CN104945352A - Piperazine benzene dinitrile compound and application thereof - Google Patents
Piperazine benzene dinitrile compound and application thereof Download PDFInfo
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- CN104945352A CN104945352A CN201410126032.6A CN201410126032A CN104945352A CN 104945352 A CN104945352 A CN 104945352A CN 201410126032 A CN201410126032 A CN 201410126032A CN 104945352 A CN104945352 A CN 104945352A
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- carbonyl
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- 0 Cc1c(*=C)c(CC*)c(*)c(*)c1* Chemical compound Cc1c(*=C)c(CC*)c(*)c(*)c1* 0.000 description 4
- LWABCWLJLIQHQV-UHFFFAOYSA-N CC(C)(C)OC(N(CC1)CCN1c(c(N)c(c(C#N)c1C)Cl)c1Cl)=O Chemical compound CC(C)(C)OC(N(CC1)CCN1c(c(N)c(c(C#N)c1C)Cl)c1Cl)=O LWABCWLJLIQHQV-UHFFFAOYSA-N 0.000 description 1
- CWXPZXBSDSIRCS-UHFFFAOYSA-N CC(C)(C)OC(N1CCNCC1)=O Chemical compound CC(C)(C)OC(N1CCNCC1)=O CWXPZXBSDSIRCS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a piperazine benzene dinitrile compound which is shown as a general formula I. The structural formula is as shown in the specification. In the formula, each substituent group is defined in the specification. The compound of the general formula I has broad spectrum bactericidal activity in the field of agriculture and has excellent effects of controlling multiple pathogenic bacteria such as cucumber downy mildew, wheat powdery mildew, corn rust, rice blast and cucumber gray mold. Particularly, the compound has excellent effects of controlling the cucumber downy mildew and rice blast under low dosage. Moreover, the raw materials for synthesizing the compounds are readily available, and the synthetic method is simple and convenient and has wide application prospects.
Description
Technical field
The invention belongs to disinfectant use in agriculture field.Relate to a kind of piperazine phenyl two nitrile compounds and application thereof particularly.
Background technology
Document Tetrahedron (2007), 63 (45), 10971-10978 disclose the compound shown in following general formula and compound K C1.Only mention in document that this general formula compound has important biomolecule activity, but do not have concrete bioactive report.
Document Tetrahedron (2002), 58 (43), 8793-8798 and Tetrahedron Letters (2001), 42 (40), 7127-7129 all disclose the compound shown in following general formula and following particular compound KC2, KC3, KC4.
The compound K C5 that patent WO2011048082 discloses following structure is used for the treatment of as Janus kinases (JAK) inhibitor or epidemic prevention, inflammatory, autoimmunity, allergic disorder and immunologically mediated disease medicine, but do not report the biological activity of this compound in pesticide field.Patent RU2447061 discloses the preparation of compound K C5, KC6, KC7 and KC8 of following structure, but reports without any biological activity.
In prior art, the compound of structure as shown in general formula I of the present invention has no report.
Summary of the invention
Modern agricultural production needs the novel pesticide continually developing out novel structure, excellent performance.The object of the present invention is to provide a kind of piperazine phenyl two nitrile compounds that can control multiple germ, it can be used for the medicine preparing controlling disease in agricultural or other field.
Technical scheme of the present invention is as follows:
The invention provides a kind of piperazine phenyl two nitrile compounds, structure is as shown in general formula I:
In formula:
A is selected from A
1, A
2or A
3
R
a, R
b, R
c, R
d, R
e, R
f, R
gand R
hindependently represent hydrogen, C separately
1-C
4alkyl, halo C
1-C
4alkyl, halo C
1-C
4alkoxyl group or C
1-C
4carbalkoxy; R
awith R
hor R
cwith R
fin conjunction with saturated five-ring, six-ring or the seven-membered ring that are formed;
R
1be selected from hydrogen, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkoxy C
1-C
12alkyl, halo C
1-C
12alkoxy C
1-C
12alkyl, C
3-C
12cycloalkyl, C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkoxy carbonyl, halo C
1-C
12alkoxy carbonyl, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl sulphonyl oxygen base, allyl group, propargyl, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzoyl, phenyloxycarbonyl, phenyl amino-carbonyl, heteroaryl, Heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl amino-carbonyl, benzyl or aryl sulfonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
12alkyl, halo C
1-C
12alkyl, C
3-C
12cycloalkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
2-C
12thiazolinyl, halo C
2-C
12thiazolinyl, C
2-C
12alkynyl, halo C
2-C
12alkynyl, C
3-C
12alkene oxygen base, halo C
3-C
12alkene oxygen base, C
3-C
12alkynyloxy group, halo C
3-C
12alkynyloxy group, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl-carbonyl-amino, C
1-C
12alkyl sulphonyl oxygen base, C
1-C
12alkoxy carbonyl, C
1-C
12alkoxy carbonyl C
1-C
12alkyl, C
1-C
12alkoxycarbonyl amino, C
1-C
12alkoxy C
1-C
12alkoxyl group, C
1-C
12alkoxy carbonyl C
1-C
12alkoxyl group, anilinocarbonyl, halogeno-benzene aminocarboxyl, CHO, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, OC (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13; N=1,2,3,4 or 5;
R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10may be the same or different, be selected from halogen, C respectively
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
3-C
12alkene oxygen base, halo C
3-C
12alkene oxygen base, C
3-C
12alkynyloxy group, halo C
3-C
12alkynyloxy group, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl-carbonyl-amino, C
1-C
12alkyl sulphonyl oxygen base, C
1-C
12alkoxy C
1-C
12alkoxyl group or C
1-C
12alkoxy carbonyl C
1-C
12alkoxyl group;
R
12, R
13may be the same or different, be selected from hydrogen, C respectively
1-C
12alkyl, halo C
1-C
12alkyl or C
3-C
12cycloalkyl.
The comparatively preferred compound of the present invention is: in general formula I
A is selected from A
1, A
2or A
3
R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hindependently represent hydrogen, C separately
1-C
4alkyl, halo C
1-C
4alkyl, halo C
1-C
4alkoxyl group or C
1-C
4carbalkoxy; R
awith R
hor R
cwith R
fin conjunction with saturated five-ring, six-ring or the seven-membered ring that are formed;
R
1be selected from hydrogen, C
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
1-C
8alkoxy C
1-C
8alkyl, halo C
1-C
8alkoxy C
1-C
8alkyl, C
3-C
8cycloalkyl, C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkoxy carbonyl, halo C
1-C
8alkoxy carbonyl, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl sulphonyl oxygen base, allyl group, propargyl, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzoyl, phenyloxycarbonyl, phenyl amino-carbonyl, heteroaryl, Heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl amino-carbonyl, benzyl or aryl sulfonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
8alkyl, halo C
1-C
8alkyl, C
3-C
6cycloalkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
2-C
8thiazolinyl, halo C
2-C
8thiazolinyl, C
2-C
8alkynyl, halo C
2-C
8alkynyl, C
3-C
8alkene oxygen base, halo C
3-C
8alkene oxygen base, C
3-C
8alkynyloxy group, halo C
3-C
8alkynyloxy group, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkyl sulphonyl oxygen base, C
1-C
8alkoxy carbonyl, C
1-C
8alkoxy carbonyl C
1-C
8alkyl, C
1-C
8alkoxycarbonyl amino, C
1-C
8alkoxy C
1-C
8alkoxyl group, C
1-C
8alkoxy carbonyl C
1-C
8alkoxyl group, anilinocarbonyl, halogeno-benzene aminocarboxyl, CHO, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, OC (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13; N=1,2,3,4 or 5;
R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10may be the same or different, be selected from halogen, C respectively
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
3-C
8alkene oxygen base, halo C
3-C
8alkene oxygen base, C
3-C
8alkynyloxy group, halo C
3-C
8alkynyloxy group, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkyl sulphonyl oxygen base, C
1-C
8alkoxy C
1-C
8alkoxyl group or C
1-C
8alkoxy carbonyl C
1-C
8alkoxyl group;
R
12, R
13may be the same or different, be selected from hydrogen, C respectively
1-C
6alkyl, halo C
1-C
6alkyl or C
3-C
6cycloalkyl.
The present invention further preferred compound is:
A is selected from A
1, A
2or A
3
R
a, R
b, R
c, R
d, R
e, R
f, R
gand R
hindependently represent hydrogen, C separately
1-C
4alkyl, halo C
1-C
4alkyl, halo C
1-C
4alkoxyl group or C
1-C
4carbalkoxy; R
awith R
htogether or R
cwith R
ftogether can in conjunction with forming saturated five-ring, six-ring or seven-membered ring;
R
1be selected from hydrogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkoxy C
1-C
4alkyl, halo C
1-C
4alkoxy C
1-C
4alkyl, C
3-C
6cycloalkyl, C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphonyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, halo C
1-C
4alkoxy carbonyl, C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkyl sulphonyl oxygen base, allyl group, propargyl, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzoyl, phenyloxycarbonyl, phenyl amino-carbonyl, heteroaryl, Heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl amino-carbonyl, benzyl or aryl sulfonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
3-C
6cycloalkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
2-C
4thiazolinyl, halo C
2-C
4thiazolinyl, C
2-C
4alkynyl, halo C
2-C
4alkynyl, C
3-C
6alkene oxygen base, halo C
3-C
6alkene oxygen base, C
3-C
6alkynyloxy group, halo C
3-C
6alkynyloxy group, C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkyl-carbonyl-amino, C
1-C
4alkyl sulphonyl oxygen base, C
1-C
4alkoxy carbonyl, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, C
1-C
4alkoxycarbonyl amino, C
1-C
4alkoxy C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl C
1-C
4alkoxyl group, anilinocarbonyl, halogeno-benzene aminocarboxyl, CHO, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, OC (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13; N=1,2,3 or 4;
R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10may be the same or different, be selected from halogen, C respectively
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl, C
3-C
4alkene oxygen base, halo C
3-C
4alkene oxygen base, C
3-C
4alkynyloxy group, halo C
3-C
4alkynyloxy group, C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkyl-carbonyl-amino, C
1-C
4alkyl sulphonyl oxygen base, C
1-C
4alkoxy C
1-C
4alkoxyl group or C
1-C
4alkoxy carbonyl C
1-C
4alkoxyl group;
R
12, R
13may be the same or different, be selected from hydrogen, C respectively
1-C
6alkyl, halo C
1-C
6alkyl or C
3-C
6cycloalkyl.
The present invention further preferred compound is:
A is selected from A
1, wherein R
2, R
3, R
4be selected from chlorine;
R
a, R
b, R
c, R
d, R
e, R
f, R
gand R
hbe selected from hydrogen;
Shown in structural formula as I-a:
R
1be selected from hydrogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, halo C
1-C
4alkoxy carbonyl, C
1-C
4alkyl sulphonyl, C
1-C
4alkoxy C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, allyl group, propargyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl, pyrimidyl, thiazolyl or pyridine-3-carbonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, methylaminocarbonyl, anilinocarbonyl, 4-chloroanilino carbonyl, carboxyl or CO
2na; N=1,2 or 3;
Or, in general formula I
A is selected from A
2, wherein R
5, R
6, R
7identical, be selected from fluorine or chlorine;
R
a, R
b, R
c, R
d, R
e, R
f, R
gand R
hbe selected from hydrogen;
Shown in structural formula as I-b:
R
1be selected from hydrogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, halo C
1-C
4alkoxy carbonyl, C
1-C
4alkyl sulphonyl, C
1-C
4alkoxy C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, allyl group, propargyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl, pyrimidyl, thiazolyl or pyridine-3-carbonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, methylaminocarbonyl, anilinocarbonyl, 4-chloroanilino carbonyl, carboxyl or CO
2na; N=1,2 or 3;
Or, in general formula I
A is selected from A
2, wherein R
5, R
6, R
7identical, be selected from fluorine or chlorine;
R
a, R
b, R
c, R
d, R
e, R
f, R
gand R
hbe selected from hydrogen;
Shown in structural formula as I-c:
R
1be selected from hydrogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, halo C
1-C
4alkoxy carbonyl, C
1-C
4alkyl sulphonyl, C
1-C
4alkoxy C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, allyl group, propargyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl, pyrimidyl, thiazolyl or pyridine-3-carbonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, methylaminocarbonyl, anilinocarbonyl, 4-chloroanilino carbonyl, carboxyl or CO
2na; N=1,2 or 3.
The present invention further preferred compound is:
In general formula I-a,
R
1be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, trifluoromethyl, seven fluorine sec.-propyls, allyl group, propargyl, CH
3c (=O), CH
3cH
2c (=O), CH
3cH
2cH
2c (=O), CH
3cH
2cH
2cH
2c (=O), (CH
3)
3cC (=O), ClCH
2c (=O), methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, methyl sulphonyl, ethylsulfonyl, methoxymethylcarbonyl, ethoxymethylcarbonyl, Methoxycarbonylmethyl, ethoxy carbonyl methyl, isopropoxy carbonyl methyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl or pyridine-3-carbonyl, wherein R
11be selected from F, Cl, Br, I, CN, NO
2, CH
3, CH
2cH
3, C (CH
3)
3, OCH
3, CO
2cH
3, CO
2cH
2cH
3, SO
2cH
3, OCH
2cF
3, CF
3or OCF
3; N=1,2 or 3;
Or, in general formula I-b,
R
5, R
6, R
7identical, be selected from fluorine or chlorine;
R
1be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, trifluoromethyl, seven fluorine sec.-propyls, allyl group, propargyl, CH
3c (=O), CH
3cH
2c (=O), CH
3cH
2cH
2c (=O), CH
3cH
2cH
2cH
2c (=O), (CH
3)
3cC (=O), ClCH
2c (=O), methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, methyl sulphonyl, ethylsulfonyl, methoxymethylcarbonyl, ethoxymethylcarbonyl, Methoxycarbonylmethyl, ethoxy carbonyl methyl, isopropoxy carbonyl methyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl or pyridine-3-carbonyl, wherein R
11be selected from F, Cl, Br, I, CN, NO
2, CH
3, CH
2cH
3, C (CH
3)
3, OCH
3, CO
2cH
3, CO
2cH
2cH
3, SO
2cH
3, OCH
2cF
3, CF
3or OCF
3; N=1,2 or 3;
Or, in general formula I-c,
R
8, R
9, R
10identical, be selected from fluorine or chlorine;
R
1be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, trifluoromethyl, seven fluorine sec.-propyls, allyl group, propargyl, CH
3c (=O), CH
3cH
2c (=O), CH
3cH
2cH
2c (=O), CH
3cH
2cH
2cH
2c (=O), (CH
3)
3cC (=O), ClCH
2c (=O), methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, methyl sulphonyl, ethylsulfonyl, methoxymethylcarbonyl, ethoxymethylcarbonyl, Methoxycarbonylmethyl, ethoxy carbonyl methyl, isopropoxy carbonyl methyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl or pyridine-3-carbonyl, wherein R
11be selected from F, Cl, Br, I, CN, NO
2, CH
3, CH
2cH
3, C (CH
3)
3, OCH
3, CO
2cH
3, CO
2cH
2cH
3, SO
2cH
3, OCH
2cF
3, CF
3or OCF
3; N=1,2 or 3.
In the definition of the compound of Formula I provided, collect the following substituting group of term general proxy used above:
Halogen: refer to fluorine, chlorine, bromine or iodine.Alkyl: straight or branched alkyl, such as methyl, ethyl, propyl group, sec.-propyl or the tertiary butyl.Cycloalkyl: substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopentyl or cyclohexyl.Substituting group is as methyl, halogen etc.Haloalkyl: straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely replace by halogen atom, such as chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl etc.Alkoxyl group: straight or branched alkyl, is connected in structure through Sauerstoffatom key.Halogenated alkoxy: straight or branched alkoxyl group, hydrogen atom on these alkoxyl groups can partly or entirely replace by halogen atom, such as chlorine methoxyl group, dichloro methoxyl group, trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, trifluoro ethoxy etc.Alkylthio: straight or branched alkyl, is connected in structure through sulphur atom key.Halogenated alkylthio: straight or branched alkylthio, hydrogen atom on these alkyl can partly or entirely replace by halogen atom, such as chloromethane sulfenyl, dichloromethane sulfenyl, trichloro-methylthio, fluorine methylthio group, difluoro methylthio group, trifluoromethylthio, chlorine fluorine methylthio group etc.Thiazolinyl: straight or branched alkene class, such as vinyl, 1-propenyl, 2-propenyl and different butenyls, pentenyl and hexenyl isomers.Thiazolinyl also comprises polyenoid class, as 1,2-propadiene base and 2,4-hexadienyl.Haloalkenyl group: straight or branched alkene class, the hydrogen atom on these thiazolinyls can partly or entirely replace by halogen atom.Alkynyl: straight or branched alkynes class, such as ethynyl, 1-proyl, 2-propynyl and different butynyl, pentynyl and hexynyl isomers.Alkynyl also comprises the group be made up of multiple triple bond, such as 2,5-hexadiyne bases.Halo alkynyl: straight or branched alkynes class, the hydrogen atom on these alkynyls can partly or entirely replace by halogen atom.Alkene oxygen base: straight or branched alkene class, is connected in structure through Sauerstoffatom key.Haloalkene oxygen base: straight or branched alkene oxygen base, the hydrogen atom on these alkene oxygen bases can partly or entirely replace by halogen atom.Alkynyloxy group: straight or branched alkynes class, is connected in structure through Sauerstoffatom key.Halo alkynyloxy group: straight or branched alkynyloxy group, the hydrogen atom on these alkynyloxy groups can partly or entirely replace by halogen atom.Alkyl sulphinyl: straight or branched alkyl is connected in structure through sulfinyl (-SO-), such as methylsulfinyl.Alkylsulfinyl: straight or branched alkyl sulphinyl, the hydrogen atom on its alkyl can partly or entirely replace by halogen atom.Alkyl sulphonyl: straight or branched alkyl is through alkylsulfonyl (-SO
2-) be connected in structure, such as methyl sulphonyl.Halogenated alkyl sulfonyl: straight or branched alkyl sulphonyl, the hydrogen atom on its alkyl can partly or entirely replace by halogen atom.Alkyl-carbonyl: alkyl is connected in structure through carbonyl, such as CH
3cO-, CH
3cH
2cO-.Halogenated alkyl carbonyl: the hydrogen atom on the alkyl of alkyl-carbonyl can partly or entirely replace by halogen atom, such as CF
3cO-.Alkyl-carbonyl oxygen base: such as CH
3cOO-, CH
3cH
2nHCOO-.Alkyl-carbonyl-amino: such as CH
3cONH-, CH
3cH
2nHCONH-.Alkyl sulphonyl oxygen base: such as alkyl-S (O)
2-O-.Alkyloxy-alkoxy: alkyl-O-alkyl-O-, such as CH
3oCH
2o-.Alkoxycarbonylalkoxy: alkyl-O-CO-alkyl-O-.Alkoxy carbonyl: alkyl-O-CO-.Alkoxy carbonyl alkyl: alkoxy carbonyl-alkyl-, such as CH
3oCOCH
2-.Alkoxycarbonyl amino: alkyl-O-CO-NH-.Anilinocarbonyl: phenyl-NH-CO-.Halogeno-benzene aminocarboxyl: the hydrogen atom of the phenyl ring of anilinocarbonyl can partly or entirely replace by halogen atom, as 4-chloro-phenyl--NH-CO-, 2,4 dichloro benzene base-NH-CO-.
In compound of Formula I of the present invention, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10preferred moieties and substituting group thereof are in table 1, but they are not limited only to these substituting groups.
Table 1R
2(R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10) substituting group
In general formula (I), (A is A
1, A
2or A
3): work as R
1when being selected from pyridyl, the substituting group on pyridine ring is in Table 2-table 4; Work as R
1when being selected from benzoyl, the substituting group on phenyl ring is in table 5; Work as R
1when being selected from pyrimidine, the substituting group on pyrimidine ring is in table 6 and table 7; Work as R
1when being selected from thiazole, the substituting group on thiazole ring is in table 8.
Table 2
Table 3
Table 4
| (R 11)n | (R 11)n | (R 11)n | (R 11)n | (R 11)n |
| 2-CN | 3-Cl | 2-OCH 3 | 2,6-2Cl | 2-OCH 3-6-Cl |
| 2-Cl | 2-Br | 2,6-2OCH 3 | 6-OPh | 2-NHCH 3-6-Cl |
Table 5
| (R 11)n | (R 11)n | (R 11)n | (R 11)n | (R 11)n |
| 2-F | 2-OPh | 2-(Ph-4-Cl) | 2-Cl-4-CH 3 | 2-OCH 3-5-CF 3 |
| 3-F | 3-OPh | 3-(Ph-4-Cl) | 2,4,6-3CH 3 | 2-CF 3-4-NO 2 |
| 4-F | 4-OPh | 4-(Ph-4-Cl) | 2,4,6-3C 2H 5 | 2,4-2NO 2-6-Cl |
| 2-Cl | 2,3-2F | 2-CH(CH 3) 2 | 2-NHCOCH 3 | 2,4-2NO 2-6-Br |
| 3-Cl | 2,4-2F | 3-CH(CH 3) 2 | 3-NHCOCH 3 | 2,3-2CH(CH 3) 2 |
| 4-Cl | 2,5-2F | 4-CH(CH 3) 2 | 4-NHCOCH 3 | 2,4-2CH(CH 3) 2 |
| 2-Br | 2,6-2F | 2-CF 3-4-Cl | 2-NHSO 2CH 3 | 2,5-2CH(CH 3) 2 |
| 3-Br | 3,4-2F | 2-CF 3-4-Br | 3-NHSO 2CH 3 | 2,6-2CH(CH 3) 2 |
| 4-Br | 3,5-2F | 2,3-2CF 3 | 3-CF 3-4-NO 2 | 3,4-2CH(CH 3) 2 |
| 2-I | 2,3-2Cl | 2,4-2CF 3 | 3-CF 3-4-F | 3,5-2CH(CH 3) 2 |
| 3-I | 2,4-2Cl | 2,5-2CF 3 | 3-CF 3-4-Cl | 2-NO 2-4-OCH 3 |
| 4-I | 2,5-2Cl | 2,6-2CF 3 | 2-Cl-4-CF 3 | 2-NO 2-4-OC 2H 5 |
| 2-CH 3 | 2,6-2Cl | 3,4-2CF 3 | 2-Br-4-CF 3 | 2,3-2C(CH 3) 3 |
| 3-CH 3 | 3,4-2Cl | 3,5-2CF 3 | 2-CH 3-5-NO 2 | 2,4-2C(CH 3) 3 |
| 4-CH 3 | 3,5-2Cl | 2,6-2SCF 3 | 2-CH 3-3-NO 2 | 2,5-2C(CH 3) 3 |
| 2-C 2H 5 | 2,3-2Br | 3,4-2SCF 3 | 2-SCH 3-5-Cl | 2,6-2C(CH 3) 3 |
| 3-C 2H 5 | 2,4-2Br | 3,5-2SCF 3 | 2,4,6-3NO 2 | 3,4-2C(CH 3) 3 |
| 4-C 2H 5 | 2,5-2Br | 2,3-2SCH 3 | 2,4-2F-6-Cl | 3,5-2C(CH 3) 3 |
| 2-CF 3 | 2,6-2Br | 2,4-2SCH 3 | 2,3-2Cl-4-Br | 4-SO 2NH 2 |
| 3-CF 3 | 3,4-2Br | 2,3-2CH 3 | 2-CH 3-6-NO 2 | 2-OCH 3-4-NO 2 |
| 4-CF 3 | 3,5-2Br | 2,4-2CH 3 | 4-NHSO 2CH 3 | 2-CH 2CH=CH 2 |
| 2-OCH 3 | 2,3-2CN | 2,5-2CH 3 | 2-NO 2-4-CF 3 | 3-CH 2CH=CH 2 |
| 3-OCH 3 | 2,4-2CN | 2,6-2CH 3 | 2-NO 2-4,6-2Br | 4-CH 2CH=CH 2 |
| 4-OCH 3 | 2,5-2CN | 3,4-2CH 3 | 2Cl-4-SO 2CH 3 | 2-C(CH 3)=CH 2 |
| 2-SCH 3 | 2,6-2CN | 3,5-2CH 3 | 2-CH 3-4-NO 2 | 3-C(CH 3)=CH 2 |
| 3-SCH 3 | 3,4-2CN | 2,3-2C 2H 5 | 2-CH 3-4-OCH 3 | 4-C(CH 3)=CH 2 |
| 4-SCH 3 | 3,5-2CN | 2,4-2C 2H 5 | 2-CH 3-6-C 2H 5 | 4-F-2,6-2Br |
| 2-OCF 3 | 2-F-4-Cl | 2,5-2C 2H 5 | 3-CO 2C 2H 5 | 2,4-2F-6-Cl |
| 3-OCF 3 | 2-F-4-Br | 2,6-2C 2H 5 | 2-NO 2-4-F | 2-F-4-Cl-6-Br |
| 4-OCF 3 | 2-F-4-I | 3,4-2C 2H 5 | 2-NO 2-4-Cl | 2,3,5,6-4F-4-CF 3 |
| 2-CN | 2-F-5-Cl | 3,5-2C 2H 5 | 2-NO 2-4-Br | 4-CH 3-2,6-2Br |
| 3-CN | 3-F-5-Cl | 2,5-2SCH 3 | 2-NO 2-5-Cl | 4-F-5-CH 3-6-Cl |
| 4-CN | 4-F-3-Cl | 2,6-2SCH 3 | 3-NO 2-4-Cl | 2-Cl-4-C(CH 3) 3 |
| 2-Ph | 4-F-6-Cl | 3,4-2SCH 3 | 3-NO 2-4-Br | 2-Cl-4-CF 3-6-Br |
| 3-Ph | 2,3,4-3F | 3,5-2SCH 3 | 2-Cl-4-NO 2 | 2-COOCH 3-4-Br |
| 4-Ph | 2,3,5-3F | 2-CH 3-5-F | 2-Cl-5-NO 2 | 2-Cl-4-COOCH 3 |
| 2-NO 2 | 2,3,6-3F | 2-CH 3-5-Cl | 2-Cl-5-CF 3 | 2-Br-4-COOCH 3 |
| 3-NO 2 | 2,4,5-3F | 2-CH 3-5-Br | 2-Br-5-CF 3 | 2,4,6-3CH(CH 3) 2 |
| 4-NO 2 | 2,4,6-3F | 2-CH 3-6-Cl | 2-CN-3-F | 2,4,6-3C(CH 3) 3 |
| 3-SCF 3 | 2,3-2NO 2 | 2-Br-3-CH 3 | 2-CN-3-Cl | 2,3-2CH 3-6-NO 2 |
| 4-SCF 3 | 2,4-2NO 2 | 3-CH 3-4-Cl | 2-CN-4-NO 2 | 2,4-2OCH 3-5-Cl |
| 2-OC 2H 5 | 2,5-2NO 2 | 3-CH 3-4-Br | 2-CN-4-Cl | 2-Cl-5-CONH 2 |
| 3-OC 2H 5 | 2,6-2NO 2 | 3-CH 3-4-I | 2-CN-4-Br | 2-NO 2-4-N(CH 3) 2 |
| 4-OC 2H 5 | 3,4-2NO 2 | 2-CH 3-4-I | 2-CF 3-4-CN | 2-NO 2-5-N(CH 3) 2 |
| 2-COCH 3 | 3,5-2NO 2 | 2-Cl-4-F | 2-Cl-4-CN | 2-NO 2-4,5-2CH 3 |
| 3-COCH 3 | 3,5-2OCH 3 | 2-Cl-4-Br | 2-NO 2-4-CN | 2-NO 2-4-F-5-Cl |
| 4-COCH 3 | 2-OCH 2Ph | 2-Cl-4-I | 2-F-5-CH 3 | 2-CN-4-NO 2-6-Cl |
| 2-CH 2Ph | 3-OCH 2Ph | 3-Cl-4-I | 2-NO 2-4-CH 3 | 2-CN-4-NO 2-6-Br |
| 3-CH 2Ph | 4-OCH 2Ph | 2-Br-4-Cl | 3-NO 2-4-CH 3 | 2-OCH 2CH=CH 2 |
| 4-CH 2Ph | 3-CONH 2 | 3,4,5-3F | 2-CN-5-CH 3 | 3-OCH 2CH=CH 2 |
| 2-C(CH 3) 3 | 4-CONH 2 | 2,3,4-3Cl | 2-F-5-NO 2 | 4-OCH 2CH=CH 2 |
| 3-C(CH 3) 3 | 2-N(CH 3) 2 | 2,3,5-3Cl | 2-CF 3-4,6-2Cl | 3-OCH 2Ph-4-CH 3 |
| 4-C(CH 3) 3 | 3-N(CH 3) 2 | 2,3,6-3Cl | 2-CF 3-4,6-2Br | 2-CH 2C(CH 3)=CH 2 |
| 2-COC 2H 5 | 4-N(CH 3) 2 | 2,4,5-3Cl | 3-CH 3-2,6-2Cl | 3-CH 2C(CH 3)=CH 2 |
| 3-COC 2H 5 | 2-N(C 2H 5) 2 | 2,4,6-3Cl | 2-CH 3-4,6-2Br | 2-CH 3-5-CONH 2 |
| 4-COC 2H 5 | 3-N(C 2H 5) 2 | 3,4,5-3Cl | 2,4,6-3OCH 3 | 2-Cl-5-NHCOCH 3 |
| 2-SOCH 3 | 4-N(C 2H 5) 2 | 2,3,4-3Br | 3,4,5-3OCH 3 | 2,6-2Br-3-Cl-4-F |
| 3-SOCH 3 | 2,3-2OCH 3 | 2,3,5-3Br | 2,4,6-3SCH 3 | 2,3-(CH 2CH 2CH 2-) |
| 4-SOCH 3 | 2,4-2OCH 3 | 2,3,6-3Br | 2,4,6-3OCF 3 | 4-O(CH 2) 3CH 3 |
| 2-SO 2CH 3 | 2,5-2OCH 3 | 2,4,5-3Br | 2,4,6-3SCF 3 | 4-O(CH 2) 2N(CH 3) 2 |
| 3-SO 2CH 3 | 2,6-2OCH 3 | 2,4,6-3Br | 2-CH 2C≡CH | 3-CH 3-4-NHCOCH 3 |
| 4-SO 2CH 3 | 3,4-2OCH 3 | 3,4,5-3Br | 3-CH 2C≡CH | 3-NHSO 2CH 3-4-CH 3 |
| 2-SOC 2H 5 | 4-CO 2C 2H 5 | 3-F-4-CH 3 | 4-CH 2C≡CH | 3-OCH 2Ph-4-CH 3-6-Br |
| 3-SOC 2H 5 | 2,3-2OCF 3 | 3-Cl-4-CH 3 | 2-F-3-Cl | 2-OCH 3-5-CH 3-4-Cl |
| 4-SOC 2H 5 | 2,4-2OCF 3 | 3-Br-4-CH 3 | 2-Cl-3-CH 3 | 2,6-2Cl-4-COCH 3 |
| 2-OCHF 2 | 2,5-2OCF 3 | 2,4,6-3CF 3 | 4-(4-F-Ph) | 2-NHCOCH 3-5-CF 3 |
| 3-OCHF 2 | 2,6-2OCF 3 | 2-CH 3-3-F | 4-(4-NO 2-Ph) | 2-CH 3-4-NO 2-6-Cl |
| 4-OCHF 2 | 3,4-2OCF 3 | 2-CH 3-3-Cl | 4-(3-Cl-Ph) | 2-CH 3-4-NO 2-6-Br |
| 2-CO 2CH 3 | 3,5-2OCF 3 | 2-CH 3-4-F | 4-(2-Cl-Ph) | 2-CH 3-4-Cl-6-NO 2 |
| 3-CO 2CH 3 | 2,3-2SCF 3 | 2-CH 3-4-Cl | 4-(4-Cl-Ph) | 2-CH 3-4-Br-6-NO 2 |
| 4-CO 2CH 3 | 2,4-2SCF 3 | 2-CH 3-4-Br | 4-(4-CH 3-Ph) | 2,5-2OCH 3-4-NO 2 |
| 2-CO 2C 2H 5 | 2,5-2SCF 3 | 2-Br-4-CH 3 | 2-OCH 2C≡CH | 2,6-2CH 3-4-C(CH 3) 3 |
| 2,3-(OCF 2O-) | 2-Br-5-NO 2 | 2-Br-4-OCF 3 | 3-OCH 2C≡CH | 2-NO 2-4-CF 3-5-Cl |
| 2,3-(OCH 2O-) | 2-OCH 3-5-Cl | 2,3,5,6-4F | 4-OCH 2C≡CH | 2-NO 2-4-CF 3-6-Cl |
| 3,4-(OCH 2O-) | 3-F-4-OCH 3 | 2-CN-4,6-2Cl | 5-NO 2-2-OCH 3 | 2-NO 2-4-CF 3-6-Br |
| 3,4-(OCF 2O-) | 3-Cl-4-OCH 3 | 2-CN-4,6-2Br | 2-OCH 3-5-CH 3 | 2-CONH 2-5-CH 3 |
| 4-(4-Br-Ph) | 3-NO 2-4-F | 2,6-2Cl-4-CN | 2,6-2Cl-4-NO 2 | 4-CH 2C(CH 3)=CH 2 |
| 4-(4-CN-Ph) | 2-OCF 3-4-CN | 2,6-2Cl-4-CF 3 | 2-NO 2-4-OCF 3 | 2-NO 2-4-O(CH 2) 3CH 3 |
| 4-O(Ph-4-Br) | 2-OCF 3-4-Cl | 2,6-2Br-4-CF 3 | 2,3,4-3F-6-NO 2 | 3-OCH 3-4-CO 2CH 3 |
| 4-O(Ph-4-CH 3) | 2-OCF 3-4-Br | 2,3,4,5,6-5Cl | 2,6-2Br-4-NO 2 | 2,3-(CH 2CH 2CH 2CH 2-) |
| 4-(4-OCH 3-Ph) | 2-F-4,6-2Br | 4-O(Ph-4-Cl) | 4-O(Ph-4-F) | 2-CH(CH 3)CH 2CH(CH 3) 2 |
| 4-(2-CH 3-Ph) | 2-Cl-4-OCF 3 | 4-(4-CF 3-Ph) | 2,5-2Cl-4-NO 2 | H |
Table 6
| (R 11)n | (R 11)n | (R 11)n | (R 11)n |
| 2-CH 3 | 2-CN-6-CH 3 | 2-SCH 3-6-CH 3 | 2-(Cyclopropyl)NH-6-CF 3 |
| 6-C 3H 7 | 2-SCH 3-5-Br | 2-CN-5,6-2CH 3 | 2-(2-Cl-Ph)NH-6-CF 3 |
| 6-Cl | 5-NH 2-6-Cl | 2-PhNH-6-CF 3 | 2-(2,3-2Cl-Ph)NH-6-CF 3 |
| 2-Cl | 2-SCH 3-5-Cl | 2-SO 2CH 3-6-CF 3 | 2-(2,4-2Cl-Ph)NH-6-CF 3 |
| 6-OH | 2-SCH 3-6-Cl | 2-SO 2CH 3-6-CH 3 | 2-(3,4-2Cl-Ph)NH-6-CF 3 |
| 5-CH 3 | 2-Ph-4-CH 3 | 2-CF 3-5,6-2CH 3 | 2-(2,4-2F-Ph)NH-6-CF 3 |
| 2-NH 2 | 2-NH 2-6-CH 3 | 2-CF 3-5-CO 2C 2H 5 | 2-(4-F-Ph)NH-6-CF 3 |
| 2-Ph | 2-PhCH 2-6-Cl | 2-CN-5-CH 3-6-Cl | 2-(2-F-Ph)NH-6-CF 3 |
| 2,6-2NH 2 | 2-NH 2-6-CF 3 | 2-SCH 3-5-OH-6-Cl | 2-(4-Cl-Ph)NH-6-CF 3 |
| 2-CN-6-Cl | 2-NH 2-6-OCH 3 | 2-(3-CH 3-Ph)-6-OH | 2-(2,3,4-3Cl-Ph)NH-6-CF 3 |
| 2-CN-6-CF 3 | 2-SCH 3-6-NH 2 | 2-CONH 2-6-CH 3 | 2-(2,6-2Cl-Ph)NH-6-CF 3 |
| 2-NH 2-5-Cl | 2-SCH 3-6-CF 3 | 2-CONH 2-6-CF 3 | 2-(2,6-2F-Ph)NH-6-CF 3 |
Table 7
| (R 11)n | (R 11)n | (R 11)n | (R 11)n | (R 11)n |
| 4-Cl | 4,6-2CH 3 | 4-CO 2CH 3 | 4-(4-Cl-Ph) | 4-CH 3-6-CO 2C 2H 5 |
| 5-Br | 4-thienyl | 4,6-2OCH 3 | 5-CO 2CH 3 | 4-CF 3-5-CO 2CH 3 |
| 4-CH 3 | 4,6-2Cl | 4,5,6-3Cl | 4-NH 2-5-CN | 4-CH 3-6-CO2CH 3 |
| 4-furyl | 6-Ph | 4-Cl-5-Br | 4-Cl-6-CH 3 | 2-Pyridyl-5-Cl-6-CH 3 |
Table 8
| (R 11)n | (R 11)n | (R 11)n | (R 11)n |
| 4-Br | 4,5-(CH 2-) 3 | 4-(Ph-4-Cl)-5-CO 2C 2H 5 | 4,5-(CH=CH-CCN=CH-) |
| 5-Cl | 4,5-(CH 2-) 4 | 4,5-(CCl=CH-CH=CH-) | 4,5-(CH=CH-CCF 3=CH-) |
| 5-CH 3 | 4-CO 2C 2H 5 | 4,5-(CH=CCl-CH=CH-) | 4,5-(CH=CH-CNO 2=CH-) |
| 4-Cl | 4-CF 3-5-CN | 4,5-(CH=CH-CCl=CH-) | 4,5-(CH=CH-CBr=CH-) |
| 5-Br | 4-CH 2CO 2C 2H 5 | 4,5-(CMe=CH-CH=CH-) | 4,5-(CMe=CH-CCl=CH-) |
| 4-CH 3 | 4-(Ph-3,4-2F) | 4,5-(CH=CMe-CH=CH-) | 4,5-(CH=CMe-CCN=CH-) |
| 5-Ph | 4-(Ph-4-Cl) | 4,5-(C(OMe)=CH-CH=CH-) | 4,5-(CMe=CH-CNO 2=CH-) |
| 4-Ph | 4-Ph-5-CO 2C 2H 5 | 4,5-(CH=C(OMe)-CH=CH-) | 4,5-(CCl=CMe-CH=CH-) |
| 5-NO 2 | 4-CH 3-5-COCH 3 | 4,5-(CCN=CH-CH=CH-) | 4,5-(CMe=CH-CNO 2=CH-) |
| 5-OPh | 4-CH 3-5-CO 2C 2H 5 | 4,5-(CCF 3=CH-CH=CH-) | 4,5-(CCN=CMe-CH=CH-) |
| 5-OCH 3 | 4-CF 3-5-CO 2C 2H 5 | 4,5-(CNO 2=CH-CH=CH-) | 4,5-(CCF 3=CH-CCl=CH-) |
| 4,5-2Cl | 5-CH 3-4-CO 2C 2H 5 | 4,5-(CBr=CH-CH=CH-) | 4,5-(CCN=CCF 3-CH=CH-) |
| 4,5-2CH 3 | 5-Ph-4-CO 2C 2H 5 | 4,5-(CH=CCN-CH=CH-) | 4,5-(CCF 3=CH-CCN=CH-) |
| 4-C(CH 3) 3 | 4-CH 3-5-CONHCH 3 | 4,5-(CH=CCF 3-CH=CH-) | 4,5-(CCl=CCF 3-CH=CH-) |
| 5-(Ph-4-Cl) | 4-CF 3-5-CONHCH 3 | 4,5-(CH=CNO 2-CH=CH-) | 4,5-(CCl=CH-CCl=CH-) |
| 4-(Ph-4-Br) | 4,5-(CH=CH-CH=CH-) | 4,5-(CH=CBr-CH=CH-) | 4,5-(CCN=CCl-CH=CH-) |
Part of compounds of the present invention can illustrate by the particular compound listed in table 9-table 50, but does not limit the present invention.
When in general formula I, A=A
1, R
1during=pyridine-2-base, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-1.
Table 9: in general formula I-1, works as R
2, R
3, R
4when being respectively Cl, substituting group (R
11) n is in table 9, representation compound is numbered 1-83.
Table 9
| Sequence number | (R 11)n | Sequence number | (R 11)n | Sequence number | (R 11)n |
| 1 | - | 29 | 3-Cl-5-CH 3 | 57 | 3,5-2Br |
| 2 | 5-I | 30 | 3-Cl-5-F | 58 | 3,5,6-3Cl |
| 3 | 5-F | 31 | 3-Cl-5-Br | 59 | 3-CO 2CH 3 |
| 4 | 6-F | 32 | 3-Cl-5-NO 2 | 60 | 5-CO 2CH 3 |
| 5 | 3-Cl | 33 | 3-Br-5-CF 3 | 61 | 3-OCH 2Ph |
| 6 | 4-Cl | 34 | 3-Br-5-CN | 62 | 3,4,5,6-4Cl |
| 7 | 5-Cl | 35 | 3-Br-5-CH 3 | 63 | 4-NO 2-6-CH 3 |
| 8 | 6-Cl | 36 | 3-Br-5-F | 64 | 5-NO 2-6-CH 3 |
| 9 | 3-CF 3 | 37 | 3-Br-5-Cl | 65 | 5-CN-6-CH 3 |
| 10 | 4-CF 3 | 38 | 3-Br-5-NO 2 | 66 | 5-Br-6-CH 3 |
| 11 | 5-CF 3 | 39 | 3-CN-6-Cl | 67 | 3-Cl-5-CF 3 |
| 12 | 6-CF 3 | 40 | 3-CN-5-Cl | 68 | 3-Cl-5-CN |
| 13 | 3-Br | 41 | 3-CN-6-Br | 69 | 3-NO 2-4-CH 3 |
| 14 | 4-Br | 42 | 3-CN-5-Br | 70 | 3-NO 2-5-CH 3 |
| 15 | 5-Br | 43 | 3-CN-5-F | 71 | 3-CN-4,6-2Cl |
| 16 | 6-Br | 44 | 3-NO 2-5-Cl | 72 | 3,5-2Br-6-CH 3 |
| 17 | 3-CH 3 | 45 | 3-NO 2-5-Br | 73 | 5-CF 3-3,6-2Cl |
| 18 | 4-CH 3 | 46 | 3-CF 3-6-Cl | 74 | 3-CO 2CH 3-6-Cl |
| 19 | 5-CH 3 | 47 | 3-CF 3-5-Cl | 75 | 5-CO 2CH 3-6-Cl |
| 20 | 3-NO 2 | 48 | 3-CF 3-5-Br | 76 | 3,5-2Cl-6-OCH 3 |
| 21 | 5-NO 2 | 49 | 3-CF 3-6-Br | 77 | 4-CF 3-5-CN-6-Cl |
| 22 | 6-NO 2 | 50 | 3-CF 3-6-CH 3 | 78 | 3-CONH 2-4,6-2Cl |
| 23 | 3-CN | 51 | 5-CF 3-6-Cl | 79 | 3-CN-4-CH 3-6-Cl |
| 24 | 4-CN | 52 | 3-CH 3-5-Br | 80 | 3-CN-4-CF 3-6-Cl |
| 25 | 5-CN | 53 | 3-CH 3-5-Cl | 81 | 4-CH 3-5-CN-6-Cl |
| 26 | 6-CN | 54 | 3-CH 3-5-NO 2 | 82 | 3-CN-5-CO 2C 2H 5-6-CF 3 |
| 27 | 3,5-2Cl | 55 | 4-CH 3-5-Br | 83 | 3,5-2Cl-6-(O-Ph-4-Cl) |
| 28 | 6-CH 3 | 56 | 4-CH 3-5-NO 2 |
Note: "-" indicates without replacement, is hydrogen and replaces, lower same.
Table 10: in general formula I-1, works as R
2, R
3, R
4when being respectively F, substituting group (R
11) n is in table 9, be corresponding in turn to the 1-83 of table 9, representation compound is numbered 84-166.
When in general formula I, A=A
1, R
1during=phenyl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-2
Table 11: in general formula I-2, works as R
2, R
3, R
4when being respectively Cl, substituting group (R
11) n is in table 11, representation compound is numbered 167-400.
Table 11
| Sequence number | (R 11)n | Sequence number | (R 11)n | Sequence number | (R 11)n |
| 167 | - | 245 | 2-Cl | 323 | 2-NHCH 3 |
| 168 | 2-F | 246 | 4-Cl | 324 | 3-F-4-CF 3 |
| 169 | 3-F | 247 | 4-CN | 325 | 2-NO 2-4-F |
| 170 | 4-F | 248 | 4-CF 3 | 326 | 3-Br-4-CF 3 |
| 171 | 3-Cl | 249 | 2,4-2Cl | 327 | 3-CH 3-4-CF 3 |
| 172 | 2-Br | 250 | 2-CONH 2 | 328 | 3-NO 2-4-CF 3 |
| 173 | 3-Br | 251 | 3-CONH 2 | 329 | 3-CN-4-CF 3 |
| 174 | 4-Br | 252 | 4-CONH 2 | 330 | 2-NO 2-4-Br |
| 175 | 2-CN | 253 | 2-Cl-4-F | 331 | 2-NO 2-4-CN |
| 176 | 3-CN | 254 | 2-Cl-4-Br | 332 | 3-OCH 2OCH 3 |
| 177 | 2-CF 3 | 255 | 3-NHCH 3 | 333 | 4-OCH 2OCH 3 |
| 178 | 3-CF 3 | 256 | 4-NHCH 3 | 334 | 2-Cl-4-OCF 3 |
| 179 | 4-NO 2 | 257 | 2-N(CH 3) 2 | 335 | 2-Cl-4-SCH 3 |
| 180 | 2-CH 3 | 258 | 2-COCH 3 | 336 | 2-Cl-4-OCH 3 |
| 181 | 3-CH 3 | 259 | 3-COCH 3 | 337 | 2-OCF 3-4-Cl |
| 182 | 4-CH 3 | 260 | 4-COCH 3 | 338 | 2-OC 2H 5-4-Cl |
| 183 | 2-C 2H 5 | 261 | 3-N(CH 3) 2 | 339 | 2-NHCH 3-4-Cl |
| 184 | 3-C 2H 5 | 262 | 4-N(CH 3) 2 | 340 | 2-COCH 3-4-Cl |
| 185 | 4-C 2H 5 | 263 | 2-Cl-4-CF 3 | 341 | 2,4-2F-6-NO 2 |
| 186 | 2-NO 2 | 264 | 2-F-4-Cl | 342 | 2,6-2F-4-NO 2 |
| 187 | 3-NO 2 | 265 | 2-Br-4-Cl | 343 | 2,4-2Cl-6-NO 2 |
| 188 | 2,3-2F | 266 | 2-Cl-4-CH 3 | 344 | 2,4-2Cl-6-CN |
| 189 | 2,4-2F | 267 | 2-Cl-4-NO 2 | 345 | 2,4-2Cl-6-CF 3 |
| 190 | 2,5-2F | 268 | 2-Cl-4-CN | 346 | 2,4-2Cl-6-CH 3 |
| 191 | 2,6-2F | 269 | 2-OCHF 2 | 347 | 2,6-2Cl-4-NO 2 |
| 192 | 3,4-2F | 270 | 3-OCHF 2 | 348 | 2,6-2Cl-4-CF 3 |
| 193 | 3,5-2F | 271 | 2-CH 3-4-Cl | 349 | 2,6-2Cl-4-CN |
| 194 | 2,3-2Cl | 272 | 2-NO 2-4-Cl | 350 | 2-Cl-4-C(CH 3) 3 |
| 195 | 2,5-2Cl | 273 | 2-CN-4-Cl | 351 | 3-Cl-4-C(CH 3) 3 |
| 196 | 2,6-2Cl | 274 | 2-C(CH 3) 3 | 352 | 2-Cl-3-C(CH 3) 3 |
| 197 | 3,4-2Cl | 275 | 3-C(CH 3) 3 | 353 | 2-Cl-5-C(CH 3) 3 |
| 198 | 3,5-2Cl | 276 | 4-C(CH 3) 3 | 354 | 2-C(CH 3) 3-4-CF 3 |
| 199 | 2,3-Br | 277 | 3-F-4-Cl | 355 | 2-Br-4-C(CH 3) 3 |
| 200 | 2,4-2Br | 278 | 3-Br-4-Cl | 356 | 2-F-4-C(CH 3) 3 |
| 201 | 2,5-2Br | 279 | 3-CH 3-4-Cl | 357 | 3-OC 2H 5-4-CF 3 |
| 202 | 2,6-2Br | 280 | 3-NO 2-4-Cl | 358 | 3-NHCH 3-4-CF 3 |
| 203 | 3,4-2Br | 281 | 3-CN-4-Cl | 359 | 3-COCH 3-4-CF 3 |
| 204 | 3,5-2Br | 282 | 3-OCF 3-4-Cl | 360 | 2-Cl-4-NCH 3 |
| 205 | 2-SCH 3 | 283 | 2-F-4-CF 3 | 361 | 2-Cl-4-COCH 3 |
| 206 | 3-SCH 3 | 284 | 2-Br-4-CF 3 | 362 | 2-Cl-4-OCO 2CH 3 |
| 207 | 4-SCH 3 | 285 | 2-CH 3-4-CF 3 | 363 | 2-OCF 3-4-CF 3 |
| 208 | 2-SCF 3 | 286 | 2-NO 2-4-CF 3 | 364 | 2-OC 2H 5-4-CF 3 |
| 209 | 3-SCF 3 | 287 | 2-CN-4-CF 3 | 365 | 2-NHCH 3-4-CF 3 |
| 210 | 4-SCF 3 | 288 | 2-COC 2H 5 | 366 | 2-COCH 3-4-CF 3 |
| 211 | 2-OCF 3 | 289 | 3-COC 2H 5 | 367 | 2,5-2Cl-4-CF 3 |
| 212 | 3-OCF 3 | 290 | 4-COC 2H 5 | 368 | 2,5-2Cl-4-CN |
| 213 | 4-OCF 3 | 291 | 2-SO 2CH 3 | 369 | 2,6-2Cl-4-CH 3 |
| 214 | 2-OCH 3 | 292 | 3-SO 2CH 3 | 370 | 2-CH 3-3-Cl-4-CF 3 |
| 215 | 3-OCH 3 | 293 | 4-SO 2CH 3 | 371 | 2-CH 3-3-Cl-6-CN |
| 216 | 4-OCH 3 | 294 | 4-OCHF 2 | 372 | 2,4,6-3NO 2 |
| 217 | 2,3,4-3F | 295 | 2-SO 2C 2H 5 | 373 | 2-Br-4-NO 2 |
| 218 | 2,3,5-3F | 296 | 3-SO 2C 2H 5 | 374 | 2-NO 2-4-CH 3 |
| 219 | 2,4,5-3F | 297 | 4-SO 2C 2H 5 | 375 | 2-NO 2-4-OCH 3 |
| 220 | 2,3,6-3F | 298 | 2-CO 2CH 3 | 376 | 2-NO 2-4-SCH 3 |
| 221 | 2,4,6-3F | 299 | 3-CO 2CH 3 | 377 | 2-NO 2-4-NCH 3 |
| 222 | 3,4,5-3F | 300 | 4-CO 2CH 3 | 378 | 3-COCH 3-4-Cl |
| 223 | 2,3,4-3Cl | 301 | 2-CO 2C 2H 5 | 379 | 2-OCOCH 2CH 3 |
| 224 | 2,3,5-3Cl | 302 | 3-CO 2C 2H 5 | 380 | 3-OCOCH 2CH 3 |
| 225 | 2,4,5-3Cl | 303 | 4-CO 2C 2H 5 | 381 | 4-OCOCH 2CH 3 |
| 226 | 2,3,6-3Cl | 304 | 2-CH 2OCH 3 | 382 | 2-Cl-4-COOCH 3 |
| 227 | 2,4,6-3Cl | 305 | 3-CH 2OCH 3 | 383 | 2-Cl-4-SO 2CH 3 |
| 228 | 3,4,5-3Cl | 306 | 4-CH 2OCH 3 | 384 | 2,6-2Cl-4-COCH 3 |
| 229 | 2,3,4-3Br | 307 | 2-OCOCH 3 | 385 | 2,6-2Cl-4-CONH 2 |
| 230 | 2,3,5-3Br | 308 | 3-OCOCH 3 | 386 | 2,6-2Br-4-CF 3 |
| 231 | 2,4,5-3Br | 309 | 4-OCOCH 3 | 387 | 2,4-2Cl-6-SCH 3 |
| 232 | 2,3,6-3Br | 310 | 2-Cl-3-CH 3 | 388 | 2,4-2Cl-6-NCH 3 |
| 233 | 2,4,6-3Br | 311 | 2-Cl-5-CH 3 | 389 | 2-NO 2-4-COCH 3 |
| 234 | 3,4,5-3Br | 312 | 2-Cl-6-CH 3 | 390 | 2-NO 2-4-CONH 2 |
| 235 | 2,4-2NO 2 | 313 | 2-Cl-3-CN | 391 | 2-CH 3-4-Cl-6-CN |
| 236 | 2,3-2CH 3 | 314 | 2-Cl-5-CN | 392 | 2-CH 3-4-Cl-5-CN |
| 237 | 2,4-2CH 3 | 315 | 2-Cl-6-CN | 393 | 2-NCH 3-4-Cl-6-CN |
| 238 | 2,5-2CH 3 | 316 | 2-OCO 2CH 3 | 394 | 2-SCH 3-4-Cl-5-CN |
| 239 | 2,6-2CH 3 | 317 | 3-OCO 2CH 3 | 395 | 2,4-2Cl-6-SO 2CH 3 |
| 240 | 3,4-2CH 3 | 318 | 4-OCO 2CH 3 | 396 | 2,6-2Cl-4-CO 2CH 3 |
| 241 | 3,5-2CH 3 | 319 | 2-OCH 2OCH 3 | 397 | 2,6-2Br-4-OCF 3 |
| 242 | 2-OC 2H 5 | 320 | 2-F-4-NO 2 | 398 | 2-Cl-4-CF 3-6-NO 2 |
| 243 | 3-OC 2H 5 | 321 | 3-OC 2H 5-4-Cl | 399 | 2-Cl-4-CF 3-5-CN |
| 244 | 4-OC 2H 5 | 322 | 3-NHCH 3-4-Cl | 400 | 2-Cl-4-CF 3-6-NHCH 3 |
Table 12: in general formula I-2, works as R
2, R
3, R
4when being respectively F, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 401-634.
When in general formula I, A=A
1, R
1during=benzoyl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-3
Table 13: in general formula I-3, works as R
2, R
3, R
4when being respectively Cl, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 635-868.
Table 14: in general formula I-3, works as R
2, R
3, R
4when being respectively F, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 869-1102.
When in general formula I, A=A
1, R
1during=benzyl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-4
Table 15: in general formula I-4, works as R
2, R
3, R
4when being respectively Cl, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 1103-1336.
Table 16: in general formula I-4, works as R
2, R
3, R
4when being respectively F, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 1337-1570.
When in general formula I, A=A
1, R
1during=pyrimidine-2-base, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-5.
Table 17: in general formula I-5, works as R
2, R
3, R
4when being respectively Cl, substituting group (R
11) n is in table 17, representation compound is numbered 1571-1586.
Table 17
| Sequence number | (R 11)n | Sequence number | (R 11)n |
| 1571 | - | 1579 | 4-CO 2C 2H 5 |
| 1572 | 4-Cl | 1580 | 4,5,6-3Cl |
| 1573 | 5-Br | 1581 | 4,6-2OCH 3 |
| 1574 | 4-CH 3 | 1582 | 4-Cl-6-CH 3 |
| 1575 | 4-CN | 1583 | 4-NH 2-5-CN |
| 1576 | 4,6-2Cl | 1584 | 4-CH 3-6-CO 2C 2H 5 |
| 1577 | 4,6-2CH 3 | 1585 | 4-CH 3-6-N(CH 3) 2 |
| 1578 | 4-CO 2CH 3 | 1586 | 4-CF 3-5-CO 2CH 3 |
Table 18: in general formula I-5, works as R
2, R
3, R
4when being respectively F, substituting group (R
11) n is in table 17, be corresponding in turn to the 1571-1586 of table 17, representation compound is numbered 1587-1602.
When in general formula I, A=A
1, R
1during=pyrimidine-4-yl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-6.
Table 19: in general formula I-6, works as R
2, R
3, R
4when being respectively Cl, substituting group (R
11) n is in table 19, representation compound is numbered 1603-1654.
Table 19
| Sequence number | (R 11)n | Sequence number | (R 11)n | Sequence number | (R 11)n |
| 1603 | - | 1621 | 2-SCH 3 | 1639 | 2-CN-5,6-2CH 3 |
| 1604 | 2-Cl | 1622 | 2,5-2Cl | 1640 | 2-CN-5-CH 3-6-Cl |
| 1605 | 5-Cl | 1623 | 2,6-2Cl | 1641 | 2-SO 2CH 3-6-CH 3 |
| 1606 | 6-Cl | 1624 | 5,6-2Cl | 1642 | 2-CF 3-5,6-2CH 3 |
| 1607 | 2-Br | 1625 | 2,5,6-3Cl | 1643 | 2-CF 3-5-CO 2C 2H 5 |
| 1608 | 5-Br | 1626 | 2,5-2OCH 3 | 1644 | 2-(4-F-Ph)NH-6-CF 3 |
| 1609 | 6-Br | 1627 | 2-CO 2C 2H 5 | 1645 | 2-(2-F-Ph)NH-6-CF 3 |
| 1610 | 5-CN | 1628 | 5-CO 2C 2H 5 | 1646 | 2-(4-Cl-Ph)NH-6-CF 3 |
| 1611 | 2-CF 3 | 1629 | 2-CN-6-Cl | 1647 | 2-(2-Cl-Ph)NH-6-CF 3 |
| 1612 | 6-CF 3 | 1630 | 2-CN-6-CF 3 | 1648 | 2-(2,3-2Cl-Ph)NH-6-CF 3 |
| 1613 | 2-CH 3 | 1631 | 2-CN-6-CH 3 | 1649 | 2-(2,4-2Cl-Ph)NH-6-CF 3 |
| 1614 | 5-CH 3 | 1632 | 5-CO 2CH 3 | 1650 | 2-(3,4-2Cl-Ph)NH-6-CF 3 |
| 1615 | 6-CH 3 | 1633 | 2-SO 2CH 3-6-CF 3 | 1651 | 2-(2,4-2F-Ph)NH-6-CF 3 |
| 1616 | 2-C 2H 5 | 1634 | 2-SCH 3-6-OCH 3 | 1652 | 2-(2,3,4-3Cl-Ph)NH-6-CF 3 |
| 1617 | 5-C 2H 5 | 1635 | 2-SCH 3-6-CH 3 | 1653 | 2-(2,6-2Cl-Ph)NH-6-CF 3 |
| 1618 | 6-C 2H 5 | 1636 | 2-SCH 3-5-Cl | 1654 | 2-(2,6-2F-Ph)NH-6-CF 3 |
| 1619 | 2-OCH 3 | 1637 | 2-SCH 3-6-Cl | ||
| 1620 | 2-CO 2CH 3 | 1638 | 2-SCH 3-6-CF 3 |
Table 20: in general formula I-6, works as R
2, R
3, R
4when being respectively F, substituting group (R
11) n is in table 19, be corresponding in turn to the 1603-1654 of table 19, representation compound is numbered 1655-1706.
When in general formula I, A=A
1time, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-7.
Table 21: in general formula I-7, works as R
2, R
3, R
4when being respectively Cl, substituent R
1in table 21, representation compound is numbered 1707-1749.
Table 21
Table 22: in general formula I-7, works as R
2, R
3, R
4when being respectively F, substituent R
1in table 21, be corresponding in turn to the 1707-1749 of table 21, representation compound is numbered 1750-1792.
When in general formula I, A=A
2, R
1during=pyridine-2-base, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-8
Table 23: in general formula I-8, works as R
5, R
6, R
7when being respectively Cl, substituting group (R
11) n is in table 9, be corresponding in turn to the 1-83 of table 9, representation compound is numbered 1793-1875.
Table 24: in general formula I-8, works as R
5, R
6, R
7when being respectively F, substituting group (R
11) n is in table 9, be corresponding in turn to the 1-83 of table 9, representation compound is numbered 1876-1958.
When in general formula I, A=A
2, R
1during=phenyl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-9
Table 25: in general formula I-9, works as R
5, R
6, R
7when being respectively Cl, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 1959-2192.
Table 26: in general formula I-9, works as R
5, R
6, R
7when being respectively F, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 2193-2426.
When in general formula I, A=A
2, R
1during=benzoyl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-10
Table 27: in general formula I-10, works as R
5, R
6, R
7when being respectively Cl, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 2427-2660.
Table 28: in general formula I-10, works as R
5, R
6, R
7when being respectively F, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 2661-2894.
When in general formula I, A=A
2, R
1during=benzyl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-11
Table 29: in general formula I-11, works as R
5, R
6, R
7when being respectively Cl, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 2895-3128.
Table 30: in general formula I-11, works as R
5, R
6, R
7when being respectively F, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 3129-3362.
When in general formula I, A=A
2, R
1during=pyrimidine-2-base, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-12.
Table 31: in general formula I-12, works as R
5, R
6, R
7when being respectively Cl, substituting group (R
11) n is in table 17, be corresponding in turn to the 1571-1586 of table 17, representation compound is numbered 3363-3378.
Table 32: in general formula I-12, works as R
5, R
6, R
7when being respectively F, substituting group (R
11) n is in table 17, be corresponding in turn to the 1571-1586 of table 17, representation compound is numbered 3379-3394.
When in general formula I, A=A
2, R
1during=pyrimidine-4-yl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-13.
Table 33: in general formula I-13, works as R
5, R
6, R
7when being respectively Cl, substituting group (R
11) n is in table 19, be corresponding in turn to the 1603-1654 of table 19, representation compound is numbered 3395-3446.
Table 34: in general formula I-13, works as R
5, R
6, R
7when being respectively F, substituting group (R
11) n is in table 19, be corresponding in turn to the 1603-1654 of table 19, representation compound is numbered 3447-3498.
When in general formula I, A=A
2time, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-14.
Table 35: in general formula I-14, works as R
5, R
6, R
7when being respectively Cl, substituent R
1in table 21, be corresponding in turn to the 1707-1749 of table 21, representation compound is numbered 3499-3541.
Table 36: in general formula I-14, works as R
5, R
6, R
7when being respectively F, substituent R
1in table 21, be corresponding in turn to the 1707-1749 of table 21, representation compound is numbered 3542-3584.
When in general formula I, A=A
3, R
1during=pyridine-2-base, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-15
Table 37: in general formula I-15, works as R
8, R
9, R
10when being respectively Cl, substituting group (R
11) n is in table 9, be corresponding in turn to the 1-83 of table 9, representation compound is numbered 3585-3667.
Table 38: in general formula I-15, works as R
8, R
9, R
10when being respectively F, substituting group (R
11) n is in table 9, be corresponding in turn to the 1-83 of table 9, representation compound is numbered 3668-3750.
When in general formula I, A=A
3, R
1during=phenyl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-16
Table 39: in general formula I-16, works as R
8, R
9, R
10when being respectively Cl, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 3751-3984.
Table 40: in general formula I-16, works as R
8, R
9, R
10when being respectively F, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 3985-4218.
When in general formula I, A=A
3, R
1during=benzoyl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-17
Table 41: in general formula I-17, works as R
8, R
9, R
10when being respectively Cl, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 4219-4452.
Table 42: in general formula I-17, works as R
8, R
9, R
10when being respectively F, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 4453-4686.
When in general formula I, A=A
3, R
1during=benzyl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-18
Table 43: in general formula I-18, works as R
8, R
9, R
10when being respectively Cl, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 4687-4920.
Table 44: in general formula I-18, works as R
8, R
9, R
10when being respectively F, substituting group (R
11) n is in table 11, be corresponding in turn to the 167-400 of table 11, representation compound is numbered 4921-5154.
When in general formula I, A=A
3, R
1during=pyrimidine-2-base, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-19.
Table 45: in general formula I-19, works as R
8, R
9, R
10when being respectively Cl, substituting group (R
11) n is in table 17, be corresponding in turn to the 1571-1586 of table 17, representation compound is numbered 5155-5170.
Table 46: in general formula I-19, works as R
8, R
9, R
10when being respectively F, substituting group (R
11) n is in table 17, be corresponding in turn to the 1571-1586 of table 17, representation compound is numbered 5171-5186.
When in general formula I, A=A
3, R
1during=pyrimidine-4-yl, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-20.
Table 47: in general formula I-20, works as R
8, R
9, R
10when being respectively Cl, substituting group (R
11) n is in table 19, be corresponding in turn to the 1603-1654 of table 19, representation compound is numbered 5187-5238.
Table 48: in general formula I-20, works as R
8, R
9, R
10when being respectively F, substituting group (R
11) n is in table 19, be corresponding in turn to the 1603-1654 of table 19, representation compound is numbered 5239-5290.
When in general formula I, A=A
3time, R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hwhen being respectively H, general formula is I-21.
Table 49: in general formula I-21, works as R
8, R
9, R
10when being respectively Cl, substituent R
1in table 21, be corresponding in turn to the 1707-1749 of table 21, representation compound is numbered 5291-5333.
Table 50: in general formula I-21, works as R
8, R
9, R
10when being respectively F, substituent R
1in table 21, be corresponding in turn to the 1707-1749 of table 21, representation compound is numbered 5334-5376.
Compound of Formula I of the present invention is prepared in accordance with the following methods, and reaction formula is as follows, and in formula, each group unless otherwise indicated defines ditto:
General formula (I) compound can react obtained in the basic conditions by general formula (II) and compound shown in general formula (III) in suitable solvent; in formula, L is leavings group, is selected from halogen, methylsulfonyl or p-toluenesulfonyl.
React and carry out in suitable solvent, the suitable optional tetrahydrofuran (THF) freely of solvent, acetonitrile, toluene, dimethylbenzene, benzene, DMF, methylene dichloride, trichloromethane or acetone etc.
The suitable optional potassium hydroxide freely of alkali, sodium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, triethylamine or pyridine etc.
Temperature of reaction between room temperature to solvent boiling point temperature, can be generally 20 ~ 130 ° of C.
Reaction times is 30 minutes to 20 hours, usual 1 ~ 10 hour.
II compound representated by general formula I I-a and the N-Boc-piperazine (commercially available) shown in II-b can be obtained by reacting Compound II per-c, then obtains through de-Boc.The concrete preparation method of general formula I I is see document CN102656163; CN101128455; Tetrahedron Letters, 52 (45), 5905-5909; Zhongguo Yaowu Huaxue Zazhi, 13 (3), 142-145; Bioorganic & Medicinal Chemistry Letters, 22 (17), 5545-5549; WO2010118367; Bioorganic & Medicinal Chemistry Letters, 19 (17), 5214-5217; European Journal of Medicinal Chemistry, 46 (4), 1404-1414; CN102481300.Wherein general formula I I-a has commercially available or according to currently known methods preparation, specifically can see such as Publication about Document Bioorganic & Medicinal Chemistry, 2011:19 (20), 6087-6097; Journal of Medicinal Chemistry, 1999:42 (5), 805-818; Journal of Heterocyclic Chemistry, 2010:47 (5), 1056-1061; Huaxue Gongye YuGongcheng Jishu, 2006:27 (5), 24-25; Journal of Heterocyclic Chemistry, 1992:29 (5), 1369-70; Journal of Organic Chemistry, 2002:67 (18), 6550-6552; WO2008117884; WO2012115480; WO2007148676; WO2009144473; US6107301.
In formula, X is selected from halogen, methylsulfonyl or p-toluenesulfonyl.
Compound of Formula I demonstrates excellent activity to the multiple germ in agricultural or other field, and therefore, technical scheme of the present invention also comprises the purposes that compound of Formula I or its salt are used as to prepare sterilant medicine in agricultural or other field.Meanwhile, due to the raw material synthesizing this compounds be easy to get, method is easy, thus compound of the present invention is with low cost, has more wide application prospect.
The example of the disease mentioned below is only used for the present invention is described, but never limits the present invention.
Compound of Formula I can be used for preventing and treating following disease: oomycetes diseases, as oidium (cucumber downy mildew, oilseed rape downy mildew, downy mildew, beet oidium, downy mildew of sugarcane, tobacco downy mildew, pea oidium, sponge gourd oidium, wax gourd oidium, muskmelon downy mildew, cabbage oidium, downy mildew of spinach, radish oidium, downy mildew of garpe, onion mildew), white rust (white rust of colza, cabbage white blister), samping off (rape samping off, Tobacco seedling diseases, tomato samping off, capsicum samping off, eggplant samping off, cucumber samping off, cotton seedling samping off), phytophthora rot (capsicum phytophthora rot, sponge gourd phytophthora rot, wax gourd phytophthora rot), epidemic disease (broad bean epidemic disease, Cucumber Blight, pumpkin epidemic disease, wax gourd epidemic disease, watermelon epidemic disease, muskmelon blight, capsicum epidemic disease, leek epidemic disease, garlic epidemic disease, Cotton blight), late blight (the late blight of potato, tomato late blight) etc., imperfect fungi disease, as blight (sweet potato blight, cotton wilt, sesame blight, castor-oil plant blight, tomato wilt, Kidney bean blight, cucumber fusarium axysporum, sponge gourd blight, pumpkin blight, wax gourd blight, watermelon blight, Muskmelon Fusarium wilt, capsicum wilt, faba bean Fusarium wilt, rape blight, soybean Fusariuming disease), root rot (Fusarium solani, Fructus Solani melongenae root maize ear rot, Bean Root maize ear rot, cucumber root rot, Root of Balsampear maize ear rot, cotton black root rot, root rot of Vicia faba), damping-off (cotton seedling blight, sesame damping-off, capsicum damping-off, cucumber rhizoctonia rot, Chinese cabbage damping-off), anthrax (anthracnose of sorghum, cotton anthracnose, bluish dogbane anthrax, jute anthrax, anthracnose of flax, Colletotricum destructivum, mulberry anthrax, pepper anthracnose, eggplant anthracnose, bean anthracnose, cucumber anthracnose, balsam pear anthrax, summer squash anthrax, wax gourd anthrax, watermelon anthrax, muskmelon anthrax, lichee anthrax), verticillium (cotton verticillium wilt, Sunflower Receptacle verticillium, tomato verticillium, capsicum verticillium, eggplant verticillium wilt), black spot (summer squash black spot, wax gourd black spot, muskmelon black spot), gray mold (cotton boll gray mold, bluish dogbane gray mold, graw mold of tomato, Botrytis cinerea, Kidney bean gray mold, celery gray mold, spinach gray mold, Kiwifruit gray mold), brown spot (cotton brown spot, jute brown spot, beet cercospora leaf spot, the cercospora brown spot of peanut, capsicum brown spot, wax gourd brown spot, Soybean Brown Spot pinta, septorial brown spot of sunflower, pea brown spot, broad bean brown spot), black spot (the false black spot of flax, alternaria stem rot of colza, sesame black spot, Sunflower Receptacle black spot, castor-oil plant black spot, tomato black spot, capsicum black spot, eggplant black spot, Kidney bean black spot, cucumber black spot, celery black spot, carrot black rot, black rot of carrot, melanose or canker of apple, the cercospora black spot of peanut), spot blight (spotted wilt of tomato, cayenne pepper spots rot, celery septoria disease), early blight (early blight of tomato, capsicum early blight, eggplant early blight, target, early blight of celery), ring spot (soybean ring spot, sesame ring spot, Kidney bean ring spot), leaf blight (sesame leaf rot, Sunflower Leaf rot, watermelon leaf rot, Muskmelon leaf rot), base rot disease (tomato base rot disease, Kidney bean base rot disease), and other (Helminthosporium carbonum, bluish dogbane waist folding is sick, rice blast, the black sheath of chestnut is sick, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem rot, soybean diplostomiasis, muskmelon leaf blight, Peanut Web Blotch Disease, the red leaf spot of tea, pepper white star disease, Leaf of Chinese Waxgourd pinta, celery Black Rotten, spinach heartrot, bluish dogbane leaf mold, bluish dogbane spot disease, jute stem pinta, purple spot of soybean, Alternaria sesami, castor-oil plant graywall, dark brown leaf spot, cercospora leaf spot of egg plant, Kidney bean red spot disease, balsam pear leukodermia, watermelon spot disease, jute withered rotten disease, Sunflower Root stem rot, Kidney bean charcoal rot, soybean target spot is sick, eggplant rod spore leaf spot, Leaf Spot Caused by Corynespora cassiicola on Cucumber, leaf muld of tomato, eggplant leaf mold, broad bean reddish macules etc.) etc., basidiomycetes disease, as rust (stripe rust of wheat, the stem rust of wheat, wheat leaf rust, Peanut Rust, rust of sunflower, sugarcane rust, leek rust, rust of onion, chestnut rust, soybean rust), smut (maize head smut, corn smut, head smut of sorghum, sorghum loose smut, covered kernel smut of kaoliang, high beam column smut disease, chestnut kernel smut, smut of sugarcane, Bean rust disease) and other (as wheat hypochnus, rice sheath blight diseases etc.) etc., ascomycetes disease, as Powdery Mildew (wheat powdery mildew, rape Powdery Mildew, sesame Powdery Mildew, Sunflower Receptacle Powdery Mildew, beet powdery mildew, eggplant Powdery Mildew, powdery mildew of pea, sponge gourd Powdery Mildew, squash marble dust, Pumpkin powdery mildew, wax gourd Powdery Mildew, melon powdery mildew, uncinula necator, broad bean Powdery Mildew), sclerotium disease (flax sclerotium disease, sclerotinia rot of colza, soybean sclerotinia crown rot, peanut sclerotium disease, tobacco sclerotium disease, capsicum sclerotium disease, eggplant sclerotium disease, bean sclerotinia rot, pea sclerotium disease, cucumber timberrot, balsam pear sclerotium disease, wax gourd sclerotinia, watermelon sclerotium disease, celery sclerotium disease), black spot (scab of apple, pear scab) etc.Especially, to cucumber downy mildew, rice blast, at lower doses still there is good prevention effect.
Due to the characteristic that it is positive, above-claimed cpd can be advantageously used in protecting agriculture and the important crop of horticulture, domestic animal and breeding stock, and the environment that often goes of the mankind avoids the injury of germ.
For obtaining ideal effect, the consumption of compound changes because of various factors, the formulation of the crop of such as compound used therefor, pre-protection, the type of harmful organism, gradient of infection, weather condition, application method, employing.
The compound dosage of per hectare 10 grams-5 kilograms can provide sufficient control.
In order to be applied to agricultural, use the composition containing one or more compound of Formula I normally useful.
Therefore, another technical scheme of the present invention also comprises a kind of fungicidal composition, and containing as the compound of Formula I of active ingredient and agriculturally acceptable carrier, in composition, the weight percentage of active ingredient is 0.5-90%.
The type of service of composition can be dry powder, wettable powder, aqueous emulsion, missible oil, microemulsion, paste, water-dispersible granules, solution, suspension agent etc.: concrete application is depended in the selection of types of compositions.
Composition is prepared in a known way, such as optional under the existence of tensio-active agent, by with solvent medium and/or solid diluent or lytic activity material.Available solid diluent or carrier are such as: silicon-dioxide, kaolin, wilkinite, talcum, diatomite, rhombspar, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicate, attapulgite, sepiolite.Than water, available liquid diluent is such as aromatic organic solvent (mixture, chlorobenzene etc. of dimethylbenzene or alkylbenzene), paraffin (petroleum fractions), alcohols (methyl alcohol, propyl alcohol, butanols, octanol, glycerine), ester class (ethyl acetate, isobutyl acetate etc.), ketone (pimelinketone, acetone, methyl phenyl ketone, isophorone, ethyl pentyl group ketone etc.), amides (DMF, N-Methyl pyrrolidone etc.).Available tensio-active agent is sodium, calcium, triethylamine or the triethanolamine salt of polyoxyethylene ester, sulfonated lignin etc. of alkylsulfonate, alkylaryl sulphonate, polyoxyethylene alkylphenol, sorbyl alcohol.Composition also can be used for specific object containing special additive, and such as tackiness agent is as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone etc.
In above-mentioned composition, the concentration of activeconstituents can change in wide region according to the preparation type of activeconstituents, its application target, envrionment conditions and employing.Usually, the concentration range of activeconstituents is 1-90%, preferred 5-50%.
If need, can add in composition can with other activeconstituentss of compound of Formula I compatibility, such as other mycocides, insecticide/miticide, plant-growth regulator, microbiotic, weedicide, fertilizer.
The compound method of several formulation is exemplified below:
The preparation of suspension agent: in common prescription, active component content is 5%-35%.Take water as medium, former medicine, dispersion agent, suspending agent and antifreezing agent etc. are added in sand mill, grinds, make suspension agent.The preparation of aqueous emulsion: former medicine, solvent and emulsifying agent are added together, makes to be dissolved into homogeneous oil phase.Water, antifreezing agent etc. are mixed, become homogeneous aqueous phase.Under high velocity agitation, aqueous phase joined oil phase or oil phase is joined aqueous phase, forming the aqueous emulsion of favorable dispersity.Aqueous emulsion active component content of the present invention is generally 5%-15%.For preparation emulsifiable concentrate, compound being soluble solution of the present invention in one or several mixed solvents, then adds emulsifying agent to strengthen the dispersion effect of compound in water.The preparation of wettable powder: by recipe requirements, by the fully mixing such as former medicine, various tensio-active agent and solid diluent, after ultra-fine pulverizer disintegrating, namely obtains the wettable powder product of predetermined content (such as 10%-40%).For preparation is suitable for the wettable powder of sprinkling, compound of the present invention can with the pressed powder of porphyrize as clay, inorganic silicate, carbonate and wetting agent, tackiness agent and/or dispersion agent composition mixture.The preparation of water-dispersible granules: former medicine and powdered solid diluents, wetting spreader-sticker and tackiness agent etc. are carried out co-grinding; add water after mediating again; add in the tablets press that 10 to 100 eye mesh screens are housed and carry out granulation, and then drying, screening (by screen cloth scope).Also can add in sand mill by former medicine, dispersion agent, disintegrating agent and wetting agent and solid diluent, take water as medium milling, make suspension agent, then carry out spray drying granulation, usual formulation content is 20%-30% granular product.
Embodiment
Following specific embodiment is used for further illustrating the present invention, but the present invention is limited to absolutely not these examples.(except as otherwise indicate outside, raw materials used all have commercially available)
Synthetic example
The preparation of embodiment 1:4-(chloro-4, the 6-dicyano phenyl of 2,3,5-tri-) the piperazinecarboxylic acid tert-butyl ester
To the 60mL N of 10.0g (0.054mol) piperazine-1-t-butyl formate, in dinethylformamide solution, add salt of wormwood 11.0g (0.081mol), slowly 2 are added under stirring, 4, 5, 6-tetra-chloro-1, 3-benzene dicarbonitrile 14.4g (0.054mol), add rear continuation stirring at room temperature reaction 5h, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase merges, washing, saturated salt is washed, dry, filter, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1:7) purifying obtains product 20.0g, be 4-(2, 3, 5-tri-chloro-4, 6-dicyano phenyl) the piperazinecarboxylic acid tert-butyl ester.Light yellow solid, yield: 89.0%, fusing point 185-187 DEG C.
The preparation of the chloro-6-of embodiment 2:2,4,5-3 (piperazine-1-base) m-dicyanobenzene hydrochloride
By 5.0g (0.012mol) 4-(2,3,5-tri-chloro-4,6-dicyano phenyl) the piperazinecarboxylic acid tert-butyl ester puts into 250mL single port bottle, add 50mL tetrahydrofuran (THF) wherein, then add 3.7g (0.036mol) concentrated hydrochloric acid wherein, room temperature reaction 4h.After completion of the reaction, removal of solvent under reduced pressure, obtains white solid 3.5g, yield: 82.6% in TLC monitoring.
Embodiment 3: the preparation of compound 3500
0.20g (0.0014mol) salt of wormwood is added in the 20mL tetrahydrofuran solution of 0.50g (0.0014mol) Compound II per, stir the lower tetrahydrofuran solution dripped containing 0.27g (0.0019mol) methyl iodide, after dropwising, stirring at room temperature 4h, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase merges, saturated salt is washed, dry, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1:3) purifying obtains product 0.25g, i.e. compound 3500.Yield: 54.2%, fusing point 171-173 DEG C.
Embodiment 4: the preparation of compound 2430
To 0.50g (0.0014mol) 2, 4, 0.29g (0.0028mol) triethylamine is added in the 20mL acetonitrile solution of the chloro-6-of 5-3 (piperazine-1-base) m-dicyanobenzene hydrochloride, stir lower dropping containing 0.23g (0.0014mol) the acetonitrile solution of fluorobenzoyl chloride, after dropwising, stirring at room temperature 4h, TLC monitoring after completion of the reaction, reaction solution is poured into water, extraction into ethyl acetate, organic phase merges, saturated salt is washed, dry, precipitation, (eluent is ethyl acetate and sherwood oil (boiling range 60-90 DEG C) to resistates column chromatography, volume ratio is 1:3) purifying obtains product 0.31g, i.e. compound 2430.Yield: 49.9%, fusing point 171-173 DEG C.
Other compounds of general formula (I) can obtain by preparation method provided by the invention.
Part of compounds fusing point and nuclear magnetic data (
1h NMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows:
Example of formulations
Each component add-on is weight percentage, and active compound is metered into after rolling over hundred.
Embodiment 5:30% wettable powder
Compound and other components are fully mixed, after ultra-fine pulverizer disintegrating, namely obtains the wettable powder product of 30%.Embodiment 6:40% suspension concentrates
Compound and other components fully mix, the suspension concentrates obtained thus, and dilute with water gained suspension agent can obtain the diluent of any desired concn.
Embodiment 7:60% water-dispersible granules
By compound and other component co-grindings, then add water mediate after, add in the tablets press of 10-100 eye mesh screen and carry out granulation, and then drying, screening (by screen cloth scope).
The compounds of this invention all shows good activity to the multiple germ in agriculture field.
Biological activity determination
The compounds of this invention all shows good activity to the multiple germ in agriculture field.Carry out Antifungal Activity in Vitro, the test of live body protected effect with the multiple fungal disease of the compounds of this invention sample to plant, and carry out comparative efficacy test with part known compound.Fungicidal activity measurement result is shown in following embodiment.
Embodiment 8: in vitro fungicidal activity measures
Measuring method is as follows: adopt high-throughput screening method, dissolves, be mixed with desired concn liquid to be measured by the test compound sample solvent (kind of solvent as acetone, methyl alcohol, DMF etc., and is selected the dissolving power of sample according to it) be applicable to.Under ultra-clean Working environment, joined by liquid to be measured in the micropore of 96 well culture plates, then add wherein by pathogenic bacteria propagulum suspension, the culture plate after process is placed in constant incubator to be cultivated.Investigate after 24 hours, estimate pathogenic bacteria propagulum during investigation and sprout or growing state, and according to the sprouting of control treatment or growing state, assessing compound bacteriostatic activity.
Antifungal Activity in Vitro (representing with the inhibiting rate) test result of part of compounds is as follows:
(1) to the inhibiting rate of rice blast fungus:
When liquor strength is 25mg/L, the inhibiting rate of compound 2430,3529,3514,3523,3524,3515,5316,5298,1736 is 100%, and the inhibiting rate of compound 3541 is 80%.
When liquor strength is 8.3mg/L, the inhibiting rate of compound 2430,3523,3524,3515,5316 is 100%.
When liquor strength is 0.9mg/L, the inhibiting rate of compound 5316 is 100%.
(2) to the inhibiting rate of botrytis cinerea pers:
When liquor strength is 25mg/L, the inhibiting rate of compound 3514,5316 is 80%.
Embodiment 9: live body prolection measures
Measuring method is as follows: adopt the potted plant measuring method of live body, by test compound sample, with a small amount of solvent, (kind of solvent is as acetone, methyl alcohol, DMF etc., and according to it, dissolving power of sample is selected, the volume ratio of quantity of solvent and spouting liquid is equal to or less than 0.05) dissolve, dilute with the water containing 0.1% tween 80, be mixed with desired concn liquid to be measured.On crops sprayer, liquid to be measured is sprayed on disease host plant (host plant is the standard Potted orchard at warm indoor cultivation), after 24 hours, carry out disease inoculation.According to disease feature, cultivate being placed in phytotron after the disease plant inoculating needing temperature control moisturizing to cultivate, after disease completes and infects, immigration hot-house culture, the disease plant cultivated not needing moisturizing is directly cultivated at warm indoor inoculation.After contrasting fully morbidity, (being generally week age) carries out the assessment of compound protection effect.
The live body prolection test result of part of compounds is as follows:
Live body prolection to cucumber downy mildew:
When liquor strength is 400mg/L, the prolection of compound 3514,3523,3524,5297,1736 is 100%, and the prolection of compound 3505,5333 is 80%.
When liquor strength is 100mg/L, the prolection of compound 3523 is 85%.
Carried out part of compounds and the active simultaneous test contrasting medicament, test result is in table 51 and table 52
The inhibiting rate of table 51 pair rice blast fungus
The live body prolection of table 52 pair cucumber downy mildew
Claims (9)
1. piperazine phenyl two nitrile compounds, structure is as shown in general formula I:
In formula:
A is selected from A
1, A
2or A
3
R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hindependently represent hydrogen, C separately
1-C
4alkyl, halo C
1-C
4alkyl, halo C
1-C
4alkoxyl group or C
1-C
4carbalkoxy; R
awith R
hor R
cwith R
fin conjunction with saturated five-ring, six-ring or the seven-membered ring that are formed;
R
1be selected from hydrogen, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkoxy C
1-C
12alkyl, halo C
1-C
12alkoxy C
1-C
12alkyl, C
3-C
12cycloalkyl, C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkoxy carbonyl, halo C
1-C
12alkoxy carbonyl, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl sulphonyl oxygen base, allyl group, propargyl, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, C (=S) NR
12r
13, SO
2nR
12r
13or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzoyl, phenyloxycarbonyl, phenyl amino-carbonyl, heteroaryl, Heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl amino-carbonyl, benzyl or aryl sulfonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
12alkyl, halo C
1-C
12alkyl, C
3-C
12cycloalkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
2-C
12thiazolinyl, halo C
2-C
12thiazolinyl, C
2-C
12alkynyl, halo C
2-C
12alkynyl, C
3-C
12alkene oxygen base, halo C
3-C
12alkene oxygen base, C
3-C
12alkynyloxy group, halo C
3-C
12alkynyloxy group, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl-carbonyl-amino, C
1-C
12alkyl sulphonyl oxygen base, C
1-C
12alkoxy carbonyl, C
1-C
12alkoxy carbonyl C
1-C
12alkyl, C
1-C
12alkoxycarbonyl amino, C
1-C
12alkoxy C
1-C
12alkoxyl group, C
1-C
12alkoxy carbonyl C
1-C
12alkoxyl group, anilinocarbonyl, halogeno-benzene aminocarboxyl, CHO, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, OC (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13; N=1,2,3,4 or 5;
R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10may be the same or different, be selected from halogen, C respectively
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkyl sulphinyl, halo C
1-C
12alkyl sulphinyl, C
1-C
12alkyl sulphonyl, halo C
1-C
12alkyl sulphonyl, C
3-C
12alkene oxygen base, halo C
3-C
12alkene oxygen base, C
3-C
12alkynyloxy group, halo C
3-C
12alkynyloxy group, C
1-C
12alkyl-carbonyl oxygen base, C
1-C
12alkyl-carbonyl-amino, C
1-C
12alkyl sulphonyl oxygen base, C
1-C
12alkoxy C
1-C
12alkoxyl group or C
1-C
12alkoxy carbonyl C
1-C
12alkoxyl group;
R
12, R
13may be the same or different, be selected from hydrogen, C respectively
1-C
12alkyl, halo C
1-C
12alkyl or C
3-C
12cycloalkyl;
But do not comprise following compound: in general formula I, R
a, R
b, R
c, R
d, R
e, R
f, R
gand R
hbe hydrogen, R
1for tert-butoxycarbonyl, A is selected from A
3and R
8, R
9, R
10be fluorine.
2. compound according to claim 1, is characterized in that: in general formula I
A is selected from A
1, A
2or A
3
R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hindependently represent hydrogen, C separately
1-C
4alkyl, halo C
1-C
4alkyl, halo C
1-C
4alkoxyl group or C
1-C
4carbalkoxy; R
awith R
hor R
cwith R
fin conjunction with saturated five-ring, six-ring or the seven-membered ring that are formed;
R
1be selected from hydrogen, C
1-C
8alkyl, halo C
1-C
8alkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
1-C
8alkoxy C
1-C
8alkyl, halo C
1-C
8alkoxy C
1-C
8alkyl, C
3-C
8cycloalkyl, C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkoxy carbonyl, halo C
1-C
8alkoxy carbonyl, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl sulphonyl oxygen base, allyl group, propargyl, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzoyl, phenyloxycarbonyl, phenyl amino-carbonyl, heteroaryl, Heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl amino-carbonyl, benzyl or aryl sulfonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
8alkyl, halo C
1-C
8alkyl, C
3-C
6cycloalkyl, C
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
2-C
8thiazolinyl, halo C
2-C
8thiazolinyl, C
2-C
8alkynyl, halo C
2-C
8alkynyl, C
3-C
8alkene oxygen base, halo C
3-C
8alkene oxygen base, C
3-C
8alkynyloxy group, halo C
3-C
8alkynyloxy group, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
1-C
8alkyl-carbonyl, halo C
1-C
8alkyl-carbonyl, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkyl sulphonyl oxygen base, C
1-C
8alkoxy carbonyl, C
1-C
8alkoxy carbonyl C
1-C
8alkyl, C
1-C
8alkoxycarbonyl amino, C
1-C
8alkoxy C
1-C
8alkoxyl group, C
1-C
8alkoxy carbonyl C
1-C
8alkoxyl group, anilinocarbonyl, halogeno-benzene aminocarboxyl, CHO, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, OC (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13; N=1,2,3,4 or 5;
R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10may be the same or different, be selected from halogen, C respectively
1-C
8alkoxyl group, halo C
1-C
8alkoxyl group, C
1-C
8alkylthio, halo C
1-C
8alkylthio, C
1-C
8alkyl sulphinyl, halo C
1-C
8alkyl sulphinyl, C
1-C
8alkyl sulphonyl, halo C
1-C
8alkyl sulphonyl, C
3-C
8alkene oxygen base, halo C
3-C
8alkene oxygen base, C
3-C
8alkynyloxy group, halo C
3-C
8alkynyloxy group, C
1-C
8alkyl-carbonyl oxygen base, C
1-C
8alkyl-carbonyl-amino, C
1-C
8alkyl sulphonyl oxygen base, C
1-C
8alkoxy C
1-C
8alkoxyl group or C
1-C
8alkoxy carbonyl C
1-C
8alkoxyl group;
R
12, R
13may be the same or different, be selected from hydrogen, C respectively
1-C
6alkyl, halo C
1-C
6alkyl or C
3-C
6cycloalkyl.
3. compound according to claim 2, is characterized in that: in general formula I
A is selected from A
1, A
2or A
3
R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hindependently represent hydrogen, C separately
1-C
4alkyl, halo C
1-C
4alkyl, halo C
1-C
4alkoxyl group or C
1-C
4carbalkoxy; R
awith R
htogether or R
cwith R
ftogether can in conjunction with forming saturated five-ring, six-ring or seven-membered ring;
R
1be selected from hydrogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkoxy C
1-C
4alkyl, halo C
1-C
4alkoxy C
1-C
4alkyl, C
3-C
6cycloalkyl, C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphonyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, halo C
1-C
4alkoxy carbonyl, C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkyl sulphonyl oxygen base, allyl group, propargyl, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzoyl, phenyloxycarbonyl, phenyl amino-carbonyl, heteroaryl, Heteroarylcarbonyl, heteroaryloxycarbonyl, heteroaryl amino-carbonyl, benzyl or aryl sulfonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
3-C
6cycloalkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
2-C
4thiazolinyl, halo C
2-C
4thiazolinyl, C
2-C
4alkynyl, halo C
2-C
4alkynyl, C
3-C
6alkene oxygen base, halo C
3-C
6alkene oxygen base, C
3-C
6alkynyloxy group, halo C
3-C
6alkynyloxy group, C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkyl-carbonyl-amino, C
1-C
4alkyl sulphonyl oxygen base, C
1-C
4alkoxy carbonyl, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, C
1-C
4alkoxycarbonyl amino, C
1-C
4alkoxy C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl C
1-C
4alkoxyl group, anilinocarbonyl, halogeno-benzene aminocarboxyl, CHO, CO
2h, CO
2na, CO
2nH
4, C (=O) NR
12r
13, OC (=O) NR
12r
13, C (=S) NR
12r
13or SO
2nR
12r
13; N=1,2,3 or 4;
R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10may be the same or different, be selected from halogen, C respectively
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkylthio, halo C
1-C
4alkylthio, C
1-C
4alkyl sulphinyl, halo C
1-C
4alkyl sulphinyl, C
1-C
4alkyl sulphonyl, halo C
1-C
4alkyl sulphonyl, C
3-C
4alkene oxygen base, halo C
3-C
4alkene oxygen base, C
3-C
4alkynyloxy group, halo C
3-C
4alkynyloxy group, C
1-C
4alkyl-carbonyl oxygen base, C
1-C
4alkyl-carbonyl-amino, C
1-C
4alkyl sulphonyl oxygen base, C
1-C
4alkoxy C
1-C
4alkoxyl group or C
1-C
4alkoxy carbonyl C
1-C
4alkoxyl group;
R
12, R
13may be the same or different, be selected from hydrogen, C respectively
1-C
6alkyl, halo C
1-C
6alkyl or C
3-C
6cycloalkyl.
4. compound according to claim 3, is characterized in that: in general formula I
A is selected from A
1, wherein R
2, R
3, R
4be selected from chlorine;
R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hbe selected from hydrogen;
Shown in structural formula as I-a:
In formula
R
1be selected from hydrogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, halo C
1-C
4alkoxy carbonyl, C
1-C
4alkyl sulphonyl, C
1-C
4alkoxy C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, allyl group, propargyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl, pyrimidyl, thiazolyl or pyridine-3-carbonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, methylaminocarbonyl, anilinocarbonyl, 4-chloroanilino carbonyl, carboxyl or CO
2na; N=1,2 or 3;
Or, in general formula I
A is selected from A
2, wherein R
5, R
6, R
7identical, be selected from fluorine or chlorine;
R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hbe selected from hydrogen;
Shown in structural formula as I-b:
In formula
R
1be selected from hydrogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, halo C
1-C
4alkoxy carbonyl, C
1-C
4alkyl sulphonyl, C
1-C
4alkoxy C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, allyl group, propargyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl, pyrimidyl, thiazolyl or pyridine-3-carbonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, methylaminocarbonyl, anilinocarbonyl, 4-chloroanilino carbonyl, carboxyl or CO
2na; N=1,2 or 3;
Or, in general formula I
A is selected from A
3, wherein R
8, R
9, R
10identical, be selected from fluorine or chlorine;
R
a, R
b, R
c, R
d, R
e, R
f, R
g, R
hbe selected from hydrogen;
Shown in structural formula as I-c:
In formula
R
1be selected from hydrogen, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkyl-carbonyl, halo C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl, halo C
1-C
4alkoxy carbonyl, C
1-C
4alkyl sulphonyl, C
1-C
4alkoxy C
1-C
4alkyl-carbonyl, C
1-C
4alkoxy carbonyl C
1-C
4alkyl, allyl group, propargyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl, pyrimidyl, thiazolyl or pyridine-3-carbonyl, wherein R
11be selected from halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, methylaminocarbonyl, anilinocarbonyl, 4-chloroanilino carbonyl, carboxyl or CO
2na; N=1,2 or 3.
5. compound according to claim 4, is characterized in that:
In general formula I-a,
R
1be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, trifluoromethyl, seven fluorine sec.-propyls, allyl group, propargyl, CH
3c (=O), CH
3cH
2c (=O), CH
3cH
2cH
2c (=O), CH
3cH
2cH
2cH
2c (=O), (CH
3)
3cC (=O), ClCH
2c (=O), methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, methyl sulphonyl, ethylsulfonyl, methoxymethylcarbonyl, ethoxymethylcarbonyl, Methoxycarbonylmethyl, ethoxy carbonyl methyl, isopropoxy carbonyl methyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl or pyridine-3-carbonyl, wherein R
11be selected from F, Cl, Br, I, CN, NO
2, CH
3, CH
2cH
3, C (CH
3)
3, OCH
3, CO
2cH
3, CO
2cH
2cH
3, SO
2cH
3, OCH
2cF
3, CF
3or OCF
3; N=1,2 or 3.
6. compound according to claim 4, is characterized in that:
In general formula I-b,
R
5, R
6, R
7identical, be selected from fluorine or chlorine;
R
1be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, trifluoromethyl, seven fluorine sec.-propyls, allyl group, propargyl, CH
3c (=O), CH
3cH
2c (=O), CH
3cH
2cH
2c (=O), CH
3cH
2cH
2cH
2c (=O), (CH
3)
3cC (=O), ClCH
2c (=O), methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, methyl sulphonyl, ethylsulfonyl, methoxymethylcarbonyl, ethoxymethylcarbonyl, Methoxycarbonylmethyl, ethoxy carbonyl methyl, isopropoxy carbonyl methyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl or pyridine-3-carbonyl, wherein R
11be selected from F, Cl, Br, I, CN, NO
2, CH
3, CH
2cH
3, C (CH
3)
3, OCH
3, CO
2cH
3, CO
2cH
2cH
3, SO
2cH
3, OCH
2cF
3, CF
3or OCF
3; N=1,2 or 3.
7. compound according to claim 4, is characterized in that:
In general formula I-c,
R
8, R
9, R
10identical, be selected from fluorine or chlorine;
R
1be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, trifluoromethyl, seven fluorine sec.-propyls, allyl group, propargyl, CH
3c (=O), CH
3cH
2c (=O), CH
3cH
2cH
2c (=O), CH
3cH
2cH
2cH
2c (=O), (CH
3)
3cC (=O), ClCH
2c (=O), methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, methyl sulphonyl, ethylsulfonyl, methoxymethylcarbonyl, ethoxymethylcarbonyl, Methoxycarbonylmethyl, ethoxy carbonyl methyl, isopropoxy carbonyl methyl or Q;
Q is selected from and does not replace or quilt (R
11) n replace phenyl, benzyl, benzoyl, benzenesulfonyl, pyridyl or pyridine-3-carbonyl, wherein R
11be selected from F, Cl, Br, I, CN, NO
2, CH
3, CH
2cH
3, C (CH
3)
3, OCH
3, CO
2cH
3, CO
2cH
2cH
3, SO
2cH
3, OCH
2cF
3, CF
3or OCF
3; N=1,2 or 3.
8. one kind is used as the purposes preparing sterilant medicine according to compound of Formula I according to claim 1 in agricultural or other field.
9. a fungicidal composition, is characterized in that: containing as the compound of Formula I as claimed in claim 1 of active ingredient and agriculturally acceptable carrier, and in composition, the weight percentage of active ingredient is 0.5-90%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164476A (en) * | 2016-12-08 | 2018-06-15 | 沈阳化工研究院有限公司 | M-dicyanobenzene class compound, its application and the drug comprising the compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210646A (en) * | 1978-04-11 | 1980-07-01 | Janssen Pharmaceutica N.V. | Antimicrobial compositions containing 1-(aryloxyphenyl)piperazines |
| JPH10175914A (en) * | 1996-12-19 | 1998-06-30 | Fujisawa Pharmaceut Co Ltd | New production |
-
2014
- 2014-03-31 CN CN201410126032.6A patent/CN104945352B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210646A (en) * | 1978-04-11 | 1980-07-01 | Janssen Pharmaceutica N.V. | Antimicrobial compositions containing 1-(aryloxyphenyl)piperazines |
| JPH10175914A (en) * | 1996-12-19 | 1998-06-30 | Fujisawa Pharmaceut Co Ltd | New production |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164476A (en) * | 2016-12-08 | 2018-06-15 | 沈阳化工研究院有限公司 | M-dicyanobenzene class compound, its application and the drug comprising the compound |
| CN108164476B (en) * | 2016-12-08 | 2021-01-26 | 沈阳化工研究院有限公司 | Isophthalonitrile compound, application thereof and medicine containing compound |
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