CN1939128A

CN1939128A - Agricultural bacteriocide-P3rimorph

Info

Publication number: CN1939128A
Application number: CN 200610081550
Authority: CN
Inventors: 覃兆海; 慕长炜; 李楠; 付滨; 张曙生; 肖玉梅
Original assignee: China Agricultural University
Current assignee: China Agricultural University
Priority date: 2005-09-27
Filing date: 2006-05-26
Publication date: 2007-04-04

Abstract

A novel agricultural bactericide Pyrimorph with excellent preventing effect to the late blight of tomato, the frosty mildew of cucumber, the blight of hot pepper, etc, its structural formula, its product and its agricultural application are disclosed. Its preparing process includes such steps as proportionally mixing compound A with surfactant and other assistants, and grinding to obtain 20% suspension.

Description

Pyrrole morpholine (Pyrimorph)---a kind of new disinfectant use in agriculture

The application of disinfectant use in agriculture is that the protection crops avoid the pathogen infringement, improve one of important measures of crop quality and output.The aryl cinnamide compound is the compound that suppresses the phytopathogen growth activity that has of a quasi-tradition, though also there are shortcomings such as activity is not high enough, fungicidal spectrum is narrow in more existing commercialization kinds.In research process to this compounds, we are by introducing pyridine heterocycle, found that a class has the compound 4-[3-(pyridin-4-yl) of high bactericidal activity-3-substituted-phenyl acryloyl] morpholine, we have further developed pyrrole morpholine (Pyrimorph, 1) on this basis.Its structural formula is:

It is synthetic to be to be initiation material with the isonicotinic acid, obtains by series reaction such as oxidation, the replacement of parent's electricity, Fu-Ke acyl groupization and Wittig-Horner.Synthetic route is as follows:

Compound 1 becomes 20% suspending agent through processing and preparing.

1 pair of phytopathogen such as tomato late blight, cucumber downy mildew, damping off and capsicum epidemic disease of compound has excellent preventive effect.

The present invention can be described further with following example, but the present invention is not limited only to these examples.

The preparation of example 1.N-oxidation isonicotinic acid

0.7mol (86.1g) isonicotinic acid is placed the 500ml three-necked bottle, the aqueous solution that adding is made into by 2.87g sodium tungstate and 200ml water, under mechanical agitation, drip 30% hydrogen peroxide 120ml in the flask, temperature maintenance is at 90-95 ℃, stoichiometric number hour all becomes acicular crystal to reacting solid, while hot reactant liquor is poured out cooling back suction filtration, washing, drying, get white needle-like crystals, yield 90%.mp：272-274℃。

The preparation of the different nicotinoyl chlorine of example 2.2-chlorine

In the 1000mL three-neck flask, add 107.5gN-oxidation isonicotinic acid and 350mLPOCl ₃, add 350gPCl under stirring in batches ₅, adding back backflow 3h, normal pressure steams most of POCl ₃, after carry out decompression distillation, collect the cut of 115-120 ℃/30-40mmHg, be product, yield 75%.

Synthesizing of example 3.2-chlorine 4-(4-tert-butyl benzene formoxyl) pyridine (2)

At 10L mechanical agitator, thermometer are housed, add the anhydrous AlCl of 900g in the four neck flasks of the condenser pipe of returning (adding drying tube) and dropping funel ₃With the 2L tert-butyl benzene, ice bath is cooled to and drips the different nicotinoyl chlorine of 985g under the 5-10 ℃ of stirring, adds the back and continues reaction 10h down at 10 ℃, pour into then in the solution of 2L concentrated hydrochloric acid and 10L frozen water, fully stir the back separatory, the water chloroform extraction merges organic facies, washing, drying, normal pressure reclaim solvent, residue with benzinum be recrystallized white solid, mp46-47 ℃, yield 71.8%.

The preparation of example 4. chloracetyl morpholines

In being furnished with the 1000mL three-necked bottle of mechanical stirring device, add the 52g morpholine, 61g triethylamine and 200mL toluene, cryosel is bathed and is cooled to below 0 ℃, stirs down and drips the toluene solution that 200mL contains the 78g chloracetyl chloride, dropwises recession deicing salt bath, react about 10h down at 10-15 ℃, remove by filter precipitation, use toluene wash, mother liquor is sloughed decompression distillation behind the toluene, collect 148-154 ℃/10mmHg cut 85g, yield 87%.

The preparation of example 5. phosphinothricin acetyl morpholines (3)

Add the 100g triethyl phosphite in being furnished with the 500mL three-necked bottle of distilling apparatus, logical nitrogen protection is heated to 160 ℃; drip 93.5g chloracetyl morpholine under stirring, approximately need 3 hours, add the back and continue under this temperature, to react 3-4 hour; obtain yellow dope 135g, yield 89%.

The preparation of example 6. target compounds (1)

Be furnished with at 2000mL and add 300g phosphinothricin acetyl morpholine in the three-neck flask of mechanical agitator; 33g2-chlorine 4-(4-tert-butyl benzene formoxyl) pyridine and 1L dioxanes; ice bath is cooled to below 5 ℃; the NaH that in batches adds 65g70%; approximately 3h adds, during the reactant liquor pulverize red and have solid to produce.Add the recession deicing and bathe, continue reaction 3-4 hour down at 10-15 ℃, decompression removes dioxanes then, and residue adds low amounts of water and stirs, solidify after a period of time, filter, with the low amounts of water washing, dry back is recrystallized with absolute ethyl alcohol, object 300g, mp129～131 ℃, yield 81%.

Elementary analysis:

Theoretical value: C 68.65%H 6.55%Cl 9.21%N 7.28%

Measured value: C 68.35%H 6.52%Cl 9.18%N 7.08%

¹H NMR(300MHz，CDCl ₃，δ)：1.34(s，9H，C(CH ₃) ₃)，3.43(s，4H，O(CH2-)2)，3.58(d，4H，N(CH ₂-) ₂)，6.50(s，1H，C＝CH)，7.13～7.18(m，3H，2Ar-H，Py-H)，7.24(dd，1H，Py-H)，7.36～7.39(m，2H，Ar-H)，8.40(dd，1H，Py-H)

ESI-MS：m/z385.3(100，M ⁺+1)

IR (KBr compressing tablet) (cm ^-1): 2910,2780,1950,1625,1524,1443,1370,1266,1200,1103,821

The preparation of example 7.20% pyrrole morpholine suspending agent

The former medicinal high speed Universalpulverizer of pyrrole morpholine is pulverized, crossed 100 mesh sieves, mix with auxiliary agent by following mass ratio: pyrrole morpholine 20%, No. 0203 surfactant 3%, sodium lignin sulfonate 3%, xanthans 0.15%, bentonite 3%, paraformaldehyde 0.3%, water 70.55%.With its with bead (diameter 3mm) join be ground to particle diameter in the sand mill and be 2～3mm till.

The test of example 8. pyrrole morpholine bactericidal activities

1. indoor activity

Table 1. pyrrole morpholine is to the Toxicity Determination of part frequently seen plants disease

Bacterial classification	ZNQ-0317 EC ₅₀(μg/ml)	Dimethomorph EC ₅₀(μg/ml)	Tpn EC ₅₀(μg/ml)	Carbendazim EC ₅₀(μg/ml)
Bacterial classification	ZNQ-0317 EC ₅₀(μg/ml)	Dimethomorph EC ₅₀(μg/ml)	Tpn EC ₅₀(μg/ml)	Carbendazim EC ₅₀(μg/ml)	The botrytis cinerea cucumber anthrax tomato vertical withered Jue Shi epidemic disease mould Rhizoctonia solani Kuhn cucumber samping off cause of disease melon grey mold cause of disease cucumber anthracnose cause of disease Asparagus Stem Blight ring rot of apple rice sheath blight disease cotton droop cotton verticillium wilt tomato late blight cucumber downy mildew of the withered tomato leaf mold of cucumber of dampinging off	49.19 58.4 56.1 74.9 55.6 4.07 0.08 0.87 26.95 10.10 35.74 18.38 44.60 28.81 26.83 19.23 0.06 5.98	128.13 184.91 139.44 274.13 104.3 109.2 60.95 86.47 80.05 56.93 110.60 96.55 50.95 103.94 66.94 0.13 5.66	20.39	1.54

2. field activity

20% pyrrole morpholine soup is added gauge water be diluted to desired concn, adopt the foliage-spray method, spray once, spray altogether 4 times, spray for the last time behind the medicine and to carry out state of an illness investigation in 10 days, calculate disease leaf rate, disease index and control efficiency every 1 week.Control efficiency adopts new multiple differential test to carry out statistical analysis.

Table 2. pyrrole morpholine is to the field test results of tomato late blight

Dosage (mL)	Effective dose (g/ mu)	Repeat	Preventive effect (%)	Average preventive effect (%)
Dosage (mL)	Effective dose (g/ mu)	Repeat	Preventive effect (%)	Average preventive effect (%)	75 100 150	15 20 30	I II III IV I II III IV I II III IV	76.1 79.3 77.9 72.3 89.1 93.5 95.6 96.3 94.7 90.9 88.6 100	76.40 93.70 93.55

Table 3. pyrrole morpholine is to the field test results of cucumber downy mildew

Dosage (mL)	Effective dose (g/ mu)	Repeat	Preventive effect (%)	Average preventive effect (%)
Dosage (mL)	Effective dose (g/ mu)	Repeat	Preventive effect (%)	Average preventive effect (%)	75 100 150	15 20 30	I II III I II III I II III	81.92 78.76 75.34 85.09 88.92 81.32 95.85 90.52 90.58	78.67 85.11 92.31

Table 4. pyrrole morpholine is to the field test results of capsicum epidemic disease

Dosage (mL)	Effective dose (g/ mu)	Control time	Inhibiting rate (%)
Dosage (mL)	Effective dose (g/ mu)	Control time	Inhibiting rate (%)	73 100	15 20	Behind the medicine behind 14 days medicines behind 21 days medicines behind 28 days medicines behind 35 days medicines behind 14 days medicines behind 21 days medicines behind 28 days medicines 35 days	42.31 53.51 57.01 60.75 62.74 68.93 73.29 74.09

125 150

25 30

Behind the medicine behind 14 days medicines behind 21 days medicines behind 28 days medicines behind 35 days medicines behind 14 days medicines behind 21 days medicines behind 28 days medicines 35 days

71.20 69.12 78.62 71.27 71.08 69.21 78.62 71.27

Claims

1. pyrrole morpholine (Pyrimorph)---a kind of compound with excellent bactericidal activity, its structural formula is:

2. the synthetic method of compound shown in the claim 1, its synthetic method is:

3. but preparation such as the missible oil prepared of compound shown in the claim 1, suspending agent wet-milling.

4. compound shown in the claim 1 and be the application of the preparation made of active component or mixture as disinfectant use in agriculture with it.