CN109721559A - A kind of 1,4- pentadiene -3- ketones derivant, the Preparation method and use of Sulfide-containing Hindered triazole - Google Patents
A kind of 1,4- pentadiene -3- ketones derivant, the Preparation method and use of Sulfide-containing Hindered triazole Download PDFInfo
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Abstract
The invention discloses the Isosorbide-5-Nitrae of a kind of Sulfide-containing Hindered triazole-pentadiene -3- ketones derivant, Preparation method and use, general structure is as follows, in which: X is 2-O or 4-O, and R is phenyl, substituted-phenyl, heterocycle or 4- methylthiazol.The present invention has preferable control efficiency to tobacco mosaic virus (TMV), tobacco ralstonia solanacearum and hundred leaf spoting bacteria of rice.
Description
Technical field
The present invention relates to chemical technology fields, relate in particular to a kind of Isosorbide-5-Nitrae-pentadiene -3- ketone of Sulfide-containing Hindered triazole
Derivative also relates to the Isosorbide-5-Nitrae-pentadiene -3- ketones derivant preparation method and the Sulfide-containing Hindered three of the Sulfide-containing Hindered triazole
Application of the 1,4- pentadiene -3- ketones derivant of azoles in terms of antiviral and bacteriostatic activity.
Background technique
Natural activity molecule and its derivative have unique structure, the mode of action novel, less toxic to people and animals and friendly to environment
Good feature has very important meaning in the discovery procedure of pesticide poullant.Curcumin is derived from as one kind
Polyphenol compound in turmeric is widely used as fragrance, food preservative, monosodium glutamate and dyestuff.1,4- pentadiene ketone
Close object, as a kind of important curcumin derivate, because its have such as desinsection, antibacterial, Antiphytoviral, anticancer, anti-inflammatory and
Anti-oxidant equal more wide spectrum biological activity, in occupation of important function in agricultural chemicals research and development work.
2013, Xue is equal, and (Xue Wei, Gong Huayu, Chou Qiujuan, Zhao Hongju, Li Haichang, Han Feifei the curcumin of esters containing oxime spread out
The synthesis of biology and its bacteriostatic activity study [J] chemical reagent, 2013,35:201-205.) oxime ester structure is introduced into single carbonyl
In base curcumin derivate Isosorbide-5-Nitrae-pentadiene -3- ketone compounds, a series of Isosorbide-5-Nitrae-pentadienes-with inhibitory activity have been synthesized
3- ketoxime ester curcumin derivate, the tested results show: when concentration is 500mg/L, the series compound is to three kinds
Germ is presented with certain inhibiting effect.
2016, sweet show sea is equal, and (Gan Xiuhai, Hu Deyu, Li Pei, Wu Jian, Chen Xuewen, Xue Wei, Song Baoan contained 1,3,4-
The design of the novel Isosorbide-5-Nitrae of oxadiazoles part-pentadiene -3- ketone derivatives, synthesis, antiviral activity and three-dimensional quantitative structure activity relationship
It is scientific to study [J] Pest Management, 2016,72:534-543.) have with Isosorbide-5-Nitrae-pentadiene -3- ketone for guide and 1,3,4- oxadiazoles
Machine synthesizes a series of containing Isosorbide-5-Nitrae-pentadiene -3- ketone structure compound, and Preliminary Determination activity shows most of target compound
Its comparison medicament virazole is above to the antiviral activity of TMV.
2018, (Zhang Juping, Li Pu, Wang Yihui, Zhang Cheng, Chen Lijuan, Tang Xu, He Ming, Xue Wei contained benzo to chrysanthemum equality
The synthesis and bacteriostatic activity Chemical Journal of Chinese Universities of the 1,4- pentadiene -3- ketone derivatives of triazinone, 2018,39:1455-
1461.) a series of Isosorbide-5-Nitrae-pentadiene -3- ketones derivant for having synthesized ketone containing phentriazine, it is found that such compound is expected into
For the inhibitor of citrus processing and tobacco ralstonia solanacearum.
It yet there are no and Sulfide-containing Hindered triazole is introduced into pentadiene structure, and test antibacterial report related to antiviral activity
Road.
Summary of the invention
A kind of pair of tobacco mosaic virus (TMV) being there is provided it is an object of the invention to overcome disadvantages mentioned above, tobacco ralstonia solanacearum and
Hundred leaf spoting bacteria of rice has the 1,4- pentadiene -3- ketones derivant of the Sulfide-containing Hindered triazole of preferable control efficiency.
Another object of the present invention is to provide the preparation sides of the 1,4- pentadiene -3- ketones derivant of the Sulfide-containing Hindered triazole
Method.
A further object of the present invention is to provide the 1,4- pentadiene -3- ketones derivants of the Sulfide-containing Hindered triazole in anti-plant
Application in terms of virus and suppression phytopathogen.
A kind of Isosorbide-5-Nitrae of Sulfide-containing Hindered triazole of the invention-pentadiene -3- ketones derivant, general structure are as follows:
Wherein: X is 2-O or 4-O, and R is phenyl, substituted-phenyl, heterocycle or 4- methylthiazol.
The Isosorbide-5-Nitrae of above-mentioned a kind of Sulfide-containing Hindered triazole-pentadiene -3- ketones derivant, in which: substituted-phenyl is to fluorobenzene
Base, rubigan, Chloro-O-Phenyl, 4- methoxyphenyl, 2,4- Dimethoxyphenyl, 3,4- Dimethoxyphenyl, 3- nitrobenzene
Base, 4- nitrobenzophenone, 3,4- dichlorophenyl or 2,4 dichloro benzene base etc..
The Isosorbide-5-Nitrae of above-mentioned a kind of Sulfide-containing Hindered triazole-pentadiene -3- ketones derivant, in which: heterocycle is furyl or thiophene
Pheno base.
A kind of Isosorbide-5-Nitrae of Sulfide-containing Hindered triazole of the invention-pentadiene -3- ketones derivant preparation method, synthetic route
It is as follows:
(1) hydrazine hydrate and carbon disulfide, by being heated to reflux, solid recrystallization prepares diazanyl thio-hydrazide (intermediate 1):
(2) diazanyl thio-hydrazide (intermediate 1) and glacial acetic acid, by being heated to reflux, solid recrystallization preparation 4- amino -5-
Methyl -4H-1,2-4- triazole -3- sulfydryl (intermediate 2):
(3) acetone, 4- hydroxy benzaldehyde prepare 4- (hydroxy phenyl)-3- butene-2 -one (intermediate under alkaline condition
3)；
(4) substituted aroma aldehyde, 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3) prepare 1- substitution under alkaline condition
Aryl -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone (intermediate 4)；
(5) 1- substituted aryl -5- (4- hydroxy phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (intermediate 4) and Bromofume, with carbon
Sour potassium is catalyst, with acetonitrile as solvents, prepares 1- substituted aryl -5- (4- (2- bromine oxethyl) phenyl)-Isosorbide-5-Nitrae-pentadiene -3-
Ketone (intermediate 5):
(6) 1- substituted aryl -5- (4- (2- bromine oxethyl) phenyl) -1,4- pentadiene -3- ketone (intermediate 5) and 4- ammonia
Base -5- methyl -4H-1,2,4- triazole -3- sulfydryls (intermediate 2), are catalyst, n,N-Dimethylformamide with potassium carbonate
(DMF) Isosorbide-5-Nitrae containing triazole-pentadiene -3- ketones derivant (target compound A) is prepared for solvent, as follows:
1,4- pentadiene -3- ketones derivant the answering in terms of resisting tobacco mosaic virus of Sulfide-containing Hindered triazole of the invention
With.
1,4- pentadiene -3- the ketones derivant of Sulfide-containing Hindered triazole of the invention is inhibiting tobacco ralstonia solanacearum and rice white
The application of leaf spoting bacteria.
Compared with prior art, the present invention having apparent beneficial effect, as can be known from the above technical solutions: the present invention is with water
Close hydrazine, carbon disulfide, glacial acetic acid, etc. for raw material generate triazole, using acetone, 4- hydroxy benzaldehyde be raw material generation 4- (hydroxy benzenes
Base)-3- butene-2 -one, substituted aroma aldehyde, 4- (hydroxy phenyl)-3- butene-2 -one are that raw material generates 1- substituted aryl-5- (4-
Hydroxy phenyl) -1,4- pentadiene -3- ketone -1- substituted aryl -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone again with dibromo second
Alkane reaction, the product and triazole of generation act on obtaining Isosorbide-5-Nitrae-pentadiene -3- ketones derivant of Sulfide-containing Hindered triazole.The present invention will have
There is the thioether triazole group of excellent activity to be introduced into Isosorbide-5-Nitrae-pentadiene -3- ketone structure, i.e. Isosorbide-5-Nitrae-pentadiene -3- ketone position 4- hydroxyl
Thioether triazole structure is connected on base.A series of Isosorbide-5-Nitrae-pentadiene -3- the ketone compounds for having synthesized Sulfide-containing Hindered triazoles, by institute
Synthesize the Isosorbide-5-Nitrae-pentadiene -3- ketones derivant Antiphytoviral and suppression phytopathogen active testing of Sulfide-containing Hindered triazole, discovery
The compound of the present invention has preferable Antiphytoviral (tobacco mosaic virus (TMV)) activity with excellent suppression phytopathogen, and (tobacco blueness is withered
Hundred leaf spoting bacteria of germ and rice) activity, it can be used for preparing Antiphytoviral pesticide and prepare disinfectant use in agriculture.
Specific embodiment
Embodiment 1
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4- nitre
Base phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A1) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Thermometer is being housed, in the three-necked flask of dropping funel and condenser (suitable for reading to be connected with tail gas delivery line) plus 20mL
85% hydrazine hydrate and 60mL water controls temperature at 50 DEG C or so.In 6mL CS2 is added dropwise in l h under electromagnetic agitation, then will
Mixed liquor is filtered in 90 DEG C of reflux 1h, cooling crystallization, is recrystallized, is obtained colourless acicular crystal (intermediate 1), yield in water:
82%.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
It takes 3.18g (0.03mol) diazanyl thio-hydrazide (intermediate 1) in flask, 10mL glacial acetic acid reflux 4h is added, it is cold
To room temperature, be evaporated under reduced pressure out unreacted acetic acid, wash crude product recrystallizes to obtain white crystals (intermediate 2) with water, yield:
77%.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3): 4- hydroxy benzaldehyde (6.1g) is added to
In the acetone of 60mL, after stir about 15min, after the ice bath reaction system about 30min, the 5% of about 100mL is added into system
NaOH solution removes ice bath room, stirring at normal temperature is about for 24 hours after being added dropwise.To after reaction, system is transferred to 500mL
Beaker in and appropriate ice water is added, after being about then 5~6 with 5% dilute hydrochloric acid solution regulation system pH, have a large amount of yellow solid
Body is precipitated, and solid is extracted out, is finally recrystallized with ethanol/water system to get yellow solid, yield 65%.
(4) preparation of 1- (4- nitro) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone (intermediate 4): by 4- (hydroxyl
Phenyl)-3- butene-2 -one (3.0g), 4- nitrobenzaldehyde (2.24mL) and 50mL ethyl alcohol is added to the three-necked flask of 250mL
In, after stir about 30min, into system, 5% NaOH solution of 60mL removes ice bath room, stirring at normal temperature after being added dropwise
About for 24 hours.To after reaction, system is transferred in the beaker of 500mL and appropriate ice water is added, then with 5% dilute hydrochloric acid
After solution regulation system pH is about 5~6, there are a large amount of yellow solids to be precipitated, solid is extracted out to get yellow solid, yield 80%.
(5) system of 1- (4- (2- bromine oxethyl) phenyl) -5- (4- nitrobenzophenone) -1,4- pentadiene -3- ketone (intermediate 5)
It is standby:
1- (4- nitro) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone is sequentially added in 100mL round-bottomed flask
After 1h that then mixed liquor flows back at 80 DEG C, 2.80mL dibromo second is added dropwise in (1.6g), K2CO3 (2.25g) and 60mL acetonitrile
Alkane continues the 7h that flows back at 80 DEG C, TLC tracking reaction (ethyl acetate: petroleum ether=1:2, V/V).After reaction stops, reaction solution
With the water dispersion of 50mL, ethyl acetate extracts (3 × 25mL), merges organic layer, with saturated common salt water washing (3 × 40mL), nothing
Water NaSO4 is dry, solvent is removed under reduced pressure, and reduced pressure chromatography separating-purifying (petroleum ether: ethyl acetate=2:1, V/V) obtains brown
Solid (intermediate 5), yield: 53%.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4-
Nitrobenzophenone) -1,4- pentadiene -3- ketone (target compound A1) preparation:
4- amino -5- methyl -4H-1,2-4- triazole -3- the sulfydryl of 0.5g is added in the single necked round bottom flask of 100mL
(intermediate 2), K2CO3 (1.33g) and 60mL DMF, stirring at normal temperature 0.5h, after be slowly added to 1- (4- (2- bromine oxethyl) benzene
Base) -5- (4- nitrobenzophenone)-Isosorbide-5-Nitrae-pentadiene -3- ketone (intermediate 5) DMF solution, continue under room temperature to stir 6-8h.TLC with
Track reaction, when reaction terminates, stopping is reacted, the water dispersion of reaction solution 100mL, and ethyl acetate extracts (3 × 25mL), is associated with
Machine layer, with saturated common salt water washing (3 × 40mL), anhydrous sodium sulfate is dry, solvent is removed under reduced pressure, and obtains crude product, chromatographs through column
(ethyl acetate: methanol=12:1~10:1, V/V) purification obtains target compound, yield: 34%.
Embodiment 2
(4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4- chlorobenzene
Base)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A2) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (4- chlorine) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 4- chlorobenzaldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (4- chlorphenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 4- chlorobenzaldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4-
Chlorphenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 4- chlorobenzaldehyde, yield: 54%.
Embodiment 3
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4- fluorine
Phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A3) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (4- fluorine) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 4- fluorobenzaldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (4- fluorophenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 4- fluorobenzaldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4-
Fluorophenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 4- fluorobenzaldehyde, yield: 50%.
Embodiment 4
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2,4-
Dimethoxyphenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A4) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (2,4- dimethoxy) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 2,4- dimethoxy benzaldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (2,4- Dimethoxyphenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 2,4- dimethoxy benzaldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2,
4- Dimethoxyphenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 2,4- dimethoxy benzaldehyde, yield: 31%.
Embodiment 5
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3- nitre
Base phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A5) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (3- nitro) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 3- nitrobenzaldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (3- nitrobenzophenone) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 3- nitrobenzaldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3-
Nitrobenzophenone) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 3- nitrobenzaldehyde, yield: 40%.
Embodiment 6
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3,4-
Dimethoxyphenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A6) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (3,4- dimethoxy) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is Veratraldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (3,4- Dimethoxyphenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is Veratraldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3,
4- Dimethoxyphenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is Veratraldehyde, yield: 41%.
Embodiment 7
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4- bromine
Phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A7) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (4- bromine) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 4- bromobenzaldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (4- bromophenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 4- bromobenzaldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4-
Bromophenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 4- bromobenzaldehyde, yield: 43%.
Embodiment 8
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2,4-
Dichlorophenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A8) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (2,4- dichloro) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 2,4- dichlorobenzaldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (2,4 dichloro benzene base) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 2,4- dichlorobenzaldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2,
4- dichlorophenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 2,4- dichlorobenzaldehyde, yield: 35%.
Embodiment 9
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4- first
Base phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A9) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (4- methyl) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 4- tolyl aldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (4- aminomethyl phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 4- tolyl aldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4-
Aminomethyl phenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 4- tolyl aldehyde, yield: 63%.
Embodiment 10
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2- chlorine
Phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A10) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (2- chlorine) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 2- chlorobenzaldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (2- chlorphenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 2- chlorobenzaldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2-
Chlorphenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 2- chlorobenzaldehyde, yield: 29%.
Embodiment 11
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4- first
Phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A11) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (4- methoxyl group) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 4-methoxybenzaldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (4- methoxyphenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 4-methoxybenzaldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (4-
Methoxyphenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 4-methoxybenzaldehyde, yield: 62%.
Embodiment 12
1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2- furan
Mutter base)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A13) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment.
(4) preparation of 1- (2- furyl) -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that R is 2 furan carboxyaldehyde.
(5) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (2- furyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that R is 2 furan carboxyaldehyde.
(6) 1- (4- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2-
Furyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that R is 2 furan carboxyaldehyde, yield: 50%.
Embodiment 13
1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2- first
Phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A14) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 2- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment, difference is that X is 2-O.
(4) preparation of 1- (2- methoxyl group) -5- (2- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that X is 2-O, and R is Benzaldehyde,2-methoxy.
(5) preparation of 1- (2- (2- bromine oxethyl) phenyl) -5- (2- methoxyphenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that X is 2-O, and R is Benzaldehyde,2-methoxy.
(6) 1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2-
Methoxyphenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that X is 2-O, and R is Benzaldehyde,2-methoxy, yield: 51%.
Embodiment 14
1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3,4-
Dimethoxyphenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A15) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 2- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment, difference is that X is 2-O.
(4) preparation of 1- (3,4- dimethoxy) -5- (2- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that X is 2-O, and R is Veratraldehyde.
(5) preparation of 1- (2- (2- bromine oxethyl) phenyl) -5- (3,4- Dimethoxyphenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that X is 2-O, and R is Veratraldehyde.
(6) 1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3,
4- Dimethoxyphenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that X is 2-O, and R is Veratraldehyde, yield: 53%.
Embodiment 15
1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3- first
Base phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A16) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 2- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment, difference is that X is 2-O.
(4) preparation of 1- (3- methyl) -5- (2- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that X is 2-O, and R is 3- tolyl aldehyde.
(5) preparation of 1- (2- (2- bromine oxethyl) phenyl) -5- (3- aminomethyl phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that X is 2-O, and R is 3- tolyl aldehyde.
(6) 1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3-
Aminomethyl phenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that X is 2-O, and R is 3- tolyl aldehyde, yield: 48%.
Embodiment 16
1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2,4-
Dichlorophenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A17) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 2- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment, difference is that X is 2-O.
(4) preparation of 1- (2,4- dichloro) -5- (2- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that X is 2-O, R 2,4- dichlorobenzaldehyde.
(5) preparation of 1- (2- (2- bromine oxethyl) phenyl) -5- (2,4 dichloro benzene base) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that X is 2-O, R 2,4- dichlorobenzaldehyde.
(6) 1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (2,
4- dichlorophenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that X is 2-O, R 2,4- dichlorobenzaldehyde, yield: 37%.
Embodiment 17
1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3,4-
Dichlorophenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A18) preparation method, comprising the following steps:
(1) preparation of diazanyl thio-hydrazide (intermediate 1):
Such as 1 (1) step of embodiment.
(2) preparation of 4- amino -5- methyl -4H-1,2,4- triazole -3- sulfydryl (intermediate 2):
Such as 1 (2) step of embodiment.
(3) preparation of 2- (hydroxy phenyl)-3- butene-2 -one (intermediate 3):
Such as 1 (3) step of embodiment, difference is that X is 2-O.
(4) preparation of 1- (3,4- dichloro) -5- (2- hydroxy phenyl) -1,4- pentadiene -3- ketone:
Such as 1 (4) step of embodiment, difference is that X is 2-O, R 3,4- dichlorobenzaldehyde.
(5) preparation of 1- (2- (2- bromine oxethyl) phenyl) -5- (3,4- dichlorophenyl) -1,4- pentadiene -3- ketone:
Such as 1 (5) step of embodiment, difference is that X is 2-O, R 3,4- dichlorobenzaldehyde.
(6) 1- (2- (2- ((4- amino -5- methyl -4H-1,2,4- triazole -3- base) sulfenyl) ethyoxyl) phenyl) -5- (3,
4- dichlorophenyl) -1,4- pentadiene -3- ketone (target compound A2) preparation:
Such as 1 (6) step of embodiment, difference is that X is 2-O, R 3,4- dichlorobenzaldehyde, yield: 40%.
The Isosorbide-5-Nitrae of synthesized Sulfide-containing Hindered triazole-pentadiene -3- ketones derivant physicochemical property is shown in Table 1, nuclear magnetic resonance spectroscopy
(1H NMR) and carbon spectrum (13C NMR) data are shown in Table 2 and table 3.
Target compound physicochemical property made from 1 embodiment 1-17 of table
Target compound hydrogen nuclear magnetic resonance modal data made from 2 embodiment 1-17 of table
Target compound carbon-13 nmr spectra data made from 3 embodiment 1-17 of table
Test example 1: activity of resisting tobacco mosaic virus test:
Test method
A. Virus purification
Quadratic method (Zhou, X.P. are avenged using week；Xu,Z.X.；Xu,J.；Li,D.B.J.South
Chin.Agric.Univ.1995,16,74-79.), inoculation 3 weeks or more are chosen, TMV systemic infection host Nicotiana
Tabacum.L plant upper blade, is homogenized in phosphate buffer, double gauze filtering, 8000g centrifugation, through 2 polyethylene glycol
Processing, then be centrifuged, precipitating phosphate buffer suspends to get the refining liquid body of TMV is arrived.Entire experiment carries out at 4 DEG C.With purple
The absorbance value of outer spectrophotometric determination 260nm wavelength calculates virus concentration according to formula.
Virus concentration (mg/mL)=(A260 × extension rate)/E0.1%1cm260nm
Wherein E indicates extinction coefficient, i.e. when wavelength 260nm, concentration is the suspension of 0.1% (1mg/mL), is in light path
Absorbance value when 1cm.The E0.1%1cm260nm of TMV is 5.0.
B. the living body therapeutic effect that medicament infects TMV
Living body therapeutic effect of the medicament to infecting: the Nicotiana glutinosa of growing way consistent 5-6 leaf phase is selected to pinch, Xiang Quanye sprinkles evenly gold
Emery dips viral juice (6 × 10-3mg/mL) full leaf virus inoculation with spread pen, is rinsed after natural drying with clear water.To blade
After dry, medicament is gently spread in Zuo Banye with writing brush, the solvent for the concentration that right half leaf spreads corresponding solvent compares, 6-7d postscript
Withered spot number is recorded, inhibiting rate is calculated according to the following formula.
C. the living body protective effect that medicament infects TMV
The living body protective effect that medicament infects TMV: it selects the Nicotiana glutinosa of growing way consistent 5~6 leaf phase to pinch, is existed with writing brush
Zuo Banye gently spreads medicament, and the solvent for the concentration that right half leaf spreads corresponding solvent compares.After for 24 hours, Xiang Quanye sprinkles evenly Buddha's warrior attendant
Sand dips viral juice (6 × 10-3mg/mL) full leaf virus inoculation with spread pen, is rinsed with clear water, withered spot number is recorded after 6~7d,
Inhibiting rate is calculated according to the following formula.
D. the living body protective effect that medicament infects TMV
Medicament is mixed into passivation 30min with isometric viral juice, the mixed liquor of medicament and virus, people are dipped with spread pen
Work frictional inoculation is supported below blade with smooth plank on the left half of blade of the blade sprinkled with diamond dust.Aqua sterilisa and virus
Right half leaf of juice combined inoculation.Every chemicals treatment sets 3 plants, and plant is then placed on moisturizing in illumination box by every plant of 5-6 piece leaf
Culture controls 23 ± 1 DEG C of temperature, the number for generating withered spot is observed and recorded after illumination 10000Lux, 6-7d.
Wherein, the average withered spot number for being not coated with application half leaf of agent and the half leaf withered spot number for spreading medicament all use each group to weigh three times
Multiple average.Calculate inhibiting rate.
The biological activity test result of resisting tobacco mosaic virus
Treatment and protection activity of the 4 embodiment 1-17 of table to tobacco mosaic virus (TMV)
It is control with virazole raw medicine and commodity medicament Ningnanmycin using half leaf withered spot method, is 500 μ g/ for examination concentration
When mL, target compound A1~A17 is tested to the therapeutic activity and protection activity (being shown in Table 4) of tobacco mosaic virus (TMV) (TMV).It should
Test result shows: most of target compound has preferable therapeutic activity and protection activity to TMV.Wherein, target chemical combination
Object A3, A11, A13, A14, A16 possess preferable therapeutic effect to TMV, inhibiting rate is respectively 53.8,53.7,62.9,
56.6,63.9%, be more than virazole raw medicine (39.9%), close to Ningnanmycin (52.7%).Target compound A7, A8, A14,
A16 possesses preferable protective effect to TMV, and inhibiting rate is respectively 69.0,67.7,66.6,85.6%, is better than virazole raw medicine
(51.8%), close to Ningnanmycin (65.7%).
Test example 2: anti-vegetative bacteria active testing:
(1) test method
Using nephelometry, under 100 and 50 μ g/mL concentration, test target compound is white to tobacco ralstonia solanacearum and rice
The external inhibitory activity of leaf spoting bacteria, comparison medicament is Yekuzuo and Thiodiazole-copper in experiment.Tobacco ralstonia solanacearum and rice is white
Leaf spoting bacteria is cultivated on NA solid medium, is subsequently placed in 28 DEG C of constant-temperature bacterial culture box and is cultivated to growing single colonie.
Suitable central yellow single colonie is chosen, puts it in NB fluid nutrient medium, is vibrated in 28 DEG C, 180r/min constant-temperature table
It is spare to cultivate logarithmic growth phase.100 and 50 μ g/mL concentration are configured by compound and comparison medicament, takes 1mL to be added to and is equipped with
In the test tube of 4mL NB fluid nutrient medium, then measure the NB liquid training that 40 μ L contain tobacco ralstonia solanacearum and rice leaf spot bacteria
It supports base to be added in test tube, in 28 DEG C, 180r/min constant-temperature table shaken cultivation 48h.On spectrophotometer, 595nm wave is measured
The OD595 value of the sterile NB fluid nutrient medium of strong point dosing, while measuring the bacterium solution OD595 value of each concentration.
Correct the OD595 value=aseptic culture medium of OD595- containing bacterium culture medium OD595
It is right after inhibiting rate (%)=(control medium bacterium solution OD595- corrects pastille culture medium OD595 after correction)/correction
According to value × 100%. culture medium bacterium solution OD
(2) the biological activity test result of anti-plant pathogen
The bacteriostatic activity (inhibiting rate %) of 5 embodiment 1-17 of tablea
aIt is average to repeat three times；bYekuzuo and Thiodiazole-copper (20% wettable powder) are used as positive control.
It is being 100,50 μ g/mL for examination concentration using commodity medicament Thiodiazole-copper and Yekuzuo as positive control using nephelometry
When, target compound is tested to the inhibitory activity (being shown in Table 5) of hundred leaf spoting bacteria of tobacco ralstonia solanacearum and rice.As the result is shown:
All compounds have certain inhibitory activity to tobacco ralstonia solanacearum and rice leaf spot bacteria.It, should to tobacco ralstonia solanacearum
Series close object the inhibiting rate of 100 μ g/mL and 50 μ g/mL be more than comparison medicine Yekuzuo and Thiodiazole-copper (respectively 58.21,
49.45,37.05,17.43%).To rice leaf spot bacteria, inhibiting rate of the series compound in 100 μ g/mL and 50 μ g/mL
Better than comparison medicine Yekuzuo and Thiodiazole-copper, (respectively 47.03,32.54,43.23,24.12%), have preferable broad spectrum activity.
The above assay activity statistics indicate that the 1,4- pentadiene -3- ketones derivant of Sulfide-containing Hindered triazole to TMV and phytopathy
Bacterium (hundred leaf spoting bacteria of tobacco ralstonia solanacearum and rice) has certain inhibiting effect, and part of target compound fights plant
Virus and inhibit phytopathogen show excellent activity, can be used as potential Antiphytoviral drug and antibacterial medicines, have compared with
Good application prospect.
In conclusion being only presently preferred embodiments of the present invention, it is not intended to limit the present invention in any form, appoints
What is to the above embodiments according to the technical essence of the invention any simply to repair without departing from technical solution of the present invention content
Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (6)
1. a kind of Isosorbide-5-Nitrae of Sulfide-containing Hindered triazole-pentadiene -3- ketones derivant, general structure are as follows:
,
Wherein: X is 2-O or 4-O, and R is phenyl, substituted-phenyl, heterocycle or 4- methylthiazol.
2. a kind of Isosorbide-5-Nitrae of Sulfide-containing Hindered triazole-pentadiene -3- ketones derivant as described in claim 1, in which: substituted-phenyl
For p-fluorophenyl, rubigan, Chloro-O-Phenyl, 4- methoxyphenyl, 2,4- Dimethoxyphenyl, 3,4- Dimethoxyphenyl,
3- nitrobenzophenone, 4- nitrobenzophenone, 3,4- dichlorophenyl or 2,4 dichloro benzene base etc..
3. a kind of Isosorbide-5-Nitrae of Sulfide-containing Hindered triazole-pentadiene -3- ketones derivant as claimed in claim 1 or 2, in which: heterocycle
For furyl or thienyl.
4. a kind of Isosorbide-5-Nitrae of Sulfide-containing Hindered triazole-pentadiene -3- ketones derivant preparation method, synthetic route are as follows:
(1) hydrazine hydrate and carbon disulfide, by being heated to reflux, solid recrystallization prepares diazanyl thio-hydrazide (intermediate 1):
；
(2) diazanyl thio-hydrazide (intermediate 1) and glacial acetic acid, by being heated to reflux, solid recrystallization preparation 4- amino -5- first
Base -4H- 1,2- 4- triazole -3- sulfydryl (intermediate 2):
；
(3) acetone, 4- hydroxy benzaldehyde prepare 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3) under alkaline condition；
(4) substituted aroma aldehyde, 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 3) prepare 1- substitution virtue under alkaline condition
Base -5- (4- hydroxy phenyl) -1,4- pentadiene -3- ketone (intermediate 4)；
；
(5) 1- substituted aryl -5- (4- hydroxy phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (intermediate 4) and Bromofume, with potassium carbonate
For catalyst, with acetonitrile as solvents, prepare 1- substituted aryl -5- (4- (2- bromine oxethyl) phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone
(intermediate 5):
；
(6) 1- substituted aryl -5- (4- (2- bromine oxethyl) phenyl) -1,4- pentadiene -3- ketone (intermediate 5) and 4- amino -
5- methyl -4H-1,2,4- triazole -3- sulfydryls (intermediate 2) are catalyst with potassium carbonate, and n,N-Dimethylformamide (DMF) is
Solvent prepares the Isosorbide-5-Nitrae containing triazole-pentadiene -3- ketones derivant (target compound A), as follows:
。
5. application of the 1,4- pentadiene -3- ketones derivant of Sulfide-containing Hindered triazole in terms of resisting tobacco mosaic virus.
6. the 1,4- pentadiene -3- ketones derivant of Sulfide-containing Hindered triazole is inhibiting tobacco ralstonia solanacearum and rice leaf spot bacteria
Using.
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| CN110078721A (en) * | 2019-05-27 | 2019-08-02 | 贵州大学 | Dioctyl glutaricate and its preparation method and application of the one kind containing triazine |
| CN110078721B (en) * | 2019-05-27 | 2022-03-25 | 贵州大学 | Triazine-containing pentadiene ketone compound and preparation method and application thereof |
| CN114085199A (en) * | 2021-11-30 | 2022-02-25 | 贵州大学 | Chalcone derivative containing sulfonyl piperazine and preparation method and application thereof |
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