CN101390641A - Preparation method of phytic acid amino-acid ester salt and use thereof as edible oil antioxidant - Google Patents
Preparation method of phytic acid amino-acid ester salt and use thereof as edible oil antioxidant Download PDFInfo
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- CN101390641A CN101390641A CNA2008101971695A CN200810197169A CN101390641A CN 101390641 A CN101390641 A CN 101390641A CN A2008101971695 A CNA2008101971695 A CN A2008101971695A CN 200810197169 A CN200810197169 A CN 200810197169A CN 101390641 A CN101390641 A CN 101390641A
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Abstract
The invention belongs to food additive preparation technical field and in particular relates to the preparation and application of edible oil antioxidants. The antioxidant is phytic acid amino-acid ester salt. The invention is characterized in that:1), mixing alcohol and amino acid, then adding thionyl chloride drop by drop, heating to react to obtain above amino acid ester; 2) dissolving water in phytic acid, adjusting the phytic acid solution to be neutral through amino acid ester, dehydrating under decompressed condition. In this way, the phytic acid amino-acid ester salt can be obtained. The phytic acid amino-acid ester salt prepared through the method is directly added into edible oil or that the phytic acid amino-acid ester salt is firstly dissolved in a small amount of ethanol and then is added to edible oil. The phytic acid amino-acid ester salt has good oil solubility, excellent antioxidant activity and stability in edible oil. The edible oil antioxidant is a new green antioxidant.
Description
Technical field
The invention belongs to the food additives preparing technical field.Be specifically related to the preparation of a class phytic acid amino-acid ester salt and as the application of edible grease antioxidant.
Background technology
Phytic acid extensively is present in the various plant species skins, edible beans, cereal, oilseed, its content reaches 1%-5% in pollen and the nut, because of containing six phosphoric acid structures, bivalent metal ion is had extremely strong coordination ability in the phytic acid, thereby can suppress radical reaction, play antioxidation by metal ion catalysis.As a kind of natural antioxidant, that phytic acid also has is antibacterial, anticancer, reducing blood lipid, physiological function such as hypoglycemic.At present, people are more and more higher to the requirement of food additives, require natural, nutrition, health care.And edible grease antioxidant commonly used is as 2,6-toluene di-tert-butyl phenol (BHT), tertiary butyl-4-hydroxy anisole chemical synthesis antioxidants such as (BHA) is because of may having carcinogenicity, and it is used and has been subjected to bigger restriction, in the use that has been under an embargo of some developed countries.And phytic acid and phytate have very strong antioxidation activity, and safety non-toxic has been food additives by state approval.Although phytic acid has good anti-Oxidation of Fat and Oils activity, it uses not industrialization as antioxidant in grease, and its key reason is that phytic acid is insoluble to grease.In order to address this problem, people have done a lot of effort, as by add some surfactants (Omichi, Teranobu.Antioxidants for fats and oils. (1984), JP59204696); Or react with tetraethyl ammonium hydroxide and to strengthen solubility (Noda, the Eiichi of phytic acid in grease; Ohshita, Kaneo.Preventing oxidation of fats andoils using a quaternary ammonium salt of phytic acid. (1972), JP47045402), above method can not tackle the problem at its root, for example use the formed system instability of method of adding surfactant, and there is safety issue in tetraethyl ammonium hydroxide itself.Also have with the phytic acid partial hydrolysis and then and fatty acid response, form phytic acid fatty acid ester derivative to strengthen its fat-soluble (Jiang Hong, Ma Xuhong .1,2,6-triphosphoric acid-3,4, the preparation of 5-triacetic acid mesoinositol and anti-Oxidation of Fat and Oils activity research thereof, food science and technology, 2008,1:120-121), but this method is also cumbersome, and industrial applications is had any problem.Consider phytic acid phosphoric acid structure, therefore can solve its fat-soluble problem as long as introduce the organic amine structure, and amino-acid ester just has amino freely, amino-acid ester also is a natural products simultaneously, for example just contains various amino-acid esters in beer, is safety non-toxic therefore, from this thinking, we have successfully solved the fat-soluble problem of phytic acid, have accomplished safety non-toxic again, and this series products has a extensive future.
Summary of the invention
The invention belongs to the preparation field of edible oil antioxidant, be specifically related to class phytic acid amino-acid ester salt and preparation method thereof, the present invention also comprises the application of this phytic acid amino-acid ester salt as edible grease antioxidant.
Solving technical scheme of the present invention is:
The applicant makes the class of amino acid ester type compound by artificial synthetic synthesizing with the preparation method, and its structural formula is as follows:
In the formula: R represents various amino acid residues, and R can be H, CH
3, CH
2OH, CH
2SH, CH (OH) CH
3, CH
3SCH
2CH
2CH, CHCH (CH
3)
2, CH
3CH
2CH (CH
3), PhCH
2, p-OHPhCH
2, HOOCCH
2, HOOCCH
2CH
2, NH
2CH
2CH
2CH
2CH
2, 3-guanidine radicals propyl group, 2-imidazoles methylene, 3-indoles methylene, Pyrrolizidine base, 4-hydroxyl Pyrrolizidine base; R ' representative contains the alkyl of the direct-connected or side chain of 1-18 carbon.
Wherein: the preparation feedback of amino-acid ester is shown below:
Concrete preparation process is: (described alcohol is the alcohol that contains the direct-connected or side chain of 1-18 carbon with amino acid and alcohol earlier, its mol ratio is 1: 1～1: 20) mix, drip and the equimolar thionyl chloride of amino acid then, heating was reacted 2-20 hour between 50-100 ℃, after reaction finishes, filter, get the amino-acid ester hydrochloride, filter, the gained solid is dissolved in the water of 2-10 times of volume, adds sodium carbonate and transfers alkalescence to cause pH to be 8-10, to make to be alkalescence, solution equal-volume extracted with diethyl ether 2-3 time also can use carrene, chloroform to replace ether.Extraction back gained organic facies dried over mgso is crossed and is filtered out magnesium sulfate, and desolventizing obtains amino-acid ester.
The preparation of phytic acid amino-acid ester salt: just phytic acid is dissolved in isopyknic water earlier, equals 7 with amino-acid ester titration plant acid solution to pH, and decompression dehydration obtains phytic acid amino-acid ester salt.
When using in edible oil and fat, the phytic acid amino-acid ester salt that can earlier the present invention be prepared is dissolved in the absolute ethyl alcohol, makes an addition to then in the edible oil, also can directly phytic acid amino-acid ester salt be made an addition in the edible oil, shakes up in shaking table then.The oxidation of product energy good restraining edible oil of the present invention, by to the phytic acid amino-acid ester salt of the present invention that adds 200mg/kg in the rape salad oil respectively and BHT antioxidant (available from Sigma-Aldrich company product, a kind of general antioxidant, down together), 60 ℃ of constant temperature strengthen store 12 days after, studies show that peroxide number (POV) value and anisidine value (AV) greatly reduce in the edible oil sample.
Compound of the present invention can be independent, the combination or with the composite use of other edible oil antioxidants.
Description of drawings
Fig. 1: the IR figure that is the glycine methyl ester that synthesizes of the present invention.
Fig. 2: the MS figure that is the glycine methyl ester that synthesizes of the present invention.
Fig. 3: the IR figure that is the glycine ethyl ester that synthesizes of the present invention.
Fig. 4: the MS figure that is the glycine ethyl ester that synthesizes of the present invention.
Fig. 5: the IR figure that is the glycine propyl ester that synthesizes of the present invention.
Fig. 6: the MS figure that is the glycine propyl ester that synthesizes of the present invention.
Fig. 7: the IR figure that is the glycine isopropyl ester that synthesizes of the present invention.
Fig. 8: the MS figure that is the glycine isopropyl ester that synthesizes of the present invention.
Fig. 9: the IR figure that is the glycine butyl ester that synthesizes of the present invention.
Figure 10: the MS figure that is the glycine butyl ester that synthesizes of the present invention.
Figure 11: the IR figure that is glycine 18 alcohol esters that synthesize of the present invention.
Figure 12: the MS figure that is glycine 18 alcohol esters that synthesize of the present invention.
Figure 13: the IR figure that is the methyl lactamine that synthesizes of the present invention.
Figure 14: the MS figure that is the methyl lactamine that synthesizes of the present invention.
Figure 15: the IR figure that is the alanine ethyl ester that synthesizes of the present invention.
Figure 16: the MS figure that is the alanine ethyl ester that synthesizes of the present invention.
Figure 17: the IR figure that is the alanine propyl ester that synthesizes of the present invention.
Figure 18: the MS figure that is the alanine propyl ester that synthesizes of the present invention.
Figure 19: the IR figure that is the alanine isopropyl ester that synthesizes of the present invention.
Figure 20: the MS figure that is the alanine isopropyl ester that synthesizes of the present invention.
Figure 21: the IR figure that is the alanine butyl ester that synthesizes of the present invention.
Figure 22: the MS figure that is the alanine butyl ester that synthesizes of the present invention.
Figure 23: the IR figure that is the alanine hexadecanol ester that synthesizes of the present invention.
Figure 24: the MS figure that is the alanine hexadecanol ester that synthesizes of the present invention.
Figure 25: the IR figure that is the TEE that synthesizes of the present invention.
Figure 26: the IR figure that is the aspartic acid ethyl ester that synthesizes of the present invention.
Figure 27: the MS figure that is the aspartic acid ethyl ester that synthesizes of the present invention.
Figure 28: the IR figure that is the leucinethylester that synthesizes of the present invention.
Figure 29: the MS figure that is the leucinethylester that synthesizes of the present invention.
Figure 30: the IR figure that is the isoleucine ethyl ester that synthesizes of the present invention.
Figure 31: the MS figure that is the isoleucine ethyl ester that synthesizes of the present invention.
Figure 32: the IR figure that is the phenylalanine ethyl ester that synthesizes of the present invention.
Figure 33: the MS figure that is the phenylalanine ethyl ester that synthesizes of the present invention
Figure 34: the IR figure that is the present invention's ethyl ester of lysine of synthesizing.
Figure 35: the MS figure that is the present invention's ethyl ester of lysine of synthesizing
Figure 36: be the glycine ethyl ester that the present invention synthesizes
1HNMR figure.
The specific embodiment
How specify the present invention below by example realizes.Only the present invention will be described for these embodiment, rather than limit the invention.
The preparation of embodiment 1 phytic acid glycine ethyl ester salt (compound 1)
Add 5.00 gram (0.067mol) glycine in the 150mL of drying there-necked flask, the 40mL absolute ethyl alcohol mixes and stirs.Cryosel is bathed and is cooled to-5 ℃, and slowly Dropwise 5 mL (0.07mol) thionyl chloride dripped off in one hour, and thermal reacting for two hours is warming up to 70 ℃, continues reaction, and solid all dissolves in flask.Cool off, have this moment a large amount of white solids to generate, decompress filter with 10mL absolute ethyl alcohol recrystallization, drying, gets product glycine ethyl ester hydrochloride 9 grams, productive rate 96.8%.Fusing point: 145 ℃-146 ℃.Use AVATAR 330 type infrared spectrometers then, IR (KBr) v, cm
-1: 3426.56 (NH
2), 1748.81 (C=O).With product glycine ethyl ester hydrochloride 5 grams, be dissolved in the 10mL distilled water, regulate PH to 9 with sodium carbonate, the 20mL ether divides extraction solution three times, and the dried over mgso organic facies removes by filter magnesium sulfate, and ether is removed in distillation, gets product glycine ethyl ester 2.86 grams.Productive rate: 77.5%.Saturn 2200 mass spectrographs and Bruker AV 400-MHz hydrogen nuclear magnetic resonance spectrometer (solvent: CDCl
3) product is carried out structural characterization.MS：m/z(％)：104((M+1)
+31)，91(44)，43(100)。
1HNMR(δ，CDCl
3)：1.26～1.30(t，3H)，1.76～1.80(s，2H)，3.41～3.43(s，2H)，4.16～4.24(q，2H)。50% plant acid solution 2mL is got in the preparation of phytic acid glycine ethyl ester salt, adds water 2mL and mixes, and is neutralized to pH with glycine ethyl ester and equals 7, and moisture is removed in decompression distillation, and vacuum drying (temperature 40-50 ℃) gets phytic acid glycine ethyl ester salt.
The preparation of embodiment 2 phytic acid glycine methyl ester salt (compound 2)
The preparation method is with embodiment 1.175 ℃-176 ℃ of glycine methyl ester hydrochloride fusing points, IR Characterization, IR (KBr) v, cm
-1: 3414.71 (NH
2), 1748.81 (C=O).The glycine methyl ester mass spectral characteristi, MS:m/z (%): 91 ((M)
+96), 40 (100).50% plant acid solution 2mL is got in the preparation of phytic acid glycine methyl ester salt, adds water 2mL and mixes, and is neutralized to pH with glycine methyl ester and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid glycine methyl ester salt.
The preparation of embodiment 3 phytic acid glycine n-propyl salt (compound 3)
The preparation method is with embodiment 1.175 ℃-176 ℃ of glycine propyl ester hydrochloride fusing points, IR Characterization, IR (KBr) v, cm
-1: 3430.08 (NH
2), 1745.65 (C=O).Glycine n-propyl mass spectral characteristi, MS:m/z (%): 102 (36), 89 (100), 50% plant acid solution 2mL is got in the preparation of phytic acid glycine propyl ester salt, adds water 2mL and mixes, be neutralized to pH with the glycine propyl ester and equal 7, moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid glycine propyl ester salt.
The preparation of embodiment 4 phytic acid glycine isopropyl ester salt (compound 4)
The preparation method is with embodiment 1.158 ℃-159 ℃ of glycine isopropyl ester hydrochloride fusing points, IR Characterization, IR (KBr) v, cm
-1: 3414.25 (NH
2), 1739.31 (C=O).Glycine isopropyl ester mass spectral characteristi, MS:m/z (%): 120 ((M)
+32), 105 (100), 43 (66).50% plant acid solution 2mL is got in the preparation of phytic acid glycine isopropyl ester salt, adds water 2mL and mixes, and is neutralized to pH with the glycine isopropyl ester and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid glycine isopropyl ester salt.
The preparation of the positive butyl ester salt of embodiment 5 phytic acid glycine (compound 5)
The preparation method is with embodiment 1.177 ℃-178 ℃ of the positive butyl ester hydrochloride of glycine fusing points, the positive butyl ester hydrochloride of glycine IR Characterization, IR (KBr) v, cm
-1: 3423.75 (NH
2), 1748.81 (C=O).The positive butyl ester mass spectral characteristi of glycine, MS:m/z (%): 132 ((M)
+99), 101 (26), 39 (100).50% plant acid solution 2mL is got in the preparation of phytic acid glycine butyl ester salt, adds water 2mL and mixes, and is neutralized to pH with the positive butyl ester of glycine and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid glycine butyl ester salt.
The preparation of embodiment 6 phytic acid glycine, 18 alcohol ester salt (compound 6)
The preparation method is with embodiment 1.70 ℃-71 ℃ of glycine 18 pure ester hydrochloride fusing points.Glycine 18 pure ester hydrochloride IR Characterization, IR (KBr) v, cm
-1: 3121.45 (NH
2), 1715.78 (C=O).Glycine 18 alcohol ester mass spectral characteristis, MS:m/z (%): 327 ((M)
+9), 281 (50), 40 (100).50% plant acid solution 2mL is got in the preparation of phytic acid glycine 18 alcohol ester salt, adds water 2mL and mixes, and causes pH with the neutralization of glycine 18 alcohol esters and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid glycine 18 alcohol ester salt.
The preparation of embodiment 7 phytic acid methyl lactamine salt (compound 7)
The preparation method is with embodiment 1.109 ℃-110 ℃ of methyl lactamine hydrochloride fusing points, IR Characterization, IR (KBr) v, cm
-1: 3420.58 (NH
2), 1742.48 (C=O).The methyl lactamine mass spectral characteristi, MS:m/z (%): 105 ((M)
+69), 43 (100).50% plant acid solution 2mL is got in the preparation of phytic acid methyl lactamine salt, adds water 2mL and mixes, and is neutralized to pH with methyl lactamine and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid methyl lactamine salt.
The preparation of embodiment 8 phytic acid alanine ethyl ester salt (compound 8)
The preparation method is with embodiment 1.76 ℃-77 ℃ of alanine ethyl ester hydrochloride fusing points, IR Characterization, IR (KBr) v, cm
-1: 3414.25 (NH
2), 1742.48 (C=O).The alanine ethyl ester mass spectral characteristi, MS:m/z (%): 118 ((M)
+100).50% plant acid solution 2mL is got in the preparation of phytic acid alanine ethyl ester salt, adds water 2mL and mixes, and causes pH with the alanine ethyl ester neutralization and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid alanine ethyl ester salt.
The preparation of embodiment 9 phytic acid alanine n-propyl salt (compound 9)
The preparation method is with embodiment 1.40 ℃-41 ℃ of alanine n-propyl hydrochloride fusing points, alanine n-propyl hydrochloride IR Characterization, IR (KBr) v, cm
-1: 3426.91 (NH
2), 1742.48 (C=O).Alanine n-propyl mass spectral characteristi, MS:m/z (%): 132 ((M)
+100).50% plant acid solution 2mL is got in the preparation of phytic acid alanine n-propyl salt, adds water 2mL and mixes, and is neutralized to pH with the alanine n-propyl and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid alanine propyl ester salt.
The preparation of embodiment 10 phytic acid alanine isopropyl ester salt (compound 10)
The preparation method is with embodiment 1.204 ℃-205 ℃ of alanine isopropyl ester hydrochloride fusing points, IR Characterization, IR (KBr) v, cm
-1: 3414.25 (NH
2), 1723.48 (C=O).Alanine isopropyl ester mass spectral characteristi, MS:m/z (%): 132 ((M)
+100), 44 (87).50% plant acid solution 2mL is got in the preparation of phytic acid alanine isopropyl ester salt, adds water 2mL and mixes, and is neutralized to pH with the alanine isopropyl ester and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid alanine isopropyl ester salt.
The preparation of embodiment 11 phytic acid alanine butyl esters (compound 11)
The preparation method is with embodiment 1.189 ℃-190 ℃ of the positive butyl ester hydrochloride of alanine fusing points, the positive butyl ester hydrochloride of alanine IR Characterization, IR (KBr) v, cm
-1: 3420.58 (NH
2), 1742.48 (C=O).The positive butyl ester mass spectral characteristi of alanine, MS:m/z (%): 147 ((M)
+34), 43 (100).50% plant acid solution 2mL is got in the preparation of phytic acid alanine butyl ester salt, adds water 2mL and mixes, and is neutralized to pH with the alanine butyl ester and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid alanine butyl ester salt.
The preparation of embodiment 12 phytic acid alanine hexadecanol ester salt (compound 12)
The preparation method is with embodiment 6.79 ℃-80 ℃ of alanine hexadecanol ester hydrochloride fusing points, IR Characterization, IR (KBr) v, cm
-1: 3352.21 (NH
2), 1736.21 (C=O).Alanine hexadecanol ester mass spectral characteristi, MS:m/z (%): 341 ((M)
+15), 281 (21), 91 (100).50% plant acid solution 2mL is got in the preparation of phytic acid alanine 18 alcohol ester salt, adds water 2mL and mixes, and is neutralized to pH with alanine 18 alcohol esters and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid alanine 18 alcohol ester salt.
The preparation of embodiment 13 phytic acid TEEs (compound 13)
The preparation method is with embodiment 1.TEE hydrochloride fusing point: 163 ℃-164 ℃, IR Characterization, IR (KBr) v, cm
-1: 3374.80 (NH
2), 1735.21 (C=O).50% plant acid solution 2mL is got in the preparation of phytic acid TEE salt, adds water 2mL and mixes, and is neutralized to pH with TEE and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid TEE salt.
The preparation of embodiment 14 phytic acid aspartic acid ethyl ester salt (compound 14)
The preparation method is with embodiment 1.Aspartic acid carbethoxy hydrochloride fusing point: 82 ℃-83 ℃, IR Characterization, IR (KBr) v, cm
-1: 3435.1 (NH
2), 1740.3 (C=O).Aspartic acid ethyl ester mass spectral characteristi, MS:m/z (%): 190 ((M+1)
+97), 116 (100).50% plant acid solution 2mL is got in the preparation of phytic acid aspartic acid ethyl ester salt, adds water 2mL and mixes, and is neutralized to pH with the aspartic acid ethyl ester and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid aspartic acid ethyl ester salt.
The preparation of embodiment 15 phytic acid leucinethylesters (compound 15)
The preparation method is with embodiment 1.The leucine ethyl ester hydrochloride salt fusing point: 122 ℃-123 ℃, IR Characterization, IR (KBr) v, cm
-1: 3436.1 (NH
2), 1740.30 (C=O).The different ethyl ester mass spectral characteristi of leucine, MS:m/z (%): 160 ((M+1)
+100).50% plant acid solution 2mL is got in the preparation of phytic acid leucinethylester salt, adds water 2mL and mixes, and is neutralized to pH with leucinethylester and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid leucinethylester salt.
The preparation of embodiment 16 phytic acid isoleucine ethyl ester salt (compound 16)
The preparation method is with embodiment 1.Isoleucine carbethoxy hydrochloride fusing point: 134 ℃-135 ℃, IR Characterization, IR (KBr) v, cm
-1: 3415.6
6(NH
2), 1740.3 (C=O).Isoleucine ethyl ester mass spectral characteristi, MS:m/z (%): 160 ((M+1)
+100).50% plant acid solution 2mL is got in the preparation of phytic acid isoleucine ethyl ester salt, adds water 2mL and mixes, and is neutralized to pH with the isoleucine ethyl ester and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid isoleucine ethyl ester salt.
The preparation of embodiment 17 phytic acid phenylalanine ethyl esters (compound 17)
The preparation method is with embodiment 1.Phenylalanine ethyl ester hydrochloride fusing point: 155 ℃-156 ℃, IR Characterization, IR (KBr) v, cm
-1: 3460.61 (NH
2), 1736.21 (C=O).The phenylalanine ethyl ester mass spectral characteristi, MS:m/z (%): 194 ((M+1)
+100), 120 (18).50% plant acid solution 2mL is got in the preparation of phytic acid phenylalanine ethyl ester salt, adds water 2mL and mixes, and is neutralized to pH with phenylalanine ethyl ester and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid phenylalanine ethyl ester salt.
The preparation of embodiment 18 phytic acid ethyl ester of lysine salt (compound 18)
The preparation method is with embodiment 1.Ethyl ester of lysine hydrochloride IR Characterization, IR (KBr) v, cm
-1: 3419.75 (NH
2), 1740.3 (C=O).The ethyl ester of lysine mass spectral characteristi, MS:m/z (%): 174 ((M)
+10), 84 (100).50% plant acid solution 2mL is got in the preparation of phytic acid ethyl ester of lysine salt, adds water 2mL and mixes, and is neutralized to pH with ethyl ester of lysine and equals 7, and moisture is removed in decompression distillation, and vacuum drying (with embodiment 1) gets phytic acid ethyl ester of lysine salt.
Embodiment 19 phytic acid glycine ethyl ester salt (compound 1) are to the antioxidation activity (applicating example 1) of rape salad oil
Get rapeseed oil 50g respectively, put into the conical flask of 100mL.The 0.1g phytic acid amino-acid ester salt is dissolved in the 5mL ethanol, gets this solution 0.5mL and add in the oil sample, stir, making its concentration is 200mg/kg.Be contrast to add 200mg/kg BHT and blank oil sample simultaneously.Rape salad oil is strengthened storage in 60 ℃ of insulating boxs, measured the peroxide value (POV value) and the anisidine value (AV value) of rapeseed oil every 1 day, experiment amounts to 12 days.Peroxide value (Peroxide Value, POV) mensuration is measured with reference to (AOAC Official Method 965.33 (2000)) method, p-anisidine value (p-anisidine Value, p-AV) with reference to (IUPAC standard method 2.504, (1979)) method is measured, the results are shown in Table 1, table 2.
The influence of table 1 phytic acid glycine ethyl ester of the present invention salt pair rape salad oil peroxide value (meq/kg oil)
| Storage time (my god) | 2 | 4 | 6 | 8 | 10 | 12 |
| Blank oil sample | 21.6 | 43.6 | 62.9 | 100.8 | 154.7 | 222.0 |
| 200mg/kg BHT oil sample (contrast) | 16.1 | 40.7 | 53.4 | 67.4 | 120.5 | 178.4 |
| 200mg/kg phytic acid glycine ethyl ester salt oil sample | 14.9 | 36.7 | 44.3 | 58.9 | 84.8 | 120.5 |
The compound of test usefulness is the compound 1 (phytic acid glycine ethyl ester salt) that the present invention prepares in the table 1
The influence of table 2 phytic acid glycine ethyl ester of the present invention salt pair rape salad oil p-anisidine value
| Storage time (my god) | 2 | 4 | 6 | 8 | 10 | 12 |
| Blank oil sample | 2.44 | 3.42 | 6.63 | 11.65 | 14.21 | 16.91 |
| 200mg/kg BHT oil sample (contrast) | 1.53 | 2.33 | 5.45 | 7.18 | 10.74 | 12.33 |
| 200mg/kg phytic acid glycine ethyl ester salt | 1.51 | 2.21 | 5.31 | 6.62 | 8.82 | 9.67 |
The compound of test usefulness is the compound 1 (phytic acid glycine ethyl ester salt) that the present invention prepares in the table 2
Other phytic acid amino-acid ester salts of embodiment 20 the present invention are to the antioxidation activity (applicating example 2) of rape salad oil
According to the method for embodiment 19, get rapeseed oil 50g respectively, put into the conical flask of 100mL.Various phytic acid amino-acid ester salt 0.1g are dissolved in the 5mL ethanol, get this solution 0.5mL and add in the oil sample, stir, making its concentration is 200mg/kg.Rape salad oil is strengthened storage after 12 days in 60 ℃ of insulating boxs, measure the peroxide value (POV value, meq/kg oil) and the anisidine value (p-AV value) of rapeseed oil, the results are shown in Table 3.
Other phytic acid amino-acid ester salt compounds of table 3 the present invention preparation are to the antioxidation activity of rape salad oil
| |
2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 |
| POV | 123.6 | 119.3 | 125.9 | 123.9 | 129.4 | 121.6 | 136.8 | 134.6 | 140.1 | 129.8 | 131.7 | 118.8 | 132.6 | 1238 | 1287 | 122.8 | 116.4 |
| p-AV | 9.82 | 9.54 | 9.81 | 9.79 | 9.91 | 9.61 | 10.21 | 10.48 | 10.96 | 10.10 | 10.21 | 9.61 | 9.98 | 9.81 | 10.01 | 9.78 | 9.53 |
Illustrate: the compound that is numbered 2-18 in the table 3 is other phytic acid amino-acid ester salt compounds that the present invention prepares.
Claims (9)
1, a class oil-soluble edible grease antioxidant, such antioxidant is a phytic acid amino-acid ester salt, and it is that phytic acid is soluble in water, with amino-acid ester described plant acid solution is transferred to neutrality, and decompression dehydration obtains described phytic acid amino-acid ester salt.
2, oil-soluble edible grease antioxidant according to claim 1, wherein said amino-acid ester is made by natural amino acid and alcohol reaction, and its structure is shown below:
In the formula:
R represents various amino acid residues, can be H therefore, CH
3, CH
2OH, CH
2SH, CH (OH) CH
3, CH
3SCH
2CH
2CH, CHCH (CH3)
2, CH
3CH
2CH (CH3), PhCH
2, p-OHPhCH
2, HOOCCH
2, HOOCCH
2CH
2, NH
2CH
2CH
2CH
2CH
2, 3-guanidine radicals propyl group, 2-imidazoles methylene, 3-indoles methylene, Pyrrolizidine base, 4-hydroxyl Pyrrolizidine base; R ' representative contains the alkyl of the direct-connected or side chain of 1-18 carbon.
3, oil-soluble edible grease antioxidant according to claim 1 and 2, alcohol wherein are the alcohol that contains the direct-connected or side chain of 1-18 carbon.
4, prepare oil-soluble edible grease antioxidant method as claimed in claim 1 or 2, it is characterized in that obtaining amino-acid ester by following reaction equation reaction:
1) earlier pure and mild amino acid is mixed, thionyl chloride adds thermal response and obtains described amino-acid ester then;
2) phytic acid is soluble in water, with amino-acid ester plant acid solution is transferred to neutrality, decompression dehydration obtains phytic acid amino-acid ester salt.
5, method according to claim 3 is characterized in that, earlier pure and mild amino acid is mixed, thionyl chloride adds thermal response then, after reaction finishes, filter,, obtain the amino-acid ester hydrochloride with the absolute ethyl alcohol recrystallization, then it is dissolved in the water of 2-10 times of volume, adding sodium carbonate accent ester pH is 8-10, uses the organic solvent extracted with diethyl ether at last, dried over mgso, desolventizing ether evaporate to dryness obtains described amino-acid ester.
6, according to claim 3 or 4 described methods, it is characterized in that phytic acid soluble in waterly, with amino-acid ester plant acid solution is transferred to neutrality, decompression dehydration obtains described phytic acid amino-acid ester salt.
7, method according to claim 3, alcohol wherein are the alcohol that contains the direct-connected or side chain of 1-18 carbon.
8, claim 1 or 2 described oil-soluble edible grease antioxidant application of compound is characterized in that as the edible oil antioxidant.
9, the described oil-soluble edible grease antioxidant of claim 1 is used, and it is characterized in that as alone or in combination or the use composite with other edible oil antioxidants.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104256295A (en) * | 2014-09-12 | 2015-01-07 | 宁波御坊堂生物科技有限公司 | Vegetarian powder capable of keeping stability by utilizing plant phenolic glycine ester phytate composition and preparation method thereof |
| CN113273606A (en) * | 2021-06-09 | 2021-08-20 | 浙江省农业科学院 | Natural antioxidant composition for nuts |
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2008
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104256295A (en) * | 2014-09-12 | 2015-01-07 | 宁波御坊堂生物科技有限公司 | Vegetarian powder capable of keeping stability by utilizing plant phenolic glycine ester phytate composition and preparation method thereof |
| CN113273606A (en) * | 2021-06-09 | 2021-08-20 | 浙江省农业科学院 | Natural antioxidant composition for nuts |
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