CN1280990A - Oligomeric conjak-glucomannan-propyl disulfur aldehydate, and its preparing process and application - Google Patents
Oligomeric conjak-glucomannan-propyl disulfur aldehydate, and its preparing process and application Download PDFInfo
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Abstract
An oligomeric conjak-glucomannan-propyl aldehydate disulfate as broad-spectrum fungus disinfectant for rice hypochnus or cotton scorch is prepared from oligomeric conjek-glucomannan aldehydic acid (molecular wt. below2000) which is prepared from refined conjak starch through enzymolysis, oxidation and degradation, through the process of dual esterifying reaction with epoxypropane and formamide-sodium thiosulfate, and them dual sulfurizing with sodium sulfide and hydrochloric acid or oxalic acid. It has the characteristic peak and 9.01% of sulfur content.
Description
The present invention relates to biological bactericide--two sulfosalts of oligomerization konjak portuguese gansu polyose uronic acid propyl ester and preparation thereof and in the application that prevents and treats on rice sheath blight disease, cotton three rots.
Rhizoma amorphophalli glucomannan (Krnjac Glucomannan is called for short KGM) is a kind of natural acidic polysaccharide, and bioaffinity that has and biodegradability can be made into multiple derivative.Wherein the most attracting is the development of oligosaccharide derivative, because oligosaccharide is the aglucon of the various biologically active factorss in the organism metabolic process, biology growing is grown metabolism play special promotion or restraining effect.If the two sulfurations of this aglucon be can be made into the metabolic toxoid material of a kind of inhibition organism.And two sulfurations of oligomerization KGM are studied, yet there are no report both at home and abroad; Because oligomerization KGM has with oligomerization glucose (seven poly oligosaccharides) close skeleton structure is arranged, the mol ratio that mainly contains D-seminose and D-glucose is 2: 1, closes with β-1.4 bond, and a small amount of β of branch-1.3 bond is closed.In the monomer whose molecule on C2, C3, the C6 position-OH, all have stronger activity.Applied Biotechnology is degraded into oligomerization KGM with KGM, modifies through hydroxypropylation, thiosulfuric acid esterification under proper condition, can be prepared into the water-soluble novel biological bactericide of a kind of weak base.
The oligomerization konjak portuguese gansu polyose uronic acid that the objective of the invention is with the oxidative degradation of konjaku powder enzymolysis is a raw material, prepares a kind of novel weak base water-soluble biological sterilant--the two sulfosalts of oligomerization konjak portuguese gansu polyose uronic acid propyl ester.
Another object of the present invention provides a kind of for the method for preparing the two sulfosalts of oligomerization konjak portuguese gansu polyose uronic acid propyl ester of producing, and proposes product simultaneously in the application that prevents and treats rice sheath blight disease and cotton three rots.
The technological line of realizing above-mentioned purpose is earlier konjaku powder to be carried out enzymolysis alcohol to wash processing, acid hydrolysis oxidative is made oligomerization konjac glucomanna aldehydic acid then, under the catalyzer existence condition, make oligomerization konjak portuguese gansu polyose uronic acid propyl ester with propylene oxide reaction, through methane amide--behind the Sulfothiorine double esterification, make the two sulfosalt products of oligomerization konjac glucomanna aldehydic acid propyl ester with the two sulfurations of sodium sulphite, hydrochloric acid or oxalic acid, its reaction principle is:
In=10 monomer molecules.
Concrete processing step is:
(1) in reactor by konjaku powder: (including massfraction 2% tween 80)=(volume) fed intake 0.2mol acetic acid--sodium-acetate in 1: 2, add cellulase (Ec3.2.1.4) 500u/ml then, be interrupted stirring reaction more than 3.5 hours at 40 ℃ of constant temperature, after decon is filtered in filtration, the rinsing of solid substance aqueous ethanolic solution, the air-dry purity 92-95% oligomerization Rhizoma amorphophalli glucomannan that obtains;
(2) the oligomerization Rhizoma amorphophalli glucomannan is made into the aqueous solution of massfraction 5%, in reactor, stir more than 2 hours in 50 ℃, dripping massfraction 5% hydrochloric acid and 5% hydrogen peroxide simultaneously reaches more than 90% to acid number, filter then, filter cake with massfraction 50% second ferment solution washing after, under 60 ℃, dry oligomerization konjak portuguese gansu polyose uronic acid more than 90%;
(3) by oligomerization konjak portuguese gansu polyose uronic acid: propylene oxide=1: 5 (volume) feeds intake, and add NaOH and KOH makes catalyzer by 1% of oligomerization konjak portuguese gansu polyose uronic acid massfraction, the stirring and refluxing reaction is more than 3 hours under 30 ℃ of-50 ℃ of normal pressures, filter, filter cake with washing with alcohol after, in 60 ℃ of oven dry down, get oligomerization konjak portuguese gansu polyose uronic acid propyl ester, standby;
(4) by (Sulfothiorine--methane amide): oligomerization konjak portuguese gansu polyose uronic acid propyl ester=5-20: 1 (ml/g) feeds intake, at 75-80 ℃ of stirring reaction 2-5 hour, the cooling back adds ethanol sedimentation, filtered water filter wash cake, filter cake gets oligomerization konjak portuguese gansu polyose uronic acid propyl ester thiosulfuric acid ester sodium salt in room temperature vacuum-drying;
(5) by oligomerization konjak portuguese gansu polyose uronic acid propyl ester thiosulfuric acid ester sodium salt: sodium sulphite=4: 1 (quality) feeds intake, adding hydrochloric acid or oxalic acid under 10-20 ℃ transfers PH to 4.0-5.0, stirring reaction is more than 3 hours, add 95% ethanol sedimentation, the water washing and precipitating thing is more than 3 times, after ultrafiltration or the dialysis, vacuum-drying under the room temperature promptly gets two sulfosalt hydrochlorates of oligomerization konjak portuguese gansu polyose uronic acid propyl ester or oxalate.
The two sulphur sodium salts of resulting oligomerization konjak portuguese gansu polyose uronic acid propyl ester have following physico-chemical property:
S content: 9.42% (elemental microanalysis method is undertaken by Experiment of Inorganic Chemstry);
Infrared absorption spectrum (Fig. 1 uses the KBr pressed disc method, and " ShimadznFIIR8300 " carries out at infrared spectrometer): at 360cm
-1, 290cm
-1, 238cm
-1, 135-144cm
-1, 125cm
-1, 180 cm
-1, absorption peak arranged;
Molecular weight: press the JJG-705-904 rules, through the stratographic analysis of HPLS efficient gel, the two sulfosalt hydrochlorate gel chromatography figure of Fig. 2 oligomerization KGM aldehydic acid propyl ester, molecular weight distribution 1320-1582d; Peak 1508d is in the following scope of oligosaccharins molecular weight 2000d.
Find out at 360cm from the infared spectrum of the two sulfosalts of oligomerization konjak portuguese gansu polyose uronic acid propyl ester
-1There is strong absorption at the place, shows the O-H stretching vibration of OH base; At 290cm
-1Absorb by force during the place has, show-CH
2Or CH
3The c h bond stretching vibration of base; In wave number 238 strong absorption is arranged, the O=S key stretching vibration of demonstration-S group; 135-144cm
-1There is strong absorption at the place, shows the stretching vibration of C-O-C (sugar ring); Glucooligosan has close absorption wavenumber, absorption peak with it, sign-S group exists charateristic avsorption band at 125cm
-1, 180cm
-1The place.
The structure that below all proves the two sulfosalts of oligomerization konjak portuguese gansu polyose uronic acid propyl ester is:
Chemical name is: 6-hydroxypropyl-2.3-two sulphur oligomerization Rhizoma amorphophalli glucomannan oxalate (or hydrochloride).
The two sulfosalts of product oligomerization konjak portuguese gansu polyose uronic acid propyl ester can be used preventing and treating on rice sheath blight disease and cotton three rots.Product is sprayed repeatedly in indoor rice sheath blight disease to refractory, cotton three rots, drop, film, shown by bacteriostatic microscopy result from section of pathogenic bacteria crop or cultivation pathogenic bacteria: this product mainly is to cause pathogenic bacteria cell deformity, produce a large amount of foaming materials, destroy cell walls, cause that cell content is excessive; Then cause mycelium distortion, protoplasma aggegation, the vegetative point that have expand, cell wall rupture, mycelium collapse.Except that mycelium being had the intensive destruction, also the pathogenic bacteria spore germination there is certain restraining effect.
The raw materials used commercially available product that is of the present invention.Konjaku powder is provided by Hubei Mei Li group, and hydrochloric acid, hydrogen peroxide, propylene oxide, Sulfothiorine, methane amide, sodium hydroxide, acetic acid, sodium-acetate, 95% ethanol, dehydrated alcohol, tween 80 are analytical pure or chemical pure.Oligosaccharide (seven poly-dextrose elements) relative molecular weight 200-1600, S content 90.8% are Rehabilitation's skill Development Co., Ltd imported products in the Wuhan, the commercially available biological reagent of fiber toxenzyme (Ec3.2.1.4).
Sulfuration reagent: add Sulfothiorine 5g in 25 ℃ of-30 ℃ of dissolvings by methane amide 20ml, standby.
Embodiment 1, takes off an influence test of the molten oxygenant of oligomerization KGM acid.
Adopt multifactor simulation to amplify orthogonal design, determine two level L8 (2
7) oligomerization KGM, HCl, H
2O
2, quality, sour dissolved oxygen mode (drip or add), reaction times, temperature seven factors, to study its interaction, select the transformation efficiency of oligomerization KGM aldehydic acid be that index is analyzed.Adopt in the reaction system and drip HCl, H
2O
2, 70 ℃ of temperature reaction 3 hours is favourable to improving transformation efficiency.
Oligomerization KGM aldehydic acid transformation efficiency C=W2/ (W1-W3) * 100%
W1 is the quality (gram) of oligomerization KGM in the formula; W2 is the quality (gram) of oligomerization KGM aldehydic acid; W3 is the quality (gram) of monomer reducing sugar.
Compare from the turbidity OD value of oligomeric KGM and the turbidity of oxidation oligomerization KGM aldehydic acid, analyze HCl and H in conjunction with its transformation efficiency
2O
2Massfraction concentration is 5% o'clock, and its acid number can be stabilized to more than 90, and transformation efficiency reaches more than 64.5%, and oligomerization KGM turbidity be 1.283 molecular weight more than 1000, the results are shown in Table 1.
Introducing hydroxypropyl in the KGM oligosaccharide molecule, mainly is in order to improve space structure, to weaken intermolecular interaction, help the permeable reactive of sulfo-sulfonated reagent, selecting propylene oxide consumption, temperature of reaction, times three factor design L9 (3
4) experiment, and make index analysis with ester value, top condition be in the reaction of 50ml oligomerization KGM aldehydic acid, the result lists table 2, Fig. 3 (the quadrature trend map of each level of factor and esterification efficient) in.When the propylene oxide consumption is 10ml, 30 ℃ of temperature of reaction during 3 hours reaction times, are calculated from the R value and to be reflected that the influence in reaction times is the most remarkable, secondly are temperature, are the propylene oxide consumption at last.
(its propylene oxide consumption is 15ml to I shown in the table 2 (its propylene oxide consumption is 10ml, 30 ℃ of temperature, 3 hours reaction times) with II, 40 ℃ of temperature, 3 hours reaction times) the gained ester value does not have very big-difference, even I is also slightly high, illustrates that temperature and propylene oxide consumption are dependency.Because elevated temperature causes the volatilization of propylene oxide, the propylene oxide boiling point is 33-35 ℃, makes itself and the minimizing that contacts of oligomerization KGM aldehydic acid, thereby has influenced the result, so I is treated to optimal selection.
The propylene oxide of three level of factor and oligomerization KGM aldehydic acid esterification best of breed trend are (A1, B2, C1) as ise apparent from FIG. 3, by esterification efficiency calculation E%=W4/W2 * 100%=93.04%.
W2 is an oligomerization KGM aldehydic acid quality (gram) in the formula
W4 is an oligomerization KGM aldehydic acid hydroxypropylation quality (gram).
Oligomerization konjaku dextran aldehyde propyl propionate is that oligomerization hydroxypropyl KGM has weakened the reactive force between glycosyl, has improved thiosulfuric acid esterification reagent permeable reactive activity.In esterification process, in order to guarantee thiosulfuric acid esterification efficient, determine that temperature of reaction is 75-80 ℃, fixing methane amide 20ml, the consumption of oligomerization hydroxypropyl KGM is 2 grams, investigate Sulfothiorine consumption and reaction times to the influence of sulphur content, the results are shown in Fig. 4 (Sulfothiorine consumption and reaction times are to the figure that influences of thiosulfuric acid esterification degree).
As can be seen from Figure 4, reducing the Sulfothiorine consumption as far as possible, guaranteeing to reach in certain reaction times best thiosulfuric acid esterification efficient promptly near oligosaccharide content.Therefore can determine 2 gram oligomerization hydroxypropyl KGM, 5 gram Sulfothiorine, 80 ℃ of 20ml methane amide, temperature of reaction, 3 hours reaction times was the suitableeest thiosulfuric acid esterification condition.
Press oligomerization hydroxypropyl KGM aldehydic acid thiosulfates sodium: sodium sulphite=4: 1 (quality) batching,
Under 10-20 ℃ of temperature of reaction, add HCl or
Transfer PH to 4.0-5.0, stirring reaction added 3 times of volume 95% ethanol sedimentations more than 3 hours, and water washing and precipitating thing, filtration, vacuum-drying promptly make two sulfosalt hydrochlorates of oligomerization hydroxypropyl KGM aldehydic acid or oxalate.Yield reaches 93.79%.
With the two sulfosalt hydrochlorates of oligomerization konjac glucomanna aldehydic acid propyl ester paddy rice rot, cotton three rots are sprayed, drop, are coated with film test, to the section of pathogenic bacteria crop, cultivate pathogenic bacteria and be the results are shown in table 3-7 as microscopy by antibacterial.Data as can be seen from table: when spraying concentration was 3ppm, its sterilization effect was 96.7%; When the liquor strength of indoor infusion method is 1ppm, reach 100% through 72 hours sterilization effects, pesticide corrosion 120 only is 80-94% through 72 hours sterilization rates when concentration 3-5ppm under the similarity condition; In field plot trial, it is 91.82%-97.80% that mu consumption 50-60 gram is prevented and treated the rice sheath blight disease drug effect.
Embodiment 6
Take by weighing 0.084 mole sulphur and 0.084 mole sodium sulphite anhydrous 99.3, add 100ml water, heated and boiled to sulphur disappears, the oligomerization hydroxypropyl KGM and the methane amide that add 0.04 mole after cooling, and 80ml ethanol, 75%-80 ℃ of thermotonus 4 hours, behind the hydrochloric acid neutralization reaction liquid with 6N, drip 0.04 mole of sodium sulfide solution, 10 ℃-20 ℃ down reactions 1 hour, use the methylbenzene extraction reaction product, use hydrochloric acid (or oxalic acid) this extracting solution that neutralizes again, separate out light yellow solid, be the two sulfosalt hydrochlorates (or oxalate) of oligomerization konjak portuguese gansu polyose uronic acid propyl ester.Its yield counts 85% with the oligomerization Rhizoma amorphophalli glucomannan, and content is 90%.
Embodiment 7
The Sulfothiorine and the 160ml concentration that take by weighing 0.084 mole are 50% aqueous ethanolic solution, and 0.04 mole oligomerization hydroxypropyl KGM and 0.04 mole of methane amide, 75%-80 ℃ of thermotonus 4 hours, the method for subsequent processing of its reaction solution is identical with embodiment 6, products obtained therefrom yield 85%, crude product is behind recrystallization, and can get fusing point is the highly finished product of 71 ℃ of 170-1, and its Measurement results is as follows:
Ultimate analysis: experimental value % C:34.97, H:5.56, S:9.70 calculated value % C:35.10, H:5.47, S:9.85
Nucleus magnetic resonance: H NMR (D
2O) 2.88 (S, 6H)
3．40(D、7：S、4H)4．28(m、1H)
Agent of table 1 acid hydrolysis oxidative and concentration thereof are to the influence of oligomerization KGM aldehydic acid
| Hl and H 2O 2Massfraction % | 1 | 3 | 5 | 7 | 9 | 11 | Remarks |
| Oligomerization KGM Shu cm A 350nm | 6．672 | 1．483 | 1．283 | 0．947 | 0．718 | 0．56 | 721 spectrophotometer colorimetric OD values |
| Oligomerization KGM (acid number) | 58 | 67 | 92 | 94 | 96 | 97 | |
| Transformation efficiency | 37．05 | 37．03 | 64．56 | 64．56 | 68．46 | 87．02 |
Table 2 different treatment is to the influence of KGM oligosaccharide hydroxypropylation
Annotate: oligomerization KGM aldehydic acid 50ml
The two sulfosalt hydrochlorate spray methodes of table 3 oligomerization KGM aldehydic acid propyl ester are to the rice sheath blight disease laboratory test results
| The medicament title | Concentration (ppm) | Sterilization spot number | Viable bacteria spot rate % | Sterilization effect % |
| Two sulphur oligomerization KGM | ?????2．5 ????12．5 | ???12．5 ????9．5 | ????0 ????25 | ????100 ????96 |
| (KGM-S-2000) | ????6．25 | ????10．5 | ????5 | ????96 |
| Pesticide corrosion 120 | ????25 ????12．5 ?????6．25 | ????10．5 ?????9．5 ?????8．5 | ????0 ????5 ????12．5 | ????100 ????92 ????80 |
| Jinggangmeisu | ????25 ????12．5 ?????6．25 | ????10．5 ?????8．5 ?????8．5 | ????0 ????5 ????7．5 | ????100 ????92 ????88．2 |
Annotate: 40 on each treating water sheath and culm blight of rice leaf, 5 days microscopy results
The two sulfosalt hydrochlorate topical applications of table 4 oligomerization KGM aldehydic acid propyl ester are to the rice sheath blight disease laboratory test results
| The medicament title | Concentration (ppm) | Sterilization spot number | Viable bacteria spot rate % | Sterilization effect % |
| Two sulphur oligomerization KGM (KGM-S-2000) | ????3 ????1．5 | ????0．5 ????1．5 | ????2．5 ????7．5 | ????96．7 ????90 |
| Pesticide corrosion 120 | ????3 ????1．5 | ????0．5 ????2．0 | ????2．5 ????10 | ????96．7 ????86．7 |
| Jinggangmeisu | ????3 ????1．5 | ????0．5 ????2．0 | ????2．5 ????10 | ????96．7 ????86．7 |
| Contrast | ????15 | ????75 |
The two sulfosalt hydrochlorate sprayings of table 5 oligomerization KGM aldehydic acid propyl ester are to the result of cotton three rot shop experiments
| The medicament title | Concentration (ppm) | Sterilization spot number | Viable bacteria spot rate % | Sterilization effect % | Remarks |
| Two sulphur oligomerization KGM (KGM-S-2000) | ????50 | ????22 | ????20 | ????83．5 | Tianmen 99 |
| Farming anti-1 20 | ????50 | ????21 | ????19．6 | ????83．5 | |
| Jinggangmeisu | ????50 | ????25 | ????19．2 | ????68．8 | |
| Contrast | ????40 | ????30 |
The two sulfosalt hydrochlorates of table 6 oligomerization KGM aldehydic acid propyl ester carry the residual effect test-results to the rice sheath blight disease basin
The two sulfosalt hydrochlorates of table 7 oligomerization KGM aldehydic acid propyl ester are prevented and treated rice sheath blight disease drug effect test of field zone result
Annotate: three repetition mean numbers
Claims (4)
1, the two sulfosalts of oligomerization konjak portuguese gansu polyose uronic acid propyl ester is characterized in that having as formula I structural formula compound,
In=10 monomer molecules.
2, the method for making of the two sulfosalts of the described oligomerization konjak portuguese gansu polyose of claim 1 uronic acid propyl ester is characterized in that step is as follows:
(1) in reactor by konjaku powder: (including massfraction 2% tween 80)=(volume) fed intake 0.2mol acetic acid--sodium-acetate in 1: 2, add cellulase (Ec3.2.1.4) 500u/ml then, be interrupted stirring reaction more than 3.5 hours at 40 ℃ of constant temperature, after decon is filtered in filtration, the rinsing of solid substance aqueous ethanolic solution, the air-dry purity 92-95% oligomerization Rhizoma amorphophalli glucomannan that obtains;
(2) the oligomerization Rhizoma amorphophalli glucomannan is made into the aqueous solution of massfraction 5%, in reactor, stir more than 2 hours in 50 ℃, dripping massfraction 5% hydrochloric acid and 5% hydrogen peroxide simultaneously reaches more than 90% to acid number, filter then, filter cake with the washing of massfraction 50% aqueous ethanolic solution after, under 60 ℃, dry oligomerization konjak portuguese gansu polyose uronic acid more than 90%;
(3) by oligomerization konjak portuguese gansu polyose uronic acid: propylene oxide=1: 5 (volume) feeds intake, and add NaOH and KOH makes catalyzer by 1% of oligomerization konjak portuguese gansu polyose uronic acid massfraction, the stirring and refluxing reaction is more than 3 hours under 30 ℃ of-50 ℃ of normal pressures, filter, filter cake with washing with alcohol after, in 60 ℃ of oven dry down, get oligomerization konjak portuguese gansu polyose uronic acid propyl ester, standby;
(4) by (Sulfothiorine--methane amide): oligomerization konjak portuguese gansu polyose uronic acid propyl ester=5-20: 1 (ml/g) feeds intake, at 75-80 ℃ of stirring reaction 2-5 hour, the cooling back adds ethanol sedimentation, filtered water filter wash cake, filter cake gets oligomerization konjak portuguese gansu polyose uronic acid propyl ester thiosulfuric acid ester sodium salt in room temperature vacuum-drying;
(5) by oligomerization konjak portuguese gansu polyose uronic acid propyl ester thiosulfuric acid ester sodium salt: sodium sulphite=4: 1 (quality) feeds intake, adding hydrochloric acid or oxalic acid under 10-20 ℃ transfers PH to 4.0-5.0, stirring reaction is more than 3 hours, add 95% ethanol sedimentation, the water washing and precipitating thing is more than 3 times, after ultrafiltration or the dialysis, vacuum-drying under the room temperature promptly gets two sulfosalt hydrochlorates of oligomerization konjak portuguese gansu polyose uronic acid propyl ester or oxalate.
3, the two sulfosalts of the described oligomerization konjak portuguese gansu polyose of claim 1 uronic acid propyl ester are in the application that prevents and treats on the rice sheath blight disease.
4, the application of the two sulfosalts of the described oligomerization konjak portuguese gansu polyose of claim 1 uronic acid propyl ester on control cotton three rots.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101849543A (en) * | 2010-05-27 | 2010-10-06 | 浙江省桐庐汇丰生物化工有限公司 | Compounded sterilizing agent of pyrimidine nucleoside antibiotics and alkene oxime amine |
| CN101856026A (en) * | 2010-05-27 | 2010-10-13 | 浙江省桐庐汇丰生物化工有限公司 | Pyrimidine nucleotide antibiotic and trifluzamide combined bactericide |
-
2000
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101849543A (en) * | 2010-05-27 | 2010-10-06 | 浙江省桐庐汇丰生物化工有限公司 | Compounded sterilizing agent of pyrimidine nucleoside antibiotics and alkene oxime amine |
| CN101856026A (en) * | 2010-05-27 | 2010-10-13 | 浙江省桐庐汇丰生物化工有限公司 | Pyrimidine nucleotide antibiotic and trifluzamide combined bactericide |
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