochloride), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：
60:1.1 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride)
60g, the nanoscale Cu-HMS catalyst 1.1g that yttrium is modified,.Other raw materials, operating procedure is as embodiment 1.Embodiment 4 is made
Phenylalanine, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride), homemade yttrium is taken to be modified
Nanoscale Cu-HMS catalyst qualities than 33：60:1.0 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride is (for producing phenylalanine
Thionyl chloride used in carbethoxy hydrochloride) 60g, the nanoscale Cu-HMS catalyst 1.0g that yttrium is modified,.Other raw materials, operation
Step is as embodiment 1.Embodiment 5 produces phenylalanine, and thionyl chloride is (for producing used in phenylalanine ethyl ester hydrochloride
The thionyl chloride arrived), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：60:0.9 sample.Phenylalanine
33g, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, the nanoscale Cu- that yttrium is modified
HMS catalyst 0.9g,.Other raw materials, operating procedure is as embodiment 1.Embodiment 6 produces phenylalanine, and thionyl chloride (is used
To produce the thionyl chloride used in phenylalanine ethyl ester hydrochloride), the nanoscale Cu-HMS catalyst matter that homemade yttrium is modified
Measure ratio 33：60:0.8 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride is (for producing the chlorination used in phenylalanine ethyl ester hydrochloride
Sulfoxide) 60g, the nanoscale Cu-HMS catalyst 0.8g that yttrium is modified,.Other raw materials, operating procedure is as embodiment 1.Implement
Example 7 produces phenylalanine, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride), homemade yttrium
Modified nanoscale Cu-HMS catalyst qualities are than 33：60:0.7 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride is (for producing phenylpropyl alcohol
Thionyl chloride used in propylhomoserin carbethoxy hydrochloride) 60g, the nanoscale Cu-HMS catalyst 0.7g that yttrium is modified.Other raw materials, behaviour
Make step as embodiment 1.Embodiment 8 produces phenylalanine, and thionyl chloride is (for producing phenylalanine ethyl ester hydrochloride institute
The thionyl chloride used), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：60:1.3 sample.Phenylalanine
33g, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, the nanoscale Cu- that yttrium is modified
HMS catalyst 1.3g.Other raw materials, operating procedure is as embodiment 1.Embodiment 9 produces phenylalanine, and thionyl chloride (is used
To produce the thionyl chloride used in phenylalanine ethyl ester hydrochloride), the nanoscale Cu-HMS catalyst matter that homemade yttrium is modified
Measure ratio 33：60:1.4 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride is (for producing the chlorination used in phenylalanine ethyl ester hydrochloride
Sulfoxide) 60g, the nanoscale Cu-HMS catalyst 1.4g that yttrium is modified,.Other raw materials, operating procedure is as embodiment 1.Implement
Example 10 produces phenylalanine, and thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) is homemade
The nanoscale Cu-HMS catalyst qualities that yttrium is modified are than 33：60:1.5 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride is (for producing benzene
Thionyl chloride used in alanine ethyl ester hydrochloride) 60g, the nanoscale Cu-HMS catalyst 1.5g that yttrium is modified,.Other are former
Material, operating procedure is as embodiment 1.Embodiment 11 produces phenylalanine, and thionyl chloride is (for producing phenylalanine ethyl ester salt
Thionyl chloride used in hydrochlorate), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：60:1.6 sample.Benzene
Alanine 33g, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, what yttrium was modified receives
Meter level Cu-HMS catalyst 1.6g.Other raw materials, operating procedure is as embodiment 1.Embodiment 12 produces phenylalanine, chlorination
Sulfoxide (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride), the nanoscale Cu-HMS that homemade yttrium is modified are urged
Agent mass ratio 33：60:1.7 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride is (for producing used in phenylalanine ethyl ester hydrochloride
Thionyl chloride) 60g, yttrium be modified nanoscale Cu-HMS catalyst 1.7g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 13 produces phenylalanine, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride), from
The nanoscale Cu-HMS catalyst qualities that the yttrium of system is modified are than 33：60:1.8 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride is (for making
Take the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, the nanoscale Cu-HMS catalyst 1.8g that yttrium is modified,.Other
Raw material, operating procedure is as embodiment 1.Embodiment 14 produces phenylalanine, and thionyl chloride is (for producing phenylalanine ethyl ester
Thionyl chloride used in hydrochloride), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：60:1.9 sample.
Phenylalanine-3,4-quinone 3g, thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, what yttrium was modified
Nanoscale Cu-HMS catalyst 1.9g,.Other raw materials, operating procedure is as embodiment 1.Embodiment 15 produces phenylalanine,
Thionyl chloride (for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride), the nanoscale Cu- that homemade yttrium is modified
HMS catalyst qualities are than 33：60:2.0 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride is (for producing phenylalanine ethyl ester hydrochloride
Used thionyl chloride) 60g, the nanoscale Cu-HMS catalyst 2.0g that yttrium is modified,.Other raw materials, operating procedure is with implementing
As example 1.
Reference examples 1 produce phenylalanine, and thionyl chloride is (for producing the protochloride used in phenylalanine ethyl ester hydrochloride
Sulfone), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：60:1.2 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride
(for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, the nanoscale Cu-HMS catalyst that yttrium is modified
1.2g,.Without magnetic agitation but mechanical agitation, other raw materials, operating procedure is as embodiment 1.
Reference examples 2 produce phenylalanine, and thionyl chloride is (for producing the protochloride used in phenylalanine ethyl ester hydrochloride
Sulfone), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：60:1.2 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride
(for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, the nanoscale Cu-HMS catalyst that yttrium is modified
1.2g,.Without ice salt bath, other raw materials, operating procedure is as embodiment 1.
Reference examples 3 produce phenylalanine, and thionyl chloride is (for producing the protochloride used in phenylalanine ethyl ester hydrochloride
Sulfone), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：60:1.2 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride
(for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, the nanoscale Cu-HMS catalyst that yttrium is modified
1.2g,.Without being heated to reflux, other raw materials, operating procedure is as embodiment 1.
Reference examples 4 produce phenylalanine, and thionyl chloride is (for producing the protochloride used in phenylalanine ethyl ester hydrochloride
Sulfone), the nanoscale Cu-HMS catalyst qualities that homemade yttrium is modified are than 33：60:1.2 sample.Phenylalanine-3,4-quinone 3g, thionyl chloride
(for producing the thionyl chloride used in phenylalanine ethyl ester hydrochloride) 60g, the nanoscale Cu-HMS catalyst that yttrium is modified
1.2g,.Without rotary evaporation, other raw materials, operating procedure is as embodiment 1.
Reference examples 5 are added without the nanoscale Cu-HMS catalyst that homemade yttrium is modified, other raw material dosages, operating procedure with
As embodiment 1.
Metal palladium catalyst 1.2g is added in reference examples 6, other raw materials, operating procedure is as embodiment 1.
Reference examples 7, method for preparing catalyst is different from embodiment 1, other raw material dosages, operating procedure is with embodiment 1
Equally, the method for preparing catalyst of this reference examples is as follows：Step 1, by 5gCu (NO3) 23H2O, will be added to 100ml ethyl alcohol
In solution, then ultrasonication 1h；
Step 2 and then addition 3ml tetraethyl orthosilicates, while opening 80 DEG C of reaction 4h of magnetic agitation water-bath；
Step 3 is then transferred into microwave treatment 2h in microwave reactor；
Step 4 and then 30ml is added contains the ethanol solutions of the 2ml lauryl amines magnetic agitation 3h at 50 DEG C；
Step 5, products therefrom centrifugation washing are then in 110 DEG C of dry 12h；
Step 6 and then the calcination processing in Muffle furnace：Under the atmosphere of nitrogen, 550 DEG C, 4h is calcined under 0.1kpa；
Step 7 and then use infusion process introduce yttrium, and the solid after calcining is all in the yttrium sulfate of 0.1mol/L
8h in solution；
It is then washed with deionized after step 8, dipping, by moisture evaporation under rotary evaporator, finally obtains
The nanoscale Cu-HMS catalyst that yttrium is modified.
Reference examples 8, method for preparing catalyst is different from embodiment 1, other raw material dosages, operating procedure is with embodiment 1
Equally, the method for preparing catalyst of this reference examples is as follows：Step 1, by 5gCu (NO3) 23H2O, will be added to 100ml ethyl alcohol
In solution, then ultrasonication 1h；
Step 2 and then addition 3ml tetraethyl orthosilicates, while opening 80 DEG C of reaction 4h of magnetic agitation water-bath；
Step 3 is then transferred into microwave treatment 2h in microwave reactor；
Step 4 and then 30ml is added contains the ethanol solutions of the 2ml lauryl amines magnetic agitation 3h at 50 DEG C；
Step 5, products therefrom centrifugation washing are then in 110 DEG C of dry 12h；
Step 6 and then the calcination processing in Muffle furnace：Under the atmosphere of air, 550 DEG C, 4h is calcined under 0.1kpa；
Step 7 and then use infusion process introduce yttrium, and the solid after calcining is all in the yttrium sulfate of 0.1mol/L
8h in solution；
It is then washed with deionized after step 8, dipping, by moisture evaporation under rotary evaporator, finally obtains
The nanoscale Cu-HMS catalyst that yttrium is modified.
Reference examples 9, method for preparing catalyst is different from embodiment 1, other raw material dosages, operating procedure is with embodiment 1
Equally, the method for preparing catalyst of this reference examples is as follows：Step 1, by 5gCu (NO3) 23H2O, will be added to 100ml ethyl alcohol
In solution, then ultrasonication 1h；
Step 2 and then addition 3ml tetraethyl orthosilicates, while opening 80 DEG C of reaction 4h of magnetic agitation water-bath；
Step 3 is then transferred into microwave treatment 2h in microwave reactor；
Step 4 and then 30ml is added contains the ethanol solutions of the 2ml lauryl amines magnetic agitation 3h at 50 DEG C；
Step 5, products therefrom centrifugation washing are then in 110 DEG C of dry 12h；
Step 6 and then the calcination processing in Muffle furnace：In nitrogen and carbon dioxide (1:1) under atmosphere, 550 DEG C,
4h is calcined under 0.1kpa；
Step 7 and then use infusion process introduce yttrium, and the solid after calcining is all in the yttrium sulfate of 0.1mol/L
8h in solution；
It is then washed with deionized after step 8, dipping, by moisture evaporation under rotary evaporator, finally obtains
The nanoscale Cu-HMS catalyst that yttrium is modified.
Reference examples 10, method for preparing catalyst is different from embodiment 1, other raw material dosages, operating procedure is with embodiment 1
Equally, the method for preparing catalyst of this reference examples is as follows：Step 1, by 5gCu (NO3) 23H2O, will be added to 100ml ethyl alcohol
In solution, then ultrasonication 1h；
Step 2 and then addition 3ml tetraethyl orthosilicates, while opening 80 DEG C of reaction 4h of magnetic agitation water-bath；
Step 3 is then transferred into microwave treatment 2h in microwave reactor；
Step 4 and then 30ml is added contains the ethanol solutions of the 2ml lauryl amines magnetic agitation 3h at 50 DEG C；
Step 5, products therefrom centrifugation washing are then in 110 DEG C of dry 12h；
Step 6 and then the calcination processing in Muffle furnace：Under the atmosphere of carbon dioxide, 550 DEG C, 4h is calcined under 0.1kpa；
Step 7 and then use infusion process introduce yttrium, and the solid after calcining is all in the yttrium sulfate of 0.1mol/L
8h in solution；
It is then washed with deionized after step 8, dipping, by moisture evaporation under rotary evaporator, finally obtains
The nanoscale Cu-HMS catalyst that yttrium is modified.
Reference examples 11, method for preparing catalyst is different from embodiment 1, other raw material dosages, operating procedure is with embodiment 1
Equally, the method for preparing catalyst of this reference examples is as follows：Step 1, by 5gCu (NO3) 23H2O, will be added to 100ml ethyl alcohol
In solution, then ultrasonication 1h；
Step 2 and then addition 3ml tetraethyl orthosilicates, while opening 80 DEG C of reaction 4h of magnetic agitation water-bath；
Step 3 is then transferred into microwave treatment 2h in microwave reactor；
Step 4 and then 30ml is added contains the ethanol solutions of the 2ml lauryl amines magnetic agitation 3h at 50 DEG C；
Step 5, products therefrom centrifugation washing are then in 110 DEG C of dry 12h；
Step 6 and then the calcination processing in Muffle furnace：Under the atmosphere of nitrogen, 4h is calcined under 0.1kpa and is obtained by 550 DEG C
Nanoscale Cu-HMS catalyst.
The yield purity of experiment test product：
1100 high performance liquid chromatographs (Agilent companies of the U.S.) are furnished with fluorescence detector, chromatographic column:AgilentSB-
C18 columns (250mm × 4.6mm, 5 μm)；Column flow rate:0.6mL/min；Sample size:50μL；Column temperature:40℃；Excitation wavelength:
450nm；Launch wavelength:495nm；Mobile phase:A is acetonitrile, and B is methanol, the acetic acid solution that C is 2%；Gradient elution program is 0
~15min, 5%A, 10%B；15~30min, 5%A~20%A, 10%B；30~40min, 20%A, 10%B；40~
45min, 20%A~5%A, 10%B；45~55min, 5%A, 10%B.Calculated purity, yield.
The purity of one each product sorbic acid phenylalanine ethyl ester of table, yield result
The experimental results showed that：It can be found that the sorbic acid phenylalanine ethyl ester product purity that 1,2 technique of embodiment obtains, is received
Rate is best, illustrates both techniques in the proportioning of raw material, the production of the operation of technique most beneficial for target product.Under other techniques
Product obtained is not especially desirable in purity, yield.Comparative example 1, comparative example 1,2,3,4,5,6 is not it can be found that
Magnetic agitation is carried out, without ice salt bath, without being heated to reflux, without rotary evaporation, is added without the nanoscale of yttrium modification
Cu-HMS catalyst, is added sorbic acid phenylalanine ethyl ester purity made from metal palladium catalyst, and yield is not high.
Comparative example 7-11 can be seen that the preparation process of catalyst for sorbic acid phenylalanine ethyl ester product purity, receive
Rate has very big influence.
Claims (1)
1. a kind of synthesis technology of preservative intermediate sorbic acid phenylalanine ethyl ester, which is characterized in that include the following steps：
100ml absolute ethyl alcohols, the 33g being added thereto are added into the 250mL three-necked flasks equipped with low-reading thermometer for step 1
Phenylalanine and 60g thionyl chlorides, then magnetic agitation 4h；
Step 2 and then the nanoscale Cu-HMS catalyst that the homemade yttriums of 1.2g are modified is added, reacts, reheat back in ice salt bath
Stream continues magnetic agitation 4h；
Remaining ethyl alcohol and SOCl is removed under reduced pressure using Rotary Evaporators in step 32, while recycling the nanoscale that homemade yttrium is modified
Cu-HMS catalyst obtains intermediate phenylalanine ethyl ester hydrochloride；
11g sorbic acids and 33g thionyl chlorides are added into 250mL round-bottomed flasks for step 4, and magnetic agitation reacts 4h at normal temperatures,
Remaining SOCl is removed under reduced pressure using Rotary Evaporators2, obtain the sorbic acid after chloride；
Step 5, by the sorbic acid molar ratio 1 after synthetic phenylalanine ethyl ester hydrochloride and chloride:1 mixing, ice salt bath
3h is reacted, 4h is reacted at room temperature, low-boiling point material is removed under reduced pressure using Rotary Evaporators, it is thick to obtain sorbic acid phenylalanine ethyl ester
Then product are recrystallized to give the sorbic acid phenylalanine ethyl ester of high-purity with absolute ethyl alcohol；
The nanoscale Cu-HMS catalyst preparation process that the homemade yttrium is modified is as follows：
Step 1, by 5gCu（NO3）2·3H2O will be added in 100ml ethanol solutions, then ultrasonication 1h；
Step 2 and then addition 3ml tetraethyl orthosilicates, while opening 80 DEG C of reaction 4h of magnetic agitation water-bath；
Step 3 is then transferred into microwave treatment 2h in microwave reactor；
Step 4 and then 30ml is added contains the ethanol solutions of the 2ml lauryl amines magnetic agitation 3h at 50 DEG C；
Step 5, products therefrom centrifugation washing are then in 110 DEG C of dry 12h；
Step 6 and then the calcination processing in Muffle furnace：In nitrogen and carbon dioxide, volume ratio 4:Under 1 atmosphere, 550 DEG C,
4h is calcined under 0.1kpa；
Step 7 and then use infusion process introduce yttrium, and the solid after calcining is all in the solution of the yttrium sulfate of 0.1mol/L
In 8h；
It is then washed with deionized after step 8, dipping, by moisture evaporation under rotary evaporator, finally obtains yttrium and change
The nanoscale Cu-HMS catalyst of property.
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