CN105732587A - 6-substituted pyrimidyl quinazolinone compound and application thereof - Google Patents
6-substituted pyrimidyl quinazolinone compound and application thereof Download PDFInfo
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- CN105732587A CN105732587A CN201410771120.1A CN201410771120A CN105732587A CN 105732587 A CN105732587 A CN 105732587A CN 201410771120 A CN201410771120 A CN 201410771120A CN 105732587 A CN105732587 A CN 105732587A
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- 0 C[C@]1C=*CC1 Chemical compound C[C@]1C=*CC1 0.000 description 3
- NWWTWLNQFPXFDP-UHFFFAOYSA-N CC1(C)NB(C(CC2CO)=CC=C2N)OC1(C)C Chemical compound CC1(C)NB(C(CC2CO)=CC=C2N)OC1(C)C NWWTWLNQFPXFDP-UHFFFAOYSA-N 0.000 description 1
- PXYRUWMZASLWJK-UHFFFAOYSA-N CCOC(Nc(cc1)c(CO)cc1-c1nccc(C)n1)=O Chemical compound CCOC(Nc(cc1)c(CO)cc1-c1nccc(C)n1)=O PXYRUWMZASLWJK-UHFFFAOYSA-N 0.000 description 1
- UACAKHXXZQDFHX-UHFFFAOYSA-N Cc1nc(Cl)[n-]cc1 Chemical compound Cc1nc(Cl)[n-]cc1 UACAKHXXZQDFHX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a 6-substituted pyrimidyl quinazolinone compound having a novel structure represented as the general formula (I) and a salt thereof, wherein the substituent groups in the formula are defined as the specification. The compound has excellent insecticidal activity and can be used for preventing and treating insect pests in agriculture, forestry or non-treatment target, especially, the application for preventing and treating aphids.
Description
Technical field
The invention belongs to agricultural insecticide field, relate to a kind of 6-substituted pyrimidyl quianzolinones and application thereof.
Background technology
Due to insecticide in use for some time, it can be produced resistance by insect, accordingly, it would be desirable to constantly invent the compound with insecticidal activity that is novel and that improve and compositions.
Some 6-substituted quinazoline ketone compounds with insecticidal activity has been reported.CN1302801A discloses the base quianzolinones KC of 6 seven fluorine isopropyls1The insecticidal activity of (in patent compound 448) final goods, English common name pyrifluquinazon.WO2013075645A1 discloses 6-substituted-phenyl quianzolinones KC2、KC3And KC4(respectively compound 7,25 and 102 in patent) have good insecticidal activity.But, the preventive effect under low dosage is unsatisfactory.
In prior art, 6-substituted pyrimidyl quianzolinones as representative of the present invention is not disclosed.
Summary of the invention
It is an object of the invention to provide a kind of 6-substituted pyrimidyl quianzolinones and application thereof..
For achieving the above object, technical scheme is as follows:
A kind of 6-substituted pyrimidyl quianzolinones and salt thereof, as shown in formula I:
In formula I:
L is selected from L1Or L2:
R1Selected from hydrogen atom, C1-C8Alkyl-carbonyl, C1-C8Halogenated alkyl carbonyl, C1-C8Alkoxy carbonyl, C1-C8Halo alkoxy carbonyl, C1-C8Alkyl sulphonyl, C1-C8Alkyloxysulfonyl or aryl-acyl that is unsubstituted or that replaced by least one following substituent group: halogen, hydroxyl, amino, nitro, cyano group, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxyl or C1-C6Halogenated alkoxy；
R2、R3、R4What may be the same or different is independently selected from hydrogen atom, halogen, C1-C8Alkyl, C1-C8Haloalkyl, C1-C8Alkoxyl, C1-C8Halogenated alkoxy, C1-C8Alkyl amino, C1-C8Haloalkylamino, C1-C8Alkyl-carbonyl-amino, C1-C8Haloalkylcarbonylamino or there are 1-3 heteroatomic 5 yuan or 6 yuan of heterocyclic acyl amino.
Or the salt of compound of Formula I.
In the present invention, preferred compound is, in formula I:
L is selected from L1Or L2:
R1Selected from hydrogen atom, C1-C4Alkyl-carbonyl, C1-C4Halogenated alkyl carbonyl, C1-C4Alkoxy carbonyl, C1-C4Halo alkoxy carbonyl, C1-C4Alkyl sulphonyl, C1-C4Alkyloxysulfonyl or aryl-acyl that is unsubstituted or that replaced by least one following substituent group: halogen, hydroxyl, amino, nitro, cyano group, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxyl or C1-C6Halogenated alkoxy；
R2、R3、R4What may be the same or different is independently selected from hydrogen atom, fluorine, chlorine, bromine, iodine, C1-C4Alkyl, C1-C4Haloalkyl, C1-C4Alkoxyl, C1-C4Halogenated alkoxy, C1-C4Alkyl amino, C1-C4Haloalkylamino, C1-C4Alkyl-carbonyl-amino, C1-C4Haloalkylcarbonylamino or there are 1-3 heteroatomic 5-or 6 yuan of heterocyclic acyl amino.
Or the salt of compound of Formula I.
In the present invention it is preferred that compound be, in formula I:
L is selected from L1Or L2:
R1Selected from hydrogen atom, C1-C4Alkyl-carbonyl or C1-C4Alkoxy carbonyl.
R2、R3、R4What may be the same or different is independent of hydrogen atom, fluorine, chlorine, bromine, iodine, C1-C3Alkyl or C1-C3Haloalkyl；
Or the salt of compound of Formula I.
In the present invention, particularly preferred compound is, in formula I:
L is selected from L1Or L2:
R1Selected from C1-C4Alkyl-carbonyl or C1-C4Alkoxy carbonyl；
R2、R3、R4What may be the same or different is independent of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl group, isopropyl, trifluoromethyl, pentafluoroethyl group, heptafluoropropyl or seven fluorine isopropyls.
Or the salt of compound of Formula I.
In the definition of general formula compound I given above, collect term used and generally define as follows:
Alkyl refers to straight or branched form, for instance the groups such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl, n-hexyl.Haloalkyl refers to the group that alkyl is optionally substituted with one or more halogen atoms.Alkoxyl refers to that alkyl end is connected with the group of oxygen atom, for instance methoxyl group, ethyoxyl, positive propoxy, isopropoxy, tert-butoxy etc..Halogenated alkoxy refers to the group that alkoxyl is optionally substituted with one or more halogen atoms.
The compound of Formula I of the present invention can be prepared by following method, and in reaction equation, each group definition is the same.
(L is selected from L to the compound of Formula I of the present invention2) can by compound of Formula I (L be selected from L1) reduction obtain.Preparation method is as follows:
(L is selected from L to formula I1) compound is in suitable solvent, temperature is under the boiling point that room temperature arrives suitable solvent, reacts 0.5-48 hour, and (L is selected from L to prepare formula I by reducing agent or the method reduced by hydrogen catalytic2) compound.
Suitable solvent is selected from halogenated hydrocarbons, such as dichloromethane, chloroform etc.；Aromatic hydrocarbon, such as toluene etc.；Nitrile, such as acetonitrile, benzonitrile etc.；Ether, such as oxolane, dioxane etc.；Alcohol, such as methanol, ethanol etc.；Amide, such as DMF etc.；Dimethyl sulfoxide；Ester, such as ethyl acetate；Water etc..
Reducing agent is selected from metallic boron hydrides such as sodium borohydride, sodium cyanoborohydride or borine etc..
Catalyst is selected from palladium carbon, palladium dioxide, Raney Ni etc..
Formula I (R1It is not that H, L are selected from L1) can by formula I (R1Selected from H, L selected from L1) compound prepare.Reaction equation is as follows:
In formula: LG represents suitable leaving group, such as chlorine atom, bromine atoms or acyloxy etc..
Formula I (R1Selected from H, L selected from L1) compound and Compounds of formula II (such as carboxylic acid halides or anhydride etc., commercially available) in suitable solvent, temperature be-10 DEG C to 0.5-48 hour prepared general formula compound I (R of reaction under the suitable solvent boiling point of reaction1It is not that H, L are selected from L1)。
Suitable solvent is selected from halogenated hydrocarbons, such as dichloromethane, chloroform etc.；Aromatic hydrocarbon, such as toluene etc.；Nitrile, such as acetonitrile, benzonitrile etc.；Ether, such as oxolane, dioxane etc.；Alcohol, such as methanol, ethanol etc.；Amide, such as DMF etc.；Dimethyl sulfoxide；Ester, such as ethyl acetate；Water etc..
Add suitable alkaloids reaction is favourable.Suitable alkali is selected from organic base such as triethylamine, DMA, pyridine, Feldalat NM, Sodium ethylate, sodium tert-butoxide or potassium tert-butoxide etc., or inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride etc..
Compound of Formula I I (the R of the present invention1Selected from H, L selected from L1) can prepare by the following method:
Compound of formula III and pyridine carboxaldehyde are in suitable solvent, and temperature is that room temperature arrives 0.5-48 hour prepared formula I (R of reaction under the solvent boiling point that reaction is suitable1Selected from H, L selected from L1) compound.
Suitable solvent is selected from halogenated hydrocarbons, such as dichloromethane, chloroform etc.；Aromatic hydrocarbon, such as toluene etc.；Nitrile, such as acetonitrile, benzonitrile etc.；Ether, such as oxolane, dioxane etc.；Alcohol, such as methanol, ethanol etc.；Amide, such as DMF etc.；Dimethyl sulfoxide；Ester, such as ethyl acetate；Water etc..
Adding suitable acid reaction is favourable, suitable acid is selected from mineral acid (such as sulphuric acid, hydrochloric acid) or organic acid (such as acetic acid, p-methyl benzenesulfonic acid etc.).
General formula compound III preparation method is as follows:
Wherein Hal represents halogen atom.
General formula compound IV and hydrazine hydrate are in suitable solvent, and temperature is that room temperature arrives 0.5-48 hour prepared general formula compound III of reaction under the boiling point of suitable solvent.
Suitable solvent is selected from dichloromethane, chloroform, toluene, acetonitrile, oxolane, dioxane, methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide or HMPA etc..
General formula compound IV preparation method is referring to US20040082586；J.Org.Chem.60,7508-7510,1995；TetrahedronLett.52,6489–6491,2011；Tetra.66,3207-3213,2010.
Table 1 lists structure and the physicochemical property of partial Formula I.
The structure of table 1 partial Formula I and physicochemical property
Part of compounds1HNMR (300MHz, DMSO) data are as follows:
Compound 1:5.06 (s, 2H), 6.97～7.00 (m, 1H), 7.34～7.37 (m, 1H), 7.49～7.54 (m, 1H), 8.14 (s, 1H), 8.19～8.26 (m, 2H), 8.32 (s, 1H), 8.58～8.60 (m, 1H), 8.82～8.84 (m, 2H), 8.90 (s, 1H), 10.17 (s, 1H)
Compound 2:2.54 (s, 3H), 5.18 (s, 2H), 7.46～7.55 (m, 2H), 7.65～7.73 (m, 1H), 7.84～7.87 (m, 1H), 8.17～8.19 (m, 1H), 8.40～8.43 (m, 1H), 8.50 (s, 1H), 8.62～8.66 (m, 1H), 8.92～8.94 (m, 3H).
Compound 3:1.15 (t, 3H), 2.95 (q, 2H), 5.16 (s, 2H), 7.44～7.51 (m, 2H), 7.82～7.85 (m, 1H), 8.17～8.19 (m, 1H), 8.39～8.42 (m, 1H), 8.49 (s, 1H), 8.61～8.65 (m, 2H), 8.91～8.92 (m, 3H).
Compound 4:0.98 (t, 3H), 1.65～1.73 (m, 2H), 2.89 (t, 2H), 5.14 (s, 2H), 7.42～7.51 (m, 2H), 7.81～7.84 (m, 1H), 8.16～8.18 (m, 1H), 8.38～8.42 (m, 1H), 8.48 (s, 1H), 8.61 (s, 2H), 8.87～8.90 (m, 3H).
Compound 6:5.04 (s, 2H), 6.97～7.00 (m, 1H), 7.45～7.52 (m, 2H), 8.16～8.27 (m, 3H), 8.72～8.75 (m, 3H), 8.93～8.97 (m, 1H), 10.15 (s, 1H).
Compound 7:2.77 (s, 3H), 5.13 (s, 2H), 7.45～7.49 (m, 1H), 7.83 (d, 1H, J=8.4Hz), 8.17 (d, 1H, J=8.1Hz), 8.32～8.35 (m, 1H), 8.42 (s, 1H), 8.59～8.62 (m, 2H), 8.88 (s, 1H), 8.93 (s, 2H).
Compound 8:1.16 (t, 3H), 2.95 (q, 2H), 5.12 (s, 2H), 7.45～7.49 (m, 1H), 7.82 (d, 1H, J=8.4Hz), 8.17 (d, 1H, J=8.1Hz), 8.34 (d, 1H, J=8.4Hz), 8.41 (s, 1H), 8.55～8.62 (m, 2H), 8.88 (s, 1H), 8.92 (s, 2H).
Compound 9:1.01 (t, 3H), 1.59～1.74 (m, 2H), 2.94 (q, 2H), 5.12 (s, 2H), 7.41～7.49 (m, 1H), 7.82 (d, 1H, J=8.7Hz), 8.17 (d, 1H, J=8.1Hz), 8.34 (d, 1H, J=8.7Hz), 8.42 (s, 1H), 8.59～8.63 (m, 2H), 8.89 (s, 1H), 8.93 (s, 2H).
Compound 11:2.50 (s, 3H), 5.05 (s, 2H), 7.26 (d, 1H, J=5.1Hz), 7.57～7.63 (m, 1H), 7.75～7.80 (m, 1H), 8.17 (s, 1H), 8.37 (d, 1H, J=7.5Hz), 8.52 (d, 1H, J=8.1Hz), 8.72～8.78 (m, 2H), 8.92 (s, 1H), 9.02～9.05 (m, 1H), 9.93 (s, 1H).
Compound 16:1.26 (t, 3H), 2.63 (q, 2H), 5.05 (s, 2H), 6.95～6.98 (m, 1H), 7.45～7.49 (m, 1H), 8.10～8.22 (m, 3H), 8.29 (s, 1H), 8.56～8.57 (m, 1H), 8.69 (s, 2H), 8.87 (s, 1H), 10.12 (s, 1H).
Compound 17:1.26 (t, 3H), 2.53 (s, 3H), 2.65 (q, 2H), 5.15 (s, 2H), 7.49～7.53 (m, 1H), 7.81～7.84 (m, 1H), 8.16～8.19 (m, 1H), 8.36～8.39 (m, 1H), 8.45 (s, 1H), 8.61～8.64 (m, 2H), 8.79～8.82 (m, 2H), 8.89 (s, 1H).
Compound 18:1.16 (t, 3H), 1.29 (t, 3H), 2.72 (q, 2H), 2.94 (q, 2H), 5.12 (s, 2H), 7.45～7.49 (m, 1H), 7.78～7.82 (m, 1H), 8.16～8.18 (m, 1H), 8.36～8.39 (m, 1H), 8.44 (s, 1H), 8.59～8.62 (m, 2H), 8.74 (s, 2H), 8.88 (s, 1H).
Compound 19:0.99 (t, 3H), 1.29 (t, 3H), 1.66～1.73 (m, 2H), 2.69 (q, 2H), 2.89 (t, 2H), 5.12 (s, 2H), 7.45～7.49 (m, 1H), 7.79～7.82 (m, 1H), 8.16～8.19 (m, 1H), 8.36～8.39 (m, 1H), 8.44 (s, 1H), 8.59～8.62 (m, 2H), 8.74 (s, 2H), 8.88 (s, 1H).
Compound 36:2.53 (s, 3H), 5.03 (s, 2H), 6.96 (d, 1H, J=8.1Hz), 7.15 (d, 1H, J=4.8Hz), 7.40～7.44 (m, 1H), 8.11 (s, 1H), 8.17～8.25 (m, 2H), 8.32 (s, 1H), 8.52～8.54 (m, 1H), 8.62 (d, 1H, J=4.8Hz), 8.86 (s, 1H), 10.07 (s, 1H).
Compound 37:2.54 (s, 3H), 2.56 (s, 3H), 5.12 (s, 2H), 7.26 (d, 1H, J=5.1Hz), 7.44～7.48 (m, 1H), 7.82 (d, 1H, J=8.7Hz), 8.16～8.19 (m, 1H), 8.38～8.42 (m, 1H), 8.46 (s, 1H), 8.58～8.60 (m, 1H), 8.64 (s, 1H), 8.69～8.70 (m, 1H), 8.88 (s, 1H).
Compound 38:1.19 (t, 3H), 2.56 (s, 3H), 2.93 (q, 2H), 5.12 (s, 2H), 7.26 (d, 1H, J=4.8Hz), 7.45～7.46 (m, 1H), 7.81 (d, 1H, J=8.4Hz), 8.16～8.19 (m, 1H), 8.39～8.42 (m, 1H), 8.46 (s, 1H), 8.58～8.59 (m, 1H), 8.64 (s, 1H), 8.68～8.70 (m, 1H), 8.88 (s, 1H).
Compound 39:0.99 (t, 3H), 1.67～1.74 (m, 2H), 2.56 (s, 3H), 2.89 (q, 2H), 5.12 (s, 2H), 7.26 (d, 1H, J=5.1Hz), 7.44～7.48 (m, 1H), 7.81 (d, 1H, J=8.4Hz), 8.16～8.19 (m, 1H), 8.38～8.42 (m, 1H), 8.46 (s, 1H), 8.58～8.60 (m, 1H), 8.64 (s, 1H), 8.68～8.70 (m, 1H), 8.89 (s, 1H).
Compound 41:5.07 (s, 2H), 7.55～7.59 (m, 2H), 7.75 (d, 1H, J=4.5Hz), 8.17 (s, 1H), 8.27～8.34 (m, 2H), 8.61 (m, 2H), 8.92 (s, 1H), 9.16 (d, 1H, J=5.1Hz), 10.21 (s, 1H).
Compound 42:2.55 (s, 3H), 5.17 (s, 2H), 7.46～7.50 (m, 1H), 7.87～7.91 (m, 2H), 8.16～8.18 (m, 1H), 8.41～8.48 (m, 2H), 8.61～8.62 (m, 2H), 8.90 (s, 1H), 9.25～9.27 (m, 1H).
Compound 43:1.17 (t, 3H), 2.96 (q, 2H), 5.16 (s, 2H), 7.45～7.50 (m, 1H), 7.85～7.93 (m, 2H), 8.16～8.19 (m, 1H), 8.41～8.48 (m, 2H), 8.60～8.63 (m, 2H), 8.89 (s, 1H), 9.24～9.26 (m, 1H).
Compound 44:0.98 (t, 3H), 1.67～1.71 (m, 2H), 2.93 (q, 2H), 5.17 (s, 2H), 7.48～7.49 (m, 1H), 7.86～7.94 (m, 2H), 8.17～8.19 (m, 1H), 8.41～8.48 (m, 2H), 8.61～8.64 (m, 2H), 8.94 (s, 1H), 9.25～9.27 (m, 1H).
Compound 45:1.22 (d, 6H), 3.51～3.53 (m, 1H), 5.20 (s, 2H), 7.48～7.50 (m, 1H), 7.85～7.94 (m, 2H), 8.18～8.20 (m, 1H), 8.42～8.49 (m, 2H), 8.61～8.64 (m, 2H), 8.92 (s, 1H), 9.26～9.29 (m, 1H).
Compound 47:2.43 (s, 3H), 4.01 (d, 2H, J=4.5Hz), 4.48 (s, 2H), 6.09 (t, 1H), 7.20～7.22 (m, 1H), 7.65～7.85 (m, 2H), 8.11～8.64 (m, 4H), 8.91 (s, 2H).
Compound 49:0.99 (t, 3H), 1.58～1.63 (m, 2H), 2.79 (q, 2H), 4.02 (d, 2H, J=4.5Hz), 4.50 (s, 2H), 6.16 (t, 1H), 7.20～7.25 (m, 1H), 7.68～7.75 (m, 2H), 8.13 (s, 1H), 8.27 (d, 1H, J=8.4Hz), 8.37～8.38 (m, 1H), 8.45 (s, 1H), 8.93 (s, 2H).
Compound 61:2.54 (s, 3H), 4.01 (m, 2H), 4.50 (s, 2H), 6.12 (t, 1H), 7.17～7.24 (m, 1H), 7.39～7.40 (m, 1H), 7.66～7.74 (m, 2H), 8.18 (s, 1H), 8.31～8.34 (m, 2H), 8.44 (s, 1H), 8.85～8.87 (m, 2H).
Compound 62:1.24 (t, 3H), 2.94 (q, 2H), 4.07 (d, 2H, J=4.8Hz), 4.82 (s, 2H), 5.93 (t, 1H), 7.19～7.26 (m, 2H), 7.63～7.66 (m, 1H), 7.84～7.87 (m, 2H), 8.40～8.49 (m, 2H), 8.55 (s, 1H), 8.80～8.82 (m, 2H)
Compound 63:0.95 (t, 3H), 1.60～1.63 (m, 2H), 2.74 (t, 2H), 4.01 (d, 2H, J=4.8Hz), 4.52 (s, 2H), 6.20 (t, 1H), 7.20～7.28 (m, 1H), 7.40～7.45 (m, 1H), 7.71～7.74 (m, 2H), 8.20 (s, 1H), 8.30～8.44 (m, 3H), 8.88～8.89 (m, 2H).
Compound 75:2.41 (s, 3H), 2.56 (s, 3H), 3.98～4.04 (m, 2H), 4.49 (s, 2H), 6.09 (m, 1H), 7.22～7.23 (m, 2H), 7.69～7.74 (m, 2H), 8.17 (s, 1H), 8.32～8.35 (m, 2H), 8.50 (s, 1H), 8.66～8.67 (m, 1H).
Compound 76:1.18 (t, 3H), 2.54 (s, 3H), 2.80 (q, 2H), 4.03 (m, 2H), 4.47 (s, 2H), 6.09 (m, 1H), 7.21 (s, 2H), 7.60～7.72 (m, 2H), 8.16 (s, 1H), 8.31～8.49 (m, 3H), 8.64 (s, 1H).
Compound 77:0.94 (t, 3H), 1.61 (m, 2H), 2.54 (s, 3H), 2.76 (m, 2H), 4.02～4.06 (m, 2H), 4.49 (s, 2H), 6.09 (m, 1H), 7.20～7.26 (m, 2H), 7.67～7.73 (m, 2H), 8.17 (s, 1H), 8.30～8.36 (m, 2H), 8.46 (s, 1H), 8.63～8.69 (m, 1H).
Compound 81:0.95 (t, 3H), 1.62～1.72 (m, 2H), 2.76 (t, 2H), 4.02 (d, 2H, J=4.5Hz), 4.62 (s, 2H), 6.07 (t, 1H), 7.18～7.22 (m, 1H), 7.66～7.83 (m, 3H), 8.06～8.62 (m, 4H), 9.20～9.22 (m, 1H).
A kind of compound of Formula I is for preparing the purposes of the insecticide of the insect pest controlling agricultural, forestry or non-treatment purpose.
A kind of Pesticidal combination, containing the compound shown in described formula I as acceptable carrier in active component and agricultural, forestry；The compound shown in formula I of active component to be weight percentage be 1-99% in compositions.
A kind of Pesticidal combination controls the method for insect pest, combinations of the above thing is imposed on the effective dose of per hectare 10 grams to 1000 grams need to control agricultural, forestry or or the insect of non-treatment purpose or the medium of its growth on.
Specifically the general formula compound I of the present invention has high insecticidal activity.Insect such as black bean aphid is had and well controls effect.Therefore, present invention additionally comprises general formula compound I for controlling the purposes of the insect pest of agricultural, forestry or non-treatment purpose；Especially, the compound of the present invention is preferred for controlling the purposes of aphid such as black bean aphid insect pest.
Present invention additionally comprises the Pesticidal combination using general formula compound I as active component.In this Pesticidal combination, the weight percentage of active component is between 1-99%.This Pesticidal combination also includes acceptable carrier in agricultural, forestry, health.
Technical scheme also includes the method for pest control: imposed on by the Pesticidal combination of the present invention on described insect or its somatomedin.The comparatively suitable effective amount being generally selected is per hectare 10 grams to 1000 grams.
The compositions of the present invention can the form of preparation be used on insect or its somatomedin.General formula compound I is dissolved or dispersed in carrier as active component or is configured to preparation so that more readily dispersible when using as insecticide.Such as: these chemicals can be made into wettable powder or cream.In these compositionss, at least add a kind of liquid or solid carrier, and suitable surfactant can be added when needed.
For some application, for instance one or more other antibacterial, Insecticides (tech) & Herbicides (tech), plant growth regulator or fertilizer etc. agriculturally can be added in the Pesticidal combination of the present invention, thus can produce advantage and the effect added.
It should be appreciated that, in the claim limited range of the present invention, various conversion and change can be carried out.
Detailed description of the invention
Following synthetic example, raw result of the test of surveying can be used to further illustrate the present invention, but be not intended to limit the present invention.
Synthetic example
Embodiment 1, compound 36,37,38,39,75,76,77 preparation
(1), the synthesis of 2-amino-5-bromobenzene methanol
O-benzyl alcohol (5.00 grams is added in reaction bulb, 40.0 mM, commercially available), DMF (25 milliliters), ice bath stirring under be dividedly in some parts NBS (7.23 grams, 40.0 mMs), reactant liquor is under agitation directly poured in frozen water after reacting 2 hours by ice bath, filter, washing, dry, obtain white solid 5.86 grams, yield 72.5%.
(2), the synthesis of (2-amino-5-(4,4,5,5-tetramethyl-1,3,2-dioxy borine-2-base) phenyl) methanol
2-amino-5-bromobenzene methanol (4.04 grams, 20.0 mMs) and connection pinacol borate (7.65 grams, 30.0 mMs, commercially available) are dissolved in dioxane (200 milliliters) entirely, add CsCO3(19.6 grams, 60.0 mMs), PdCl2Dppf (0.88 gram, 1.2 mMs) and dppf (0.55 gram, 1.0 mMs), heating reflux reaction.Reactant liquor was cooled to room temperature after 2 hours by back flow reaction, it is filtered to remove insoluble matter, solvent evaporated, residue with water (200 milliliters), ethyl acetate (2 × 200 milliliters) extracts, and organic layer is through saturated common salt water washing, anhydrous magnesium sulfate dries, concetrated under reduced pressure, residue, through chromatography over CC (leacheate is PE:EA=3:1), obtains light yellow solid 3.39 grams.Yield 68.0%
(3), the synthesis of the chloro-4-methylpyrimidine of 2-
It is sequentially added into 2 in reaction bulb, the chloro-6-methylpyrimidine of 4-bis-(15.00 grams, 92.00 mMs), zinc powder (18.05 grams, 276.00 mMs), ammonia (38.70 grams, 276 mMs), stirring downhill reaction bottle adds water (120 milliliters).After heating reflux reaction 2 hours, reactant liquor is down to room temperature, sucking filtration, filtrate is extracted with ethyl acetate (2x200 milliliter), organic layer saturated aqueous common salt (150 milliliters) washs, anhydrous magnesium sulfate is dried, concetrated under reduced pressure, and residue is through chromatography over CC (leacheate is PE:EA=5:1), obtain white solid 8.8 grams, yield 74.4%
(4), the synthesis of (2-amino)-5-(4-methylpyrimidine-2-base) benzyl alcohol
(2-amino-5-(4 it is sequentially added in reaction bulb, 4,5,5-tetramethyl-1,3,2-dioxy boron penta ring-2-base) phenyl) methanol (15.00 grams, 60.20 mM), the chloro-4-methylpyrimidine of 2-(8.52 grams, 66.20 mM), tetra-triphenylphosphine palladium (1.39 grams, 1.20 mMs), add dioxane (120 milliliters) to dissolve, stirring downhill reaction bottle adds water (120 milliliters) solution of potassium carbonate (24.97 grams, 181.00 mMs).After heating reflux reaction 8 hours, reactant liquor is down to room temperature, rotation is except after major part dioxane, it is extracted with ethyl acetate (2x200 milliliter), organic layer saturated aqueous common salt (150 milliliters) washs, anhydrous magnesium sulfate is dried, concetrated under reduced pressure, and residue is through chromatography over CC (leacheate is PE:EA=3:1), obtain yellow solid 6.8 grams, yield 52.5%
(5), the synthesis of 2-(methylol)-4-(4-methylpyrimidine-2-base) ethyl phenylcarbamate
(2-amino)-5-(4-methylpyrimidine-2-base) benzyl alcohol (7.00 grams it is sequentially added in reaction bulb, 32.5 mM), dichloromethane (200 milliliters), pyridine (2.89 grams, 35.8 mM), ethyl chloroformate (3.53 grams, 32.5 mM), after being stirred at room temperature 0.5 hour, stopped reaction, reactant liquor is with first with water (200 milliliters) washing, saturated aqueous common salt (150 milliliters) washs, anhydrous magnesium sulfate is dried, concetrated under reduced pressure, residue is through chromatography over CC (leacheate is PE:EA=5:1), obtain yellow solid 6.24 grams, yield 66.8%.
(6), the synthesis of 2-(chloromethyl)-4-(4-methylpyrimidine-2-base) ethyl phenylcarbamate
2-(methylol)-4-(4-methylpyrimidine-2-base) ethyl phenylcarbamate (6.24 grams it is sequentially added in reaction bulb, 21.72 mM), acetonitrile (50 milliliters), triethylamine (8.79 grams, 87 mMs), thionyl chloride (10.33 grams is dripped in reaction bulb, 87 mMs), after dropwising, reactant liquor is warming up to backflow.After back flow reaction 2 hours, stopped reaction, concentrating under reduced pressure, adding water (100 milliliters) in residue, extract by ethyl acetate (2 × 100 milliliters), organic layer washs through saturated aqueous common salt (50 milliliters), anhydrous magnesium sulfate is dried, concetrated under reduced pressure, residue, through chromatography over CC (leacheate is PE:EA=3:1), obtains pale yellow oily liquid body 4.00 grams, yield 60.2%.
(7), the synthesis of 3-amino-6-(4-methyl-pvrimidine-2-base)-3,4-dihydroquinazoline-2 (1H)-one
2-(chloromethyl)-4-(4-methylpyrimidine-2-base) ethyl phenylcarbamate (4.00 grams it is sequentially added in reaction bulb, 13.08 mM), ethanol (30 milliliters) and 85% hydrazine hydrate (6.16 grams, 105 mMs), reactant liquor is heated to backflow.After back flow reaction 3 hours, reactant liquor is down to room temperature, has white solid to precipitate out, solid collected by filtration, use ethanol (10 milliliters) washing gained white solid, obtain white solid 2.40 grams, yield 71.9% after drying.
(8), the preparation of compound 36
3-amino-6-(4-methyl-pvrimidine-2-base)-3 it is sequentially added in reaction bulb, 4-dihydroquinazoline-2 (1H)-one (2.14 grams, 8.38 mMs), ethanol (35 milliliters), (1.37 grams of cigarette aldehyde, 10.90 mM), concentrated sulphuric acid 1, reactant liquor is warming up to backflow.After back flow reaction 2 hours, reactant liquor is down to room temperature, has a large amount of solid to precipitate out, solid collected by filtration, wash gained solid, dried faint yellow solid 2.50 grams, yield 87.0% with ethanol (10 milliliters).
(9), the preparation of compound 37
In reaction bulb, it is sequentially added into compound 36 (0.80 gram, 2.32 mMs), DMF (20 milliliters), is stirred at room temperature to solid entirely molten.Add sodium hydride (0.38 gram, 9.29 mMs), have bubble to produce, stir and after producing to bubble-free, add acetic anhydride (0.97 gram, 9.52 mMs).After room temperature reaction 2 hours, water (100 milliliters) is added in reactant liquor, extract by ethyl acetate (2 × 100 milliliters), organic layer washs through saturated aqueous common salt (50 milliliters), anhydrous magnesium sulfate is dried, concetrated under reduced pressure, residue, through chromatography over CC (leacheate is PE:EA=1:1), obtains white solid 0.66 gram, yield 71.7%.
(10), the preparation of compound 38
In reaction bulb, it is sequentially added into compound 36 (0.80 gram, 2.32 mMs), DMF (20 milliliters), is stirred at room temperature to solid entirely molten.Add sodium hydride (0.38 gram, 9.29 mMs), have bubble to produce, stir and after producing to bubble-free, add propionic andydride (1.21 grams, 9.29 mMs).After room temperature reaction 2 hours, water (100 milliliters) is added in reactant liquor, extract by ethyl acetate (2 × 100 milliliters), organic layer washs through saturated aqueous common salt (50 milliliters), anhydrous magnesium sulfate is dried, concetrated under reduced pressure, residue, through chromatography over CC (leacheate is PE:EA=1:1), obtains white solid 0.70 gram, yield 75.0%.
(11), the preparation of compound 39
In reaction bulb, it is sequentially added into compound 36 (0.80 gram, 2.32 mMs), DMF (20 milliliters), is stirred at room temperature to solid entirely molten.Add sodium hydride (0.38 gram, 9.29 mMs), have bubble to produce, stir and after producing to bubble-free, add butyryl oxide. (1.47 grams, 9.29 mMs).After room temperature reaction 2 hours, water (100 milliliters) is added in reactant liquor, extract by ethyl acetate (2 × 100 milliliters), organic layer washs through saturated aqueous common salt (50 milliliters), anhydrous magnesium sulfate is dried, concetrated under reduced pressure, residue, through chromatography over CC (leacheate is PE:EA=1:1), obtains yellow solid 0.65 gram, yield 67.5%.
(12), the preparation of compound 75
In reaction bulb, it is sequentially added into compound 37 (0.55 gram, 1.42 mMs), 5% methanolic HCl solution (4 milliliters), is stirred at room temperature to solid entirely molten.Add sodium cyanoborohydride (0.11 gram, 1.71 mMs).After being stirred at room temperature 2 hours, water (40 milliliters) is added in reactant liquor, extract by ethyl acetate (2x150 milliliter), organic layer washs through saturated aqueous common salt (50 milliliters), anhydrous magnesium sulfate is dried, concetrated under reduced pressure, residue, through chromatography over CC (leacheate is PE:EA=1:1), obtains brown oil liquid 0.10 gram, yield 18.09%.
(13), the preparation of compound 76
In reaction bulb, it is sequentially added into compound 38 (0.50 gram, 1.25 mMs), 5% methanolic HCl solution (4 milliliters), is stirred at room temperature to solid entirely molten.Add sodium cyanoborohydride (0.09 gram, 1.50 mMs).After being stirred at room temperature 2 hours, water (40 milliliters) is added in reactant liquor, extract by ethyl acetate (2x150 milliliter), organic layer washs through saturated aqueous common salt (50 milliliters), anhydrous magnesium sulfate is dried, concetrated under reduced pressure, residue, through chromatography over CC (leacheate is PE:EA=1:1), obtains brown oil liquid 0.10 gram, yield 19.90%.
(14), the preparation of compound 77
In reaction bulb, it is sequentially added into compound 39 (0.55 gram, 1.33 mMs), 5% methanolic HCl solution (4 milliliters), is stirred at room temperature to solid entirely molten.Add sodium cyanoborohydride (0.10 gram, 1.59 mMs).After being stirred at room temperature 2 hours, water (40 milliliters) is added in reactant liquor, extract by ethyl acetate (2 × 150 milliliters), organic layer washs through saturated aqueous common salt (50 milliliters), anhydrous magnesium sulfate is dried, concetrated under reduced pressure, residue, through chromatography over CC (leacheate is PE:EA=1:1), obtains brown oil liquid 0.10 gram, yield 18.09%.
Raw survey example
Example 2, kill the insecticidal activity assay of black bean aphid
The mixed solvent taking 2.5mL acetone-methanol (volume ratio 1:1) joins in the weighing botle filling the 3mg former medicine of above-claimed cpd to be measured, stirring makes it fully dissolve, add the 2.5mL standing tap water containing 2 ‰ Tween 80s, obtaining the testing compound solution 5mL of 600mg/L after stirring, dilution obtains the solution of variable concentrations further.Process and adopt infusion process.If taking the Semen Viciae fabae Seedling being connected to black bean aphid 3 age in days aphid, impregnation process 5s in the solution prepared, putting in culture plate after taking-up, covering gas permeable glass cover, often process 3 times and repeat, process and be placed on standard sight room, 72h " Invest, Then Investigate " is dead, borer population of living, and calculates mortality rate.
Under 10ppm test concentrations, the preventive effect of 1,4,8,9,17,18,19,47,62,63 pairs of black bean aphids of compound is more than 80%.
Under 5ppm test concentrations, the preventive effect of 1,4,8,17,18,19,47 pairs of black bean aphids of compound is more than 80%.
According to the method described above, by the compounds of this invention 18,19 and known compound KC1(in CN1302801A compound 448), KC2、KC3And KC4(respectively compound 7,25 and 102 in patent WO2013075645A1) have carried out killing the parallel assay of black bean aphid activity, and result of the test is in Table 2.
Table 2: kill black bean aphid activity data (mortality rate, %)
Claims (7)
1. a 6-substituted pyrimidyl quianzolinones, it is characterised in that: compound is such as shown in formula I:
In formula I:
L is selected from L1Or L2:
L1=L2=
R1Selected from hydrogen atom, C1-C8Alkyl-carbonyl, C1-C8Halogenated alkyl carbonyl, C1-C8Alkoxy carbonyl, C1-C8Halo alkoxy carbonyl, C1-C8Alkyl sulphonyl, C1-C8Alkyloxysulfonyl or aryl-acyl that is unsubstituted or that replaced by least one following substituent group: halogen, hydroxyl, amino, nitro, cyano group, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxyl or C1-C6Halogenated alkoxy；
R2、R3、R4What may be the same or different is independently selected from hydrogen atom, halogen, C1-C8Alkyl, C1-C8Haloalkyl, C1-C8Alkoxyl, C1-C8Halogenated alkoxy, C1-C8Alkyl amino, C1-C8Haloalkylamino, C1-C8Alkyl-carbonyl-amino, C1-C8Haloalkylcarbonylamino or there are 1-3 heteroatomic 5 yuan or 6 yuan of heterocyclic acyl amino；
Or the salt of compound of Formula I.
2. the compound described in claim 1, it is characterised in that in formula I:
L is selected from L1Or L2:
L1=L2=
R1Selected from hydrogen atom, C1-C4Alkyl-carbonyl, C1-C4Halogenated alkyl carbonyl, C1-C4Alkoxy carbonyl, C1-C4Halo alkoxy carbonyl, C1-C4Alkyl sulphonyl, C1-C4Alkyloxysulfonyl or aryl-acyl that is unsubstituted or that replaced by least one following substituent group: halogen, hydroxyl, amino, nitro, cyano group, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxyl or C1-C6Halogenated alkoxy；
R2、R3、R4What may be the same or different is independently selected from hydrogen atom, fluorine, chlorine, bromine, iodine, C1-C4Alkyl, C1-C4Haloalkyl, C1-C4Alkoxyl, C1-C4Halogenated alkoxy, C1-C4Alkyl amino, C1-C4Haloalkylamino, C1-C4Alkyl-carbonyl-amino, C1-C4Haloalkylcarbonylamino or there are 1-3 heteroatomic 5 yuan or 6 yuan of heterocyclic acyl amino；
Or the salt of compound of Formula I.
3. the compound described in claim 2, it is characterised in that in formula I:
L is selected from L1Or L2:
L1=L2=
R1Selected from hydrogen atom, C1-C4Alkyl-carbonyl or C1-C4Alkoxy carbonyl；
R2、R3、R4What may be the same or different is independently selected from hydrogen atom, fluorine, chlorine, bromine, iodine, C1-C3Alkyl or C1-C3Haloalkyl；
Or the salt of compound of Formula I.
4. the compound described in claim 3, it is characterised in that in formula I:
L is selected from L1Or L2:
L1=L2=
R1Selected from C1-C4Alkyl-carbonyl or C1-C4Alkoxy carbonyl；
R2、R3、R4What may be the same or different is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl group, isopropyl, trifluoromethyl, pentafluoroethyl group, heptafluoropropyl or seven fluorine isopropyls；
Or the salt of compound of Formula I.
5. the compound of Formula I described in claim 1 is for preparing the purposes of the insecticidal materials of the insect pest controlling agricultural, forestry or non-treatment purpose.
6. a Pesticidal combination, it is characterised in that: containing the compound shown in described formula I as acceptable carrier in active component and agricultural, forestry；The compound shown in formula I of active component to be weight percentage be 1-99% in compositions.
7. the method that Pesticidal combination described in a claim 6 controls insect pest, it is characterised in that: combinations of the above thing is imposed on the effective dose of per hectare 10 grams to 1000 grams need to control agricultural, forestry or or the insect of non-treatment purpose or the medium of its growth on.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109705094A (en) * | 2019-02-15 | 2019-05-03 | 湖南速博生物技术有限公司 | A kind of preparation method of pyridine quinazoline |
| CN115583939A (en) * | 2022-11-04 | 2023-01-10 | 苏州莱安医药化学技术有限公司 | Synthesis method of Tepontinib intermediate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302801A (en) * | 1999-11-02 | 2001-07-11 | 日本农药株式会社 | Substituted aminoquinazolone (thio-ketone) derivative or its salt, its intermediate and pest controlling agent and its application method |
| CN103130771A (en) * | 2011-11-25 | 2013-06-05 | 中国中化股份有限公司 | 6-substituted phenyl quinazoline ketone compound and application thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302801A (en) * | 1999-11-02 | 2001-07-11 | 日本农药株式会社 | Substituted aminoquinazolone (thio-ketone) derivative or its salt, its intermediate and pest controlling agent and its application method |
| CN103130771A (en) * | 2011-11-25 | 2013-06-05 | 中国中化股份有限公司 | 6-substituted phenyl quinazoline ketone compound and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 万琴 等: "新杀虫剂R—768", 《世界农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705094A (en) * | 2019-02-15 | 2019-05-03 | 湖南速博生物技术有限公司 | A kind of preparation method of pyridine quinazoline |
| CN115583939A (en) * | 2022-11-04 | 2023-01-10 | 苏州莱安医药化学技术有限公司 | Synthesis method of Tepontinib intermediate |
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