CN105884665B - A kind of cyclohexenone compounds and preparation method and application - Google Patents
A kind of cyclohexenone compounds and preparation method and application Download PDFInfo
- Publication number
- CN105884665B CN105884665B CN201610251891.7A CN201610251891A CN105884665B CN 105884665 B CN105884665 B CN 105884665B CN 201610251891 A CN201610251891 A CN 201610251891A CN 105884665 B CN105884665 B CN 105884665B
- Authority
- CN
- China
- Prior art keywords
- cyclohexenone compounds
- compound
- application
- herbicidal composition
- cyclohexenone
- 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.)
- Active
Links
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
- C07C323/23—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/46—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
- C07C323/47—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
-
- 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
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
- A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- 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
Abstract
The invention discloses a kind of cyclohexenone compounds and preparation method and application.Cyclohexenone compounds, it is characterised in that:The structural formula of compound such as formula(Ⅰ)It is shown, in formula, R1Selected from H, CH3CO、CH3CH2CO or CH3CH2CH2CO, R2Selected from CH3、CH3CH2、CH3CH2CH2、(CH3)2CH2、CH3CH2CH2CH2、(CH3)2CH2CH2Or CH3CH(CH3)CH2, R3Selected from CH3、CH3CH2、CH3CH2CH2、(CH3)2CH2、CH3CH2CH2CH2、(CH3)2CH2CH2Or CH3CH(CH3)CH2, R4Selected from H, CH3Or Cl.The compound of the present invention not only has high activity of weeding, and to crop safety, suitable for wide popularization and application.
Description
(One)Technical field
The present invention relates to technical field of pesticide, more particularly to a kind of cyclohexenone compounds and preparation method thereof are with answering
With.
(Two)Background technology
The presence of weeds, a large amount of underproduction of crop are caused, the use of herbicide, can effectively reduce danger caused by weeds
Evil.But with a large amount of uses of existing herbicide, Weed Resistance problem is increasingly severe, some weeds turn into existing herbicide
It is difficult to the weeds prevented and kill off;Meanwhile some existing herbicides are not high to the security of crop, key is easily caused to crop, therefore,
It is constantly needed to herbicide new, that security is good.
US5563114 discloses following compound CPD-1(Numbering is 4.20 in patent)Preparation and its as herbicide
Purposes:
。
Cyclohexenone compounds as representative of the present invention are not disclosed.
(Three)The content of the invention
The present invention is in order to make up the deficiencies in the prior art, there is provided a kind of activity of weeding is high, to the cyclohexene of crop safety
Ketone compounds and preparation method and application.
The present invention is achieved through the following technical solutions:
A kind of cyclohexenone compounds, it is characterised in that:The structural formula of compound such as formula(Ⅰ)It is shown,
,
In formula, R1Selected from H, CH3CO、CH3CH2CO or CH3CH2CH2CO,
R2Selected from CH3、CH3CH2、CH3CH2CH2、(CH3)2CH2、CH3CH2CH2CH2、(CH3)2CH2CH2Or CH3CH(CH3)
CH2,
R3Selected from CH3、CH3CH2、CH3CH2CH2、(CH3)2CH2、CH3CH2CH2CH2、(CH3)2CH2CH2Or CH3CH(CH3)
CH2,
R4Selected from H, CH3Or Cl;
Wherein, the R3 on carbon-carbon double bond and R4 is cis or trans,
X1Selected from H, F, Cl, Br or I,
X2Selected from F, Cl, Br, I or nitro.
Its preferable technical scheme is:
R1Selected from H, CH3CO or CH3CH2CO,
R2Selected from CH3、CH3CH2、CH3CH2CH2Or CH3CH2CH2CH2,
R3Selected from CH3Or CH3CH2, R4Selected from H or CH3,
X1Selected from H,
X2Selected from F, Cl, Br or I.
More excellent technical scheme is:R3Selected from CH3, R4Selected from H.
The formula of the present invention(Ⅰ)Compound can be prepared by the following method, R in formula1、R2、R3、R4、X1Or X2Group definition is the same.
It is equal according to the difference of reaction condition or the difference of initiation material, compound V, VII, chemical compounds I -1 and chemical compounds I -2
It is possible to cis-trans isomerization at double bond be present.By selecting appropriate initiation material or control reaction condition, can obtain
A kind of excessive product of isomers or individual isomer.Can also be by the separation to crude product progress conventional meanses, such as lead to
The methods of crossing column chromatography, recrystallization, obtains individual isomer.The structure of these isomers can pass through X-ray single crystal diffraction, core
The conventionals method of analysis such as magnetic resonance determine.
Work as R1Selected from CH3CO、CH3CH2CO or CH3CH2CH2During CO, the compounds of this invention can be raw material with I -1, with phase
The acyl chloride reaction answered is made.Reaction can be carried out in atent solvent, sometimes, can add inorganic base such as sodium carbonate,
Or the promotion such as organic base such as triethylamine reaction is complete.
The preparation of intermediate II, with reference to clethodim synthesis method US63300281 in example carry out.
Following table lists the structure and physical property of partial Formula I.
Part of compounds1HNMR(CDCl3, 300MHz) and δ (ppm) data are as follows:
Compound 1:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(M, 2H, CH2), 2.28(M,
2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 6.99
(D, 2H, CH), 7.52(D, 2H, CH);
Compound 2:
1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.38(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H,
CH3), 1.84;1.59(D, 2H, CH2), 2.28(M, 2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 2.91
(S, 3H, CH3), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 7.24(D, 2H, CH), 7.48(D, 2H, CH);
Compound 3:
0.84(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.37(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.28(M, 2H, CH2), 2.50(M,
1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 7.24(D, 2H, CH), 7.48(D,
2H, CH);
Compound 4:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.28(M,
2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 7.24
(D, 2H, CH), 7.48(D, 2H, CH)
Compound 5:
0.84(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.37(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.28(M, 2H, CH2), 2.50(M,
1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 7.35(D, 2H, CH), 7.41(D,
2H, CH);
Compound 6:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.28(M,
2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 7.35
(D, 2H, CH), 7.41(D, 2H, CH);
Compound 7:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.28(M,
2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 7.12
(D, 1H, CH), 7.28(S, 1H, CH), 7.41(D, 1H, CH);
Compound 8:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.28(M,
2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.28(S, 1H, CH), 7.83
(D, 2H, CH), 8.01(D, 2H, CH);
Compound 9:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.28(M,
2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 7.24
(D, 2H, CH), 7.48(D, 2H, CH);
Compound 10:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.22(S,
3H, CH3), 2.28(M, 2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 7.12
(D, 2H, CH), 7.24(D, 2H, CH);
Compound 11:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 1.92(S,
3H, CH3), 2.28(M, 2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14
(S, 1H, CH), 7.24(D, 2H, CH), 7.48(D, 2H, CH);
Compound 12:
0.7(T, 3H, CH3), 0.89(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H,
CH2), 1.38(M, 2H, CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D,
2H, CH2), 1.92(S, 3H, CH3), 2.07(M, 2H, CH2), 2.28(M, 2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57
(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 7.24(D, 2H, CH), 7.48(D, 2H, CH);
Compound 13:
0.7(M, 6H, CH3), 0.89(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H,
CH2), 1.38(M, 2H, CH2), 1.42(M, 2H, CH2), 1.47(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3),
1.84;1.59(D, 2H, CH2), 1.92(S, 3H, CH3), 2.1(T, 2H, CH2), 2.28(M, 2H, CH2), 2.50(M, 1H, CH1),
2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14(S, 1H, CH), 7.24(D, 2H, CH), 7.48(D, 2H, CH);
Compound 14:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.11(M, 2H, CH2), 1.27(M, 2H,
CH2), 1.33(M, 2H, CH2), 1.38(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D,
2H, CH2), 2.28(M, 2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.14
(S, 1H, CH), 7.24(D, 2H, CH), 7.48(D, 2H, CH);
Compound 15:
0.84(M, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.54(M, 1H, CH), 1.84;1.59(D, 2H, CH2), 2.28(M, 2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57
(D, 2H, CH2), 4.00(S, 2H, CH2), 6.18(S, 1H, CH), 7.12(D, 2H, CH)7.24(D, 2H, CH);
Compound 16:
0.7(T, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.84;1.59(D, 2H, CH2), 2.28(M, 2H, CH2), 2.50(M,
1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 6.18(S, 1H, CH), 7.12(D, 2H, CH)7.24(D,
2H, CH);
Compound 17:
0.84(M, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.28(M, 2H, CH2), 2.50(M,
1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 7.12(D, 2H, CH)7.24(D, 2H, CH);
Compound 18:
0.7(M, 3H, CH3), 1.05(T, 3H, CH3), 1.06(D, 3H, CH3), 1.33(M, 2H, CH2), 1.38(M, 2H,
CH2), 1.42(M, 2H, CH2), 1.54(M, 1H, CH), 1.62(S, 3H, CH3), 1.84;1.59(D, 2H, CH2), 2.28(M,
2H, CH2), 2.50(M, 1H, CH1), 2.82;2.57(D, 2H, CH2), 4.00(S, 2H, CH2), 7.12(D, 2H, CH)7.24(D,
2H, CH).
In organic molecule, after replacing hydrogen with alkyl, whole molecule can be made to have in electronegativity, space structure etc. larger
Difference so that whole molecule is translocatable widely different in the organisms such as plant.The suitable transporting of bioactive molecule
Performance of the performance to drug effect plays an important role.The well-formedness of bioactive molecule migrating capability be it is unpredictable, it is necessary to
Substantial amounts of creative work can just be known.
Compared with published compound CPD1, the present invention such as formula(Ⅰ)Shown compound not only shows high weeding
Activity, and unexpected crop safety is shown, especially to crop safeties such as rice, rapes.Therefore the present invention also wraps
Include formula(Ⅰ)Purposes of the shown compound as herbicide.
Application of the cyclohexenone compounds of the present invention in herbicidal composition, it is characterised in that:The ring
Hexene ketone compounds, which are dissolved or dispersed in carrier, is configured to herbicidal composition, wherein, the weight of cyclohexenone compounds
Amount percentage composition is 5-90%.
The Herbicidal combinations of the present invention can be applied in the form of several formulations.Generally the compound of the present invention is dissolved or divided
Dissipate more readily dispersible when being configured to preparation in carrier to be used as herbicide.Such as:These chemicals can be made into
Wettable powder or missible oil.Therefore, in these compositions, a kind of liquid or solid carrier is at least added, and usually require
Add appropriate surfactant.
The cyclohexenone compounds be used alone or with known insecticide, bactericide, plant growth regulator
Or fertilizer is used in mixed way.
Other embodiments of the present invention are the method for controlling weeds, and this method is included the of the invention of herbicidally effective amount
Herbicidal combinations are imposed on the place of the weeds or the weed growth or the surface of its somatomedin.Generally select more
Suitable effective amount is 10 grams to 5000 grams of per hectare, and preferably effective dose is 50 grams to 500 grams of per hectare., can for some applications
One or more other herbicides are added in the Herbicidal combinations of the present invention, thus can produce the advantages of additional and effect.
It should be appreciated that in scope defined by the claims of the present invention, various conversion and change can be carried out.
The compound of the present invention not only has high activity of weeding, and to crop safety, is provided for herbicide new
Raw material, suitable for wide popularization and application.
(Four)Embodiment
Following synthesis example, raw test result can be used to further illustrate the present invention, but be not intended to limit the present invention.
Synthesize example 1:The synthesis of compound 4
Step 1:
KOH3.6g is added in the mono- neck bottles of 1L, the dissolving of 30mL water is rear to add 430mL ethanol, stirring, adds 70.28g pairs
Chlorobenzaldehyde, is added dropwise propionic aldehyde 43.46g dropwise at 0 DEG C, and drop is to slowly warm up to room temperature after finishing, continues to stir.TLC is supervised after about 4h
Extent of reaction is controlled, -10 DEG C is cooled to after completion of the reaction, has solid precipitation, filtered after 1h, the ethanol of a small amount of precooling:Water=1:1 washes
To wash, the dissolving of filter cake 300mL dichloromethane, the washing of saturation NaCl solution, liquid separation separates dichloromethane phase, anhydrous sodium sulfate drying,
Filtering, concentration, it is yellow solid 51g to obtain compound 1, yield 56.7%.
Step 2:
Step 1 compound 27.09g, 300mL tetrahydrofuran stirring and dissolving is added in the mono- neck bottles of 500mL, is cooled to 0 DEG C,
NaBH is added portionwise45.7g, room temperature is to slowly warm up to, TLC monitors extent of reaction after about 2h, adds 150mL after completion of the reaction and satisfies
With saline solution and 150mL ethyl acetate, stirring, liquid separation, organic phase, anhydrous sodium sulfate drying, filtering, a small amount of acetic acid second are separated
Ester washs, and concentration, obtains yellow solid 26.74g, yield 97.9%.
Step 3:
Step 2 compound 43.8g, phthalyl hydroxyl imines 39.1g, triphenylphosphine are added in 500mL four-necked bottles
75.5g, 300mL tetrahydrofuran stirring and dissolvings are added, are cooled to less than 0 DEG C.DEAD tetrahydrofuran solution is added dropwise dropwise
(50.1gDEAD is dissolved in 50mL tetrahydrofurans), control temperature is below 5 DEG C.Room temperature is warmed naturally to after being added dropwise, it is stirred
Night.
Next day TLC monitors extent of reaction, and 200mL water is added dropwise dropwise after completion of the reaction, has solid precipitation, is cooled to 0 DEG C of analysis
Brilliant 1h, filter, the mixed solution (1 of a small amount of tetrahydrofuran and water:1) wash, the dissolving of filter cake 200mL dichloromethane, saturation NaCl
Solution washs, liquid separation, separates dichloromethane phase, anhydrous sodium sulfate drying, filters, concentration, obtains 50.2g white-yellowish solids, yield
64%。
Step 4:
Add step 3 compound 52.44g in the mono- neck bottles of 500mL, 300mLEA dissolvings, stirring, after ethanol is added dropwise dropwise
Amine 11.73g, room temperature continue to stir, and can observe that solid first dissolves and separate out afterwards, TLC monitoring extent of reactions, have been reacted after about 2h
Finish, saturation NaCl solution (200mL × 3) washing, liquid separation, separate ethyl acetate phase, anhydrous sodium sulfate drying, filtering.EA phases are put
In the mono- neck bottles of 500mL, stirring, 0 DEG C is cooled to, hydrochloric ethyl acetate solution 71.5g is added dropwise dropwise(9.8%), there is a large amount of solids
Separate out, 0 DEG C of growing the grain 1h, filtering, a small amount of EA washings, drying, obtain white solid 27g, yield 85.4%.
Step 5:The synthesis of target compound 4
Step 4 compound 3.94g, compound butyryl pentylcyclohexanone are added in the mono- neck bottles of 100mL(By document US63300281 systems
It is standby)6.82g, 50mLPE being added afterwards, being stirred, 5%NaOH solution adjusts pH to 7, is stirred overnight.Next day HPLC is monitored, and treats compound
II -1 surplus less than 3%, which is considered as reaction, finishes, and stands, liquid separation.Organic phase 3mol/L salt acid elutions, there are a large amount of solids to separate out, rear saturation
NaCl solution (100mL × 3) is washed, until solid disappears.Organic phase is separated, anhydrous sodium sulfate drying, filtering, is concentrated to give 9.1g
Object, yield 97.3%.
As stated above, other compounds of the present invention can be made.
It is raw to survey example 2:The measure of activity of weeding and crop safety
Testing compound is configured to 1 ‰ acetone soln.Every time before use, acetone by the compound of required usage amount
Solution is diluted with water to the 8ml aqueous solution.
Spraying treatment is carried out with sprayer(Sprinkler pressure is 2kg/m2, Conic nozzle flow is 50ml/min).After seedling is tried
Test, by quantitative weeds(Barnyard grass, moleplant seed)And crop(Rice)Seed is sowed in a diameter of 8cm Culture basin respectively, is broadcast
Earthing 1cm afterwards, cultivated according to a conventional method in greenhouse after suppression, water drenching.Grassy weed, rice length to 2-3 leaf phases are treated, chooses life
The examination material of long uniformity carries out after seedling cauline leaf spraying treatment, and control is used as using the aqueous acetone solution processing of same concentrations.Try material
Dry ventilation is placed on after processing, after decoction natural air drying, is placed in greenhouse and manages according to a conventional method, after processing in 48 hours
Using the method poured water from bottom, decoction is avoided to be washed.The examination material of unused compound processing compares.Experiment sets 3 repetitions.
Investigated within 25 days after processing, measure the death rate of weeds and crop and calculate a plant preventive effect.Partial test result is shown in
Following table.
Partial Formula(I)The activity of weeding and crop safety of compound(After seedling, strain preventive effect %):
。
Choose compound 7 and known compound CPD-1 has carried out the parallel determination of activity of weeding and security(After seedling, strain
Preventive effect %).As a result see the table below:
。
Claims (7)
- A kind of 1. cyclohexenone compounds, it is characterised in that:The structural formula of compound such as formula(Ⅰ)It is shown,,In formula, R1Selected from H, CH3CO or CH3CH2CO, R2Selected from CH3、CH3CH2、CH3CH2CH2Or CH3CH2CH2CH2, R3It is selected from CH3, R4Selected from H, X1Selected from H, X2Selected from F, Cl, Br or I.
- 2. the preparation method of cyclohexenone compounds according to claim 1, it is characterized in that, reactions steps are as follows:,Work as R1Selected from CH3CO、 CH3CH2CO or CH3CH2 CH2It is raw material with I -1 during CO, is made with corresponding acyl chloride reaction.
- 3. application of the cyclohexenone compounds according to claim 1 in herbicidal composition.
- 4. application of the cyclohexenone compounds according to claim 3 in herbicidal composition, it is characterised in that:Institute State cyclohexenone compounds and be dissolved or dispersed in carrier and be configured to herbicidal composition, wherein, cyclohexenone compounds Weight percentage be 5-90%.
- 5. application of the cyclohexenone compounds according to claim 3 in herbicidal composition, it is characterised in that:Institute Cyclohexenone compounds are stated to be used alone or mix with known insecticide, bactericide, plant growth regulator or fertilizer Use.
- 6. application of the cyclohexenone compounds according to claim 3 in herbicidal composition, it is characterised in that:Institute The dosage for stating cyclohexenone compounds is 10-5000 grams of per hectare.
- 7. application of the cyclohexenone compounds according to claim 6 in herbicidal composition, it is characterised in that:Institute The dosage for stating cyclohexenone compounds is 50-500 grams of per hectare.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610251891.7A CN105884665B (en) | 2016-04-21 | 2016-04-21 | A kind of cyclohexenone compounds and preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610251891.7A CN105884665B (en) | 2016-04-21 | 2016-04-21 | A kind of cyclohexenone compounds and preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105884665A CN105884665A (en) | 2016-08-24 |
CN105884665B true CN105884665B (en) | 2017-12-22 |
Family
ID=56704340
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610251891.7A Active CN105884665B (en) | 2016-04-21 | 2016-04-21 | A kind of cyclohexenone compounds and preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105884665B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106588836B (en) * | 2016-12-15 | 2018-09-18 | 西华大学 | 2- cyclohexenone derivates and its application in pesticide |
CN114591230A (en) * | 2022-03-07 | 2022-06-07 | 沈阳万菱生物技术有限公司 | Cyclohexenone compound, application thereof and pesticide herbicide |
CN115417791B (en) * | 2022-09-23 | 2023-10-27 | 郑州手性药物研究院有限公司 | Oxime ether 1, 3-cyclohexanedione compound and synthetic method and application thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1026283C (en) * | 1985-10-07 | 1994-10-26 | 切夫尔昂研究公司 | 2-[1-(3-chloroallyloxyamino) alkyliaene]-5-alkylthioalkyl-cyclohexane-1,3-dione herbicides |
DE3838309A1 (en) * | 1988-11-11 | 1990-05-31 | Basf Ag | CYCLOHEXENONE OXIMETHER, METHOD FOR THE PRODUCTION THEREOF, AND ITS USE AS HERBICIDE |
DE4014983A1 (en) * | 1990-05-09 | 1991-11-14 | Basf Ag | CYCLOHEXENONOXIMETHER, METHOD AND INTERMEDIATE PRODUCTS FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES |
DE19545212A1 (en) * | 1995-12-05 | 1997-06-12 | Basf Ag | Cyclohexenone oxime ether metal salts |
-
2016
- 2016-04-21 CN CN201610251891.7A patent/CN105884665B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN105884665A (en) | 2016-08-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111961041B (en) | Thiotriazinone isoxazoline compound, preparation method and application thereof, protoporphyrinogen oxidase inhibitor and herbicide | |
JPH0381266A (en) | Pyrazoleamides and insecticide and acaricide containing same compound as active ingredient | |
CN105884665B (en) | A kind of cyclohexenone compounds and preparation method and application | |
CN115417791B (en) | Oxime ether 1, 3-cyclohexanedione compound and synthetic method and application thereof | |
CN114957166B (en) | Phenylacetamide compound and preparation method and application thereof | |
CN105859698B (en) | N- (oxoethyl) -2- [4- (pyridine -2- bases epoxide) phenoxy group] amide derivatives | |
RU2050348C1 (en) | (s)-enantiomer or racemate of 2-chloro-5-(2-chloro-4-trifluoromethylphenoxy)-benzoate derivative showing herbicide activity | |
JPS60172946A (en) | Fluorine-containing benzophenone derivative and its use | |
CN105294674B (en) | Azabicyclic derivatives and its preparation and application | |
CN105859669B (en) | N (2 oximido ethyl) amide derivatives and preparation method and application | |
CN109761939B (en) | Substituted aryl methylene type Rubrolide compound and preparation method and application thereof | |
JPS6051175A (en) | Pyrazole derivative and selective herbicide | |
EP0118982A1 (en) | Organic phosphorous quinoxalinone and their production and use | |
JPH08301846A (en) | Carbazole derivative, its production and agricultural fungicide comprising the same as active ingredient | |
KR20090024394A (en) | Synthesis of new fluoroaromatic formamidines and their biological activity | |
CN106243084B (en) | A kind of Pyridylpyrrole quinoline compound and preparation method and application containing trifluoromethyl | |
CN114773388A (en) | Novel isoxazole derivative and application thereof | |
US20210009554A1 (en) | N-alkyl-n-cyanoalkylbenzamide compound and use thereof | |
JPS61291573A (en) | 2-phenyl-4,5,6,7-tetrahydro-2h-indazole derivative, production thereof and herbicide | |
CN113620849A (en) | Cyclohexenone compounds and preparation method and application thereof | |
JPH07149701A (en) | Itaconic acid derivative | |
JPS5911561B2 (en) | Soil fungicide for agriculture and horticulture | |
CN113831298A (en) | Optically active carboxylic ester compound and application thereof | |
JP2726404B2 (en) | Substituted phenyl carbonate derivatives | |
KR840001555B1 (en) | Process for the preparation of substituted cycloproplymethoxy anilides |
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 |