CN1348692A - Hymexazol and its water phase synthesis process - Google Patents
Hymexazol and its water phase synthesis process Download PDFInfo
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- CN1348692A CN1348692A CN 01128145 CN01128145A CN1348692A CN 1348692 A CN1348692 A CN 1348692A CN 01128145 CN01128145 CN 01128145 CN 01128145 A CN01128145 A CN 01128145A CN 1348692 A CN1348692 A CN 1348692A
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- hymexazol
- medicine
- azanol
- pulvis
- water phase
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Abstract
The present invention discloses hymexazol crude drug and its water phase synthesis method, the raw materials used include: 99% azanol sulfate azanol hydrochloride; 99% methyl acetoactate or ethyl acetoacetate; 30% NaOH solution; 31% hydrochloric acid; 99% chloroform; azanol sulfate or azanol hydrochlorie is passed through synthesis, ring-closing, acidifying, extraction, desolvent, centrifuging, kiln drying to obtain hymexazol crude drug with effective component content 95-98%, the invented hymexazol crude drug is a high effect, low toxicity, residue less soil bactericidal mainly used for preventing and treating paddy damping-off, soil infected diseases of vegetable and other crops. The water phase synthesis method is low in cost, safe and reliable and high in yield.
Description
Technical field
The present invention relates to a kind of pesticide chemical technical field, be specifically related to a kind of disinfectant use in agriculture.
Background technology
The soil germ is big an obstacle, the particularly rice seedling blight road blocking tiger of the early stage seedling-cultivation technique of paddy rice especially that influences the crops healthy growth always for a long time.
Dislike mould spirit and be the soil fungicides of a kind of efficient, low toxicity, noresidue, has stronger interior absorption, lasting medicine, no poisoning, pollution-free, be mainly used in the control rice seedling blight, the soil-borne disease fungus damage of vegetables and other crop all has remarkable result to damping off, seedling rot, anthracnose, stalk break, root rot etc.
At present, hymexazol medicine synthetic route has four:
1, after the reaction of sodium methyl-acetylide and ethyl chloroformate, azanol aminolysis, closed loop;
2, ethyl acetoacetate and Pcl
sAfter the reaction, with azanol reaction, closed loop;
3, ethyl acetoacetate spent glycol protection back and hydroxylamine hydrochloride reaction, closed loop;
4, diketene and azanol reaction, closed loop.
Route 1 technology is complicated, and cost is higher, and yield is low; Route 2 synthesis cycles are longer, and consumption of raw materials is bigger, and reaction requires temperature lower, are difficult to realize; Route 3 complex process, it is more to participate in reaction raw materials, and cost is higher; Route 4 yields are higher, and reaction condition is relatively gentleer, but the transportation of diketene, storage and instructions for use are anhydrous, thereby inconvenient.
Summary of the invention
The object of the present invention is to provide a kind of hymexazol medicine and aqueous synthesis method thereof, this former medicine not only has the sterilizing disease-preventing effect to multiple kinds of crops, but also has functions such as plant growth regulation and resistance, this technology advanced person, be easy to realize that consumption of raw materials is less, be easy to obtain.
Technical scheme of the present invention is:
The raw material composition is respectively: (in 1 ton of hymexazol medicine of every production)
99% HAS or hydroxylamine hydrochloride 1.5-3.5T;
99% methyl acetoacetate or ethyl acetoacetate 3-3.5T;
30%NaOH solution 3-7T;
31% hydrochloric acid 12-22T;
99% chloroform 2-4T;
Hymexazol medicine production method is:
A, synthetic, closed loop
Earlier with HAS or the dissolving of hydroxylamine hydrochloride water, stirring is cooled to+5 ℃～-5 ℃ between, add alkali NaOH neutralization, transfer between PH=8.0～10.0, drip methyl acetoacetate or acetyl triethyl, pH value be controlled between 8.0～10.0 all the time, temperature is controlled at+5 ℃～-5 ℃ between, after dripping methyl acetoacetate or ethyl acetoacetate, reacted 90 minutes.
B, acidifying
With the reactant liquor acidifying, insulation reaction is 4 hours between 60～70 ℃ with technical hydrochloric acid.
C, extraction
With chloroform extraction 8～10 times.
D, precipitation
Will be whole extracts add in the precipitation stills and add thermal distillation, recycle after solvent is deviate from, will dislike mould clever solution at last and emit, cool off.
E, centrifugal, the oven dry, the packing
The hymexazol medicine that crystallisation by cooling is gone out is centrifugal and will dislike mould former medicine and send into the drying chamber oven dry.Check content back up to standard packing.
The advantage that mould spirit is disliked in aqueous phase synthesis method production of the present invention is:
1, this method production hymexazol medicine effective content reaches 95～98%, and cost is lower;
2, this method production hymexazol medicine is low-temp low-pressure production, and is not only safe and reliable, and yield exceeds 10～20% than additive method;
3, this method production hymexazol medicine has been discarded traditional dichloroethane solvent, and first adopts chloroform precipitation, improves yield greatly.
4, field trial shows, the bactericide of hymexazol medicine preparation of the present invention shows very strong antibacterial activity in soil, can promote the increase of the tillering of crops root, root hair again, to prevent the physiological disorder disease, improve the inherent quality of rice shoot and the survival rate after the transplanting, have the double action of sterilization, promotion seedling growth.
Be primary raw material with the hymexazol medicine below, preparation is disliked. the report of first pulvis control rice seedling damping off field control effectiveness test.
One, test controlling object
The rice seedling damping off
Two, test medicine
1,3.0% dislike. the first pulvis, 90% dislikes mould clever powder, and Heilongjiang Qida Pesticide Development Co., Ltd. provides.
2,25% metalaxyl pulvis, Wen Zhou Lucheng City insecticide factory produces, and market is bought.
Three, experimental scheme
Test is established 7 processing altogether and is respectively:
1,3.0% dislike. first pulvis 21.5 grams/square metre;
2,3.0% dislike. first pulvis 25.0 grams/square metre;
3,3.0% dislike. first pulvis 28.0 grams/square metre;
4,3.0% dislike. first pulvis 31.5 grams/square metre;
5,90% dislike mould clever powder 1.5 grams/square metre;
6,25% metalaxyl pulvis 0.9 gram/square metre;
7, not dispenser contrast.
Test each and handle repetition 4 times, amount to 24 sub-districts, 1.1 square metres of each sub-district areas adopt district's group arrangement at random.
Four, test basic condition
1, condition experimental field
Experimental field be located at the Shangzhi City seed multiplication farm, soil property is a white muddy soil, P in soil H6.5, and the content of organic matter 4% is tested the bed of growing seedlings and is dropped in the rice on honda.
2, rice varieties experimental field: experimental field the rice varieties of planting be No. 2, pine stalk.
3, dispenser, sowing and management: tested April 9 and soak seed, dragging for seed on April 17, made bed on April 19, dislike. the first pulvis is handled when broadcasting the previous crops bed, admix 25 kilograms in the dry land soil of local PH6.5 equably by design quantity, sieve after mixing be sprinkling upon equably for the examination respectively handle on the seedbed, sub-district, thickness is about 2.5cm, after shakeout, water the water of revealing the exact details, kind of an earthing is pressed in sowing; Dislike mould spirit, metalaxyl is handled medicament and is used 3 kilograms of square metre spouting liquids in conjunction with watering the end during water.Experimental field sowing on April 20, the every square meter amount of broadcasting 350-400 gram is broadcast the back earthing, adopts little shed seedling, broadcasts the back Routine Management.
Five, investigation method:
1, efficacy survey
Investigate the living situation that each handles the sub-district damping off in test region damping off occurance peak (mid-May), method accounts for the percentage of the test region gross area for the onset area of each sub-district damping off of investigation.
2, security survey: record seedling-growing time when emerging, investigation emergence rate when seedling all sprouts substantially, and record rice growth situation, each treatment region is got 40 strain rice seedlings at random before seedling, indexs such as investigation plant height, leaf make, hundred strain fresh weights, leaf look, band tiller rate, pilot survey the results are shown in Table one.
Six, test results and analysis
By table one as seen, to dislike. first pulvis 21.5 gram/square meters, 25.0 gram/square meters, 28.0 gram/square meters, 31.5 gram/square meters, the mould clever 1.5 gram/square meters of evil, metalaxyl 0.90 gram/square meter are handled the rice seedling blight control efficiency are respectively 84.5%, 90.7%, 94.2%, 98.0%, 92.8%, dislike. and the preventive effect that the first pulvis is respectively handled the rot that opposes all reaches more than 84%.
Variance comparative result to the germ rate of getting a haircut everywhere, each chemicals treatment district is with the applying area comparing difference is not remarkable, to dislike. first pulvis 21.5 gram/square meters are handled with 31.5 gram/square meters and are handled significant difference, and it is not remarkable that 25.0 gram/square meters and 31.5 gram/square meters are handled comparing difference.
To observe after the dispenser, dislike. each treatment region rice seedling seeding stage unanimity of first pulvis, emergence rate be more than 90%, and with applying area no significant difference not, the back rice growth of emerging is normal, and the leaf look is green, no poisoning generation; The preceding measurement result of rice transplanting to each treatment region rice seedling quality, wherein dislike indexs such as first pulvis processing rice seedling plant height, hundred strain fresh weights and all be better than not applying area, wherein plant height compares not applying area increase 69.3%-87.9%, hundred strain fresh weights ratio not applying area increases 64.9%-84.0%, and evil is described. and the first pulvis is to rice growth safety.
Seven, conclusion:
Test shows that 3.0% dislikes. the first pulvis has preventive effect preferably to the rice seedling damping off under test dose, rice growth is had no adverse effects.Comprehensive preventive effect and rice shoot growing way to damping off, suggestion 3.0% is disliked. and the consumption of first pulvis is a 21.5-25.0 gram/square meter, evenly admixes dry land soil 25-30 kilogram when paddy rice is broadcast the previous crops bed, and sieving after mixing is sprinkling upon on the 1 square meter seedbed equably, shakeout, spray reveal the exact details water, sowing, pressure kind, earthing.Table one 3.0% is disliked. the investigation of first pulvis control rice seedling damping off test effect
Annotate: control efficiency=[(check plot diseased plant rate-treatment region diseased plant rate)/check plot diseased plant rate] * 100%
| Project is handled | Damping off a situation arises the investigation | Average attack rate % | Significantly than .01 | Control efficiency % | Investigation when emerging | The seedling quality investigation | ||||||||||||
| Repeat 1 district | Repeat 2 districts | Repeat 3 districts | Repeat 4 districts | Seedling-growing time | Emergence rate % | Have or not poisoning | The leaf order | Plant height % | Comparison is according to increasing % | Hundred strain fresh weight g/ strains | Comparison is according to increasing % | The leaf look | The root look | Band tiller rate % | ||||
| Incidence of disease % | Incidence of disease % | Incidence of disease % | Incidence of disease % | |||||||||||||||
| 3.0% dislikes. first pulvis 21.5 gram/square meters | 2.01 | ??1.78 | ??2.76 | ??2.45 | ??2.25 | ??B | ??84.5 | ??4.27 | ??92.4 | Do not have | ??3.1 | ??17.1 | ??87.9 | ??16.0 | ??70.2 | Green | White | ??0.0 |
| 3.0% dislikes. first pulvis 2 5.0 gram/square meters | 1.27 | ??1.60 | ??1.41 | ??1.12 | ??1.35 | ??BC | ??90.7 | ??4.27 | ??94.5 | Do not have | ??3.3 | ??16.4 | ??80.2 | ??17.2 | ??83.0 | Green | White | ??0.0 |
| 3.0% dislikes. first pulvis 28.0 gram/square meters | 0.90 | ??1.24 | ??0.57 | ??0.69 | ??0.85 | ??BC | ??94.2 | ??4.27 | ??97.4 | Do not have | ??3.2 | ??18.6 | ??69.3 | ??17.3 | ??84.0 | Green | White | ??0.0 |
| 3.0% dislikes. first pulvis 31.5 gram/square meters | 0.35 | ??0.21 | ??0.00 | ??0.96 | ??0.38 | ??C | ??97.4 | ??4.27 | ??96.5 | Do not have | ??3.6 | ??16.6 | ??82.4 | ??15.5 | ??64.9 | Green | White | ??0.0 |
| 90% dislikes mould clever pulvis 1.5 gram/square meters | 0.00 | ??0.64 | ??0.18 | ??0.34 | ??0.29 | ??C | ??98.0 | ??4.27 | ??91.0 | Do not have | ??2.8 | ??10.2 | ??12.1 | ??10.1 | ??7.4 | Yellowish green | White | ??0.0 |
| 25% dislikes. first pulvis 0.90 gram/square meter | 1.28 | ??0.77 | ??1.12 | ??1.03 | ??1.05 | ??BC | ??92.8 | ??4.27 | ??94.4 | Do not have | ??2.7 | ??10.3 | ??13.2 | ??9.4 | ??0.0 | Yellowish green | White | ??0.0 |
| Not dispenser contrast | 11.3 | ??15.9 | ??13.2 | ??17.6 | ??14.5 | ??A | ??4.27 | ??93.1 | Do not have | ??3.0 | ??9.1 | ??9.4 | Yellowish green | White | ??0.0 | |||
Claims (2)
1, a kind of hymexazol medicine is characterized in that: the raw material composition is respectively: (in 1 ton of hymexazol medicine of every production)
99% HAS or hydroxylamine hydrochloride 1.5-3.5T;
99% methyl acetoacetate or ethyl acetoacetate 3-3.5T;
30%NaOH solution 3-7T;
31% hydrochloric acid 12-22T;
99% chloroform 2-4T;
HAS or hydroxylamine hydrochloride through synthetic, closed loop, acidifying, extraction, precipitation, centrifugal, oven dry, are produced effective content and are 95～98% hymexazol medicine.
2, a kind of hymexazol liquid medicine is combined to method, it is characterized in that: earlier with HAS or the dissolving of hydroxylamine hydrochloride water, stir be cooled to+5 ℃～-5 ℃ between, add alkali NaOH neutralization, drip methyl acetoacetate or acetyl triethyl, reacted 90 minutes; With the reactant liquor acidifying, insulation reaction is 4 hours between 60～70 ℃ with technical hydrochloric acid; With chloroform extraction 8～10 times; Will be whole extracts add in the precipitation stills and add thermal distillation, recycle after solvent is deviate from, will dislike mould clever solution at last and emit, cool off; The hymexazol medicine that crystallisation by cooling is gone out is centrifugal and will dislike mould former medicine oven dry, check content back up to standard packing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011281456A CN1151721C (en) | 2001-09-05 | 2001-09-05 | Hymexazol and its water phase synthesis process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011281456A CN1151721C (en) | 2001-09-05 | 2001-09-05 | Hymexazol and its water phase synthesis process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1348692A true CN1348692A (en) | 2002-05-15 |
| CN1151721C CN1151721C (en) | 2004-06-02 |
Family
ID=4668030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011281456A Expired - Lifetime CN1151721C (en) | 2001-09-05 | 2001-09-05 | Hymexazol and its water phase synthesis process |
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| Country | Link |
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| CN (1) | CN1151721C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516189A (en) * | 2011-12-06 | 2012-06-27 | 西北农林科技大学 | Oxazole organic copper compound, and preparation method and preparation thereof and purpose thereof in control of agricultural plant disease |
| CN104920433A (en) * | 2015-06-08 | 2015-09-23 | 柳州市天姿园艺有限公司 | Composition used for controlling cymbidium kanran makino anthracnose |
| CN104920385A (en) * | 2015-06-08 | 2015-09-23 | 柳州市天姿园艺有限公司 | Composition for controlling anthracnose of gladiolus |
| CN104938501A (en) * | 2015-06-09 | 2015-09-30 | 柳州市天姿园艺有限公司 | Composition for preventing and controlling anthracnose of cymbidium sinensis |
| CN106316974A (en) * | 2016-08-23 | 2017-01-11 | 潍坊华诺生物科技有限公司 | Production process of hymexazol technical material |
| CN106946809A (en) * | 2017-03-22 | 2017-07-14 | 京博农化科技股份有限公司 | A kind of hymexazol synthetic method |
-
2001
- 2001-09-05 CN CNB011281456A patent/CN1151721C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516189A (en) * | 2011-12-06 | 2012-06-27 | 西北农林科技大学 | Oxazole organic copper compound, and preparation method and preparation thereof and purpose thereof in control of agricultural plant disease |
| CN102516189B (en) * | 2011-12-06 | 2014-04-09 | 西北农林科技大学 | Oxazole organic copper compound, and preparation method and preparation thereof and purpose thereof in control of agricultural plant disease |
| CN104920433A (en) * | 2015-06-08 | 2015-09-23 | 柳州市天姿园艺有限公司 | Composition used for controlling cymbidium kanran makino anthracnose |
| CN104920385A (en) * | 2015-06-08 | 2015-09-23 | 柳州市天姿园艺有限公司 | Composition for controlling anthracnose of gladiolus |
| CN104938501A (en) * | 2015-06-09 | 2015-09-30 | 柳州市天姿园艺有限公司 | Composition for preventing and controlling anthracnose of cymbidium sinensis |
| CN106316974A (en) * | 2016-08-23 | 2017-01-11 | 潍坊华诺生物科技有限公司 | Production process of hymexazol technical material |
| CN106946809A (en) * | 2017-03-22 | 2017-07-14 | 京博农化科技股份有限公司 | A kind of hymexazol synthetic method |
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| Publication number | Publication date |
|---|---|
| CN1151721C (en) | 2004-06-02 |
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Effective date of registration: 20180806 Address after: 100095 1, 102, 4 building, 1 High Court Road, Haidian District, Beijing. Patentee after: Beijing Beinong Luheng Sci-Tech Development Co., Ltd. Address before: 152000 288 Sui Lan Road, Suihua, Heilongjiang Patentee before: Heilongjiang Qida Pesticide Development Co., Ltd. |
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Effective date of registration: 20200716 Address after: 061000 east of Jingsi road and south of Huahua Avenue, Lingang Chemical Industrial Park, Cangzhou City, Hebei Province Patentee after: Cangzhou lanrun biopharmaceutical Co.,Ltd. Address before: 100095, No. 1, building 4, building 1, Gao Li Lu, Beijing, Haidian District, 102 Patentee before: Beijing Beinong Luheng Sci-Tech Development Co.,Ltd. |
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Granted publication date: 20040602 |
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