CN105566185A - Compound inhibiting algae growth and preparation method thereof and algicide and application of compound and algicide - Google Patents
Compound inhibiting algae growth and preparation method thereof and algicide and application of compound and algicide Download PDFInfo
- Publication number
- CN105566185A CN105566185A CN201610050658.2A CN201610050658A CN105566185A CN 105566185 A CN105566185 A CN 105566185A CN 201610050658 A CN201610050658 A CN 201610050658A CN 105566185 A CN105566185 A CN 105566185A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- algicide
- algae
- iii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- SFWMPCSWDRFFGF-UHFFFAOYSA-N O=C(CCSCSCC(Nc1ccc(CC(F)(F)F)cc1)=O)Nc1ccc(C(F)(F)F)cc1 Chemical compound O=C(CCSCSCC(Nc1ccc(CC(F)(F)F)cc1)=O)Nc1ccc(C(F)(F)F)cc1 SFWMPCSWDRFFGF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom not containing sulfur-to-oxygen bonds, e.g. polysulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the field of pesticides and environment, and discloses a compound inhibiting algae growth and a preparation method thereof and algicide and application of the compound and the algicide. The compound inhibiting the algae growth has a structure shown in a formula (I). The compound inhibiting the algae growth can inhibit activity of blue algae fructose-1, 6-/sedoheptulose-1, 7-biphosphatase and can serve as the algicide for use. The compound shown in the formula (I) has the advantages of being high in inhibition ratio, small in toxicity and high in selectivity when the compound inhibits the growth of the algae or kills algae. Please see the formula in the description.
Description
Technical field
The present invention relates to agricultural chemicals and environmental area, particularly, relate to a kind of suppress the compound of algal grown, a kind of prepare suppress algal grown the method for compound, this compound at suppression algal grown or the application of killing in algae and this compound at suppression blue-green algae fructose-1, application in 6-/sedoheptulose 1,7-bisphosphatase activity, a kind of for suppressing the algicide of algal grown.
Background technology
Blue-green algae is a kind of ancient and biology that vitality is extremely strong, and in recent years, along with the raising of modern water body eutrophication degree, various places water body frequently breaks out blue-green alga bloom event.Algae evil directly affects surrounding area domestic water and process water, havoc ecotope, brings huge financial loss, also bring very big hidden danger to public health to fish production and tourism development.
Chemical algicide is used to have economy, the advantage such as efficient, convenient and rapid-action, therefore, chemistry algicide is indispensable important component part in algae evil comprehensive regulation system always, especially, during algal bloom large-scale outbreak, short-term is administered fast and is controlled the topmost means of prevention of emergency situation such as algae evil especially.
The heavy metal compound class algicide that it is representative that existing chemical algicide mainly contains with copper sulfate and complex compound thereof; The strong oxidizer class algicide being representative with potassium permanganate, ferrate, superoxide; The classes of herbicides algicide etc. being representative with triazolineone, triazines etc.But these algicides exist poor selectivity, consumption large, to problems such as the animal toxicities such as the fish in water are larger, significantly limit giving full play to of the usefulness making chemically to prevent and treat algae evil.
With enzyme important in the photosynthesizer of blue-green algae for target, exploration discovery is inhibited to this enzyme, and also have the compound of higher algicdal activity, be one of approach addressed this problem simultaneously.
Research shows, ubiquitous fructose-1 in blue-green algae body, 6-/sedoheptulose-1,7-diphosphatase (cy-FBP/SBPase) is in strategic status in blue-green algae Calvin cyclic carbon metabolic regulation process, applicant has also proved that in the transgenic research in early stage this enzyme is a potential algicide target, suppresses blue-green algae fructose-1,6-/sedoheptulose-1,7-diphosphatase is active or enzyme is undergone mutation, will cause blue-green algae cannot normal growth even dead.
Summary of the invention
The object of the invention is the defect overcoming prior art, a kind of algicide of suppression algal grown is newly provided.
To achieve these goals, first aspect, the invention provides a kind of compound suppressing algal grown, and this compound has the structure shown in formula (I):
Wherein, in formula (I), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55identical or not identical, be selected from the alkyl of hydrogen, halogen, the alkyl of unsubstituted C1-C4 and the C1-C4 of halogen substiuted independently of one another, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen.
Second aspect, the invention provides the method for the compound shown in a kind of preparation formula (I), the method comprises:
(1) in the presence of a catalyst, paraformaldehyde is mixed with Thiovanic acid, obtain the compound shown in formula (II);
(2) under dewatering agent and solvent exist, the compound shown in the compound shown in formula (II) and formula (III-1) and/or formula (III-2) is reacted;
Wherein, in formula (I), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55identical or not identical, be selected from the alkyl of hydrogen, halogen, the alkyl of unsubstituted C1-C4 and the C1-C4 of halogen substiuted independently of one another, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen;
In formula (III-1) and formula (III-2), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55respectively with the described R in formula (I)
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55corresponding identical.
The third aspect, the invention provides the compound shown in previously described formula (I) in the application suppressing algal grown or kill in algae.
Fourth aspect, the invention provides the compound shown in previously described formula (I) and is suppressing the application in blue-green algae fructose-1,6-/sedoheptulose 1,7-bisphosphatase activity.
5th aspect, the invention provides a kind of for suppressing the algicide of algal grown, containing the compound shown in the aforesaid formula of the present invention (I) in this algicide.
The present invention is directed to the regulation and control enzyme fructose-1 in algae photosynthesis system, 6-/sedoheptulose-1,7-diphosphatase is that action target has designed and synthesized N, N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds (compound shown in formula (I)), this compounds can be applied to and suppress algae fructose-1,6-/sedoheptulose 1,7-bisphosphatase is active, suppress algal grown or kill algae.
Compound shown in formula provided by the invention (I) suppress algae growth or when killing algae, there is the advantage that inhibiting rate is high, toxicity is little and selectivity is high.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
First aspect, the invention provides a kind of compound suppressing algal grown, and this compound has the structure shown in formula (I):
Wherein, in formula (I), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55identical or not identical, be selected from the alkyl of hydrogen, halogen, the alkyl of unsubstituted C1-C4 and the C1-C4 of halogen substiuted independently of one another, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen.
The alkyl of described unsubstituted C1-C4 comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-.
Described halogen comprises fluorine, chlorine, bromine, iodine.
The alkyl of the C1-C4 of described halogen substiuted comprises chloromethyl, dichloromethyl, trichloromethyl, a brooethyl, chlorine one brooethyl, single methyl fluoride, difluoromethyl, trifluoromethyl, 1, the chloro-1-bromotrifluoromethane of 2-Dichloroethyl, 1-chloroethyl, 1-, 2-chloroethyl, 1,1,1-trichloroethyl, 1,1,1-trifluoroethyl, CH
2clCH
2cH
2-, CH
2fCH
2cH
2-, CHF
2cH
2cH
2-, CF
3cH
2cH
2-, CH
2brCH
2cH
2-, CHCl
2cH
2cH
2-, CH
2clCHClCH
2-, CH
2clCH (CH
3)-, CH
2brCH (CH
3)-, CH
2fCH (CH
3)-, CHF
2cH (CH
3)-, CF
3cH (CH
3)-, CH
2clCH
2cH
2cH
2-, CHCl
2cH
2cH
2cH
2-, CCl
3cH
2cH
2cH
2-, CH
2fCH
2cH
2cH
2-, CHF
2cH
2cH
2cH
2-and CF
3cH
2cH
2cH
2-.
Preferably, in formula (I), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be selected from the sec.-propyl of hydrogen, halogen, methyl, ethyl, n-propyl, sec.-propyl, the methyl of halogen substiuted, the ethyl of halogen substiuted, the n-propyl of halogen substiuted and halogen substiuted independently of one another, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen.
Preferably, in formula (I), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl and trifluoromethyl independently of one another, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen.
More preferably, in formula (I), described R
1with R
11, R
2with R
22, R
3with R
33, R
4with R
44and R
5with R
55identical respectively, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen.
According to the preferred embodiment of one, in formula (I), described R
1with R
11, R
2with R
22, R
3with R
33, R
4with R
44and R
5with R
55identical respectively, and described R
1, R
2, R
3, R
4and R
5be selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl and trifluoromethyl independently of one another, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen.
Second aspect, the invention provides the method for the compound shown in a kind of preparation formula (I), the method comprises:
(1) in the presence of a catalyst, paraformaldehyde is mixed with Thiovanic acid, obtain the compound shown in formula (II);
(2) under dewatering agent and solvent exist, the compound shown in the compound shown in formula (II) and formula (III-1) and/or formula (III-2) is reacted;
Wherein, in formula (I), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55identical or not identical, be selected from the alkyl of hydrogen, halogen, the alkyl of unsubstituted C1-C4 and the C1-C4 of halogen substiuted independently of one another, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen;
In formula (III-1) and formula (III-2), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55respectively with the described R in formula (I)
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55corresponding identical.
Preferably, in step (1), described catalyzer is concentrated hydrochloric acid.
Preferably, in step (1), the condition of described mixing comprises: temperature is 30-150 DEG C, and the time is 0.5-100h.
Preferably, in step (1), the consumption mol ratio of described paraformaldehyde and Thiovanic acid is 1:0.5-3.
Preferably, in step (2), described dewatering agent is dicyclohexylcarbodiimide (DCC).
Preferably, described step (2) is carried out under shielding gas exists.
Preferably, in step (2), described solvent is tetrahydrofuran (THF) (DMF).
Preferably, in step (2), the condition that compound shown in described formula (II) and formula (III-1) and/or the compound shown in formula (III-2) carry out reacting comprises: temperature is subzero 30 DEG C to 50 DEG C above freezing, and the time is 0.5-48h.
Preferably, in step (2), total consumption mol ratio of the compound shown in described formula (II) and formula (III-1) and/or the compound shown in formula (III-2) is 1:0.5-3.Total consumption of described formula (III-1) and/or the compound shown in formula (III-2) refers to: when only using the compound shown in formula (III-1), and total consumption of described formula (III-1) and/or the compound shown in formula (III-2) is only the consumption of the compound shown in formula (III-1); When only using the compound shown in formula (III-2), total consumption of described formula (III-1) and/or the compound shown in formula (III-2) is only the consumption of the compound shown in formula (III-2); When using the compound shown in formula (III-1) and formula (III-2) simultaneously, total consumption that total consumption of described formula (III-1) and/or the compound shown in formula (III-2) is the compound shown in formula (III-1) and formula (III-2).
According to the preferred embodiment of one, the method for the compound shown in described preparation formula (I) of the present invention can adopt following synthetic route:
Or the method for the compound shown in described preparation formula (I) of the present invention can adopt following synthetic route:
Can target product be separated out after being poured into water by the reaction solution obtained after step of the present invention (2), highly purified target product can be obtained by suction filtration, ethyl alcohol recrystallization subsequently.
The third aspect, the invention provides the compound shown in previously described formula (I) in the application suppressing algal grown or kill in algae.
Preferably, relative to every 1 × 10
6individual algae, shown in described formula (I), the consumption of the compound of structure is 0.1-100 micromole; Be more preferably 0.5-50 micromole.
Preferably, described algae comprises red algae and blue-green algae.
Preferably, described blue-green algae comprises DNC wireless, anabena, joint ball algae, nostoc and microcystic aeruginosa 912.
Fourth aspect, the invention provides the compound shown in previously described formula (I) and is suppressing the application in blue-green algae fructose-1,6-/sedoheptulose 1,7-bisphosphatase activity.
5th aspect, the invention provides a kind of for suppressing the algicide of algal grown, containing the compound shown in the aforesaid formula of the present invention (I) in this algicide.
Preferably, with the total weight of described algicide, shown in described formula (I), the content of the compound of structure is 0.1-100 % by weight.
Compound shown in formula of the present invention (1) as algicide activeconstituents use time, the carrier allowed in above-claimed cpd and water body or mixing diluents can be modulated into normally used various formulation, as hydrating agents, emulsion, water solvent, can flowing agent etc., use as algicide of the present invention.
Preferably, the formulation of described algicide is at least one in hydrating agents, pulvis, emulsion, suspension agent and granula.
The compound shown in described formula (1) of the present invention is adopted to suppress to have the advantage that inhibiting rate is high, toxicity is little and selectivity is high when the growth of algae or algae.
Efficient and significant algae killing effect can be demonstrated when adopting the compound shown in formula of the present invention (1) to apply in the comprehensive regulation of algal bloom as the effective ingredient of algicide.
Below will be described the present invention by embodiment.
In case of no particular description, the material below used is all from being purchased.
Ubiquitous fructose 1 in blue-green algae body, 6-/sedoheptulose-1,7-diphosphatase (Cy-FBP/SBPase) is in critical role in blue-green algae Calvin cyclic carbon metabolic regulation process, it is a potential algicide target, as well known to those skilled in the art, if Cy-FBP/SBPase is suppressed or undergos mutation, blue-green algae will be caused to grow even dead.And it is fructose-6-phosphate and inorganic phosphate that Cy-FBP/SBPase is hydrolyzed fructose-1,6-diphosphate.Therefore, the increasing amount by testing inorganic phosphate in following examples of the present invention and comparative example measures the activity of Cy-FBP/SBPase, thus for inquiring into the inhibiting rate of compound of the present invention to algae.
Preparation example 1-9 is for illustration of compound shown in (I) of the present invention and preparation method thereof.
Embodiment 1-2 is for illustration of the application of the compound shown in (I) of the present invention.
Preparation example 1
Preparation N, N'-bis-(4-chloro-phenyl-) methylene-bis thioacetamide:
The first step: paraformaldehyde (20mmol) solution (solution of 40 % by weight) is mixed with Thiovanic acid (40mmol) solution (solution of 90 % by weight), 0.2mL concentrated hydrochloric acid is dripped under agitation in mixed solution, stir under 45 DEG C of conditions and spend the night, 2h is stirred again under 95 DEG C of conditions, then at subzero 18 DEG C, 48h is preserved, gained mixture suction filtration, obtains pure intermediate II with after water recrystallization, and productive rate is 60%;
Second step: the compound ii of 3mmol and the p-Chlorobenzoic acid amide of 6.6mmol are joined in the dry DMF of 6.0mL; Ar protects, and ice-water bath is chilled to 0 DEG C, is then dissolved in the dry DMF of 2mL by the DCC of 6.6mmol; again the solution of DCC is added drop-wise to above-mentioned mixed solution, control 3min adds.Stirring at room temperature 2h, hold over night, filter, filtrate is poured in 80mL water, separates out white precipitate, filter, washing, dry, ethyl alcohol recrystallization, pure N is obtained, N'-bis-(4-chloro-phenyl-) methylene-bis thioacetamide, productive rate 45%, m.p.184-186 DEG C after oven dry.
Molecular formula: C
17h
16c
l2n
2o
2s
2;
1HNMR(600MHz,DMSO-d
6)δ10.29(s,2H),7.60(d,J＝8.8Hz,4H),7.36(d,J＝8.8Hz,4H),4.02(s,2H),3.46(s,4H).
13CNMR(151MHz,DMSO-d
6)δ168.06,138.22,128.99,127.31,121.06,36.24,34.91。
Preparation example 2
Preparation N, N'-bis-(4-iodophenyl) methylene-bis thioacetamide:
Adopt the method similar to preparation example 1 to prepare, difference is, adopts the p-Chlorobenzoic acid amide in paraiodoaniline replacement preparation example 1.
Gained sterling is white powder, and productive rate is 22%, m.p.241-242 DEG C.
Molecular formula: C
17h
16i
2n
2o
2s
2;
1HNMR(600MHz,DMSO-d
6)δ10.24(s,2H),7.64(d,J＝8.5Hz,4H),7.42(d,J＝8.5Hz,4H),4.01(s,2H),3.45(s,4H)。
13CNMR(151MHz,DMSO-d
6)δ167.76,138.77,137.41,121.38,86.98,35.90,34.64。
Preparation example 3
Preparation N, N'-bis-(4-bromophenyl) methylene-bis thioacetamide:
Adopt the method similar to preparation example 1 to prepare, difference is, adopts the p-Chlorobenzoic acid amide in para-bromoaniline replacement preparation example 1.
Gained sterling is white powder, and productive rate is 52%, m.p.214-216 DEG C.
Molecular formula: C
17h
16br
2n
2o
2s
2;
1HNMR(600MHz,DMSO-d
6)δ10.28(s,2H),7.55(d,J＝8.7Hz,4H),7.48(d,J＝8.6Hz,4H),4.01(s,2H),3.46(s,4H)。
13CNMR(151MHz,DMSO-d
6)δ168.18,138.73,132.00,121.53,115.43,36.32,35.03。
Preparation example 4
Preparation N, N'-bis-(4-aminomethyl phenyl) methylene-bis thioacetamide:
Adopt the method similar to preparation example 1 to prepare, difference is, adopts the p-Chlorobenzoic acid amide in open-chain crown ether replacement preparation example 1.
Gained sterling is white powder, and productive rate is 50%, m.p.161-162.
Molecular formula: C
19h
22n
2o
2s
2;
1HNMR(600MHz,DMSO-d
6)δ10.05(s,2H),7.46(d,J＝8.1Hz,4H),7.10(d,J＝8.0Hz,4H),4.03(s,2H),3.45(s,4H),2.25(s,6H)。
13CNMR(151MHz,DMSO-d
6)δ167.35,136.46,132.34,129.14,119.21,35.95,34.52,20.48。
Preparation example 5
Preparation N, N'-bis-(4-fluorophenyl) methylene-bis thioacetamide:
Adopt the method similar to preparation example 1 to prepare, difference is, adopts the p-Chlorobenzoic acid amide in para-fluoroaniline replacement preparation example 1.
Gained sterling is white powder, and productive rate is 50%, m.p.179-181 DEG C.
Molecular formula: C
17h
16f
2n
2o
2s
2;
1HNMR(600MHz,DMSO-d
6)δ10.22(s,2H),7.61(dd,J＝8.7,5.1Hz,4H),7.15(t,J＝8.8Hz,4H),4.04(s,2H),3.47(s,4H)。
13CNMR(151MHz,DMSO-d
6)δ167.78,159.14,157.55,135.63,121.28,121.23,115.68,115.53,36.21,34.79。
Preparation example 6
Preparation N, N'-bis-(4-trifluoromethyl) methylene-bis thioacetamide:
Adopt the method similar to preparation example 1 to prepare, difference is, adopts the p-Chlorobenzoic acid amide in p-trifluoromethylaniline replacement preparation example 1.
Gained sterling is white powder, and productive rate is 15%, m.p.190-192 DEG C.
Molecular formula: C
19h
16f
6n
2o
2s
2;
1HNMR(600MHz,DMSO-d
6)δ10.52(s,2H),7.79(d,J＝8.4Hz,4H),7.67(d,J＝8.5Hz,4H),4.04(s,2H),3.52(s,4H)。
13CNMR(151MHz,DMSO-d
6)δ168.52,142.78,127.33,126.37,126.35,125.53,123.99,123.78,123.73,123.57,123.36,121.93,119.34,36.12,34.97。
Preparation example 7
Preparation N, N'-bis-(3-aminomethyl phenyl) methylene-bis thioacetamide:
Adopt the method similar to preparation example 1 to prepare, difference is, adopts the p-Chlorobenzoic acid amide in 3-monomethylaniline replacement preparation example 1.
Gained sterling is white powder, and productive rate is 34%, m.p.127-129 DEG C.
Molecular formula: C
19h
22n
2o
2s
2;
1HNMR(600MHz,DMSO-d
6)δ10.07(s,2H),7.44(s,2H),7.36(d,J＝7.9Hz,2H),7.18(t,J＝7.6Hz,2H),6.87(d,J＝7.2Hz,2H),4.03(s,2H),3.46(s,4H),2.27(s,6H)。
13CNMR(151MHz,DMSO-d
6)δ167.86,139.21,138.27,128.92,124.44,120.04,116.71,36.23,34.87,21.53。
Preparation example 8
Preparation N, N'-bis-(2-chloro-phenyl-) methylene-bis thioacetamide:
Adopt the method similar to preparation example 1 to prepare, difference is, adopts the p-Chlorobenzoic acid amide in 2-chloroaniline replacement preparation example 1.
Gained sterling is white powder, and productive rate is 25%, m.p.144-145 DEG C.
Molecular formula: C
17h
16c
l2n
2o
2s
2;
1HNMR(600MHz,DMSO-d
6)δ9.74(s,2H),7.77(d,J＝7.7Hz,2H),7.50(d,J＝7.8Hz,2H),7.33(t,J＝7.4Hz,2H),7.20(t,J＝7.3Hz,2H),4.06(s,2H),3.58(s,4H)。
13CNMR(151MHz,DMSO-d
6)δ168.34,135.03,129.86,127.83,126.72,126.55,126.10,36.28,34.52。
Preparation example 9
Preparation N, N'-bis-(2-methyl-4-chloro-phenyl-) methylene-bis thioacetamide:
Adopt the method similar to preparation example 1 to prepare, difference is, adopts the p-Chlorobenzoic acid amide in 2-methyl-4-chloroaniline replacement preparation example 1.
Gained sterling is white powder, and productive rate is 52%, m.p.176-178 DEG C.
Molecular formula: C
19h
20c
l2n
2o
2s
2;
1HNMR(600MHz,DMSO-d
6)δ9.54(s,2H),7.46(d,J＝8.5Hz,2H),7.30(s,2H),7.21(d,J＝8.5Hz,2H),4.04(s,2H),3.52(s,4H),2.21(s,6H)。
13CNMR(151MHz,DMSO-d
6)δ168.20,135.43,134.26,130.21,129.37,126.64,126.18,36.29,34.47,17.96。
Embodiment 1
Measure Tris-HCl (pH8.3), the dithiothreitol (DTT) (DTT) of 10mM, the MgCl of 15mM of reaction buffer system containing 50mM of Cy-FBP/SBPase activity
2.Get the compound that above-mentioned preparation example 1-9 prepares respectively, dissolve N with DMSO, N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds is configured to finite concentration, and final concentration is 50 μMs (hereinafter also referred to inhibitor).In described solution, add substrate fructose 1, the 6-bisphosphate of 5mM, at 30 DEG C, react 5min.With multi-functional microplate reader (BioteckSynergy2, USA)) absorbance value of determined wavelength when being 620nm.Absorbance value characterizes the enzyme amount of product inorganic phosphorus that generates of catalytic substrate under given conditions.Absorbance value and enzymic catalytic reaction speed proportional.Absorbance value is large, then enzymic catalytic reaction speed is just large.Calculated the inhibiting rate of each compound by formula 1, then obtain IC with the matching of Origin8.0 software
50.The IC of each compound
50list in table 1.
Formula 1: inhibiting rate %=(A
0-A
i)/A
0× 100%, wherein, A
0the light absorption value of fructose 1,6-/sedoheptulose 1,7-bisphosphatase during for not having an inhibiting, A
ithe light absorption value of fructose 1,6-/sedoheptulose 1,7-bisphosphatase during for adding inhibitor.
Embodiment 2
DNC wireless and microcystic aeruginosa 912 are most important pattern algae in blue-green algae.Select DNC wireless and microcystic aeruginosa 912 as the effect of experiment made on the living object for checking N, N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds of the present invention to suppress algal grown in the present embodiment.
DNC wireless and the microcystic aeruginosa 912 of getting identical amount are respectively incubated in the BG11 liquid nutrient medium containing the compound of different concns preparation example 1-9, cultivate in artificial climate incubator.Controlling incubator temperature is 28 DEG C ± 1 DEG C, and humidity 60%, light intensity is 8000lx, 12h (illumination): 12h (dark).
Concrete operations are as follows:
The a collection of DNC wireless of preculture and microcystic aeruginosa 912, in the logarithmic phase later stage to be grown to, survey its OD730, inoculate stand-by;
Dilute above-mentioned logarithmic phase algae liquid with fresh BG11 substratum, obtain inoculation algae liquid, and control frustule concentration about 1 × 10
6individual/mL, suppresses algae growth experiment;
Weigh compound in advance, dissolve with DMSO, the N of preparation different concns, (concentration is respectively N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds: 0,0.01mM, 0.03mM, 0.1mM, 0.3mM, 1mM, 3mM, 10mM.The inoculation algae liquid that 200 μ L have diluted is added in each hole in 96 orifice plates, and then the compound that the preparation example 1-9 adding the above-mentioned each concentration of 2 μ L respectively prepares, the final concentration of compound is respectively 0,0.1 μM, 0.3 μM, 1 μM, 3 μMs, 10 μMs, 30 μMs, 100 μMs.Arrange not containing blank (adding DMSO in algae liquid system) and N, N'-bis-(substituted-phenyl) the methylene-bis thioacetyl aminated compounds ground control (dissolving the compound system of preparation with DMSO) of compound;
Cultivate in artificial climate incubator after 6 days and survey OD730 by microplate reader, calculate different concns N according to formula 2, the inhibiting rate of N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds;
Formula 2: inhibiting rate %=[blank group OD730-(experimental group OD730-N, N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds ground control group OD730)]/blank group OD730 × 100%;
With the N of preparation example 1-9, the concentration of N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds is X-coordinate, the inhibiting rate that formula 2 calculates is ordinate zou mapping, with formula logistic matching in Origin, try to achieve N, the EC of N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds
50value, the results are shown in Table 1.
Table 1
Comparative example 1
This comparative example adopts the method similar to embodiment 1 to carry out, difference is, the N in embodiment 1 is replaced with algicide copper sulfate of the prior art in this comparative example, N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds tests inhibiting rate according to formula 3, under the prerequisite that all the other conditions are all identical, result use copper sulfate 100 μMs time to the inhibiting rate of Cy-FBP/SBPase lower than 40%, the IC that copper sulfate suppresses Cy-FBP/SBPase
50be greater than 100 μMs.
Formula 3: inhibiting rate %=(A
0-A
i)/A
0× 100%, wherein, A
0the light absorption value of Cy-FBP/SBPase during for not adding copper sulfate, A
ithe light absorption value of Cy-FBP/SBPase during for adding copper sulfate.
Shown by contrast comparative example 1 and the result of embodiment 1, the inhibiting rate of the copper sulfate that the inhibiting rate of N, N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds of the present invention uses apparently higher than prior art.
Comparative example 2
This comparative example adopts the method similar to embodiment 2 to carry out, difference is, the N in embodiment 2 is replaced with algicide copper sulfate of the prior art in this comparative example, N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds suppresses the growth of DNC wireless and microcystic aeruginosa 912, under the prerequisite that all the other conditions are all identical, formula 4 is adopted to calculate inhibiting rate, the EC that copper sulfate suppresses DNC wireless
50it is 0.86 μM.
Formula 4: inhibiting rate %=[blank group OD730-(experimental group OD730-copper sulfate ground control group OD730)]/blank group OD730 × 100%;
Shown by the result of contrast comparative example 2 and embodiment 2, the inhibiting rate of N, N'-bis-(substituted-phenyl) methylene-bis thioacetyl aminated compounds of the present invention to blue-green algae reaches even higher than the inhibiting rate to blue-green algae during prior art use copper sulfate.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. suppress a compound for algal grown, this compound has the structure shown in formula (I):
Wherein, in formula (I), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55identical or not identical, be selected from the alkyl of hydrogen, halogen, the alkyl of unsubstituted C1-C4 and the C1-C4 of halogen substiuted independently of one another, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen.
2. compound according to claim 1, wherein, described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be selected from the sec.-propyl of hydrogen, halogen, methyl, ethyl, n-propyl, sec.-propyl, the methyl of halogen substiuted, the ethyl of halogen substiuted, the n-propyl of halogen substiuted and halogen substiuted independently of one another; Preferably
Described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl and trifluoromethyl independently of one another.
3. a method for the compound shown in preparation formula (I), the method comprises:
(1) in the presence of a catalyst, paraformaldehyde is mixed with Thiovanic acid, obtain the compound shown in formula (II);
(2) under dewatering agent and solvent exist, the compound shown in the compound shown in formula (II) and formula (III-1) and/or formula (III-2) is reacted;
Wherein, in formula (I), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55identical or not identical, be selected from the alkyl of hydrogen, halogen, the alkyl of unsubstituted C1-C4 and the C1-C4 of halogen substiuted independently of one another, and described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55be asynchronously hydrogen;
In formula (III-1) and formula (III-2), described R
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55respectively with the described R in formula (I)
1, R
2, R
3, R
4, R
5, R
11, R
22, R
33, R
44and R
55corresponding identical.
4. the compound in claim 1-3 described in any one is in the application suppressing algal grown or kill in algae.
5. application according to claim 4, wherein, relative to every 1 × 10
6individual algae, shown in described formula (I), the consumption of the compound of structure is 0.1-100 micromole; Be preferably 0.5-50 micromole.
6. the application according to claim 4 or 5, described algae comprises red algae and blue-green algae; Preferably
Described blue-green algae comprises DNC wireless, anabena, joint ball algae, nostoc and microcystic aeruginosa 912.
7. the compound in claim 1-3 described in any one is suppressing the application in blue-green algae fructose-1,6-/sedoheptulose 1,7-bisphosphatase activity.
8. for suppressing an algicide for algal grown, it is characterized in that, containing the compound shown in formula (I) in claim 1-3 described in any one in this algicide.
9. algicide according to claim 8, wherein, with the total weight of described algicide, shown in described formula (I), the content of the compound of structure is 0.1-100 % by weight.
10. algicide according to claim 8 or claim 9, wherein, the formulation of described algicide is at least one in hydrating agents, pulvis, emulsion, suspension agent and granula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610050658.2A CN105566185B (en) | 2016-01-26 | 2016-01-26 | Suppress compound of algal grown and preparation method thereof and algicide and their application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610050658.2A CN105566185B (en) | 2016-01-26 | 2016-01-26 | Suppress compound of algal grown and preparation method thereof and algicide and their application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105566185A true CN105566185A (en) | 2016-05-11 |
| CN105566185B CN105566185B (en) | 2017-10-10 |
Family
ID=55876891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610050658.2A Active CN105566185B (en) | 2016-01-26 | 2016-01-26 | Suppress compound of algal grown and preparation method thereof and algicide and their application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105566185B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110810425A (en) * | 2018-08-07 | 2020-02-21 | 华中师范大学 | Application of phenylacetamide compound and algicide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5023275A (en) * | 1989-07-28 | 1991-06-11 | Rohm And Haas Company | S-substituted beta-thioacrylamide biocides and fungicides |
| US5707929A (en) * | 1995-05-08 | 1998-01-13 | Troy Chemical Corporation | Biocidal compositions comprising mixtures of haloproynyl compounds and sulfur containing triazines |
| US5922113A (en) * | 1993-08-24 | 1999-07-13 | Janssen Pharmaceutica, N.V. | Antibacterial and antifouling oxathiazines and their oxides |
| CN104844507A (en) * | 2015-04-01 | 2015-08-19 | 华中师范大学 | Application of quinolinone compounds to inhibit growth of alga and algicide for inhibiting growth of alga |
| CN104920387A (en) * | 2015-05-25 | 2015-09-23 | 华中师范大学 | Application of thiadiazole compound in inhibiting growth of algae and activity of enzyme and algicide for inhibiting growth of algae |
-
2016
- 2016-01-26 CN CN201610050658.2A patent/CN105566185B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5023275A (en) * | 1989-07-28 | 1991-06-11 | Rohm And Haas Company | S-substituted beta-thioacrylamide biocides and fungicides |
| US5922113A (en) * | 1993-08-24 | 1999-07-13 | Janssen Pharmaceutica, N.V. | Antibacterial and antifouling oxathiazines and their oxides |
| US5707929A (en) * | 1995-05-08 | 1998-01-13 | Troy Chemical Corporation | Biocidal compositions comprising mixtures of haloproynyl compounds and sulfur containing triazines |
| CN104844507A (en) * | 2015-04-01 | 2015-08-19 | 华中师范大学 | Application of quinolinone compounds to inhibit growth of alga and algicide for inhibiting growth of alga |
| CN104920387A (en) * | 2015-05-25 | 2015-09-23 | 华中师范大学 | Application of thiadiazole compound in inhibiting growth of algae and activity of enzyme and algicide for inhibiting growth of algae |
Non-Patent Citations (3)
| Title |
|---|
| BECKURTS, H.等: "p-Anisidide and p-phenetidide of thioglycolic acid", 《ARCHIV DER PHARMAZIE (WEINHEIM, GERMANY)》 * |
| PACHA, W.等: "Synthesis of 4-thiazolidinone derivatives", 《HELVETICA CHIMICA ACTA》 * |
| 陈晓雯 等: "合成杀藻剂先导化合物的筛选和杀藻效果分析", 《化学与生物工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110810425A (en) * | 2018-08-07 | 2020-02-21 | 华中师范大学 | Application of phenylacetamide compound and algicide |
| CN110810425B (en) * | 2018-08-07 | 2021-11-16 | 华中师范大学 | Application of phenylacetamide compound and algicide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105566185B (en) | 2017-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101319063B1 (en) | 1,2-benzisothiazole derivative, and agricultural or horticultural plant disease-controlling agent | |
| CN1262552C (en) | N-(5,7-dimethoxy[1,2,4] triazolo[1,5-a]pyrimidin-2-yl) arylsulfonamide compounds and their use as herbicides | |
| PL159541B1 (en) | Fungicide | |
| BG62077B1 (en) | New 3-phenylpyrazol derivatives and their application as fungicides | |
| KR900001196B1 (en) | Process for preparing pyrazol derivatives | |
| CN105566185A (en) | Compound inhibiting algae growth and preparation method thereof and algicide and application of compound and algicide | |
| JPS6172739A (en) | Amide derivative, manufacture and fungicidal composition | |
| CN104844507B (en) | Application of the quinolinones compound in algal grown is suppressed and the algicide for suppressing algal grown | |
| CN103664795B (en) | Pyridazinone compound and application thereof | |
| EA000146B1 (en) | Pyrazole derivatives and herbicide composition thereof | |
| CN106135234B (en) | Application of (substituted-amino formyl the methylthiol) -1,3,4- thiadiazole compounds of 2,5- bis- in inhibiting blue algae growth | |
| CN111747888A (en) | Pyridyloxyphenoxypropionamide compound with herbicidal activity and synthetic method and application thereof | |
| KR980009261A (en) | 1,2,3-benzothiadiazole derivatives | |
| CN104920387A (en) | Application of thiadiazole compound in inhibiting growth of algae and activity of enzyme and algicide for inhibiting growth of algae | |
| AU734862B2 (en) | Iodopropargylamine compounds, and industrial antibacterial and antifungal agents, algicides, and agents for preventing adhesion of organisms containing the same | |
| WO1998031228A1 (en) | Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing n-quinoxalylanilines | |
| CN110810425B (en) | Application of phenylacetamide compound and algicide | |
| JPH0925279A (en) | Triketone derivative | |
| JPS6078990A (en) | Tetrazolo-1,2,4-benzthiadiazine derivative, agricultural and horticultural fungicide | |
| CN109020841A (en) | A kind of N- nitro-N- (2,4,6- trifluorophenyl) benzenesulfonamides and application thereof | |
| JPS60214785A (en) | Pyrazolesulfonyl urea derivative and plant growth regulator or herbicide | |
| EA002310B1 (en) | Triketone derivatives | |
| CN106614600B (en) | A kind of Herbicidal combinations for rice safety | |
| JPS6383004A (en) | Fungicide for agricultural and horticultural use | |
| JP2001288183A (en) | Benzoyl derivative having condensed ring and herbicide composition using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |