CN102993183A - Pyrrolidine diketone compound containing pyridylaldehyde hydrazone group, preparation method and application of compound - Google Patents
Pyrrolidine diketone compound containing pyridylaldehyde hydrazone group, preparation method and application of compound Download PDFInfo
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- CN102993183A CN102993183A CN2012105802141A CN201210580214A CN102993183A CN 102993183 A CN102993183 A CN 102993183A CN 2012105802141 A CN2012105802141 A CN 2012105802141A CN 201210580214 A CN201210580214 A CN 201210580214A CN 102993183 A CN102993183 A CN 102993183A
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Abstract
The invention belongs to the field of herbicides and discloses a pyrrolidine diketone compound containing a pyridylaldehyde hydrazone group, a preparation method and an application of the compound. The structure of the compound is shown in the general formula (I) in the specification, wherein the definitions of R1, R2, R3, R4 and R5 are shown in the specification.
Description
Technical field
The invention belongs to the weedicide field, be specifically related to contain pyrrolidine-diones compounds, preparation method and the application thereof of pyridylaldehyde hydrazone groups.
Background technology
Pyridine is active group common in the pesticide structure, all is widely used in weedicide, sterilant and sterilant.The application that contains the weedicide of pyridine groups has had the history of over half a century, has become type important on the weedicide market.As, diflufenzopyr (diflufenzopyr) is a kind of pyridine structure contained amino carbamide herbicides.Greenweed pyridine (triclopyr) is a kind of pyridine oxycarboxylic acid class weedicide.Diflufenican (diflufenican) belongs to substituted pyridine acyl phenyl amines weedicide.Paraquat (paraquat) and diquat (diquat) are the weedicides that contains pyridine dipyridyl structure.
Hydrazone groups also is the important activity unit in the pesticide molecule structure, all contains the structure of hydrazone in the molecular structure such as weedicide diflufenzopyr (diflufenzopyr), sterilant Hydramethylnon Bait (hydramethylnon), sterilant ferimzone (ferimzone) etc.
The pyrrolidine-diones compounds usually has the biological activitys such as desinsection, sterilization, weeding.As, US5504057 has described a class 3-(2,4-3,5-dimethylphenyl) tetramethyleneimine-2, and the 4-cyclohexadione compounds has weeding activity.Patent CN200510013206.9, CN201010232595.5, CN201010202871.3, CN201010576398.5 have successively described respectively 3-aroyl pyrrolidine-diones compounds, 3-substituted cyclopropane carbonyl pyrrolidine cyclohexadione compounds, 3-acyl-pyrrolidine diketone semicarbazone compounds, 3-acyl group-5-substituent methyl pyrrolidine-diones compounds, all have weeding activity.
Summary of the invention
The object of the invention is to, a kind of pyrrolidine-diones compounds that contains the pyridylaldehyde hydrazone groups is provided.
Another object of the present invention is to provide the preparation method of the pyrrolidine-diones compounds that contains the pyridylaldehyde hydrazone groups.
Another object of the present invention is to provide the application of above-claimed cpd.
A first aspect of the present invention provides a kind of pyrrolidine-diones compounds that contains the pyridylaldehyde hydrazone groups or its isomer with structure shown in the general formula (I).
Wherein,
Optional the 2nd carbon of pyridine ring, the 3rd carbon, the 4th carbon of being connected in of carbon atom on the aldehyde hydrazone group (NHN=CH);
R
1Be selected from hydrogen, C
1～C
12Alkyl, phenyl, substituted-phenyl;
R
2Be selected from hydrogen, C
1～C
12Alkyl;
R
3, R
4Be independently from each other hydrogen, C
1～C
12Alkyl, benzyl, substituted benzyl;
R
5Be selected from H, F, Cl, Br, I, C
1～C
6Alkyl, single replacement or polysubstituted;
Substituted-phenyl, the substituted benzyl mentioned in the definition of above group simultaneously refer to that phenyl in the described group is by F, Cl, Br, I, C
1～C
5The alkyl list replaces or is polysubstituted.
Second aspect of the present invention provides and prepared the method that contains the pyrrolidine-diones compounds (I) of pyridylaldehyde hydrazone groups of the present invention, and the method is prepared according to following reaction scheme with intermediate II and III:
Wherein in each structural formula of above-mentioned reaction formula:
R
1To R
5All has foregoing implication;
Above-mentioned reaction is preferably carried out in solvent solvent-free or have under the solvent condition and carry out, and described solvent is selected from inert solvent commonly used, and preferred solvent comprises: alcohols, such as methyl alcohol, ethanol, Virahol; Ethers is such as ether, diisopropyl ether, tetrahydrofuran (THF); Nitrile is such as acetonitrile, propionitrile; Amides is such as DMF, N,N-dimethylacetamide; The ester class is such as ethyl acetate, methyl acetate; Hydro carbons is such as normal hexane, hexanaphthene, sherwood oil; Halogenated hydrocarbon is such as methylene dichloride, trichloromethane, tetracol phenixin, ethylene dichloride; The sulfone class is such as dimethyl sulfoxide (DMSO); Perhaps their mixture.
Above-mentioned reaction is carried out under normal temperature, heating or cooling conditions, adopts the normal experiment working method such as dropping, stirring, washing, chromatography, distillation, underpressure distillation, recrystallization, drying after the reaction neutralization reaction.
The 3rd aspect of the present invention relates to the application of pyrrolidine-diones compounds in management of weeds that contains the pyridylaldehyde hydrazone groups of the present invention, can be applicable to pesticide field, as weedicide.
In the present invention, the implication of weeds is construed as broad-leaved, dogstail and nutgrass flatsedge.Compound of the present invention can management of weeds after processing.
Compound of the present invention is suitable for be used to preventing and kill off broadleaf weeds, as: Tender Catchweed Bedstraw Herb, veronica, shepherd's purse, Sheathed Monochoria, Eclipta prostrata, Amaranthus retroflexus, Herba Viviae Sativae, mexicana, purslane, Herba Commelinae, adhesive hair grasswort; Gramineous weeds, as: barnyard grass, lady's-grass, Herba Eleusines Indicae, Herba Setariae Viridis, annual bluegrass, wild avena sativa, amur foxtail, Alopecurus, Wang grass, hard grass; And nutgrass flatsedge, as: cyperus iria.
Among the present invention, the described pyrrolidine-diones compounds (I) that contains the pyridylaldehyde hydrazone groups can exist with the form of the possible mixture that contains the different isomerization body, also can be with the form Individual existence of possible wherein a kind of isomer, described isomer comprises geometrical isomer, such as Z formula or E formula, perhaps cis or trans, optical isomer are such as R type or S type, tautomer, such as keto-acid or enol form.Disclosed by the invention and claimed isomeric forms comprises geometrical isomer, such as Z formula or E formula, optical isomer, and such as R type or S type, and the mixture that contains the described isomer of arbitrary proportion.
Among the present invention, the described geometrical isomer that contains the pyrrolidine-diones compounds of pyridylaldehyde hydrazone groups, can refer to cis or trans-isomer(ide), perhaps Z formula or E formula isomer, and both mixture that contains arbitrary proportion, Z formula and E formula isomer can be with following general formula (Ia) and (Ib) expressions:
Among the present invention, the described optical isomer that contains the pyrrolidine-diones compounds of pyridylaldehyde hydrazone groups, such as R type or S type, and both mixture that contains arbitrary proportion.R type or S type refer to radicals R
3With R
4Mutually not produced simultaneously steric isomer, the steric isomer of wherein said general formula (Ia) can with following general formula (Ic) with (Id) expression, described general formula (Ib) also can produce two kinds of corresponding steric isomers, and wherein which is R type or S type, because of radicals R
3With R
4Difference and determine:
In formula (I), described each group has preferred definition as described below, and following preferred definition is applicable to prepare all intermediates of this compound too:
Optional the 2nd carbon of pyridine ring, the 3rd carbon, the 4th carbon of being connected in of carbon atom on the aldehyde hydrazone group (NHN=CH);
R
1Be selected from hydrogen, C
1～C
12Alkyl, phenyl, C
1～C
6The mono-substituted phenyl of alkyl;
R
2Be selected from C
1～C
12Alkyl;
R
3, R
4In one be selected from hydrogen, another is selected from hydrogen, C
1～C
12Alkyl, benzyl;
R
5Be selected from H, F, Cl, Br, I, C
1～C
6Alkyl, the single replacement.
In formula (I), described each group has further preferred definition as described below, and following further preferred definition is applicable to prepare all intermediates of this compound too:
Optional the 2nd carbon of pyridine ring, the 3rd carbon, the 4th carbon of being connected in of carbon atom on the aldehyde hydrazone group (NHN=CH);
R
1Be selected from hydrogen, C
1～C
6Alkyl, phenyl, C
1～C
6The mono-substituted phenyl of alkyl;
R
2Be selected from C
1～C
6Alkyl;
R
3, R
4In one be selected from hydrogen, another is selected from hydrogen or at R
1Be selected from C when being selected from hydrogen
1～C
6Alkyl, benzyl;
R
5Be selected from H.
In formula (I), described each group has further preferred definition as described below, and following preferred definition is applicable to all intermediates too:
Optional the 2nd carbon of pyridine ring, the 4th carbon of being connected in of carbon atom on the aldehyde hydrazone group (NHN=CH);
R
1Be selected from hydrogen, C
1～C
6Alkyl, phenyl, 4-aminomethyl phenyl;
R
2Be selected from methyl;
R
3, R
4In one be selected from hydrogen, another is selected from hydrogen or at R
1Be selected from C when being selected from hydrogen
1～C
6Alkyl, benzyl;
R
5Be selected from H.
Beneficial effect:
1, the present invention introduces the pyridylaldehyde hydrazone groups at the side chain of No. 3 positions of pyrrolidine-diones, obtains the novel pyrrolidine-diones compounds that contains the pyridylaldehyde hydrazone groups suc as formula the novel structure shown in (I).
2, the preparation method of the described pyrrolidine-diones compounds that contains the pyridylaldehyde hydrazone groups of patent of the present invention is simple, easy and simple to handle.
3, the described pyrrolidine-diones compounds that contains the pyridylaldehyde hydrazone groups of patent of the present invention has weeding activity, can be used as the control that weedicide is applied to weeds, this pyrrolidine-diones compounds that contains the pyridylaldehyde hydrazone groups has weeding activity and has no precedent report.
Embodiment
Substantive distinguishing features of the present invention can be embodied from following embodiment, but it should not to be considered as be any limitation of the invention.
Preparation Example
Embodiment 1:3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene)-1-p-methylphenyl tetramethyleneimine-2, the preparation of 4-diketone (I-1)
Synthetic route:
Synthesis step:
II-10.4g (1.630mmol) and 2-pyridine aldehydes (III-1) 0.2g (1.867mmol), add in the 50mL dehydrated alcohol, reflux, TLC monitors (developping agent: ethyl acetate/methanol/sherwood oil/Glacial acetic acid=10/2/2/0.2), until II-1 disappears substantially, stopped reaction, suction filtration, absolute ethanol washing, dry, get yellow powder, be target compound I-1, yield 45.5%.
Adopt the method for embodiment 1, prepared following I-1～I-16 series compound:
3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene)-1-p-methylphenyl tetramethyleneimine-2,4-diketone (I-1)
Yellow powder, mp 248.4-249.1 ℃; Yield: 45.5%; IR (KBr, cm
-1) v 3428,1687,1640,1611,1515,808,774,740;
1H NMR (DMSO-d
6, 400MHz) δ: E-isomer (34%): 2.29 (s, 3H, Ph-CH
3), 2.84 (s, 3H, NCCH
3), 4.24 (s, 2H, CH
2, Pyrrole), 7.15-7.71 (m, 4H, PhH), 8.50 (s, 1H, NHNCH), 7.46-8.61 (m, 4H, PyridineH), 13.31 (s, 1H, NHNCH); Z-isomer (66%): 2.27 (s, 3H, Ph-CH
3), 2.80 (s, 3H, NCCH
3), 4.20 (s, 2H, CH
2, Pyrrole), 7.15-7.71 (m, 4H, PhH), 8.50 (s, 1H, NHNCH), 7.46-8.61 (m, 4H, PyridineH), 13.12 (s, 1H, NHNCH); MSm/z (%): 334 (M
+, 100), 229 (6), 186 (50), 131 (24), 120 (60), 107 (30), 91 (47), 79 (38); Anal.Calcd for C
19H
18N
4O
2: C, 68.25; H, 5.43; N, 16.76; Found:C, 68.16; H, 5.68; N, 16.24.
1-phenyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-2)
Yellow powder, mp 234.7-235.6 ℃; Yield: 68.6%; IR (KB r, cm
-1) v 3445,1682,1641,1620,1499,807,771,755,688;
1H NMR (DMSO-d
6, 400MHz) δ: E-isomer (33%): 2.85 (s, 3H, NCCH
3), 4.28 (s, 2H, CH
2, Pyrrole), 7.06-7.79 (m, 4H, PhH), 8.52 (s, 1H, NHNCH), 7.46-8.68 (m, 4H, Pyridine H), 13.33 (s, 1H, NHNCH); Z-isomer (67%): 2.82 (s, 3H, NCCH
3), 4.23 (s, 2H, CH
2, Pyrrole), 7.06-7.79 (m, 4H, PhH), 8.52 (s, 1H, NHNCH), 7.46-8.68 (m, 4H, Pyridine H), 13.12 (s, 1H, NHNCH); MS m/z (%): 320 (M
+, 100), 242 (19), 186 (50), 173 (4), 130 (28), 118 (20), 106 (45), 92 (24), 79 (40); Anal.Calcd for C
18H
16N
4O
2: C, 67.49; H, 5.03; N, 17.49; Found:C, 67.33; H, 5.11; N, 17.37.
(S)-5-methyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-3)
Yellow powder, mp 244.2-244.6 ℃; Yield: 73.6%; IR (KBr, cm
-1) v 3206,3071,1655,1615,1595,1574,781;
1HNMR (DMSO-d
6, 400MHz) δ: E-isomer (30%): 1.19 (d, J=8.0Hz, 3H, CH
3, Pyrrole), 2.77 (s, 3H, NCCH
3), 3.80 (q, J=6.8Hz, 1H, CH, Pyrrole), 7.75 (s, 1H, NH, Pyrrole), 8.43 (s, 1H, NHNCH), 7.44-7.48 (m, 1H, Pyridine H
5), 7.88-7.99 (m, 2H, PyridineH
3,4), 8.65-8.66 (m, 1H, PyridineH
6), 13.23 (s, 1H, NHNCH); Z-isomer (70%): 1.17 (d, J=7.2Hz, 3H, CH
3, Pyrrole), 2.72 (s, 3H, NCCH
3), 3.71 (q, J=6.8Hz, 1H, CH, Pyrrole), 8.08 (s, 1H, NH, Pyrrole), 8.36 (s, 1H, NHNCH), 7.44-7.48 (m, 1H, PyridineH
5), 7.88-7.99 (m, 2H, PyridineH
3,4), 8.65-8.66 (m, 1H, PyridineH
6), 13.15 (s, 1H, NHNCH); MS m/z (%): 258 (M
+, 100), 215 (95), 186 (75), 159 (23), 137 (59), 130 (44), 118 (34), 79 (75), 65 (42); Anal.Calcd for C
13H
14N
4O
2: C, 60.45; H, 5.46; N, 21.69; Found:C, 60.12; H, 5.88; N, 21.39.
(S)-5-benzyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-4)
Pale yellow powder, mp 248.4-250.0 ℃; Yield: 62.2%; IR (KB r, cm
-1) v 3026,3060,1651,1613,1595,1573,1509,735,717;
1H NMR (DMSO-d
6, 400MHz) δ: E-isomer (30%): 2.68 (s, 3H, NCCH
3), 2.85-3.00 (m, 2H, PhCH
2), 4.07 (t, J=5.6Hz, 1H, CH, Pyrrole), 7.16-7.26 (m, 5H, PhH), 7.73 (s, 1H, NH, Pyrrole), 7.43-7.46 (m, 1H, PyridineH
5), 7.88-7.97 (m, 2H, PyridineH
3,4), 8.66 (d, J=4.8Hz, 1H, PyridineH
6), 8.46 (s, 1H, NHNCH), 13.13 (s, 1H, NHNCH); Z-isomer (70%): 2.68 (s, 3H, NCCH
3), 2.85-3.00 (m, 2H, PhCH
2), 4.01 (t, J=4.8Hz, 1H, CH, Pyrrole), 7.16-7.26 (m, 5H, PhH), 8.07 (s, 1H, NH, Pyrrole), 7.43-7.46 (m, 1H, PyridineH
5), 7.88-7.97 (m, 2H, Pyri dineH
2,3,4), 8.63 (d, J=4.8Hz, 1H, Pyri dineH
6), 8.30 (s, 1H, NHNCH), 13.07 (s, 1H, NHNCH); MSm/z (%): 334 (M
+, 55), 243 (100), 226 (27), 215 (47), 186 (22), 120 (20), 91 (25), 79 (33), Anal.C alcd for C
19H
18N
4O
2: C, 68.25; H, 5.43; N, 16.76; Found:C, 68.66; H, 5.12; N, 16.36.
(S)-5-sec.-propyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-5)
Yellow powder, mp 225.2-227.3 ℃; Yield: 28.8%; IR (KB r, cm
-1) v 3277,3048,1687,1649,1598,1383,779,744;
1H NMR (CDCl
3, 400MHz) δ: E-isomer (37%): 0.85-0.89 (m, 3H, CH
3CHCH
3), 1.02-1.09 (m, 3H, CH
3CHCH
3), 2.21-2.23 (m, 1H, CH
3CHCH
3), 2.90 (s, 3H, NCCH
3), 3.78 (d, J=3.6Hz, 1H, CH, Pyrrole), 5.78 (s, 1H, NH, Pyrrole), 7.40-7.47 (m, 1H, PyridineH
5), 7.89-7.94 (m, 1H, PyridineH
3), 8.09-8.12 (m, 1H, PyridineH
4), 8.68-8.71 (m, 1H, PyridineH
6), 8.35 (s, 1H, NHNCH), 13.57 (s, 1H, NHNCH); Z-isomer (63%): 0.85-0.89 (m, 3H, CH
3CHCH
3), 1.02-1.09 (m, 3H, CH
3CHCH
3), 2.21-2.23 (m, 1H, CH
3CHCH
3), 2.85 (s, 3H, NCCH
3), 3.75 (d, J=3.2Hz, 1H, CH, Pyrrole), 6.28 (s, 1H, NH, Pyrrole), 7.40-7.47 (m, 1H, PyridineH
5), 7.89-7.94 (m, 1H, PyridineH
3), 8.09-8.12 (m, 1H, PyridineH
4), 8.68-8.71 (m, 1H, Pyri dineH
6), 8.55 (s, 1H, NHNCH), 13.40 (s, 1H, NHNCH); MSm/z (%): 286 (M
+, 100), 244 (85), 215 (82), 186 (90), 137 (58), 107 (53), 79 (77), 78 (51), 65 (44); Anal.Calcd for C
15H
18N
4O
2: C, 62.92; H, 6.34; N, 19.57; Found:C, 62.75; H, 6.14; N, 19.88.
3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-6)
Yellow powder, mp 241.9-242.7 ℃; Yield: 70.7%; IR (KBr, cm
-1) v 3215,3068,1648,1616,1598,781;
1H NMR (DMSO-d
6, 400MHz) δ: E-isomer (30%): 2.78 (s, 3H, NCCH
3), 3.68 (s, 2H, CH
2, Pyrrole), 7.60 (s, 1H, NH, Pyrrole), 7.45-7.47 (m, 1H, PyridineH
5), 7.88-7.89 (m, 2H, Py ridineH
3,4), 8.65-8.67 (m, 1H, PyridineH
6), 8.44 (s, 1H, NHNCH), 13.18 (s, 1H, NHNCH); Z-isomer (70%): 2.73 (s, 3H, NCCH
3), 3.65 (s, 2H, CH
2, Pyrrole), 7.45-7.47 (m, 1H, PyridineH
5), 7.88-7.89 (m, 3H, NH-Pyrrole, PyridineH
3,4), 8.65-8.67 (m, 1H, PyridineH
6), 8.36 (s, 1H, NHNCH), 13.21 (s, 1H, NHNCH); MSm/z (%): 244 (M
+, 100), 215 (47), 186 (50), 166 (25), 137 (47), 130 (43), 118 (36), 107 (34), 92 (59), 79 (77); 78 (38), 65 (59); Anal.Calcd for C
12H
12N
4O
2: C, 59.01; H, 4.95; N, 22.94; Fonud:C, 59.52; H, 4.25; N, 22.33.
1-sec.-propyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-7)
Yellow powder, mp 187.4-188.6 ℃; Yield: 73.4%; IR (KBr, cm
-1) v 3296,3051,1668,1625,1598,1355,1338,777,755;
1H NMR (CDCl
3, 400MHz) δ: E-isomer (27%): 1.20[d, J=5.2Hz, 6H, NCH (CH3)
2], 2.90 (s, 3H, NCCH
3), 3.71 (s, 2H, CH
2, Pyrrole), 4.60-4.71[m, 1H, NCH (CH3)
2], 7.40-7.57 (m, 1H, PyridineH
5), 7.85-8.22 (m, 2H, PyridineH
3,4), 8.69 (d, J=4.8Hz, 1H, PyridineH
6), 8.40 (s, 1H, NHNCH), 13.43 (s, 1H, NHNCH); Z-isomer (73%): 1.21[d, J=6.8Hz, 6H, NCH (CH3)
2], 2.83 (s, 3H, NCCH
3), 3.68 (s, 2H, CH
2, Pyrrole), 4.50-4.58[m, 1H, NCH (CH3)
2], 7.40-7.57 (m, 1H, PyridineH
5), 7.85-8.22 (m, 2H, PyridineH
3,4), 8.69 (d, J=4.8Hz, 1H, PyridineH
6), 8.36 (s, 1H, NHNCH), 13.53 (s, 1H, NHNCH); MSm/z (%): 286 (M
+, 100), 271 (78), 208 (20), 186 (44), 149 (39), 130 (25), 107 (34), 92 (25), 79 (45), 65 (34); Anal.Calcd for C
15H
18N
4O
2: C, 62.92; H, 6.34; N, 19.57; Found:C, 62.32; H, 6.15; N, 19.93.
The 1-tertiary butyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-8)
Yellow powder, mp 213.0-213.7 ℃; Yield: 31.7%; IR (KBr, cm
-1) v 3443,3055,1670,1637,1593,1242,1222,781,748;
1H NMR (CDCl
3, 400MHz) δ: E-isomer (18%): 1.49[s, 9H, NC (CH
3)], 2.88 (s, 3H, NCCH
3), 3.82 (s, 2H, CH
2, Pyrrole), 7.41-7.57 (m, 1H, PyridineH
5), 7.87-7.99 (m, 1H, PyridineH
3), 8.11 (d, J=8.0Hz, 1H, PyridineH
4), 8.68 (d, J=4.8Hz, 1H, PyridineH
6), 8.36 (s, 1H, NHNCH), 13.51 (s, 1H, NHNCH); Z-isomer (82%): 1.49[s, 9H, NC (CH
3)], 2.82 (s, 3H, NCCH
3), 3.79 (s, 2H, CH
2, Pyrrole), 7.41-7.57 (m, 1H, PyridineH
5), 7.87-7.99 (m, 1H, Py ridineH
3), 8.11 (d, J=8.0Hz, 1H, Py ridineH
4), 8.68 (d, J=4.8Hz, 1H, Pyri dineH
6), 8.40 (s, 1H, NHNCH), 13.71 (s, 1H, NHNCH); MSm/z (%): 300 (M
+, 52), 285 (100), 186 (18), 149 (6), 120 (14), 79 (25), 70 (27), 57 (25); Anal.Calcdfor C
16H
20N
4O
2: C, 63.98; H, 6.71; N, 18.65; Found:C, 63.46; H, 6.32; N, 18.66.
3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene)-1-p-methylphenyl tetramethyleneimine-2,4-diketone (I-9)
Yellow powder, mp 230.8-231.1 ℃; Yield: 58.7%; IR (KBr, cm
-1) v 3434,3029,1687,1640,1588,812,745;
1HNMR (DMSO-d
6, 400MHz) δ: Z-isomer (33%): 2.27 (s, 3H, PhCH
3), 2.84 (s, 3H, NCCH
3), 4.25 (s, 2H, CH
2, Pyrrole), 7.62-7.72 (m, 4H, PhH), 7.17 (d, J=8.8Hz, 2H, PyridineH
3,5), 8.58 (s, 1H, NHNCH), 8.70 (d, J=4.8Hz, 2H, PyridineH
2,6), 13.35 (s, 1H, NHNCH); E-isomer (67%): 2.28 (s, 3H, PhCH
3), 2.80 (s, 3H, NCCH
3), 4.20 (s, 2H, CH
2, Pyrrole), 7.62-7.72 (m, 4H, PhH), 7.17 (d, J=8.8Hz, 2H, Pyri dineH
3,5), 8.58 (s, 1H, NHNCH), 8.70 (d, J=4.8Hz, 2H, PyridineH
2,6), 13.20 (s, 1H, NHNCH); MSm/z (%): 334 (M
+, 100), 319 (4), 256 (15), 120 (62), 109 (16), 91 (33), 78 (10), 67 (15); Anal.Calcd for C
19H
18N
4O
2: C, 68.25; H, 5.43; N, 16.76; Found:C, 68.60; H, 5.14; N, 16.86.
1-phenyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-10)
Yellow powder, mp 238.8-239.1 ℃; Yield: 64.8%; IR (KB r, cm
-1) v 3448,3028,1688,1638,1599,1566,805,748;
1H NMR (DMSO-d
6, 400MHz) δ: Z-isomer (33%): 2.85 (s, 3H, NCCH
3), 4.29 (s, 2H, CH
2, Pyrrole), 7.06-7.78 (m, 5H, PhH), 7.34-7.40 (m, 2H, Pyri dineH
3,5), 8.59 (s, 1H, NHNCH), 8.69 (d, J=4.8Hz, 2H, PyridineH
2,6), 13.37 (s, 1H, NHNCH); E-isomer (67%): 2.80 (s, 3H, NCCH
3), 4.23 (s, 2H, CH
2, Pyrrole), 7.06-7.78 (m, 5H, PhH), 7.34-7.40 (m, 2H, PyridineH
3,5), 8.59 (s, 1H, NHNCH), 8.69 (d, J=4.8Hz, 2H, PyridineH
2,6), 13.37 (s, 1H, NHNCH); MSm/z (%): 320 (M
+, 100), 242 (15), 216 (12), 159 (14), 106 (61), 77 (36); Anal.Calcd for C
18H
16N
4O
2: C, 67.49; H, 5.03; N, 17.49; Found:C, 67.32; H, 5.16; N, 17.69.
(S)-5-methyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-11)
Yellow powder, mp 216.4-218.7 ℃; Yield: 60.7%; IR (KBr, cm
-1) v 3445,3183,3051,1690,1640,1617,1581,793,724;
1H NMR (DMSO-d
6, 400MHz) δ: Z-isomer (37%): 1.19 (d, J=8.0Hz, 3H, CH
3, Pyrrole), 2.77 (s, 3H, NCCH
3), 3.80 (q, J=6.4Hz, 1H, CH, Pyrrole), 7.78 (s, 1H, NH, Pyrrole), 7.68 (d, J=6.0Hz, 2H, PyridineH
3,5), 8.67-8.69 (m, 2H, PyridineH
2,6), 8.50 (s, 1H, NHNCH), 13.19 (s, 1H, NHNCH); E-isomer (63%): 1.17 (d, J=6.8Hz, 3H, CH
3, Pyrrole), 2.71 (s, 3H, NCCH
3), 3.73 (q, J=7.2Hz, 1H, CH, Pyrrole), 8.13 (s, 1H, NH, Pyrrole), 7.68 (d, J=6.0Hz, 2H, Pyridine H
3,5), 8.67-8.69 (m, 2H, Pyri dineH
2,6), 8.46 (s, 1H, NHNCH), 13.30 (s, 1H, NHNCH); MSm/z (%): 258 (M
+, 100), 243 (20), 216 (30), 137 (30), 109 (70), 83 (27), 67 (50); Anal.Calcd for C
13H
14N
4O
2: C, 60.45; H, 5.46; N, 21.69; Found:C, 60.19; H, 5.12; N, 21.95.
(S)-5-benzyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-12)
Pale yellow powder, mp 223.8-224.1 ℃; Yield: 34.6%; IR (KBr, cm
-1) v 3435,3197,3046,1696,1642,1613,1571,792,740;
1H NMR (DMSO-d
6, 400MHz) δ: Z-isomer (28%): 2.67 (s, 3H, NCCH
3), 2.83-2.99 (m, 2H, PhCH
2), 4.09 (t, J=5.6Hz, 1H, CH, Pyrrole), 7.16-7.26 (m, 5H, PhH), 7.68 (d, J=6.0Hz, 2H, PyridineH
3,5), 7.76 (s, 1H, NH, Pyrrole), 8.68 (d, J=6.0Hz, 2H, PyridineH
2,6), 8.53 (s, 1H, NHNCH), 13.18 (s, 1H, NHNCH); E-isomer (72%): 2.67 (s, 3H, NCCH
3), 2.83-2.99 (m, 2H, PhCH
2), 4.02 (t, J=5.6Hz, 1H, CH, Pyrrole), 7.16-7.26 (m, 5H, PhH), 7.65 (d, J=5.6Hz, 2H, PyridineH
3,5), 8.13 (s, 1H, NH, Pyrrole), 8.66 (d, J=6.0Hz, 2H, PyridineH
2,6), 8.39 (s, 1H, NHNCH), 13.14 (s, 1H, NHNCH); MS m/z (%): 334 (M
+, 45), 243 (100), 215 (17), 91 (20), 105 (14), 124 (33), 67 (15); Anal.Calcd for C
19H
18N
4O
2: C, 68.25; H, 5.43; N, 16.76; Found:C, 68.66; H, 5.77; N, 16.15.
(S)-5-sec.-propyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-13)
Yellow powder, mp 198.4-200.3 ℃; Yield: 37.3%; IR (KBr, cm
-1) v 3448,3195,3049,1692,1642,1612,1578,1386,805,758;
1H NMR (DMSO-d
6, 400MHz) δ: Z-isomer (30%): 0.96 (d, J=6.8Hz, 3H, CH
3CHCH
3), 0.76 (d, J=6.8Hz, 3H, CH
3CHCH
3), 2.00-2.08 (m, 1H, CH
3CHCH
3), 2.77 (s, 3H, NCCH
3), 3.66 (d, J=3.2Hz, CH, Pyrrole), 7.83 (s, 1H, NH, Pyrrole), 7.68 (d, J=6.0Hz, 2H, PyridineH
3,5), 8.67-8.69 (m, 2H, PyridineH
2,6), 8.51 (s, 1H, NHNCH), 13.26 (s, 1H, NHNCH); E-isomer (70%): 0,96 (d, J=6.8Hz, 3H, CH
3CHCH
3), 0.73 (d, J=6.8Hz, 3H, CH
3CHCH
3), 2.00-2.08 (m, 1H, CH
3CHCH
3), 2.72 (s, 3H, NCCH
3), 3.60 (d, J=2.8Hz, CH, Pyrrole), 8.18 (s, 1H, NH, Pyrrole), 7.68 (d, J=6.0Hz, 2H, PyridineH
3,5), 8.67-8.69 (m, 2H, PyridineH
2,6), 8.46 (s, 1H, NHNCH), 13.28 (s, 1H, NHNCH); MSm/z (%): 286 (M
+, 30), 271 (5), 244 (100), 215 (17), 109 (49), 67 (22), 72 (30); Anal.Calcd forC
15H
18N
4O
2: C, 62.92; H, 6.34; N, 19.57; Found:C, 62.56; H, 6.12; N, 19.88.
3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-14)
Pale yellow powder, 267.5 ℃ of decomposition of mp; Yield: 68.9%; IR (KBr, cm
-1) v 3432,3178,3105,1692,1631,1614,1582,785,707;
1H NMR (DMSO-d
6, 400MHz) δ: Z-isomer (30%): 2.77 (s, 3H, NCCH
3), 3.69 (s, 2H, CH
2, Pyrrole), 7.63 (s, 1H, NH, Pyrrole), 7.67-7.69 (m, 2H, PyridineH
3,5), 8.66-8.69 (m, 2H, Pyri dineH
2,6), 8.52 (s, 1H, NHNCH), 13.22 (s, 1H, NHNCH); E-isomer (70%): 2.72 (s, 3H, NCCH
3), 3.65 (s, 2H, CH
2, Pyrrole), 7.98 (s, 1H, NH, Pyrrole), 7.67-7.69 (m, 2H, Pyri dineH
3,5), 8.66-8.69 (m, 2H, Py ridineH
2,6), 8.46 (s, 1H, NHNCH), 13.27 (s, 1H, NHNCH); MS m/z (%): 244 (M
+, 100), 229 (33), 166 (30), 137 (38), 120 (18), 105 (23), 67 (84), 58 (40); Anal.Calcd forC
12H
12N
4O
2: C, 59.01; H, 4.95; N, 22.94; Found:C, 59.13; H, 4.51; N, 22.22.
The 1-tertiary butyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-15)
Yellow powder, mp 184.1-185.7 ℃; Yield: 38.9%; IR (KBr, cm
-1) v 3412,3014,1683,1632,1614,1581,1239,1221,799,749;
1H NMR (CDCl
3, 400MHz) δ: Z-isomer (17%): 1.49 (s, 9H, N (CH
3)
3, 2.87 (s, 3H, NCCH
3), 3.82 (s, 2H, CH
2, Pyrrole), 7.58 (d, J=6.0Hz, 2H, PyridineH
3,5), 8.04 (s, 1H, NHNCH), 8.72 (d, J=6.0Hz, 2H, PyridineH
2,6), 13.50 (s, 1H, NHNCH); E-isomer (83%): 1.49 (s, 9H, N (CH
3)
3, 2.81 (s, 3H, NCCH
3), 3.79 (s, 2H, CH
2, Pyrrole), 7.55 (d, J=5.6Hz, 2H, Pyri dineH
3,5), 8.04 (s, 1H, NHNCH), 8.70 (d, J=6.0Hz, 2H, PyridineH
2,6), 13.62 (s, 1H, NHNCH); MS m/z (%): 300 (M
+, 27), 285 (100), 180 (8), 166 (8), 109 (12), 70 (20), 57 (20); Anal.Calcd forC
16H
20N
4O
2: C, 63.98; H, 6.71; N, 18.65; Found:C, 63.51; H, 6.45; N, 18.89.
1-sec.-propyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2,4-diketone (I-16)
Yellow powder, mp 203.1-203.8 ℃; Yield: 78.6%; IR (KBr, cm
-1) v 3433,3041,1688,1639,1611,1579,799,752;
1H NMR (CDCl
3, 400MHz) δ: Z-isomer (24%): 1.20[d, J=6.8Hz, 6H, NCH (CH
3)
2], 2.89 (s, 3H, NCCH
3), 3.70 (s, 2H, CH
2, Pyrrole), 4.59-4.70[m, 1H, NCH (CH
3)
2], 8.04 (s, 1H, NHNCH), 7.58 (d, J=6.0Hz, 2H, PyridineH
3,5), 8.72 (d, J=6.8Hz, 2H, PyridineH
2,6), 13.42 (s, 1H, NHNCH); E-isomer (76%): 1.22[d, J=6.8Hz, 6H, NCH (CH
3)
2], 2.82 (s, 3H, NCCH
3), 3.68 (s, 2H, CH
2, Pyrrole), 4.48-4.59[m, 1H, NCH (CH
3)
2], 8.00 (s, 1H, NHNCH), 7.56 (d, J=6.0Hz, 2H, PyridineH
3,5), 8.71 (d, J=6.0Hz, 2H, PyridineH
2,6), 13.46 (s, 1H, NHNCH); MS m/z (%): 286 (M
+, 44), 271 (100), 181 (11), 166 (15), 105 (15), 67 (20), 56 (18); Anal.Calcd for C
15H
18N
4O
2: C, 62.92; H, 6.34; N, 19.57; Found:C, 62.34; H, 6.65; N, 19.19.
Purposes embodiment
Embodiment 2: the weeding activity of compound of the present invention
Adopt Plating to measure above-mentioned synthetic part of compounds I-11～I-16 to the weeding activity of barnyard grass (Echinochloacrusgalli (L.) Beauv.) and rape (Brassica campestris L.).Accurately a certain amount of testing compound of weighing is in the 25mL volumetric flask, and with a small amount of DMF dissolving (solvent strength is less than 0.5%), agricultural newborn 2201 aqueous solution with 0.1% are settled to scale, are mixed with the solution of 100mg/L.Do not contain the aqueous solution of reagent agent with the DMF that contains same volume and farming breast 2201 in contrast.
Select 15 consistent seeds that just show money or valuables one carries unintentionally, germinate to put in the culture dish that is lined with filter paper, (direction of the root and plumula of seed will be consistent), and drive bubble below the filter paper out of, in culture dish, add the medicament that 5mL prepares, and fully seed is impregnated with liquid.Culture dish after processing is placed in the biochemical cultivation case, is (25 ± 1) ℃ in temperature, and humidity is to cultivate under the dark condition of 80-90%.Measure the rape radicle length behind the 48h, the root of measuring barnyard grass after 72 hours is long.If three repetitions.Calculate inhibition percentage.Test-results is as shown in table 1:
The weeding activity of table 1 Compound I (100mg/L, inhibiting rate %)
Annotate: TeA be thin friendship Fusariumsp ketone acid, i.e. 3-(1-hydroxy ethylene)-5-sec-butyl tetramethyleneimine-2,4-diketone, in contrast medicament.
Compound I-11～I-16 is inhibited to the growth of 2 kinds of test plants.Wherein Compound I-11, I-13, I-14 and I-16 have surpassed 50% to the long inhibiting rate of barnyard grass root, have reached respectively 52.50%, 67.14%, 50.15% and 54.45%.Compound I-12, I-13 and I-15 have reached respectively 72.00%, 63.96% and 52.41% to rape root inhibiting rate has been surpassed 50%.
Claims (9)
1. the pyrrolidine-diones compounds that contains the pyridylaldehyde hydrazone groups or its isomer of formula (I),
Wherein,
Optional the 2nd carbon of pyridine ring, the 3rd carbon, the 4th carbon of being connected in of carbon atom on the aldehyde hydrazone group (NHN=CH);
R
1Be selected from hydrogen, C
1～C
12Alkyl, phenyl, substituted-phenyl;
R
2Be selected from hydrogen, C
1～C
12Alkyl;
R
3, R
4Be independently from each other hydrogen, C
1～C
12Alkyl, benzyl, substituted benzyl;
R
5Be selected from H, F, Cl, Br, I, C
1～C
6Alkyl, single replacement or polysubstituted;
Substituted-phenyl, the substituted benzyl mentioned in the definition of above group simultaneously refer to that phenyl in the described group is by F, Cl, Br, I, C
1～C
5The alkyl list replaces or is polysubstituted.
2. pyrrolidine-diones compounds or its isomer that contains the pyridylaldehyde hydrazone groups according to claim 1 is characterized in that:
Optional the 2nd carbon of pyridine ring, the 3rd carbon, the 4th carbon of being connected in of carbon atom on the aldehyde hydrazone group (NHN=CH);
R
1Be selected from hydrogen, C
1～C
12Alkyl, phenyl, C
1～C
6The mono-substituted phenyl of alkyl;
R
2Be selected from C
1～C
12Alkyl;
R
3, R
4In one be selected from hydrogen, another is selected from hydrogen, C
1～C
12Alkyl, benzyl;
R
5Be selected from H, F, Cl, Br, I, C
1～C
6Alkyl, the single replacement.
3. pyrrolidine-diones compounds or its isomer that contains the pyridylaldehyde hydrazone groups according to claim 2 is characterized in that:
Optional the 2nd carbon of pyridine ring, the 3rd carbon, the 4th carbon of being connected in of carbon atom on the aldehyde hydrazone group (NHN=CH);
R
1Be selected from hydrogen, C
1～C
6Alkyl, phenyl, C
1～C
6The mono-substituted phenyl of alkyl;
R
2Be selected from C
1～C
6Alkyl;
R
3, R
4In one be selected from hydrogen, another is selected from hydrogen or at R
1Be selected from C when being selected from hydrogen
1～C
6Alkyl, benzyl;
R
5Be selected from H.
4. pyrrolidine-diones compounds or its isomer that contains the pyridylaldehyde hydrazone groups claimed in claim 3 is characterized in that:
Optional the 2nd carbon of pyridine ring, the 4th carbon of being connected in of carbon atom on the aldehyde hydrazone group (NHN=CH);
R
1Be selected from hydrogen, C
1～C
6Alkyl, phenyl, 4-aminomethyl phenyl;
R
2Be selected from methyl;
R
3, R
4In one be selected from hydrogen, another is selected from hydrogen or at R
1Be selected from C when being selected from hydrogen
1～C
6Alkyl, benzyl;
R
5Be selected from H.
5. the pyrrolidine-diones compounds that contains the pyridylaldehyde hydrazone groups claimed in claim 4, or its isomer, it is characterized in that: 3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene)-1-p-methylphenyl tetramethyleneimine-2, the 4-diketone, 1-phenyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, (S)-5-methyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, (S)-5-benzyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, (S)-5-sec.-propyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, 3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, 1-sec.-propyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, the 1-tertiary butyl-3-(1-(N '-pyridine-2-methylene diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, 3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene)-1-p-methylphenyl tetramethyleneimine-2, the 4-diketone, 1-phenyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, (S)-5-methyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, (S)-5-benzyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, (S)-5-sec.-propyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, 3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, the 1-tertiary butyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone, 1-sec.-propyl-3-(1-(N '-pyridin-4-yl methylene radical diazanyl) ethylidene) tetramethyleneimine-2, the 4-diketone.
6. each described pyrrolidine-diones compounds or its isomer that contains the pyridylaldehyde hydrazone groups in 5 according to claim 1 is characterized in that described isomer is geometrical isomer, and described geometrical isomer refers to Z formula or E formula isomer.
7. each described pyrrolidine-diones compounds or its isomer that contains the pyridylaldehyde hydrazone groups in 5 according to claim 1 is characterized in that described isomer is optical isomer, and described optical isomer is R type or S type isomer.
8. one kind prepares the described pyrrolidine-diones compounds of pyridylaldehyde hydrazone groups or the method for its isomer of containing of claim 1～5, it is characterized in that being prepared according to the method shown in the following reaction equation:
Wherein in each structural formula of above-mentioned reaction formula:
R
1To R
5All has the implication described in claim 1 to 5.
9. each described pyrrolidine-diones compounds or application in management of weeds of its isomer that contains the pyridylaldehyde hydrazone groups in the claim 1～5.
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| CN107652296A (en) * | 2016-07-26 | 2018-02-02 | 南开大学 | Loop coil Oxoindole acyl hydrazone derivative and preparation method thereof and the application in terms of preventing and treating plant virus, sterilization, desinsection |
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Application publication date: 20130327 |