CN102442983A - Preparation method of preservative 6-L-ascorbyl trans-beta- methoxy carbonyl acrylates - Google Patents
Preparation method of preservative 6-L-ascorbyl trans-beta- methoxy carbonyl acrylates Download PDFInfo
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Abstract
The invention discloses a preparation method of preservative 6-L-ascorbyl trans-beta methoxy carbonyl acrylates, belonging to the technical field of food preservatives. The preparation method comprises the following steps: (1) preparing monomethyl maleate; (2) isomerizing the prepared monomethyl maleate; and (3) adding L-ascorbic acid, fumaric monoalkylester, and concentrated sulfuric acid for reacting for a certain time at a certain reaction temperature to obtain a reaction product, and extracting the reaction product with ethyl acetate to obtain the preservative 6-L-ascorbyl trans-beta- methoxy carbonyl acrylates. The 6-L-ascorbyl trans-beta- methoxy carbonyl acrylates is obtained by carrying out molecular modification on L-ascorbic acid for increasing the stability and oil solubility of L-ascorbic acid, and the product can be developed into a food additive having a plurality of functions.
Description
Technical field
The invention belongs to the food preservatives technical field, be specifically related to a kind of anti--β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester synthetic preparation method.
Background technology
Food is the base substance that the mankind depend on for existence, and fresh food then is the pacing items that ensures human health.Contain many richs in protein, glucide and fats nutritive substance in the food, under the effect of physics, biological chemistry and harmful microorganism etc., can lose original color, shape and rot.Wherein the harmful microbe effect is the major cause that causes food decay rotten.Usually can prevent that harmful microbe from destroying with physical method or chemical process, physical method be through deepfreeze, secluding air, drying, height ooze, high acidity, radiation waits sterilization or antibacterial; Chemical process utilizes sanitas to come sterilization or antibacterial exactly.Therefore, food fresh-keeping and anticorrosion be the matter of utmost importance of food processing and production.
α, the beta-unsaturated carbonyl structure is the effective efficiency structure of sanitas show antibacterial activity, the butylene diester is the typical material with this structure.The butylene diester comprises maleic diester-toxilic acid and anti-butylene diester-fumaric acid, and fumaric acid is because have the synthetic parent that stronger stability often is used as sanitas.And the L-xitix is a kind of inhibitor safely and efficiently, and it is of many uses, not only is used for foodstuffs industry as powerful antioxidant, also is the necessary nutrient substance of a kind of human body simultaneously, is used to health care.The L-xitix also is widely used in beauty treatment, fields such as animal husbandry and aquaculture in addition.The L-xitix is destroyed by heat or oxygenant easily, and light, micro heavy and fluorescent substance etc. more can promote its oxidation, and simultaneously, the L-xitix is dissolved in oil phase hardly, and its application receives very big restriction.Therefore, the stability and the oil soluble that how to improve the L-xitix are the problems that domestic and international investigator is concerned about.The present invention introduces L-xitix at esterification process; Make synthetic compound have good fungistatic effect; Has anti-oxidant function simultaneously; The foodstuff additive of exploitation versatility, working out with the fumaric acid is that parent carries out esterification, synthetic to temperature-insensitive, efficient food sanitas that the applicable pH value is wide.
Summary of the invention
The purpose of this invention is to provide the preparation method of anti--beta-methoxy-carbonyl vinylformic acid-6-L-acid ascorbyl ester, mainly is that fumaric acid is that parent carries out esterification, introduces L-xitix at esterification process, makes synthetic compound have good fungistatic effect.
The object of the invention can reach through following measure, anti--beta-methoxy-carbonyl vinylformic acid-6-L-acid ascorbyl ester synthetic technology route is as follows:
Instead-and the preparation method of β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester, carry out according to following step:
(1) preparation of monomethyl maleate: maleic anhydride and the methyl alcohol of mol ratio 1:1 are added in the reactor drum, dissolve 40-60 ℃ of insulation reaction 1-3h, preferred 60 ℃ at 40 ℃ of stirred in water bath to maleic anhydrides fully; Insulation reaction 2.5h;
(2) isomerizing of monomethyl maleate: monomethyl maleate adds isomerization catalyst, 90 ℃ of reaction for some time; Be cooled to the NaHCO that adds 10% (w/w) after the room temperature
3Behind the aqueous solution elimination insolubles, add concentrated hydrochloric acid and regulate pH to 3, get the white crystal fumaric monoalkylester behind the precipitate filtration drying;
(3) use ethyl acetate extraction at the product of certain reaction temperature, adding L-xitix, fumaric monoalkylester, the vitriol oil, reaction certain hour, generation, promptly get instead-β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester.
Wherein the for some time described in the step (2) is 1-4h, preferred 3h.
Wherein the isomerization catalyst described in the step (2) is an aluminum trichloride (anhydrous);
Wherein the L-xitix described in the step (3) and the mol ratio of fumaric monoalkylester are respectively 2.5-1.1:1, preferred 2.5:1.
Wherein the reaction times described in the step (3) is 22-30h, preferred 28h.
Wherein the temperature of reaction described in the step (3) is 25 ℃-35 ℃, preferred 25 ℃.
Wherein the consumption of the vitriol oil described in the step (3) is 0.15:1 with (L-xitix+fumaric monoalkylester)/vitriol oil mol ratio.
Wherein the extraction agent described in the step (3) is ETHYLE ACETATE, benzene or methylene dichloride, ethyl acetate.
The present invention carries out molecular modification through chemical method to the L-xitix; Obtain anti--β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester; In the hope of improving the stability and the oil soluble of L-xitix, with one type of foodstuff additive of this product exploitation becoming with multiple function.
Description of drawings
The relation of Fig. 1 following time of differing temps and esterification yield,
Fig. 2 isomerization reaction time is to the influence of isomerization rate,
Fig. 3 reactant molar ratio is to the influence of productive rate,
Fig. 4 reaction times is to the influence of productive rate,
Fig. 5 temperature of reaction is to the influence of productive rate,
The relation of Fig. 6 extraction agent and productive rate,
The infrared spectrogram of Fig. 7 product,
Fig. 8 intestinal bacteria growth curve,
Fig. 9 milk spoilage organism bacteria growing curve,
The growth curve of Figure 10 black mold,
Figure 11 synthesizes the antioxidant property of Vc ester in lard,
Figure 12 synthesizes the removing ability of Vc ester to HO,
Figure 13 synthesizes the removing ability of Vc ester to O2-,
The synthetic Vc ester of Figure 14 is to the removing ability of DPPH.
Embodiment
The measuring method of monomethyl fumarate esterification yield of the present invention is following: the condition by the monomethyl maleate preparation is carried out insulation reaction; Every at a distance from mensuration half a hour; Adding 20mL water, is indicator with 0.1% phenolphthalein, and the titration of application 1 mol/LNaOH solution is to blush; Record consumes the volume of NaOH solution, calculates esterification yield with this.
The present invention is anti--and the method for calculation of β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester synthetic ratio are following:
In the formula: m0---product AW (g);
M---theoretical weight (g).
Different time, temperature are seen Figure of description 1 to the influence of monomethyl maleate esterification yield, because the steric hindrance of methyl alcohol is little, the alcoholysis reaction of maleic anhydride and methyl alcohol is as easy as rolling off a log carries out.But reaction temperature is spent low, sluggish, and improving temperature of reaction can accelerated reaction, and temperature of reaction is too high, forms diester easily, and productive rate is reduced greatly.As can beappreciated from fig. 1, along with the rising of temperature and the prolongation of time, esterification yield improves constantly.Under the differing temps, when reaction reached 2.5h, esterification yield did not all have obvious raising.Therefore select 60 ℃ of reaction 2.5h for use, esterification yield can reach 91.86%
The isomerization reaction time, isomerisation temperature was 90 ℃, only changes the isomerized reaction times to the influence of isomerization rate, and the productive rate change curve that obtains is as shown in Figure 2.Can find out that by figure along with the prolongation in reaction times, productive rate obviously raises, this mainly is under identical isomerisation temperature, and the prolongation of isomerizing time helps carrying out fully of isomerization reaction.When isomerizing time during at 3h, productive rate is maximum.When the isomerization reaction time lengthening, productive rate has reduction trend, mainly is to prolong in the reaction times isomerizing is carried out thoroughly; Productive rate is improved, when the reaction times is long, some side reactions can takes place; Cause product yield to reduce, so the reaction times is that 3h is best.
Embodiment 3
L-xitix/fumaric monoalkylester mol ratio is to the influence of product synthetic ratio; In temperature is under 25 ℃, (L-xitix+fumaric monoalkylester)/vitriol oil mol ratio 0.15:1, reaction 28h, the condition of product with ethyl acetate extraction; The L-xitix/when toxilic acid monoesters mol ratio was respectively 2.5:1,2:1,1.5:1,1.25:1,1.1:1, its result was as shown in Figure 3: as can beappreciated from fig. 3, and in the L-xitix/process of fumaric monoalkylester mol ratio from 1.1:1 to 2:1; Productive rate significantly rises; Productive rate when mol ratio is 2:1 is 53.14%, and increasing the mol ratio productive rate does not afterwards have obvious increase trend, is 54.07% during 2.5:1.
Reaction times is to the influence of product synthetic ratio; In L-xitix/toxilic acid monoesters mol ratio is that 2:1, (L-xitix+fumaric monoalkylester)/vitriol oil mol ratio are that 0.15:1, temperature are under 25-26 ℃, the condition of product with ethyl acetate extraction, reacts 22,24,26,28 respectively, 30h.Its result is as shown in Figure 4.Can find out that by Fig. 4 the reaction times is mentioned 26h from 22h, productive rate has increase by a small margin; Mention 28h from 26h, productive rate then increases considerably; When the reaction times is 28h, and productive rate reaches peak, 55%.Continue to increase the reaction times, because the aggravation of L-Ascorbic Acid Oxidation, product reason such as be decomposed, productive rate descends on the contrary.
Temperature of reaction is to the influence of product synthetic ratio; In L-xitix/fumaric monoalkylester mol ratio is that 2:1, (L-xitix+fumaric monoalkylester)/vitriol oil mol ratio are under 0.15:1, reaction 24h, the condition of product with ethyl acetate extraction; Choose temperature of reaction and be respectively 25 ℃, 30 ℃, 35 ℃, as shown in Figure 5, the thermotolerance of L-xitix is relatively poor; Easy oxidation under the high temperature, so temperature of reaction can not be too high.But temperature is too low, and reaction is difficult to carry out.The esterification of L-xitix is generally all selected for use under 25 ℃ of conditions of room temperature and is carried out, and proves also that through experiment reaction can be carried out smoothly under this temperature condition, and the oxidation rate of L-xitix is also slower.When temperature was raised to 30 ℃, the L-Ascorbic Acid Oxidation was quickened, the reaction system color burn, and reaction yield reduces.
Different extraction agents are to methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester extraction yield, pour the 50g trash ice dissolving of quick stirring into a collection of product after, draw three parts respectively; Every part of 20mL; Come extraction product with ETHYLE ACETATE, benzene, three kinds of extraction agents of methylene dichloride respectively, its result is as shown in Figure 6: can find out, ETHYLE ACETATE to the percentage extraction of product up to more than 78.1%; Ether is 21.7% to the percentage extraction of product, and methylene dichloride is 15.1%.Therefore, in this experiment, ETHYLE ACETATE is the suitable extraction agent of product.
The infared spectrum of experiment one anti--beta-methoxy-carbonyl vinylformic acid-6-L-acid ascorbyl ester
Adopting German burker company model is the Fourier transformation infrared spectrometer of Tensor27, and it is as shown in Figure 7 that the KBr pressed disc method records the infrared spectrum of product.From spectrogram, can know: 3084 cm
-1It is the absorption peak of O-H; 1250cm
-1It is the absorption peak of C-O-C; 1715cm
-1Be the C=O charateristic avsorption band; 1687cm
-1Charateristic avsorption band for C=C.In conjunction with the solvability of product, confirm that the gained material is a product.
Testing the bacteriostatic activity of two synthetic compounds measures
Select for use food service industry potassium sorbate preservative commonly used to carry out the experiment of anti-microbial activity as contrast.The addition of POTASSIUM SORBATE GRANULAR WHITE and product is 0.05%, and as blank, wherein the thermal stability determination measured with bacteriostasis property of the research method of bacteriostatic activity, minimum inhibitory concentration (MIC) all adopts ordinary method mensuration with the sample that do not add POTASSIUM SORBATE GRANULAR WHITE and product
(1) synthetic product is to colibacillary restraining effect
Can find out after having added POTASSIUM SORBATE GRANULAR WHITE, toxilic acid Vc methyl esters, fumaric acid Vc methyl esters, fumaric acid list benzyl methyl esters by Fig. 8; Colibacillary growth adaptation phase is 4h, 4h, 5h, 6h respectively, explains that three kinds of compounds of synthetic are the same with POTASSIUM SORBATE GRANULAR WHITE can obviously reduce its increment.In the sample of affixture, toxilic acid Vc methyl esters is inferior to POTASSIUM SORBATE GRANULAR WHITE to the carryover effects of intestinal bacteria growth adaptation phase, and other two kinds of compounds then are better than POTASSIUM SORBATE GRANULAR WHITE.But the inhibition effect to its growth is superior to POTASSIUM SORBATE GRANULAR WHITE.The bacteriostasis rate that has added POTASSIUM SORBATE GRANULAR WHITE after cultivating through 48h is 11.73%, and synthetic product toxilic acid Vc methyl esters, fumaric acid Vc methyl esters, fumaric acid list benzyl methyl esters bacteriostasis rate are respectively 36.16%, 39.24%, 48.47%.It is thus clear that three kinds of synthetic compounds are superior to POTASSIUM SORBATE GRANULAR WHITE to the inhibition effect that intestinal bacteria grow.Reason possibly be that when nutritive substance lacked in the substratum, POTASSIUM SORBATE GRANULAR WHITE can be used as carbon source and is utilized, and has reduced restraining effect because cultivate through long-time, and three kinds of synthetic compounds then are difficult for by microbiological degradation.
(2) synthetic product is to the restraining effect of milk spoilage organism growth
The usage quantity of Sodium Benzoate is 0.3g/kg in this experiment, and the synthetic compound addition is 0.5g/kg.Experimental result is as shown in Figure 9, and the antibacterial curve and the Sodium Benzoate of toxilic acid Vc methyl esters remain basically stable, and the fungistatic effect of fumaric acid Vc methyl esters, fumaric acid list benzyl methyl esters is better than Sodium Benzoate.Through 48 hours cultivation, Sodium Benzoate, toxilic acid Vc methyl esters, fumaric acid Vc methyl esters, fumaric acid list benzyl methyl esters were respectively 36.90%, 46.23%, 55.55%, 56.23% to the inhibiting rate of milk spoilage organism,
(3) synthetic product is to the restraining effect of black mold growth
Can find out by Figure 10, Sodium Benzoate and three kinds of synthetic compounds to black mold growth-inhibiting t
0.5All surpass 10h.Through Sodium Benzoate, toxilic acid Vc methyl esters, fumaric acid Vc methyl esters, fumaric acid list benzyl methyl esters after the cultivation of 80h the inhibiting rate of black mold is respectively 35.24%, 42.28%, 52.91%, 61.40%.
(4) the MIC value of synthetic product
Measured the minimum inhibitory concentration of three kinds of synthetic compounds to intestinal bacteria, cereuisiae fermentum, black mold.Can find out that from table 1 three kinds of compounds can suppress microbial growth under low concentration.
The MIC value of three kinds of synthetic compounds of table 1
Testing the anti-oxidant activity of three synthetic compounds measures
(1) antioxidant property in lard of synthetic Vc ester
Foodstuff additive use in the grease of hygienic standard regulation between the inhibitor optimum addition 0.01%～1.0%, and are the most frequently used 0.02%, and the addition of each sample is 0.02% in this experiment.
As can beappreciated from fig. 11; The peroxide value that under 0.02% interpolation concentration, contains toxilic acid Vc methyl esters, fumaric acid Vc methyl esters oil sample is lower than adds the L-xitix; And the increase of the peroxide value that grows with time is also slower, but peroxide value is higher than the oil sample that has added TBHQ all the time.Possible cause is: the L-xitix has been introduced the toxilic acid monoesters, fumaric monoalkylester has strengthened its oil soluble, make it better be dissolved in oil phase, so its antioxidant effect is better than the L-xitix behind over-churning.
Present synthetic L-ascorbyl esters; Great majority have been introduced the lipid acid of straight chain; Its antioxidation mechanism mainly is the oil soluble that has improved the L-xitix; Two kinds of acid ascorbyl esters of this paper synthetic not only have good oil soluble, and the introducing of toxilic acid monoesters, fumaric monoalkylester has strengthened stability of structure.Toxilic acid Vc methyl esters, fumaric acid Vc methyl esters add under the concentration 0.02%, and the POV value of lard has significant antioxidant effect than more than the blank low 50meq/kg behind 100 ℃ of insulation 12h.
(2) synthetic Vc ester is removed ability to hydroxy radical qiao
Visible by Figure 12, L-xitix and toxilic acid Vc methyl esters, fumaric acid Vc methyl esters all have scavenging(action) to hydroxy radical qiao, and toxilic acid Vc methyl esters, fumaric acid Vc methyl esters removing ability are better than the L-xitix.L-xitix, toxilic acid Vc methyl esters, fumaric acid Vc methyl esters are removed the EC of hydroxy radical qiao
50Value is respectively 0.31mg/mL, 0.18mg/mL, 0.12 mg/mL.
(3) synthetic Vc ester is removed ability to ultra-oxygen anion free radical
O
2 -Play the part of important role at spoiled by rancid oil or fat, Food Oxidation in going bad, it can cause other oxidizing reaction, shortens the shelf-lives of food, is the extremely strong radical of a kind of destructiveness.Under alkaline condition autoxidation can take place according to pyrogallol, produce O
2 -And the principle of coloured intermediate material, this paper adopts pyrogallol autoxidation method, and toxilic acid Vc methyl esters, fumaric acid Vc methyl esters are removed the ultra-oxygen anion free radical ability and measured.Visible by Figure 13, toxilic acid Vc methyl esters when concentration is low, fumaric acid Vc methyl esters are close with the L-xitix to the clearance rate of ultra-oxygen anion free radical, along with its clearance rate of increase of concentration greater than the L-xitix.L-xitix, toxilic acid Vc methyl esters, fumaric acid Vc methyl esters are removed the EC of ultra-oxygen anion free radical
50Value is respectively 0.1 mmol/mL, 0.09mmol/mL, 0.51 mmol/mL.
(4) synthetic Vc ester is to the DPPH radical scavenging activity
Visible by Figure 14, scavenging(action) is lower than contrast TBHQ to DPPH for toxilic acid Vc methyl esters, fumaric acid Vc methyl esters.Toxilic acid Vc methyl esters, fumaric acid Vc methyl esters are removed the EC of hydroxy radical qiao
50Value is respectively 0.09mmol/mL, 0.08mg/mL, and TBHQ is 0.06 mmol/mL.
The synthetic α that contains of the present invention; The verivate of beta-unsaturated carbonyl structure is anti--and β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester kept its functional groups separately; Make the compound that obtains have good antibacterial, anti-oxidant function simultaneously, for the polyfunctional food additive of development of new provides a new thinking.
Claims (3)
- Sanitas anti--preparation method of β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester, it is characterized in that carrying out according to following step:(1) preparation of monomethyl maleate: maleic anhydride and the methyl alcohol of mol ratio 1:1 are added in the reactor drum, dissolve 40-60 ℃ of insulation reaction 1-3h, insulation reaction 2.5h at 40 ℃ of stirred in water bath to maleic anhydrides fully;(2) isomerizing of monomethyl maleate: monomethyl maleate adds isomerization catalyst, 90 ℃ of reaction for some time; Be cooled to the NaHCO that adds mass concentration 10% after the room temperature 3Behind the aqueous solution elimination insolubles, add concentrated hydrochloric acid and regulate pH to 3, get white crystal behind the precipitate filtration drying and be fumaric monoalkylester;(3) use ethyl acetate extraction at the product of certain reaction temperature, adding L-xitix, fumaric monoalkylester, the vitriol oil, reaction certain hour, generation, promptly get instead-β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester.
- 2. sanitas according to claim 1 is anti--preparation method of β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester, it is characterized in that wherein the for some time described in the step (2) is 1-4h,Wherein the isomerization catalyst described in the step (2) is an aluminum trichloride (anhydrous);Wherein the L-xitix described in the step (3) and the mol ratio of fumaric monoalkylester are respectively 2.5-1.1:1,Wherein the reaction times described in the step (3) is 22-30h,Wherein the temperature of reaction described in the step (3) is 25 ℃-35 ℃,Wherein the consumption of the vitriol oil described in the step (3) is 0.15:1 with (L-xitix+fumaric monoalkylester)/vitriol oil mol ratio;Wherein the extraction agent described in the step (3) is ETHYLE ACETATE, benzene or methylene dichloride.
- 3. sanitas according to claim 2 is anti--preparation method of β methoxycarbonyl vinylformic acid-6-L-acid ascorbyl ester, it is characterized in that wherein the for some time described in the step (2) is 3h;Wherein the L-xitix described in the step (3) and the mol ratio of fumaric monoalkylester are respectively 2.5:1;Wherein the reaction times described in the step (3) is 28h;Wherein the temperature of reaction described in the step (3) is 25 ℃;Wherein the extraction agent described in the step (3) is an ETHYLE ACETATE.
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Application publication date: 20120509 |