CN105732587B - 6- substituted pyrimidyl quianzolinones and application thereof - Google Patents
6- substituted pyrimidyl quianzolinones and application thereof Download PDFInfo
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Abstract
The invention discloses the 6 substituted pyrimidyl quianzolinones and its salt of a kind of structure novel, as shown in general formula I：
Description
Technical field
The invention belongs to agricultural insecticide field, it is related to a kind of 6- substituted pyrimidyls quianzolinones and its use
On the way.
Background technology
In use for some time due to insecticide, pest can generate resistance to it, novel therefore, it is necessary to constantly invent
With improved compound and composition with insecticidal activity.
Certain 6- substituted quinazoline ketone compounds with insecticidal activity have been reported.CN1302801A discloses 6
The base quianzolinones KC of hepta-fluoroiso-propyl1The insecticidal activity and final goods of (compound 448 in patent), English
Common name pyrifluquinazon.WO2013075645A1 discloses 6- substituted-phenyl quianzolinones KC2、KC3With
KC4(being respectively compound 7,25 and 102 in patent) has good insecticidal activity.But the preventive effect under low dosage is not made us
It is satisfied.
In the prior art, as representative of the present invention 6- substituted pyrimidyl quianzolinones are not disclosed.
Invention content
The object of the present invention is to provide a kind of 6- substituted pyrimidyls quianzolinones and application thereof..
To achieve the above object, technical scheme is as follows：
A kind of 6- substituted pyrimidyls quianzolinones and its salt, as shown in general formula I：
In general formula I：
L is selected from L1Or L2：
R1Selected from hydrogen atom, C1-C8Alkyl-carbonyl, C1-C8Halogenated alkyl carbonyl, C1-C8Alkoxy carbonyl, C1-C8Alkyl halide
Epoxide carbonyl, C1-C8Alkyl sulphonyl, C1-C8Alkyloxysulfonyl is unsubstituted or replaced by least one following substituent groups
Aryl-acyl：Halogen, hydroxyl, amino, nitro, cyano, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6It is halogenated
Alkoxy；
R2、R3、R4What be may be the same or different is independently selected from hydrogen atom, halogen, C1-C8Alkyl, C1-C8Halogenated alkyl, C1-C8
Alkoxy, C1-C8Halogenated alkoxy, C1-C8Alkyl amino, C1-C8Haloalkylamino, C1-C8Alkyl-carbonyl-amino, C1-C8Halogen
Fluoroalkylcarbonyl amino has 1-3 heteroatomic 5 yuan or 6 circle heterocyclic ring acyl aminos.
Or the salt of compound of Formula I.
Preferred compound is in the present invention, in general formula I：
L is selected from L1Or L2：
R1Selected from hydrogen atom, C1-C4Alkyl-carbonyl, C1-C4Halogenated alkyl carbonyl, C1-C4Alkoxy carbonyl, C1-C4Alkyl halide
Epoxide carbonyl, C1-C4Alkyl sulphonyl, C1-C4Alkyloxysulfonyl is unsubstituted or replaced by least one following substituent groups
Aryl-acyl：Halogen, hydroxyl, amino, nitro, cyano, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6It is halogenated
Alkoxy；
R2、R3、R4What be may be the same or different is independently selected from hydrogen atom, fluorine, chlorine, bromine, iodine, C1-C4Alkyl, C1-C4Alkyl halide
Base, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkyl amino, C1-C4Haloalkylamino, C1-C4Alkyl-carbonyl ammonia
Base, C1-C4Haloalkylcarbonylamino has 1-3 heteroatomic 5- or 6 circle heterocyclic ring acyl aminos.
Or the salt of compound of Formula I.
Further preferred compound is in the present invention, in general formula I：
L is selected from L1Or L2：
R1Selected from hydrogen atom, C1-C4Alkyl-carbonyl or C1-C4Alkoxy carbonyl.
R2、R3、R4What be may be the same or different is independent selected from hydrogen atom, fluorine, chlorine, bromine, iodine, C1-C3Alkyl or C1-C3It is halogenated
Alkyl；
Or the salt of compound of Formula I.
Particularly preferred compound is in the present invention, in general formula I：
L is selected from L1Or L2：
R1Selected from C1-C4Alkyl-carbonyl or C1-C4Alkoxy carbonyl；
R2、R3、R4May be the same or different it is independent selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl,
Trifluoromethyl, pentafluoroethyl group, heptafluoropropyl or hepta-fluoroiso-propyl.
Or the salt of compound of Formula I.
In the definition of general formula compound I given above, collects term used and be generally defined as follows：
Alkyl refers to linear chain or branched chain form, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
The groups such as base, tertiary butyl, n-pentyl, isopentyl, n-hexyl.Halogenated alkyl refers to what alkyl was optionally substituted with one or more halogen atoms
Group.Alkoxy refers to the group that alkyl end is connected with oxygen atom, for example, methoxyl group, ethyoxyl, positive propoxy, isopropoxy,
Tert-butoxy etc..Halogenated alkoxy refers to the group that alkoxy 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 each group definition is the same in reaction equation.
(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 side
Method is as follows：
(L is selected from L to general formula I1) for compound in suitable solvent, temperature is under room temperature to the boiling point of suitable solvent, instead
It answers 0.5-48 hours, general formula I is made in the method restored by reducing agent or by hydrogen catalytic, and (L is selected from L2) compound.
Suitable solvent is selected from halogenated hydrocarbons, such as dichloromethane, chloroform；Aromatic hydrocarbon, such as toluene；Nitrile, such as acetonitrile, benzonitrile
Deng；Ether, such as tetrahydrofuran, dioxane；Alcohol, such as methanol, ethyl alcohol；Amide, such as n,N-Dimethylformamide；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..
General formula I (R1It is not H, L is selected from L1) can be by general formula I (R1It is selected from L selected from H, L1) compound be made.Reaction equation is such as
Under：
In formula：LG represents suitable leaving group, such as chlorine atom, bromine atom or acyloxy.
General formula I (R1It is selected from L selected from H, L1) compound and Compounds of formula II (such as carboxylic acid halides or acid anhydrides, commercially available) be suitable
Solvent in, temperature is -10 DEG C and reacts 0.5-48 hours obtained general formula compound I (R under suitable solvent boiling point to reacting1No
It is selected from L for H, L1)。
Suitable solvent is selected from halogenated hydrocarbons, such as dichloromethane, chloroform；Aromatic hydrocarbon, such as toluene；Nitrile, such as acetonitrile, benzonitrile
Deng；Ether, such as tetrahydrofuran, dioxane；Alcohol, such as methanol, ethyl alcohol；Amide, such as n,N-Dimethylformamide；Dimethyl
Sulfoxide；Ester, such as ethyl acetate；Water etc..
Suitable alkaloids are added to reacting advantageous.Suitable alkali is selected from organic base such as triethylamine, N, N- dimethyl benzenes
Amine, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide etc. or inorganic base such as sodium hydroxide, potassium hydroxide, carbonic acid
Sodium, potassium carbonate or sodium hydride etc..
Compound of Formula I I (the R of the present invention1It is selected from L selected from H, L1) can be prepared as follows：
For compound of formula III with pyridine carboxaldehyde in suitable solvent, temperature is room temperature to the suitable solvent boiling point of reaction
0.5-48 hours obtained general formula I (R of lower reaction1It is selected from L selected from H, L1) compound.
Suitable solvent is selected from halogenated hydrocarbons, such as dichloromethane, chloroform；Aromatic hydrocarbon, such as toluene；Nitrile, such as acetonitrile, benzonitrile
Deng；Ether, such as tetrahydrofuran, dioxane；Alcohol, such as methanol, ethyl alcohol；Amide, such as n,N-Dimethylformamide；Dimethyl
Sulfoxide；Ester, such as ethyl acetate；Water etc..
Be added suitable acid to react advantageous, suitable acid be selected from inorganic acid (such as sulfuric acid, hydrochloric acid) or organic acid (such as
Acetic acid, p-methyl benzenesulfonic acid etc.).
General formula compound III preparation methods are as follows：
Wherein Hal represents halogen atom.
For general formula compound IV with hydrazine hydrate in suitable solvent, temperature is to be reacted under room temperature to the boiling point of suitable solvent
0.5-48 hours obtained general formula compound III.
Suitable solvent is selected from dichloromethane, chloroform, toluene, acetonitrile, tetrahydrofuran, dioxane, methanol, ethyl alcohol, N,
Dinethylformamide, dimethyl sulfoxide (DMSO) or hexamethylphosphoramide etc..
General formula compound IV preparation methods are referring to US20040082586；J.Org.Chem.60,7508-7510,1995；
Tetrahedron Lett.52,6489–6491,2011；Tetra.66,3207-3213,2010.
Table 1 lists the structure and physicochemical property of partial Formula Compound I.
The structure and physicochemical property of 1 partial Formula Compound I of table
Part of compounds1H NMR (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 used to prepare the purposes of agriculture, forestry or the insect pest of non-treatment purpose the insecticide of control.
A kind of Pesticidal combination, contain the general formula I compounds represented as active component and agricultural, can in forestry
The carrier of receiving；Active component is the general formula I compounds represented that weight percentage is 1-99% in composition.
The method of a kind of Pesticidal combination control insect pest, by combinations of the above object with the effective of 10 grams to 1000 grams of per hectare
Dosage impose on need control agricultural, forestry or non-treatment purpose pest or growth medium on.
Specifically general formula compound I of the invention has high insecticidal activity.There is control effect well to pest such as black bean aphid
Fruit.Therefore, the invention also includes general formula compound I to be used to control agricultural, the purposes of forestry or the insect pest of non-treatment purpose；Especially
Ground, the compound of the present invention are preferred for controlling the purposes of aphid such as black bean aphid insect pest.
The invention also includes the Pesticidal combinations using general formula compound I as active component.It is active in the Pesticidal combination
The weight percentage of component is between 1-99%.It further include agricultural, forestry in the Pesticidal combination, acceptable load in health
Body.
Technical scheme of the present invention further includes the method for pest control：The Pesticidal combination of the present invention is imposed on to the evil
On worm or growth medium.The more suitable effective amount generally selected is 10 grams to 1000 grams of per hectare.
The composition of the present invention can be applied in the form of preparation on pest or growth medium.General formula compound I is as work
Property component is more readily dispersible when being dissolved or dispersed in carrier or being configured to preparation to be used as insecticide.Such as：These
Chemicals can be made into wettable powder or missible oil.In these compositions, a kind of liquid or solid carrier is at least added, and
And surfactant appropriate can be added when needed.
For certain applications, such as agriculturally one or more others can be added in the Pesticidal combination of the present invention
Thus fungicide, Insecticides (tech) ＆ Herbicides (tech), plant growth regulator or fertilizer etc. can generate additional advantage and effect.
It should be appreciated that in scope defined by the claims of the present invention, various transformation and change can be carried out.
Specific implementation mode
Following synthetic example, raw test result can be used to further illustrate the present invention, but be not intended to limit this hair
It is bright.
Synthetic example
The preparation of embodiment 1, compound 36,37,38,39,75,76,77
(1), the synthesis of 2- amino -5- bromobenzene methanol
O-benzyl alcohol (5.00 grams, 40.0 mMs, commercially available), DMF (25 milliliters) are added into reaction bulb, ice bath stirs
It mixes down and NBS (7.23 grams, 40.0 mMs) is added portionwise, reaction solution is directly poured into ice by ice bath under stiring after reacting 2 hours
It in water, filters, washs, it is dry, obtain 5.86 grams of white solid, yield 72.5%.
(2), the synthesis of (2- amino -5- (4,4,5,5- tetramethyl -1,3,2- dioxy borine -2- bases) phenyl) methanol
By 2- amino -5- bromobenzenes methanol (4.04 grams, 20.0 mMs) and connection pinacol borate, (7.65 grams, 30.0 in the least
Mole, it is commercially available) it is dissolved in entirely in dioxane (200 milliliters), CsCO is added3(19.6 grams, 60.0 mMs), PdCl2·dppf
(0.88 gram, 1.2 mMs) and dppf (0.55 gram, 1.0 mMs), heating reflux reaction.Back flow reaction will reaction after 2 hours
Liquid cools to room temperature, is filtered to remove insoluble matter, solvent evaporated, residue water (200 milliliters), ethyl acetate (2 × 200 milliliters)
Extraction, organic layer depressurize lower concentration through saturated common salt water washing, anhydrous magnesium sulfate drying, and residue purifies (elution through column chromatography
Liquid is PE：EA=3:1) 3.39 grams of light yellow solid, is obtained.Yield 68.0%
(3), the synthesis of the chloro- 4- methylpyrimidines of 2-
2,4-, bis- chloro- 6- methylpyrimidines (15.00 grams, 92.00 mMs), zinc powder (18.05 are sequentially added into reaction bulb
Gram, 276.00 mMs), ammonium hydroxide (38.70 grams, 276 mMs), under stirring into reaction bulb be added water (120 milliliters).Heating
After back flow reaction 2 hours, reaction solution is down to room temperature, is filtered, filtrate is extracted with ethyl acetate (2x200 milliliters), and organic layer is full
After the washing of (150 milliliters) of saline solution, anhydrous magnesium sulfate drying, lower concentration is depressurized, residue purifies that (leacheate is through column chromatography
PE：EA=5:1) 8.8 grams of white solid, yield 74.4%, are obtained
(4), the synthesis of (2- amino) -5- (4- methylpyrimidine -2- bases) benzyl alcohol
(2- amino -5- (penta ring -2- bases of 4,4,5,5- tetramethyl -1,3,2- dioxies boron) benzene is sequentially added into reaction bulb
Base) methanol (15.00 grams, 60.20 mMs), the chloro- 4- methylpyrimidines of 2- (8.52 grams, 66.20 mMs), tetra-triphenylphosphine palladium
(1.39 grams, 1.20 mMs) are added (120 milliliters) dissolvings of dioxane, potassium carbonate are added under stirring into reaction bulb
Water (120 milliliters) solution of (24.97 grams, 181.00 mMs).After heating reflux reaction 8 hours, reaction solution is down to room temperature,
After rotation is except most of dioxane, it is extracted with ethyl acetate (200 milliliters of 2x), organic layer saturated salt solution (150 milliliters) is washed
It washs, after anhydrous magnesium sulfate drying, depressurizes lower concentration, residue purifies (leacheate PE through column chromatography：EA=3:1) yellow, is obtained
6.8 grams of solid, yield 52.5%
(5), the synthesis of 2- (methylol) -4- (4- methylpyrimidine -2- bases) euphorin
Sequentially added into reaction bulb (2- amino) -5- (4- methylpyrimidine -2- bases) benzyl alcohol (7.00 grams, 32.5 mmoles
You), dichloromethane (200 milliliters), pyridine (2.89 grams, 35.8 mMs), ethyl chloroformate (3.53 grams, 32.5 mMs),
After being stirred at room temperature 0.5 hour, stop reaction, reaction solution with first being washed with water (200 milliliters), wash by saturated salt solution (150 milliliters)
It washs, after anhydrous magnesium sulfate drying, depressurizes lower concentration, residue purifies (leacheate PE through column chromatography：EA=5:1) yellow, is obtained
6.24 grams of solid, yield 66.8%.
(6), the synthesis of 2- (chloromethyl) -4- (4- methylpyrimidine -2- bases) euphorin
2- (methylol) -4- (4- methylpyrimidine -2- bases) euphorin (6.24 is sequentially added into reaction bulb
Gram, 21.72 mMs), acetonitrile (50 milliliters), triethylamine (8.79 grams, 87 mMs), thionyl chloride is added dropwise into reaction bulb
Reaction solution after being added dropwise, is warming up to reflux by (10.33 grams, 87 mMs).After back flow reaction 2 hours, stops reaction, subtract
Pressure concentration, water (100 milliliters) is added into residue, and with (2 × 100 milliliters) extractions of ethyl acetate, organic layer is through saturated common salt
After (50 milliliters) washings of water, anhydrous magnesium sulfate drying, lower concentration is depressurized, residue purifies (leacheate PE through column chromatography：EA=
3:1) 4.00 grams of pale yellow oily liquid, yield 60.2%, are obtained.
(7), the synthesis of 3- amino -6- (4- methyl-pvrimidine -2- bases) -3,4- dihydroquinazolines -2 (1H) -one
2- (chloromethyl) -4- (4- methylpyrimidine -2- bases) euphorin (4.00 is sequentially added into reaction bulb
Gram, 13.08 mMs), ethyl alcohol (30 milliliters) and 85% hydrazine hydrate (6.16 grams, 105 mMs), reaction solution is heated to
Reflux.After back flow reaction 3 hours, reaction solution is down to room temperature, there is white solid precipitation, be collected by filtration solid, with ethyl alcohol (10 milli
Rise) washing gained white solid, obtain 2.40 grams of white solid, yield 71.9% after dry.
(8), the preparation of compound 36
3- amino -6- (4- methyl-pvrimidine -2- bases) -3,4- dihydroquinazolines -2 (1H) -one is sequentially added into reaction bulb
(2.14 grams, 8.38 mMs), ethyl alcohol (35 milliliters), cigarette aldehyde (1.37 grams, 10.90 mMs), the concentrated sulfuric acid 1 drip, by reaction solution
It is warming up to reflux.After back flow reaction 2 hours, reaction solution is down to room temperature, there are a large amount of solids to be precipitated, solid is collected by filtration, uses second
(10 milliliters) washing obtained solids of alcohol, 2.50 grams of faint yellow solid, yield 87.0% are obtained after dry.
(9), the preparation of compound 37
Compound 36 (0.80 gram, 2.32 mMs), DMF (20 milliliters) are sequentially added into reaction bulb, be stirred at room temperature to
Solid is entirely molten.Sodium hydride (0.38 gram, 9.29 mMs) is added, second is added after having bubble generation, stirring to bubble-free to generate
Acid anhydrides (0.97 gram, 9.52 mMs).After room temperature reaction 2 hours, water (100 milliliters) is added into reaction solution, uses ethyl acetate
(2 × 100 milliliters) extractions, organic layer depressurize lower concentration after (50 milliliters) washings of saturated salt solution, anhydrous magnesium sulfate drying,
Residue purifies (leacheate PE through column chromatography：EA=1:1) 0.66 gram of white solid, yield 71.7%, are obtained.
(10), the preparation of compound 38
Compound 36 (0.80 gram, 2.32 mMs), DMF (20 milliliters) are sequentially added into reaction bulb, be stirred at room temperature to
Solid is entirely molten.Sodium hydride (0.38 gram, 9.29 mMs) is added, third is added after having bubble generation, stirring to bubble-free to generate
Acid anhydrides (1.21 grams, 9.29 mMs).After room temperature reaction 2 hours, water (100 milliliters) is added into reaction solution, uses ethyl acetate
(2 × 100 milliliters) extractions, organic layer depressurize lower concentration after (5 0 milliliters) washings of saturated salt solution, anhydrous magnesium sulfate drying,
Residue purifies (leacheate PE through column chromatography：EA=1:1) 0.70 gram of white solid, yield 75.0%, are obtained.
(11), the preparation of compound 39
Compound 36 (0.80 gram, 2.32 mMs), DMF (20 milliliters) are sequentially added into reaction bulb, be stirred at room temperature to
Solid is entirely molten.Sodium hydride (0.38 gram, 9.29 mMs) is added, fourth is added after having bubble generation, stirring to bubble-free to generate
Acid anhydrides (1.47 grams, 9.29 mMs).After room temperature reaction 2 hours, water (100 milliliters) is added into reaction solution, uses ethyl acetate
(2 × 100 milliliters) extractions, organic layer depressurize lower concentration after (50 milliliters) washings of saturated salt solution, anhydrous magnesium sulfate drying,
Residue purifies (leacheate PE through column chromatography：EA=1:1) 0.6 5 grams of yellow solid, yield 67.5%, are obtained.
(12), the preparation of compound 75
Compound 37 (0.55 gram, 1.42 mMs), 5% methanolic HCl solution (4 milliliters) are sequentially added into reaction bulb,
It is stirred at room temperature entirely molten to solid.Add sodium cyanoborohydride (0.11 gram, 1.71 mMs).After being stirred at room temperature 2 hours, to anti-
It answers and water (40 milliliters) is added in liquid, extracted with ethyl acetate (150 milliliters of 2x), organic layer is washed through saturated salt solution (50 milliliters)
It washs, after anhydrous magnesium sulfate drying, depressurizes lower concentration, residue purifies (leacheate PE through column chromatography：EA=1:1) brown, is obtained
0.10 gram of oily liquids, yield 18.09%.
(13), the preparation of compound 76
Compound 38 (0.50 gram, 1.25 mMs), 5% methanolic HCl solution (4 milliliters) are sequentially added into reaction bulb,
It is stirred at room temperature entirely molten to solid.Add sodium cyanoborohydride (0.09 gram, 1.50 mMs).After being stirred at room temperature 2 hours, to anti-
It answers and water (40 milliliters) is added in liquid, extracted with ethyl acetate (150 milliliters of 2x), organic layer is washed through saturated salt solution (50 milliliters)
It washs, after anhydrous magnesium sulfate drying, depressurizes lower concentration, residue purifies (leacheate PE through column chromatography：EA=1:1) brown, is obtained
0.10 gram of oily liquids, yield 19.90%.
(14), the preparation of compound 77
Compound 39 (0.55 gram, 1.33 mMs), 5% methanolic HCl solution (4 milliliters) are sequentially added into reaction bulb,
It is stirred at room temperature entirely molten to solid.Add sodium cyanoborohydride (0.10 gram, 1.59 mMs).After being stirred at room temperature 2 hours, to anti-
It answers and water (40 milliliters) is added in liquid, with (2 × 150 milliliters) extractions of ethyl acetate, organic layer is washed through saturated salt solution (50 milliliters)
It washs, after anhydrous magnesium sulfate drying, depressurizes lower concentration, residue purifies (leacheate PE through column chromatography：EA=1:1) brown, is obtained
0.10 gram of oily liquids, yield 18.09%.
It is raw to survey example
Example 2, the insecticidal activity assay for killing black bean aphid
Take 2.5mL acetone-methanols (volume ratio 1:1) mixed solvent, which is added to, fills 3mg above compound active compounds to be measured
Measuring cup in, stirring makes it fully dissolve, and 2.5mL is added and contains the standing tap water of 2 ‰ Tween 80s, is obtained after stirring evenly
The testing compound solution 5mL of 600mg/L, further dilution obtain the solution of various concentration.Processing uses infusion process.It takes and is connected to
The broad bean seedling of 3 age in days larvae aphid of black bean aphid, the impregnation 5s in the solution prepared are put into culture plate after taking-up, cover ventilative
Cloche often handles 3 repetitions, and processing is placed on standard sight room, and number of dead and live insects is investigated after 72h, calculates the death rate.
Under 10ppm test concentrations, compound 1, the preventive effect of 4,8,9,17,18,19,47,62,63 pairs of black bean aphids are 80%
More than.
Under 5ppm test concentrations, compound 1, the preventive effect of 4,8,17,18,19,47 pairs of black bean aphids are 80% or more.
According to the method described above, by the compounds of this invention 18,19 and known compound KC1(compound 448 in CN1302801A
Number), KC2、KC3And KC4(being respectively compound 7,25 and 102 in patent WO2013075645A1) has carried out killing black bean aphid activity
Parallel determination, test result is shown in Table 2.
Table 2：Kill black bean aphid activity data (death rate, %)
Claims (5)
1. a kind of 6- substituted pyrimidyls quianzolinones, it is characterised in that：Compound is as shown in general formula I：
In general formula I：
L is selected from L1Or L2：
R1Selected from hydrogen atom or C1-C4Alkyl-carbonyl；
R2、R3、R4What be may be the same or different is independently selected from hydrogen atom, halogen, C1-C4Alkyl or C1-C4Halogenated alkyl.
2. a kind of compound described in claim 1, which is characterized in that in general formula I：
L is selected from L1Or L2：
R1Selected from acetyl group, propiono, bytyry or isobutyryl；
R2、R3、R4What be may be the same or different is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, fluoroform
Base, pentafluoroethyl group, heptafluoropropyl or hepta-fluoroiso-propyl.
3. a kind of compound of Formula I described in claim 1 is used to prepare control agricultural, forestry or the insect pest of non-treatment purpose
The purposes of insecticidal materials.
4. a kind of Pesticidal combination, it is characterised in that：Activearm containing general formula I compounds represented described in claim 1
Point and agricultural, acceptable carrier in forestry, the weight percentage of active component is 1-99% in composition.
5. a kind of method of the Pesticidal combination control insect pest described in claim 4, it is characterised in that：By combinations of the above object with
The effective dose that 10 grams to 1000 grams of per hectare imposes on pest or growth of the agricultural, forestry or the non-treatment purpose that need to control
Medium on.
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| 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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| 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 |
|---|
| 新杀虫剂R—768;万琴 等;《世界农药》;19991231;第二十一卷(第六期);57-59 * |
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