CN106749703B - A kind of benzyl triazolium salt starch and its preparation method and application - Google Patents

A kind of benzyl triazolium salt starch and its preparation method and application Download PDF

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CN106749703B
CN106749703B CN201611204768.6A CN201611204768A CN106749703B CN 106749703 B CN106749703 B CN 106749703B CN 201611204768 A CN201611204768 A CN 201611204768A CN 106749703 B CN106749703 B CN 106749703B
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starch
benzyl
triazolium salt
nitrine
bromo
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CN106749703A (en
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郭占勇
谭文强
李青
董方
张晶晶
栾芳
魏丽杰
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Yantai Institute of Coastal Zone Research of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles

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Abstract

The present invention relates to daily chemicals field and pharmaceuticals industry, specifically a kind of benzyl triazolium salt starch and its preparation method and application.Shown in benzyl triazolium salt starch structure formula such as formula (1), wherein average degree of polymerization n value range is 5-12000.Efficiently, easy to spread, required equipment and raw material are easy to get for present invention reaction.Research shows that the benzyl triazolium salt starch good water solubility of synthesis, has fabulous fungicidal activities, enhances the bioactivity of starch, expand the application range of starch, can be widely applied to daily use chemicals and field of medicaments.

Description

A kind of benzyl triazolium salt starch and its preparation method and application
Technical field
The present invention relates to daily chemicals field and pharmaceuticals industry, specifically a kind of benzyl triazolium salt starch and preparation method thereof and Using.
Background technique
Starch (Starch) is to be formed by macromolecule carbon hydrate together through α -1,4 glucosides key connection by D-Glucose Object.Starch is mainly derived from the crops such as corn, wheat, potato, is the most important food supply source of the mankind.Starch is cheap It is renewable, it is green non-poisonous, there is good biocompatibility and biodegradability, in addition to as the main energy of humans and animals It supplies outside source, has also obtained certain application in the industry such as pharmacy, papermaking, packaging and weaving.However, native starch molecule Because only that a kind of active group of hydroxyl, lack carboxyl, sulfate group, amino isoreactivity group and be unable to get deeper into extensive Application.Therefore, by carrying out targetedly modifying for chemical structure to it, active group is introduced, its application range is expanded, is improved Its application value becomes the new hot spot of the high-valued development and utilization of starch.
By the measurement of the bacteriostatic activity to starch it is found that the bacteriostatic activity of starch itself is very low, it is not enough to develop and use, Therefore carrying out appropriate modifying for chemical structure then to it is to solve the problems, such as the effective method.
Summary of the invention
It is an object of the present invention to provide a kind of benzyl triazolium salt starch and preparation method thereof with preferable fungicidal activities And application.
To achieve the above object, the technical scheme adopted by the invention is as follows:
A kind of benzyl triazolium salt starch, shown in benzyl triazolium salt starch structure formula such as formula (1),
Wherein, average degree of polymerization n value range is 5-12000.
A kind of preparation method of benzyl triazolium salt starch is reacted using click chemistry butynol being linked into nitrine starch In, the triazole starch containing ethoxy is obtained, benzyl triazolium salt starch shown in formula (1) is then obtained with benzyl bromine reaction；Wherein, The mole of butynol is 2-3 times of nitrine starch.
The nitrine starch is to react starch with N- bromo-succinimide and triphenylphosphine to obtain bromo starch, gained Bromo starch reacts to obtain nitrine starch with Sodium azide again；Wherein, the mole of Sodium azide is 2-3 times of bromo starch.
The bromo starch is that starch is activated 1-2h at 120-130 DEG C in excessive DMF, then cools to 80- 90 DEG C, adding mole is 2-3 times of starch of lithium bromide as hydrotropy, and then under ice bath, it is sub- to add N- bromo succinyl Amine and triphenylphosphine then use ethanol precipitation in 70-80 DEG C of reaction 3-4h, then are successively freeze-dried through ethyl alcohol, acetone washing, Obtain bromo starch；Wherein, the mole of N- bromo-succinimide and triphenylphosphine is respectively 3-4 times of starch.
The bromo starch reacts 18-24h at 70-80 DEG C with Sodium azide, then directly uses ethanol precipitation, then successively through second Alcohol, acetone washing, freeze-drying is to get stand-by to nitrine starch.
Butynol is linked into nitrine starch by described reacted using click chemistry specifically: nitrine starch and butynol exist Triethylamine and under cuprous iodide catalysis, in 75-80 DEG C of reaction 12-24h, through acetone precipitation, then through acetone washing, freezing is done It is dry to get arrive the triazole starch containing ethoxy；Wherein, triethylamine additional amount is 1-2 times of mole of nitrine starch, cuprous iodide Additional amount be 0.1-0.2 times of mole of nitrine starch.
The triazole starch containing ethoxy reacts 12-24h at 60-70 DEG C with benzyl bromide, through acetone precipitation, sediment It is re-dissolved in distilled water, and is placed in bag filter and is dialysed 36-48h with distilled water, then obtains benzyl shown in formula (1) after being freeze-dried Triazolium salt starch.
A kind of application of benzyl triazolium salt starch, benzyl triazolium salt starch shown in the formula (1) are preparing restraining epiphyte Application in agent.
Advantage for present invention:
(1) the compounds of this invention reacts three generated containing ethoxy with butynol after introducing azido compared with starch After nitrogen azoles starch, benzyl triazolium salt starch directly can be generated with benzyl bromine reaction.
(2) after the present invention is prepared into benzyl triazolium salt starch, bioactivity is improved.
(3) synthesis step of the present invention is simple on synthesis technology, required equipment and raw material is easy to get, cost is relatively low, is easy to push away Extensively, and this product yield is higher, up to 60% or more.Products obtained therefrom of the present invention can be widely used for biology, medicine, food, change The fields such as work.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of starch.
Fig. 2 provides the infrared spectrum of bromo starch for the embodiment of the present invention, as can be seen from Figure 3 compared with starch raw material, 667cm-1The absorption peak at place is the absorption peak of C-Br key, the above analysis data, it was demonstrated that bromo Starch synthesis.
Fig. 3 provides the infrared spectrum of nitrine starch for the embodiment of the present invention, as can be seen from Figure 4 compared with starch raw material, increases newly The 2105cm added-1Locate the absorption peak that absorption peak is azido group, while compared with Fig. 2,667cm-1Locate absorption peak to disappear, show Nitrine starch is made in nucleophilic displacement of fluorine bromine to azido.
Fig. 4 provides the infrared spectrum of the triazole starch containing ethoxy for the embodiment of the present invention, folded with Fig. 3 as can be seen from Figure 4 Nitrogen starch is compared, 2105cm-1Azido group absorption peak disappear, 1542cm-1Place is the absorption of unsaturated bond on triazole ring Peak shows that nitrine starch is reacted with butynol completely and generates the triazole starch containing ethoxy.
Fig. 5 provides the infrared spectrum of benzyl triazolium salt starch for the embodiment of the present invention, as can be seen from Figure 5 with Fig. 4 second containing hydroxyl The triazole starch of base is compared, and due to the introducing of benzyl, the absorption peak of triazole is moved to 1577cm-1, occur 1496 and 728cm-1Phenyl absorption peak, therefore can prove the successful synthesis of benzyl triazolium salt starch.
Specific embodiment
The present invention passes through steric effect first, adjusts chemo-selective with triphenylphosphine and 6 bromines are specifically prepared For starch, nitrine starch then is made using Sodium azide nucleophilic displacement of fluorine bromine, is reacted using click chemistry and butynol is accessed into nitrine In starch molecule, the triazole starch containing ethoxy is obtained, then with benzyl bromine reaction, has obtained benzyl triazolium salt starch, And have studied its inhibiting effect to cucumber anthracnose and the withered plant pathogen of watermelon.Analog derivative preparation simplicity, condition Mildly, the development for carbohydrate fungistat provides feasible thinking.
Embodiment 1
The synthetic route of benzyl triazolium salt starch is as follows:
Wherein, average degree of polymerization n value range is 5-12000.
The present embodiment presses the above synthetic route synthesising target compound benzyl triazolium salt starch.
1) preparation of bromo starch: 1.62g starch (referring to Fig. 1) in 50mL DMF (N,N-dimethylformamide) 1h is activated at 130 DEG C, is then cooled down 90 DEG C, and 2.0g lithium bromide hydrotropy is added.Then under ice bath, 7.12g N- bromo fourth two is added Acid imide, 10.49g triphenylphosphine, in 80 DEG C of reaction 3h.Ethanol precipitation is then used, through ethyl alcohol and acetone washing, is freeze-dried, Product bromo starch (referring to fig. 2) 2.01g is obtained, for use.
2) preparation of nitrine starch: 0.225g bromo starch (referring to fig. 2) is added in 15mL DMSO (dimethyl sulfoxide), so 0.16g Sodium azide is added afterwards, the lower 80 DEG C of reactions of argon gas protection for 24 hours, then directly use ethanol precipitation, and washed with ethyl alcohol and acetone It washs, freeze-drying obtains nitrine starch (referring to Fig. 3) 0.16g, for use.
3) preparation of the triazole starch containing ethoxy: 0.187g nitrine starch (referring to Fig. 3) is added to 10mL DMSO (two First sulfoxide) in, then be added 0.227mL butynol, the triethylamine of 0.14mL, the cuprous iodide of 20mg, argon gas protection under 12h is reacted under the conditions of 80 DEG C, after reaction, with acetone precipitation, is filtered, washing, vacuum freeze drying is obtained containing ethoxy Triazole starch (referring to fig. 4) 0.236g, for use.
4) preparation of benzyl triazolium salt starch: triazole starch (referring to fig. 4) of the 0.257g containing ethoxy is in 15mL In DMSO (dimethyl sulfoxide), 0.356mL benzyl bromide is added, is reacted for 24 hours under the conditions of lower 60 DEG C of argon gas protection, after reaction, uses Acetone precipitation filters, and washing, deionized water dialysis 36h, vacuum freeze drying obtains benzyl three shown in target product formula (1) Azoles salt starch (referring to Fig. 5).
Embodiment 2
Difference from Example 1 is:
1) preparation of bromo starch: 1.62g starch (referring to Fig. 1) in 50mL DMF (N,N-dimethylformamide) 1h is activated at 130 DEG C, is then cooled down 80 DEG C, and 2.0g lithium bromide hydrotropy is added.Under ice bath, it is sub- that 5.34g N- bromo succinyl is added Amine, 7.87g triphenylphosphine, in 70 DEG C of reaction 3h.Ethanol precipitation is then used, through ethyl alcohol and acetone washing, freeze-drying is produced Object bromo starch (referring to fig. 2) 1.84g, for use.
3) preparation of nitrine starch: 0.225g bromo starch (referring to fig. 2) is added in 10mL DMSO (dimethyl sulfoxide), so 0.13g Sodium azide is added afterwards, the lower 70 DEG C of reactions of argon gas protection for 24 hours, then directly use ethanol precipitation, and washed with ethyl alcohol and acetone It washs, freeze-drying obtains nitrine starch (referring to Fig. 3) 0.14g, for use.
4) preparation of the triazole starch containing ethoxy: 0.187g nitrine starch (referring to Fig. 3) is added to 10mL DMSO (two First sulfoxide) in, then be added 0.151mL butynol, the triethylamine of 0.14mL, the cuprous iodide of 20mg, argon gas protection under It reacts under the conditions of 75 DEG C for 24 hours, after reaction, with acetone precipitation, filters, washing, vacuum freeze drying is obtained containing ethoxy Triazole starch (referring to fig. 4) 0.219g, for use.
5) preparation of benzyl triazolium salt starch: triazole starch (referring to fig. 4) of the 0.257g containing ethoxy is in 15mL In DMSO (dimethyl sulfoxide), 0.238mL benzyl bromide is added, is reacted for 24 hours under the conditions of lower 60 DEG C of argon gas protection, after reaction, uses Acetone precipitation filters, and washing, deionized water dialysis 36h, vacuum freeze drying obtains benzyl three shown in target product formula (1) Azoles salt starch (referring to Fig. 5).
Embodiment 3
Difference from Example 1 is:
1) preparation of bromo starch: 1.62g starch (referring to Fig. 1) in 50mL DMF (N,N-dimethylformamide) 1h is activated at 120 DEG C, is then cooled down 90 DEG C, and 2.0g lithium bromide hydrotropy is added.Under ice bath, it is sub- that 7.12g N- bromo succinyl is added Amine, 10.49g triphenylphosphine, in 60 DEG C of reaction 4h.Ethanol precipitation is then used, through ethyl alcohol and acetone washing, freeze-drying is obtained Product bromo starch (referring to fig. 2) 1.82g, for use.
2) preparation of nitrine starch: 0.225g bromo starch (referring to fig. 2) is added in 10mL DMSO (dimethyl sulfoxide), so Be added 0.2g Sodium azide afterwards, the lower 70 DEG C of reactions of argon gas protection for 24 hours, then directly with ethanol precipitation, and with ethyl alcohol and acetone washing, Freeze-drying obtains nitrine starch (referring to Fig. 3) 0.17g, for use.
3) preparation of the triazole starch containing ethoxy: 0.187g nitrine starch (referring to Fig. 3) is added to 10mL DMSO (two First sulfoxide) in, then be added 0.227mL butynol, the triethylamine of 0.14mL, the cuprous iodide of 20mg, argon gas protection under It reacts under the conditions of 75 DEG C for 24 hours, after reaction, with acetone precipitation, filters, washing, vacuum freeze drying is obtained containing ethoxy Triazole starch (referring to fig. 4) 0.225g, for use.
5) preparation of benzyl triazolium salt starch: triazole starch (referring to fig. 4) of the 0.257g containing ethoxy is in 15mL In DMSO (dimethyl sulfoxide), 0.356mL benzyl bromide is added, is reacted for 24 hours under the conditions of lower 70 DEG C of argon gas protection, after reaction, uses Acetone precipitation filters, and washing, deionized water dialysis 36h, vacuum freeze drying obtains benzyl three shown in target product formula (1) Azoles salt starch (referring to Fig. 5).
Application examples
Inhibit the measurement of cucumber anthracnose and the withered plant pathogen ability of watermelon:
Measure the shallow lake of benzyl triazolium salt shown in formula synthesized by above-described embodiment (1) respectively using mycelial growth rate method The rejection ability of powder, the triazole starch containing ethoxy and starch to cucumber anthracnose and the withered plant pathogen of watermelon: will implement The benzyl triazolium salt starch, the triazole starch containing ethoxy and the experiment starch vacuum freeze drying that prepare are to constant weight in example Afterwards, with water as solvent, after being configured to the sample aqueous solution of 5mg/mL, take respectively 0.3mL, 1.5mL and 3mL sample solution be added to Volume is in the commercially available fungi culture medium of 14.7mL, 13.5mL and 12mL, and being configured to sample concentration is 0.1mg/mL, 0.5mg/ The culture medium of mL and 1.0mg/mL.Using the carbendazim of isoconcentration as positive control, using isometric sterile water replace sample as Blank control.Culture medium is shaken up and is poured into the culture dish that diameter is 9cm, after its completely solidification, is connect in each culture dish The bacteria cake that kind diameter is 5mm.After cultivating 48h to 72h at 27 DEG C, crossing method measures colony diameter, calculates the suppression of sample Bacterium rate, all experimentss are repeated once.
Bacteriostasis rate (%)=1- [(DSample-5)/(DBlank-5)]×100
The ability of the inhibition cucumber anthracnose of table 1, benzyl triazolium salt starch, triazole starch and starch containing ethoxy (%)
The withered pathogenic bacteria of inhibition watermelon of table 2, benzyl triazolium salt starch, the triazole starch containing ethoxy and starch Ability (%)
Experimental result: benzyl triazolium salt starch synthesized by the present invention, the triazole starch containing ethoxy and starch Inhibit the ability of cucumber anthracnose and withered germ of water-melon as shown in Tables 1 and 2, the triazole containing ethoxy synthesized by the present invention forms sediment The bacteriostasis of powder is slightly above starch, it may be possible to because of the introducing of 1,2,3- triazole groups；Benzyl three synthesized by the present invention The bacteriostasis of azoles salt starch is apparently higher than triazole starch and starch raw material containing ethoxy, especially in 1.0mg/mL When, the bacteriostasis rate of benzyl triazolium salt starch is up to 80% or more.The antibacterial activity and triazolium salt of benzyl triazolium salt starch And the groups such as benzyl are related, the presence of these active groups can greatly improve the antibacterial activity of starch, improve answering for starch With value, expand the application range of starch.

Claims (8)

1. a kind of benzyl triazolium salt starch, it is characterised in that: shown in benzyl triazolium salt starch structure formula such as formula (1),
Wherein, average degree of polymerization n value range is 5-12000.
2. a kind of preparation method of benzyl triazolium salt starch described in claim 1, it is characterised in that: anti-using click chemistry Butynol should be linked into nitrine starch, obtain the triazole starch containing ethoxy, formula (1) institute is then obtained with benzyl bromine reaction Show benzyl triazolium salt starch；Wherein, the mole of butynol is 2-3 times of nitrine starch.
3. the preparation method of benzyl triazolium salt starch as described in claim 2, it is characterised in that: the nitrine starch be by Starch reacts to obtain bromo starch with N- bromo-succinimide and triphenylphosphine, and gained bromo starch is reacted with Sodium azide again Nitrine starch；Wherein, the mole of Sodium azide is 2-3 times of bromo starch.
4. the preparation method of benzyl triazolium salt starch according to claim 3, it is characterised in that: the bromo starch be by Starch activates 1-2h at 120-130 DEG C in excessive DMF, then cools to 80-90 DEG C, and adding mole is starch 2- 3 times of lithium bromide is as hydrotropy, then under ice bath, adds N- bromo-succinimide and triphenylphosphine, reacts at 70-80 DEG C 3-4h then uses ethanol precipitation, then successively through ethyl alcohol, acetone washing, is freeze-dried to get bromo starch is arrived；Wherein, N- bromo The mole of succimide and triphenylphosphine is respectively 3-4 times of starch.
5. the preparation method of benzyl triazolium salt starch according to claim 3, it is characterised in that: the bromo starch and folded Nitrogen sodium then directly uses ethanol precipitation in 70-80 DEG C of reaction 18-24h, then is successively freeze-dried, i.e., through ethyl alcohol, acetone washing It is stand-by to obtain nitrine starch.
6. the preparation method of benzyl triazolium salt starch as described in claim 2, it is characterised in that: described to utilize click chemistry Butynol is linked into nitrine starch by reaction specifically: is catalyzed nitrine starch and butynol in triethylamine and with cuprous iodide Under, in 75-80 DEG C of reaction 12-24h, through acetone precipitation, then through acetone washing, it is freeze-dried to get three nitrogen containing ethoxy are arrived Azoles starch；Wherein, triethylamine additional amount is 1-2 times of mole of nitrine starch, and the additional amount of cuprous iodide is nitrine starch mole 0.1-0.2 times of amount.
7. the preparation method of benzyl triazolium salt starch as described in claim 2, it is characterised in that: three containing ethoxy Nitrogen azoles starch reacts 12-24h at 60-70 DEG C with benzyl bromide, and through acetone precipitation, sediment is re-dissolved in distilled water, and is placed on The interior distilled water dialysis 36-48h of bag is analysed, then obtains benzyl triazolium salt starch shown in formula (1) after being freeze-dried.
8. a kind of application of benzyl triazolium salt starch described in claim 1, it is characterised in that: benzyl shown in the formula (1) Triazolium salt starch is preparing the application in fungistat.
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