CN1124621A - Wettable powder of niclosamide salt - Google Patents
Wettable powder of niclosamide salt Download PDFInfo
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- CN1124621A CN1124621A CN 94112267 CN94112267A CN1124621A CN 1124621 A CN1124621 A CN 1124621A CN 94112267 CN94112267 CN 94112267 CN 94112267 A CN94112267 A CN 94112267A CN 1124621 A CN1124621 A CN 1124621A
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- wettable powder
- clonitrilide
- niclosamide
- water
- carboxymethyl cellulose
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Abstract
The wettable powder made of chloronitro-salamino ethanolamine salt, sodium laurylsulphate and carboxy-methylcellulose for killing amphibious oncomelania (an intermediate host of blood fluke) features high suspension nature and long sustained period.
Description
The present invention relates to compound formulas, relate to snail control with drugs specifically.
Snail control with drugs be the blocking-up schistosomicide propagation by way of, prevent one of effective measures of schistosomiasis infection, searching is gone out the medicine of spiral shell at first by a large amount of chemical compound of screening test, found that therefrom many chemical substances have the effect of spiral shell extremely, but because various factors makes that its overwhelming majority fails to be promoted application.The sixties from the beginning of, chemists have carried out a large amount of research to niclosamide, find that it has significant killing action to oncomelania, and extremely low to the toxicity of mammal, to the person poultry harmless, to all nonhazardous effects such as crops and other plant, in earth, there is not savings.From its effect, toxicity, it is a comparatively ideal molluscicide, but because its chemical constitution determines, niclosamide itself is water insoluble, directly apply to that extremely spiral shell is very undesirable, influenced its positive role greatly, scientists is made amine salt to niclosamide, make its wettable powder again, form a kind of water dispersant, make it can suspend in water equably to spray with soaking and kill spiral shell and use, but it is very low to make the wettable powder suspendability, and the particle requirement of powder is crushed to less than 75 μ m, its suspensibility then reached the sinking principal agent and is no more than 50% in 0.5 hour.And homemade niclosamide 50% paste of China is called Niclosamide, but it very easily dewaters and condense into lump, can not use.External oncomelania; the two umbilicus spiral shells of example, lamnaeid, ramshorn, vesicle spiral shell etc. all inhabit water body and do not inhabit land; and the oncomelania hupensis of China unique propagation Schistosoma japonicum; it both can inhabit water body; can inhabit land again; as careless beach, phragmites communis beach, foot of the hill grove ground; ground such as barren hillside; the volution border of going out is very complicated, the extensive or large tracts of land of the basic unit spiral shell that goes out, generally from preparating liquid to spraying the time that finishes; substantially exceed 0.5 hour; press practical situation, the requirement of suspensibility will be kept within 4-8 hour at least, and the principal agent of sinking can not surpass 50%.
Therefore, at present the spiral shell preparation that goes out used of home and abroad has very big shortcoming, can not bring into play better snail killing function effectively and guarantee the go out quality of spiral shell work of the extensive or large tracts of land of basic unit, can influence the schistosomicide radical cure work of China.
Purpose of the present invention; be to utilize the significant snail killing function of niclosamide; and the advantage that has no side effect; overcome its water-fast shortcoming; it is good to be mixed with a kind of suspensibility; the long wettable powder of holding time makes it can more effective performance snail killing function, the quality that guarantees to go out the extensive or large tracts of land of basic unit spiral shell five does.
Characteristics of the present invention, be to utilize an end possess hydrophilic property group, the other end has the chemical compound of hydrophobic group as the preparation foundation of uphanging the buoyancy wettable powder, select for use the suspending agent and 50% Clonitrilide of good water solubility to be mixed with wettable powder again, it makes through the following steps:
The preparation of niclosamide: with 5-chloro-salicylic acid and 2-chloro-4-nitroaniline, press etc. gram-molecular weight mixed after, in benzene or toluene solution, reflux, drip the phosphorous oxychloride (or Phosphorous chloride .) of amount of calculation, after dropwising, backflow 4-6 hour, the collecting precipitation thing, ethyl alcohol recrystallization gets light yellow crystalline powder.Mp229-232 ℃ (document: Brit.pat., 284,345,1959).
The preparation of Clonitrilide: with above-mentioned niclosamide and ethanolamine in alcoholic solution after the warm-heat effect, the leaching precipitation, behind the recrystallization orange colour acicular crystal, mp219-222 ℃, be insoluble in water (document: Ger, 1,126,374.1962).
Sodium lauryl sulphate (Sodicm Laurysulfate SDS) experiment reagent, total alcohol amount＞55%, dissolubility and basicity are all qualified, and this product is white powder or crystallization, and m.p is about, and 180 ℃ of branches are situated between, and are dissolved in H
2O is slightly soluble in alcohol, and it is used as wetting agent this experiment, buys from the market.
Sodium carboxymethyl cellulose (Sodium Carboxy Methyl Cellulose) or title carboxymethyl cellulose.This product is a white powder, and is tasteless, harmless, and aqueous solution is neutrality or alkalescence has good dispersion force and adhesion, is used as strong emulsifying agent, and market is buied, and conforms to homemade commercially available specification, this experiment it as diluent or suspending agent, specifically be formulated as follows:
Clonitrilide 50%
Sodium lauryl sulphate 2%-30%
Sodium carboxymethyl cellulose 48%-20% mixes with sodium lauryl sulphate Clonitrilide by different proportion, it is evenly mixed to aequum to add carboxymethyl cellulose again, in dismembyator, grind evenly, be and make Clonitrilide 50% wettable powder.
Containing Clonitrilide in Clonitrilide 50% wettable powder is 50 ± 2.5%, get above-mentioned wettable powder an amount of (being equivalent to Clonitrilide 0.5g approximately), add water 50ml, stir and make molten Jie as far as possible, filter, filtrate is evaporated to dried in water-bath, get residue, residue carries out organic destruction according to oxygen flask combustion (Chinese Pharmacopoeia 1990 editions, 38 pages of appendix), get residue 100mg and add every liter of solution 10ml that contains 1 mole hydrochloride, add zinc powder 0.2g,, put cold heating in water bath 10 minutes, filter, in filtrate, add 1% sodium nitrite liquid 1mg, placed 10 minutes, add 2% Ammonium sulfamate liquid 4ml, shake up, placed 10 minutes, add 0.5%N-naphthodiamide dihydrochloride liquid 4ml, promptly show peony.
Suspensibility is measured the accurate this product an amount of (being equivalent to Clonitrilide 0.25g) crossed through thermal stabilization treatment that takes by weighing, put in the conical flask, (dissolving anhydrous calcium chloride 0.304g and Magnesium dichloride hexahydrate 0.139g are in distilled water to add 500ml water or standard hard water, and with distilled water diluting to 1000ml), immediately this conical flask is done the ring shape jolting, reach each 50 commentaries on classics of jolting to the right left, promptly divide in device 100ml or the 250ml graduated cylinder (temperature of liquid during operation be preferably in warm in the big water-bath in the time of 30 ° ± 1 ℃, carry out) to leave standstill 0.5 hour and required various different times immediately, avoid vibration (if produce excessive floccule in the process of the test in the put procedure, be indicated as dissatisfied product), to be about 40cm then, one end internal diameter is that the glass tubing of 5mm is connected to vacuum pump, the other end is that the mouth of pipe of 2-3mm remains just under the suspendible liquid level, at 10-15 suspension of 9/10 in the sucking-off graduated cylinder in second, be 90ml or 225ml, discard this liquid, remaining 1/10 suspension, promptly 10ml or 25ml are provided with down measuring and use.
(1) with pyridine 25ml and dimethyl formamide 50ml remaining 25ml suspension is comprised that precipitate quantitatively transfers in the 500ml conical flask, titrimetry (document: WHO/SMF/1.R3,1983) is carried out by measure, suspensibility must not＜50%.This volumetric method is very loaded down with trivial details, time-consuming, needs at CO again
2Carry out in the air-flow, very inconvenience is so can select for use following easy ultraviolet spectrophotometry to carry out.
(2) quantitatively transfer to remaining 1/10 suspension 10ml in the small beaker with suitable quantity of water, add 5% hydrochloric acid solution acidify, with this acid solution of ether extraction, extract altogether 3 times, merge ether extracted liquid, in hot bath, steam and remove ether, residue is quantitatively transferred in the 50ml volumetric flask with the 20ml dehydrated alcohol, add dehydrated alcohol to scale, prepare solution again into about 12.5 μ g/ml concentration, by the method in the ultraviolet spectrophotometry item of following assay, measure trap at 333nm wavelength place, obtain the percent content of niclosamide, calculate the Clonitrilide percent content again after, by formula calculate the suspensibility of Clonitrilide 50% wettable powder.
P
2The percent content of Clonitrilide in=1/10 suspension that records
P
1Clonitrilide total content percentage rate in the=sample.
Assay active volume titrimetry or ultraviolet spectrophotometry record.
(1) volumetric precipitation method
This method is WHO/SMF/1R
3(1983) volumetric precipitation method.Given this above-mentioned shortcoming of titrimetry existence so set up following ultraviolet spectrophotometry in addition, is carried out the assay of this product.
(2) ultraviolet spectrophotometry
Precision takes by weighing Clonitrilide 50% wettable powder 25mg, adds the 20ml distilled water, after shaking up, adds several dilute hydrochloric acid and makes and be acid.Use this solution of ether extraction 3 times then, merge ether extracted liquid, in hot bath, steam and remove ether, residue quantitatively moves in the 50ml volumetric flask with the 20ml dehydrated alcohol, add dehydrated alcohol to scale, redilution is prepared into about 12.5 μ g/ml solution, measures trap at 333nm wavelength place.When measuring, compare with niclosamide standard solution (concentration is 12.5 μ g/ml).Calculate niclosamide content by following formula, obtain the percentage rate that is equivalent to the Clonitrilide labelled amount again.
Calculate:
The normal concentration of C=reference substance
A
1The trap of=sample
A
2The trap of=reference substance
This wettable powder is the mixture of a homogeneous, is yellow.The water slurry of wettable powder is neutral (pH=7), and additive that is not added and the material of bringing into and cause the variation of color, pH are to principal agent or claim other character of active component also not exert an influence.
The sn ail control effect of this wettable powder is comparatively desirable, indoor snail killing test is for adopting the oncomelania of area, Anqing, Anhui Province beach, every group 30, the medication component is the niclosamide group, the Clonitrilide group, Clonitrilide and sodium lauryl sulphate combined group, Clonitrilide and sodium carboxymethyl cellulose combined group, the sodium lauryl sulphate group, the sodium carboxymethyl cellulose group, sodium lauryl sulphate and sodium carboxymethyl cellulose combined group and not administration clear water matched group, every group of administration 100mg/ liter, 10mg/ liter and 1mg/ rise variable concentrations and soak extremely, soak and kill 24 hours, to test oncomelania takes out, clear water was placed 3 days after cleaning, and observed the oncomelania survival condition.The inertia oncomelania is differentiated anyway with hammering method, the statistics mortality rate.Result of the test shows, except that last 3 groups and clear water matched group do not present the snail killing function, all the other each groups are when 3 kinds of variable concentrations, killing snail rate is 100%, show that list does not all have snail killing function with wetting agent and suspending agent, after principal agent mixes, does not influence the original snail killing function of principal agent yet.
On-the-spot snail killing test all realizes satisfactory results.Table 1 Clonitrilide 50% wettable powder
The spraying molluscicide site test results
Dosage sprays natural law (d) and this day mortality of snails (%) medicine
(g/m
2) d1 d3 d5 d7 niclosamide 0.25 55.9 (170) * 80.3 (178) 50.0 (162) 67.7 (167) ethanolamine salts 0.50 59.8 (169) 79.3 (150) 81.3 (160) 75.9 (174) (test group) 1.0 68.0 (172) 70.5 (146) 70.1 (174) 83.4 (169)
2.0 75.2 (165) 95.1 (164) 76.6 (171) 92.3 (194) like product * * 0.25 53.6 (166) 69.8 (149) 62.6 (163) 64.8 (150) (matched group) 0.50 54.4 (180) 89.1 (184) 70.1 (154) 84.7 (176)
1.0 70.4(186) 86.5(171) 82.6(167) 84.8(197)
Check the spiral shell number 2.0 be in 69.1 (175) 90.2 (174) 83.8 (148) 93.4 (181) clear water 22.4 (174) 56/4 (173) 13.1 (173) 33.8 (198) (matched group) the * parantheses.* simultaneously stirs when implementing, and one side is sprayed.Time: on April 26th, 1993 to May 3 (fine day on the 29th, 3 are cloudy, and all the other are the rainy day, 28 days and 30 days
Be thunder shower).Temperature: 21 °-28 ℃.Table 2 Clonitrilide 50% wettable powder
The corrected mortality of on-the-spot spraying molluscicide
Dosage sprays natural law (d) and this day oncomelania corrected mortality (%) medicine
(g/m
2) d1 d3 d5 d7 niclosamide 0.25 43.2 (55.9) * 54.8 (80.3) 42.5 (50.0) 51.2 (67.7) ethanolamine salts 0.50 48.2 (59.8) 52.5 (79.3) 78.5 (81.3) 63.6 (75.9) (test group) 1.0 58.8 (68.0) 32.3 (70.5) 65.6 (70.1) 74.9 (83.4)
2.0 68.0 (75.2) 88.7 (95.1) 73.1 (76.6) 88.4 (92.3) like products 0.25 40.2 (53.6) 30.7 (69.8) 57.0 (62.6) 46.8 (64.8) (matched group) 0.50 41.2 (54.4) 75.0 (89.1) 65.6 (70.1) 76.9 (84.7)
1.0 61.8(70.4) 69.0(86.5) 80.0(82.6) 77.0(84.8)
2.0 be mortality of snails in 60.2 (69.1) 77.5 (90.2) 81.3 (83.8) 90.0 (93.4) clear water (22.4) (56.4) (13.1) (33.8) (matched group) the * parantheses.Table 3 Clonitrilide 50% wettable powder
Soak and kill spiral shell site test results drug concentration and soak extremely natural law (d) and this day mortality of snails (%)
(g/m
3Water) d1 d3 d5 d7 niclosamide 0.25 97.0 97.0 98.0 100 ethanolamine salt 0.50 100 99.0 100 100 (test group) 1.0 100 100 100 100
2.0 100 100 100 100 like products 0.25 100 100 100 100 (matched group) 0.50 100 100 100 100
1.0 99.0 100 100 100
2.0 same during 100 100 100 100 clear water 11.0 11.0 12.0 17.0 (matched group): on April 30th, 1993 was to May 6, except that 30,2,5 and 6 days 4 it rains, all the other are fine.Temperature: 21 °-23 ℃; Water temperature: 19 °-21.5 ℃.Table 4 Clonitrilide 50% wettable powder
The scene is soaked the corrected mortality drug concentration of killing spiral shell and is soaked natural law (d) and this day oncomelania corrected mortality (%) extremely
(9/m
3Water) d1 d3 d5 d7 niclosamide 0.25 96.6 (97.0) * 96.6 (97.0) 97.7 (98.0) 100 (100) ethanolamine salts 0.50 100 (100) 98.9 (99.0) 100 (100) 100 (100) (test group) 1.0 100 (100) 100 (100) 100 (100) 100 (100)
2.0 100 (100) 100 (100) 100 (100) 100 (100) like products 0.25 100 (100) 100 (100) 100 (100) 100 (100) (matched group) 0.50 100 (100) 100 (100) 100 (100) 100 (100)
1.0 98.9(99.0) 100(100) 100(100) 100(100)
2.0 be mortality of snails in 100 (100) 100 (100) 100 (100) 100 (100) clear water (11.0) (11.0) (12.0) (17.0) (matched group) the * parantheses.
As seen from last, the sn ail control effect of this wettable powder and the like product of Clonitrilide import are that the effect of matched group is consistent, spraying with soak extremely method relatively, be and soak extremely that effect is better than spray effect.
This wettable powder characteristics are higher suspension rate (91%-97%), continue suspension time long (greater than 24 hours), domestic at present, behind outer wettable powder and the water suspendible, left standstill 0.5 hour, promptly there is tangible principal agent to sink, the oncomelania effect is killed in influence, 0.5 hour suspensibility is this 50%-60% only generally, because the suspensibility of at present domestic and international wettable powder is low and suspendability is poor, therefore must the Drawing upon physical method, the granule of this powder is crushed to＜75 μ m, just can keep this powder and be not less than 50% at the suspensibility that leaves standstill 0.5 hour, and this wettable powder is because suspendability is good, do not need that granular size requirement to some extent after leaving standstill the long period, is still had good suspendability.Therefore, can save the technology of pulverizing aborning.Because this wettable powder suspendability is good, the characteristics that suspension time is long, thus guarantee the homogeneity of dosage in the spraying molluscicide operating process, be particularly suitable for the extensive or large-area spiral shell dispenser work of going out in various complicated place and basic unit that China's oncomelania is perched.
Be the embodiment of preparation below, illustrate further the present invention, and the restriction to inventing anything but.
Embodiment 1:
Clonitrilide 50g
Sodium lauryl sulphate 2g
Sodium carboxymethyl cellulose adds to 100g
After above-mentioned three kinds of chemical compounds grind mixing, to seal, be put in dry shady and cool place stand-by.
Embodiment 2:
Clonitrilide 50g
Sodium lauryl sulphate 5g
Sodium carboxymethyl cellulose adds to 100g
After above-mentioned three kinds of chemical compounds grind mixing, to seal, be put in dry shady and cool place stand-by.
Embodiment 3:
Clonitrilide 50g
Sodium lauryl sulphate 10g
Sodium carboxymethyl cellulose adds to 100g
After above-mentioned three kinds of chemical compounds grind mixing, to seal, be put in dry shady and cool place stand-by.
Embodiment 4:
Clonitrilide 50g
Sodium lauryl sulphate 20g
Sodium carboxymethyl cellulose adds to 100g
After above-mentioned three kinds of chemical compounds grind mixing, to seal, be put in dry shady and cool place stand-by.
Embodiment 5:
Nitrogen nitre willow amine ethanolamine salt 50g
Sodium lauryl sulphate 30g
Sodium carboxymethyl cellulose adds to 100g
After above-mentioned three kinds of chemical compounds grind mixing, to seal, be put in dry shady and cool place stand-by.
Claims (2)
1. one kind by Clonitrilide, and the wettable powder that sodium lauryl sulphate and carboxymethyl cellulose are formed is characterized in that the ratio of filling a prescription is:
Clonitrilide 50%
Sodium lauryl sulphate 2%-30%
Carboxymethyl cellulose 20-48%
After above-mentioned three kinds of chemical compounds grind mixing, to seal, be put in dry place stand-by.
2. wettable powder according to claim 1 is used to prepare the medicine of killing oncomelania.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94112267 CN1068518C (en) | 1994-08-19 | 1994-08-19 | Wettable powder of niclosamide salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94112267 CN1068518C (en) | 1994-08-19 | 1994-08-19 | Wettable powder of niclosamide salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1124621A true CN1124621A (en) | 1996-06-19 |
| CN1068518C CN1068518C (en) | 2001-07-18 |
Family
ID=5036056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94112267 Expired - Fee Related CN1068518C (en) | 1994-08-19 | 1994-08-19 | Wettable powder of niclosamide salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1068518C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1985813B (en) * | 2006-12-07 | 2010-10-06 | 江苏省血吸虫病防治研究所 | Metronidazole ethanolamine spray as blood flukedisease preventing and treating medicine for farm cattle and its preparing method |
| CN102687718A (en) * | 2011-03-21 | 2012-09-26 | 复旦大学 | Depositing molluscicidal method |
| CN104430338A (en) * | 2014-12-08 | 2015-03-25 | 江苏艾津农化有限责任公司 | Niclosamide ethanolamine salt wettable powder as well as preparation method and application thereof |
| CN106070190A (en) * | 2016-06-17 | 2016-11-09 | 杨美玲 | Two-in-one " Lac Bovis seu Bubali shape " pesticide of a kind of efficient stable and the preparation of compounding suspending agent thereof |
| CN106614590A (en) * | 2016-12-04 | 2017-05-10 | 九江学院 | Snail-killing combination drug |
-
1994
- 1994-08-19 CN CN 94112267 patent/CN1068518C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1985813B (en) * | 2006-12-07 | 2010-10-06 | 江苏省血吸虫病防治研究所 | Metronidazole ethanolamine spray as blood flukedisease preventing and treating medicine for farm cattle and its preparing method |
| CN102687718A (en) * | 2011-03-21 | 2012-09-26 | 复旦大学 | Depositing molluscicidal method |
| CN104430338A (en) * | 2014-12-08 | 2015-03-25 | 江苏艾津农化有限责任公司 | Niclosamide ethanolamine salt wettable powder as well as preparation method and application thereof |
| CN106070190A (en) * | 2016-06-17 | 2016-11-09 | 杨美玲 | Two-in-one " Lac Bovis seu Bubali shape " pesticide of a kind of efficient stable and the preparation of compounding suspending agent thereof |
| CN106614590A (en) * | 2016-12-04 | 2017-05-10 | 九江学院 | Snail-killing combination drug |
| CN106614590B (en) * | 2016-12-04 | 2019-01-29 | 九江学院 | A kind of water-snail eradication composition of medicine |
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| Publication number | Publication date |
|---|---|
| CN1068518C (en) | 2001-07-18 |
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