CN106046183B - A kind of iodo-methyl triazole starch of niacinamide-containing base and its preparation method and application - Google Patents

A kind of iodo-methyl triazole starch of niacinamide-containing base and its preparation method and application Download PDF

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CN106046183B
CN106046183B CN201610293062.5A CN201610293062A CN106046183B CN 106046183 B CN106046183 B CN 106046183B CN 201610293062 A CN201610293062 A CN 201610293062A CN 106046183 B CN106046183 B CN 106046183B
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starch
niacinamide
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CN106046183A (en
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郭占勇
谭文强
李青
董方
高振鹏
邱帅
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Yantai Institute of Coastal Zone Research of CAS
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Abstract

The present invention relates to household chemicals field and pharmaceuticals industry, iodo-methyl triazole starch of specifically a kind of niacinamide-containing base and its preparation method and application.Shown in the iodo-methyl triazole starch structure formula such as formula (1) of niacinamide-containing base, wherein, average degree of polymerization n spans are 5 12000.Present invention reaction is efficient, and easy to spread, required equipment and raw material are easy to get.Research shows the iodo-methyl triazole starch good water solubility of the niacinamide-containing base of synthesis, has fabulous fungicidal activities, enhances the bioactivity of starch, expand the application of starch, can be widely applied to daily use chemicals and field of medicaments.

Description

A kind of iodo-methyl triazole starch of niacinamide-containing base and its preparation method and application
Technical field
The present invention relates to household chemicals field and pharmaceuticals industry, the iodo-methyl triazole starch of specifically a kind of niacinamide-containing base And its preparation method and application.
Background technology
Starch (Starch) is the macromolecule carbon hydrate for linking together formed through α -1,4 glycosidic bonds by D-Glucose Thing, chemical structural formula are (C6H10O5)n.Starch is mainly derived from the crops such as corn, wheat, potato, is that the mankind are most important Food supply source.Starch can form the starch point of two kinds of various configurations according to two kinds of different connected modes of glucose unit Son, i.e. amylose and amylopectin.Starch cheap reproducible, it is green non-poisonous, have good biocompatibility and biology can Degradability, in addition to the energy supply source main as humans and animals, in the industry such as pharmacy, papermaking, packaging and weaving Certain application is obtained.However, native starch molecule because only that a kind of active group of hydroxyl, lack carboxyl, sulfate group, Amino isoreactivity group and can not obtain deeper into being widely applied.Therefore, repaiied by carrying out targetedly chemical constitution to it Decorations, active group is introduced, expands its application, improves its application value, turn into the new focus of the high-valued utilization of starch.
By the measure of the bacteriostatic activity to starch, the bacteriostatic activity of starch in itself is very low, is not enough to develop, Therefore it is then to solve the effective method of the problem that appropriate modifying for chemical structure is carried out to it.1,2,3- triazole chemical combination Thing is obtained by Huisgen 1,3- Dipolar Cycloadditions (click chemistry).Click chemistry is simple to operate, reaction condition temperature With product easy purification, high income, have been widely used for drug development, Macroscopic single crystal, surface modification and nano-particle, micro- The biomedical sector such as array and self assembly.Iodo-methyl triazole compound is on 1,2,3- triazole compounds basis On, obtained using the nucleophilicity of nitrogen-atoms with iodomethane reaction.It is reported that iodo-methyl triazole compound has more preferably Antibacterial activity.Accessed in starch molecule, to improve the antibacterial activity of starch molecule, strengthen the application value of starch, Expand the application of starch.
The content of the invention
It is an object of the present invention to provide a kind of iodo-methyl triazole of niacinamide-containing base with preferable fungicidal activities shallow lake Powder and its preparation method and application.
To achieve the above object, the technical solution adopted in the present invention is:
A kind of iodo-methyl triazole starch of niacinamide-containing base, the iodo-methyl triazole starch structure of niacinamide-containing base Shown in formula such as formula (1),
Wherein, average degree of polymerization n spans are 5-12000.
A kind of preparation method of the iodo-methyl triazole starch of niacinamide-containing base, reacts (end alkynes using click chemistry The reaction of 1,2,3- triazoles is efficiently synthesized under monovalence copper catalysis with azide reaction) propargylamine and nicotinoyl chloride hydrochloride will be used Salt synthesis N- propargyl niacinamide be linked into nitrine starch, obtain the triazole starch of niacinamide-containing base, then with iodine first Alkane react niacinamide-containing base shown in formula (1) iodo-methyl triazole starch;Wherein, the mole of N- propargyls niacinamide is 1.5-2 times of nitrine starch.
The N- propargyl niacinamide that the propargylamine synthesizes with nicotinoyl chloride hydrochloride is by propargylamine, with propargylamine mole 1-2 times of triethylamine and it is dissolved in the DMAP of 0.1-0.2 times of propargylamine mole in excessive dichloromethane, with The nicotinoyl chloride hydrochloride of 0.9-1.0 times of propargylamine mole, at 0-4 DEG C, 0.5-1h is reacted, in ambient temperature overnight after reaction, then Extracted with excessive hydrochloric acid and sodium hydrate aqueous solution, then dried through anhydrous magnesium sulfate respectively, filtered, evaporate, that is, obtain N- alkynes Propyl group niacinamide.
The nitrine starch is to react to obtain bromo starch, gained by starch and N- bromo-succinimides and triphenylphosphine Bromo starch reacts to obtain nitrine starch with Sodium azide again;Wherein, the mole of N- bromo-succinimides and triphenylphosphine is respectively 3-4 times of starch;The mole of Sodium azide is 2-3 times of bromo starch.
The bromo starch is that in the DMF of excess at 120-130 DEG C starch is activated into 1-2h, then cools to 80- 90 DEG C, add the lithium bromide hydrotropy that mole is 2-3 times of starch, then under ice bath, add N- bromo-succinimides and Triphenylphosphine, 3-4h is reacted at 70-80 DEG C, then with ethanol precipitation, then wash, freeze-drying, produced through ethanol, acetone successively To bromo starch.
The bromo starch reacts 18-24h with Sodium azide at 70-80 DEG C, then directly uses ethanol precipitation, then successively through second Alcohol, acetone washing, freeze-drying, that is, it is stand-by to obtain nitrine starch.
Described nitrine starch and N- propargyls niacinamide are in the triethylamine and and nitrine with 1-2 times of nitrine starch mole Under the cuprous iodide catalysis of 0.1-0.2 times of starch mole, 12-24h is reacted at 75-80 DEG C, is washed through acetone precipitation, then through acetone Wash, be freeze-dried, that is, obtain the triazole starch of niacinamide-containing base.
The triazole starch of described niacinamide-containing base reacts 12-24h with iodomethane at 60-70 DEG C, through acetone precipitation, sinks Starch is re-dissolved in distilled water, is then placed in the interior distilled water dialysis 36-48h of bag filter, then obtained after being freeze-dried shown in formula (1) The iodo-methyl triazole starch of niacinamide-containing base.
A kind of application of the iodo-methyl triazole starch of niacinamide-containing base, the iodine of niacinamide-containing base shown in the formula (1) For application of the methyl triazole starch in restraining epiphyte preparation is prepared.
Advantage for present invention:
(1) the compounds of this invention after azido is introduced, contains cigarette with the reaction generation of N- propargyls niacinamide compared with starch After the triazole starch of amide groups, the iodo-methyl triazole starch of niacinamide-containing base can be directly generated with iodomethane reaction.
(2) after the present invention is prepared into the iodo-methyl triazole starch of niacinamide-containing base, its water-soluble and bioactivity obtains To improve.
(3) synthesis step of the present invention is simple on synthesis technique, 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 more than 50%.Products obtained therefrom of the present invention can be widely used for biology, medicine, food, change The fields such as work.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of starch.
Fig. 2 provides the N- infrared spectrums of propargyl niacinamide, as can be seen from Figure 2,3224,2113 Hes for the embodiment of the present invention 628cm-1The absworption peak at place be terminal acetylene absworption peak, 3046,1596cm-1For the absorption of the unsaturated c h bond on pyridine ring Peak, 1658cm-1For the absworption peak of amido link, above analyze data, it was demonstrated that N- propargyl niacinamide synthesizes successfully.
Fig. 3 provides the infrared spectrum of bromo starch for the embodiment of the present invention, as can be seen from Figure 3 compared with starch material, 667cm-1The absworption peak at place be C-Br keys absworption peak, above analyze data, it was demonstrated that bromo Starch synthesis.
Fig. 4 provides the infrared spectrum of nitrine starch for the embodiment of the present invention, as can be seen from Figure 4 compared with starch material, increases newly The 2105cm added-1Locate the absworption peak that absworption peak is azido group, while compared with Fig. 3,667cm-1Locate absworption peak to disappear, show Nitrine starch is made in nucleophilic displacement of fluorine bromine to azido.
Fig. 5 provides the infrared spectrum of the triazole starch of niacinamide-containing base for the embodiment of the present invention, as can be seen from Figure 5 with Fig. 4 Nitrine starch is compared, 2105cm-1Azido group absworption peak disappear, 1542cm-1Locate as the absorption of unsaturated bond on triazole ring Peak, 1650cm-1For the absworption peak of amido link, 3081,1596cm-1Locate for the absworption peak of unsaturated bond C-H on pyridine ring, to show Nitrine starch reacts the triazole starch of generation niacinamide-containing base with N- propargyls niacinamide completely.
Fig. 6 provides the infrared spectrum of the iodo-methyl triazole starch of niacinamide-containing base for the embodiment of the present invention, can from Fig. 6 Know compared with the triazole starch of Fig. 5 niacinamide-containing bases, 1361cm-1Locate the absworption peak for methyl, due to the introducing of methyl, acid amides The absworption peak of key is moved to 1670cm-1, therefore the successful synthesis of the iodo-methyl triazole starch of niacinamide-containing base can be proved.
Embodiment
By steric effect, 6 bromines are specifically prepared with triphenylphosphine regulation chemo-selective first in the present invention For starch, nitrine starch then is made using Sodium azide nucleophilic displacement of fluorine bromine, propargylamine and nicotinoyl will be used using click chemistry reaction In the N- propargyls niacinamide access nitrine starch molecule of villaumite hydrochlorate synthesis, the triazole starch of niacinamide-containing base is obtained, so Afterwards with iodomethane reaction, obtained the iodo-methyl triazole starch of niacinamide-containing base, and have studied its to cucumber anthracnose and The inhibitory action of the withered plant pathogen of watermelon.The analog derivative prepares easy, mild condition, is the development of carbohydrate fungistat Provide feasible thinking.
Embodiment 1
The synthetic route of the iodo-methyl triazole starch of niacinamide-containing base is as follows:
Wherein, average degree of polymerization n spans are 5-12000.
The present embodiment presses the iodo-methyl triazole starch of above synthetic route synthesising target compound niacinamide-containing base.
1) synthesis of N- propargyls niacinamide:At 0 DEG C, 0.65mL propargylamines, 1.4mL triethylamines, 24mg DMAP (4- bis- Methylamino pyridine) in 20mL dichloromethane, 1.78g nicotinoyl chloride hydrochlorides are added in above-mentioned system.0.5h is reacted under ice bath, Then reaction overnight at room temperature.After reaction terminates, it is extracted twice with 2 × 10mL 0.1M hydrochloric acid, then with 2 × 10mL's 0.1M sodium hydrate aqueous solution is extracted twice, and after 3 × 20mL washing three times, is dried with anhydrous magnesium sulfate, after filtering, is steamed Dry solvent, product N- propargyls niacinamide (referring to Fig. 2) 0.471g is obtained, it is stand-by.
2) 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 90 DEG C, adds 2.0g lithium bromide hydrotropies.Then under ice bath, 7.12g N- bromos fourth two is added Acid imide, 10.49g triphenylphosphines, react 3h at 80 DEG C.Ethanol precipitation is then used, is washed through ethanol and acetone, freeze-drying, Product bromo starch (referring to Fig. 3) 2.01g is obtained, it is stand-by.
3) preparation of nitrine starch:0.225g bromos starch is added to (referring to Fig. 3) in 15mL DMSO (dimethyl sulfoxide), so 0.16g Sodium azides are added afterwards, the lower 80 DEG C of reactions 24h of argon gas protection, then directly use ethanol precipitation, and washed with ethanol and acetone Wash, freeze-drying obtains nitrine starch (referring to Fig. 4) 0.16g, stand-by.
4) preparation of the triazole starch of niacinamide-containing base:0.187g nitrine starch is added to 10mL DMSO (referring to Fig. 4) In (dimethyl sulfoxide), 320mg N- propargyls niacinamide (referring to Fig. 2), 0.14mL triethylamine, 20mg iodate are then added It is cuprous, 12h is reacted under argon gas protection under the conditions of 80 DEG C, after reaction terminates, with acetone precipitation, is filtered, washing, vacuum refrigeration is done Dry triazole starch (referring to Fig. 5) 0.336g for obtaining niacinamide-containing base, it is stand-by.
5) preparation of the iodo-methyl triazole starch of niacinamide-containing base:Triazole starch (the ginseng of 347mg niacinamide-containing bases See Fig. 5) in 15mL DMSO (dimethyl sulfoxide), 0.187mL iodomethane is added, reacts 24h under the conditions of lower 60 DEG C of argon gas protection, After reaction terminates, with acetone precipitation, filter, washing, deionized water dialysis 36h, vacuum freeze drying obtains target product formula (1) The iodo-methyl triazole starch of shown niacinamide-containing base (referring to Fig. 6).
Embodiment 2
Difference from Example 1 is:
1) synthesis of N- propargyls niacinamide:At 0 DEG C, 0.65mL propargylamines, 1.4mL triethylamines, 24mg DMAP (4- bis- Methylamino pyridine) in 20mL dichloromethane, 1.6g nicotinoyl chloride hydrochlorides are added in above-mentioned system.0.5h is reacted under ice bath, Then reaction overnight at room temperature.After reaction terminates, it is extracted twice with 2 × 10mL 0.1M hydrochloric acid, then with 2 × 10mL's 0.1M sodium hydrate aqueous solution is extracted twice, and after 3 × 20mL washing three times, is dried with anhydrous magnesium sulfate, after filtering, is steamed Dry solvent, product N- propargyls niacinamide (referring to Fig. 2) 0.416g is obtained, it is stand-by.
2) 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 80 DEG C, adds 2.0g lithium bromide hydrotropies.Under ice bath, it is sub- to add 5.34g N- bromos succinyl Amine, 7.87g triphenylphosphines, react 3h at 70 DEG C.Ethanol precipitation is then used, is washed through ethanol and acetone, freeze-drying, is produced Thing bromo starch (referring to Fig. 3) 1.84g, it is stand-by.
3) preparation of nitrine starch:0.225g bromos starch is added to (referring to Fig. 3) in 10mL DMSO (dimethyl sulfoxide), so 0.13g Sodium azides are added afterwards, the lower 70 DEG C of reactions 24h of argon gas protection, then directly use ethanol precipitation, and washed with ethanol and acetone Wash, freeze-drying obtains nitrine starch (referring to Fig. 4) 0.14g, stand-by.
4) preparation of the triazole starch of niacinamide-containing base:0.187g nitrine starch is added to 10mL DMSO (referring to Fig. 4) In (dimethyl sulfoxide), 240mg N- propargyls niacinamide (referring to Fig. 2), 0.14mL triethylamine, 20mg iodate are then added It is cuprous, 24h is reacted under argon gas protection under the conditions of 75 DEG C, after reaction terminates, with acetone precipitation, is filtered, washing, vacuum refrigeration is done Dry triazole starch (referring to Fig. 5) 0.319g for obtaining niacinamide-containing base, it is stand-by.
5) preparation of the iodo-methyl triazole starch of niacinamide-containing base:Triazole starch (the ginseng of 347mg niacinamide-containing bases See Fig. 5) in 15mL DMSO (dimethyl sulfoxide), 0.125mL iodomethane is added, reacts 24h under the conditions of lower 60 DEG C of argon gas protection, After reaction terminates, with acetone precipitation, filter, washing, deionized water dialysis 36h, vacuum freeze drying obtains target product formula (1) The iodo-methyl triazole starch of shown niacinamide-containing base (referring to Fig. 6).
Embodiment 3
Difference from Example 1 is:
1) synthesis of N- propargyls niacinamide:At 0 DEG C, 0.65mL propargylamines, 2.8mL triethylamines, 24mg DMAP (4- bis- Methylamino pyridine) in 20mL dichloromethane, 1.78g nicotinoyl chloride hydrochlorides are added in above-mentioned system.0.5h is reacted under ice bath, Then reaction overnight at room temperature.After reaction terminates, it is extracted twice with 2 × 10mL 0.1M hydrochloric acid, then with 2 × 10mL's 0.1M sodium hydrate aqueous solution is extracted twice, and after 3 × 20mL washing three times, is dried with anhydrous magnesium sulfate, after filtering, is steamed Dry solvent, product N- propargyls niacinamide (referring to Fig. 2) 0.487g is obtained, it is stand-by.
2) 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 90 DEG C, adds 2.0g lithium bromide hydrotropies.Under ice bath, it is sub- to add 7.12g N- bromos succinyl Amine, 10.49g triphenylphosphines, react 4h at 60 DEG C.Ethanol precipitation is then used, is washed through ethanol and acetone, freeze-drying, is obtained Product bromo starch (referring to Fig. 3) 1.82g, it is stand-by.
3) preparation of nitrine starch:0.225g bromos starch is added to (referring to Fig. 3) in 10mL DMSO (dimethyl sulfoxide), so 0.2g Sodium azides are added afterwards, the lower 70 DEG C of reactions 24h of argon gas protection, then directly use ethanol precipitation, and are washed with ethanol and acetone, Freeze-drying obtains nitrine starch (referring to Fig. 4) 0.17g, stand-by.
4) preparation of the triazole starch of niacinamide-containing base:0.187g nitrine starch is added to 10mL DMSO (referring to Fig. 4) In (dimethyl sulfoxide), 320mg N- propargyls niacinamide (referring to Fig. 2), 0.14mL triethylamine, 20mg iodate are then added It is cuprous, 24h is reacted under argon gas protection under the conditions of 75 DEG C, after reaction terminates, with acetone precipitation, is filtered, washing, vacuum refrigeration is done Dry triazole starch (referring to Fig. 5) 0.325g for obtaining niacinamide-containing base, it is stand-by.
5) preparation of the iodo-methyl triazole starch of niacinamide-containing base:Triazole starch (the ginseng of 347mg niacinamide-containing bases See Fig. 5) in 15mL DMSO (dimethyl sulfoxide), 0.187mL iodomethane is added, reacts 24h under the conditions of lower 70 DEG C of argon gas protection, After reaction terminates, with acetone precipitation, filter, washing, deionized water dialysis 36h, vacuum freeze drying obtains target product formula (1) The iodo-methyl triazole starch of shown niacinamide-containing base (referring to Fig. 6).
Application examples
Suppress the measure of cucumber anthracnose and the withered plant pathogen ability of watermelon:
Determine the iodo of the niacinamide-containing base shown in formula synthesized by above-described embodiment (1) respectively using mycelial growth rate method Methyl triazole starch (contains nicotinoyl to the rejection ability of cucumber anthracnose and the withered plant pathogen of watermelon with starch due to synthesis The triazole starch of amido it is water-soluble very poor, therefore do not survey its antibacterial activity):By the iodine of the niacinamide-containing base prepared in embodiment For methyl triazole starch and experiment with after starch vacuum freeze drying to constant weight, with water as solvent, 5mg/mL sample is configured to After the product aqueous solution, 0.3mL, 1.5mL and 3mL sample solution is taken to add to the city that volume is 14.7mL, 13.5mL and 12mL respectively In the fungi culture medium sold, the culture medium that sample concentration is 0.1mg/mL, 0.5mg/mL and 1.0mg/mL is configured to.With isoconcentration Carbendazim be positive control, blank control is used as instead of sample using isometric sterilized water.Culture medium is shaken up and pours into diameter For in 9cm culture dish, after its completely solidification, a diameter of 5mm bacteria cake is inoculated with each culture dish.Cultivated at 27 DEG C After 48h to 72h, crossing method measures colony diameter, calculates the bacteriostasis rate of sample, and all experimentss are repeated once.
Bacteriostasis rate (%)=1- [(DSample-5)/(DBlank-5)]×100
The ability (%) of the suppression cucumber anthracnose of table 1, the iodo-methyl triazole starch of niacinamide-containing base and starch
The ability for suppressing the withered pathogenic bacteria of watermelon of table 2, the iodo-methyl triazole starch of niacinamide-containing base and starch (%)
Experimental result:The iodo-methyl triazole starch of niacinamide-containing base synthesized by the present invention and the suppression cucumber of starch Anthrax and the ability of withered germ of water-melon as shown in Tables 1 and 2, the present invention synthesized by niacinamide-containing base iodo-methyl triazole The bacteriostasis of starch is substantially better than starch, especially in 1.0mg/mL, the iodo-methyl triazole starch of niacinamide-containing base Bacteriostasis rate up to more than 70%.Water solubility and the iodo-methyl triazol radical of the iodo-methyl triazole starch of niacinamide-containing base Group and iodo-methyl pyridiniujm are relevant;The antibacterial activity of the iodo-methyl triazole starch of niacinamide-containing base and iodo-methyl three The groups such as nitrogen azoles, amide groups and iodo-methyl pyridiniujm are relevant, the presence of these active groups, can be greatly enhanced starch Antibacterial activity, improve the application value of starch, expand the application of starch.

Claims (9)

  1. A kind of 1. iodo-methyl triazole starch of niacinamide-containing base, it is characterised in that:The nitrogen of iodo-methyl three of niacinamide-containing base Shown in azoles starch structure formula such as formula (1),
    Wherein, average degree of polymerization n spans are 5-12000.
  2. A kind of 2. preparation method of the iodo-methyl triazole starch of the niacinamide-containing base described in claim 1, it is characterised in that: Reacted using click chemistry and the N- propargyl niacinamide synthesized with propargylamine with nicotinoyl chloride hydrochloride be linked into nitrine starch, The triazole starch of niacinamide-containing base is obtained, the iodo-methyl three of niacinamide-containing base shown in formula (1) is then obtained with iodomethane reaction Nitrogen azoles starch;Wherein, the mole of N- propargyls niacinamide is 1.5-2 times of nitrine starch.
  3. 3. the preparation method of the iodo-methyl triazole starch of the niacinamide-containing base as described in claim 2, it is characterised in that:Institute It is that propargylamine, triethylamine and DMAP is molten to state the N- propargyl niacinamide that propargylamine synthesizes with nicotinoyl chloride hydrochloride In the dichloromethane of excess, then with nicotinoyl chloride hydrochloride at 0-4 DEG C, 0.5-1h is reacted, in ambient temperature overnight after reaction, then Extracted with excessive hydrochloric acid and sodium hydrate aqueous solution, then dried through anhydrous magnesium sulfate respectively, filtered, evaporate, that is, obtain N- alkynes Propyl group niacinamide;Wherein, propargylamine, triethylamine and DMAP mole ratio are 1:1-2:0.1-0.2;Propargylamine with The mole ratio of nicotinoyl chloride hydrochloride is 1:0.9-1.0.
  4. 4. the preparation method of the iodo-methyl triazole starch of the niacinamide-containing base as described in claim 2, it is characterised in that:Institute It is to react to obtain bromo starch by starch and N- bromo-succinimides and triphenylphosphine to state nitrine starch, and gained bromo starch is again Nitrine starch is reacted to obtain with Sodium azide;Wherein, the mole of N- bromo-succinimides and triphenylphosphine is respectively the 3-4 of starch Times;The mole of Sodium azide is 2-3 times of bromo starch.
  5. 5. the preparation method of the iodo-methyl triazole starch of the niacinamide-containing base as described in claim 4, it is characterised in that:Institute It is that in the DMF of excess at 120-130 DEG C starch is activated into 1-2h to state bromo starch, then cools to 80-90 DEG C, adds Mole is the lithium bromide hydrotropy of 2-3 times of starch, then under ice bath, adds N- bromo-succinimides and triphenylphosphine, 70-80 DEG C of reaction 3-4h, then with ethanol precipitation, then washed successively through ethanol, acetone, freeze-drying, that is, obtain bromo starch.
  6. 6. the preparation method of the iodo-methyl triazole starch of the niacinamide-containing base as described in claim 4, it is characterised in that:Institute State bromo starch and react 18-24h at 70-80 DEG C with Sodium azide, then directly use ethanol precipitation, then washed successively through ethanol, acetone Wash, be freeze-dried, that is, it is stand-by to obtain nitrine starch.
  7. 7. the preparation method of the iodo-methyl triazole starch of the niacinamide-containing base as described in claim 2, it is characterised in that:Institute The nitrine starch stated and N- propargyls niacinamide with the triethylamine of 1-2 times of nitrine starch mole and with nitrine starch mole Under 0.1-0.2 times of cuprous iodide catalysis, 12-24h is reacted at 75-80 DEG C, is washed through acetone precipitation, then through acetone, freezing is dry It is dry, that is, obtain the triazole starch of niacinamide-containing base.
  8. 8. the preparation method of the iodo-methyl triazole starch of the niacinamide-containing base as described in claim 2, it is characterised in that:Institute The triazole starch for the niacinamide-containing base stated reacts 12-24h with iodomethane at 60-70 DEG C, and through acetone precipitation, sediment is re-dissolved in Distilled water, the interior distilled water dialysis 36-48h of bag filter is then placed in, then niacinamide-containing base shown in formula (1) is obtained after being freeze-dried Iodo-methyl triazole starch.
  9. A kind of 9. application of the iodo-methyl triazole starch of the niacinamide-containing base described in claim 1, it is characterised in that:It is described Application of the iodo-methyl triazole starch of niacinamide-containing base in restraining epiphyte preparation is prepared shown in formula (1).
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