CN1038679C - Sulfonylurea compound herbicide - Google Patents

Sulfonylurea compound herbicide Download PDF

Info

Publication number
CN1038679C
CN1038679C CN94118793A CN94118793A CN1038679C CN 1038679 C CN1038679 C CN 1038679C CN 94118793 A CN94118793 A CN 94118793A CN 94118793 A CN94118793 A CN 94118793A CN 1038679 C CN1038679 C CN 1038679C
Authority
CN
China
Prior art keywords
compound
formula
sulfonylurea compound
halogen
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CN94118793A
Other languages
Chinese (zh)
Other versions
CN1106393A (en
Inventor
李正名
贾国锋
王玲秀
范传文
杨炤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nankai University
Original Assignee
Nankai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nankai University filed Critical Nankai University
Priority to CN94118793A priority Critical patent/CN1038679C/en
Publication of CN1106393A publication Critical patent/CN1106393A/en
Application granted granted Critical
Publication of CN1038679C publication Critical patent/CN1038679C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to the synthesis of a sulfonylurea compound, the general formula of which is I. X is C1-4 alkyl, C1-4 alkoxyl, C1-4 carbalkoxy, halogen, or nitryl; Y is C1-4 alkyl, C1-4 alkoxyl, C1-4 alkylthio or halogen; Z is N or CH, and W is O or S. The present invention has favorable weeding activity, and the sulfonylurea compound can be used for the field weeding of crops, such as maize, wheat, soybeans, etc.

Description

Sulfonyl urea compound and weeding purpose thereof
The present invention relates to sulfonyl urea compound, particularly can be used as the farm crop weedicide.
Sulfonyl urea compound is as the existing many reports of weedicide.U.S. Pat 4,191,533 and US 4,419,121 following formula: compound is disclosed respectively:
Figure C9411879300031
European patent EP 30,140 discloses following formula: compound:
Figure C9411879300032
Chinese patent CN 1080116A discloses following formula: compound, as corn field herbicide
Figure C9411879300033
In the sulfonyl urea compound of having reported, the overwhelming majority is not only to the weeds sensitivity, and to some farm crop (as corn etc.) also performance is responsive sometimes, because these compounds may cause serious harm to following batch farm crop, be that the weedicide (swelling as chlorine sulphur) of active ingredient has been limited use in some areas therefore with some sulfonyl urea compound.All has disubstituted constitutional features on the heterocycle of kind of sulfonylurea herbicide in its molecule surplus in the of commercial ten.The G.Levitt of du pont company particularly points out, the sulfonylurea molecule must be at 4 of its heterocyclic moiety, enough weeding activity (Synthesis andChemistry of Agrochemicals II is just arranged when all substituting group being arranged on 6 two positions, edited by D.R.Baker, et al, A.C.S., 1991, P.16).
The object of the present invention is to provide a kind of sulfonylurea weedicide, broken through the structural pattern of selected sulfonyl urea compound weedicide in the past, promptly heterocyclic moiety has single substituent sulfonyl urea compound enough weeding activity is also arranged.Compound provided by the invention has excellent herbicidal and security, and demonstrates bigger superiority on bioactive selectivity, can be used in field weedings such as wheat, corn, soybean and these farming rotations of crops.
The present invention is that following structure is that the compound of effective ingredient is as weedicide
Figure C9411879300041
Wherein, X is C 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Carbalkoxy, halogen or nitro; Y is C 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Alkylthio or halogen; Z is N or CH; W is O or S.
Formula of the present invention (I) compound is to react in The suitable solvent and under the suitable temperature and prepare with formula (II) compound and formula (III) compound:
Figure C9411879300051
The synthetic method of formula (III) compound is referring to U.S. Pat 3,169,719.
The weeding activity that has two substituent solsonylurea compounds at heterocyclic moiety that the present invention has the weeding activity of formula (I) compound and a report in the past at heterocyclic moiety is (seeing Table 2) quite, through the greenhouse soil processes and displays, formula (I) compound is to farm crop safety such as wheat, corn, soybean, and selectivity is superior.
Substantive distinguishing features of the present invention can be embodied from following embodiment, but these embodiment are only as an illustration, rather than limits the invention:
The preparation of example 1 formula (I) compound thing
Add the adjacent ethoxycarbonyl benzsulfamide of 4.6g (0.02mol) in the 100ml reaction flask, 35ml toluene and 7.0g oxalyl chloride are kept reaction 10 hours between 50-90 ℃, cooling, filter, slough solvent, the residue adding is contained in the reaction flask of 1.0g2-amino-4-methylpyrimidine and 20ml acetonitrile, react 1.5 hours after-filtration, solid purifying with reaction obtains promptly gets product, heavy 3.6g, total recovery 50%, m.p.135.0 ℃ (distillation) 1H NMR (CDCl 3, δ), 1.28 (3H, t ,-CH 3), 2.56 (3H, s ,-CH 3), 4.28 (2H, q, CH 2), 6.76-8.44 (6H, m, Ar), 9.52 (1H, br, NH), 12.64 (1H, br, NH), IR (cm -1, the KBr compressing tablet), 3400 (ν N-H), 1712 (ν C-O), 1352 (ν As, SO 2), 1163 (ν s, SO 2).
Can synthesize other formula (I) compound by this method, table 1 is the fusing point and the ultimate analysis value of segment bounds (I) compound.
Listed compound has only numbering 12,20 once to give in disclosed document and mention (US-4,169,719) in the table 1, but the lifeless matter determination data, other each compounds there is no report.
Example 2 IC 50Measure
3 milliliters of medicament to be measured and 25 Semen Brassicae campestriss that are dissolved in the innoxious solvent are put into the culture dish that is lined with 6 centimetres of 2 filter paper diameters, and medicament to be measured will have 4 to 5 concentration at least, and each concentration repeats 2 times, establish the clear water contrast.All culture dish are placed in 28 ℃ of constant temperature darkrooms, after 45 hours, measure rape epicotyl length.Between weedicide concentration and the growth-inhibiting degree linear relationship is arranged, the susceptibility of sulfonylurea is low to moderate 0.0003ppm.Compare with blank, calculate and suppress percentage.Ask IC with method of least squares 50, table 2 is IC of segment bounds (I) compound 50Value.
Example 3 potted plant drug effect and crop-selectives
With several responsive single, double cotyledon weeds and crop seed kind in growth medium, through the identical time, when monocotyledons tool two leaves wholeheartedly, dicotyledons 3 to 4 leaves are when (comprising cotyledon), after other uses the same method and repeats plantation, do cauline leaf and soil treatment with the medicament to be measured that is dissolved in the innoxious solvent, handle after 15 to 21 days, divide the overground part fresh weight of another name plant, handle the blank ratio with clear water, calculate it and suppress percentage, kill careless power and to crop safety in order to evaluation.Table 3 is greenhouse pot culture drug effects (soil treatment) of segment bounds (I) compound
Example 4 is tested with the grand active comparison expression of doing contrast of chlorine sulphur
(1) pot-culture method:
Adorn 100 gram sandy loams in 11 * 7.5 * 6cm plastics casing, first water is drenched, and the every box plantation in back is sprouted the barnyard grass grass, each 15 of Semen Brassicae campestriss.Cover the fine earth 0.6cm that sieves, do with every mu 20 gram formula (I) compound respectively immediately and broadcast the preceding soil treatment of back seedling, do the contrast medicament with the grand 2 gram/mus of chlorine sulphur, other establishes the clear water contrast, handle back 15 days survey barnyard grass grass and compare with the clear water contrast, calculate it and suppress percentage with rape over-ground part fresh weight.
(2) rape root regular way:
The 25ppm solution of 3ml formula (I) compound and 20 Semen Brassicae campestriss are put into and are lined with two filter paper, diameter is in the culture dish of 6cm, culture dish is put in 28 ℃ of constant temperature darkrooms, after 45-48 hour, measure rape seedling primary root length and clear water comparison film, calculate it respectively and suppress percentage.
(3) the little agar diffusion method of barnyard grass grass:
The 25ppm solution of 5ml formula (I) compound and 10 barnyard grass grass seeds of having sprouted, put into glass heelpiece the 50ml beaker of putting a filter paper consistent with the cup end on one deck 5mm glass sphere and the ball is arranged, beaker is put into 28 ℃, the thermostatic chamber of 3200Lux fluorescence irradiation, after 72-96 hour, survey barnyard grass grass seedling overground part and underground part length, with the clear water contrast ratio, calculate it respectively and suppress percentage.
Table 4 is weeding activity data of segment bounds (I) compound.
Table 1
Numbering X Y Z W Fusing point (℃) Ultimate analysis value (%)
Calculated value Measured value
C H N C H N
1 CO 2Et Me CH O (135.0 distillation) 49.44 4.42 15.38 48.15 5.13 15.67
2 CO 2Et OMe CH O 167.5-9 47.36 4.24 14.73 47.15 4.12 14.42
3 CO 2Et OEt CH O 164-6 48.72 4.60 14.21 49.10 4.71 14.50
4 CO 2Et OPr-i CH O 166.5-8 49.99 4.94 13.72 49.67 4.96 13.49
5 CO 2Et Cl CH O 189-90.5 43.70 3.40 14.56 44.03 3.18 14.22
6 CO 2Et Et CH O 178.5-80 50.78 4.79 14.81 50.50 4.70 14.85
7 CO 2Et Prn CH O 150-1.4 52.03 5.14 14.28 52.37 5.38 14.00
8 CO 2Et Pr-i CH O 169-70 52.03 5.14 14.28 52.14 5.07 14.03
9 CO 2Me OMe CH O 184-5.5 45.90 3.80 15.29 46.20 4.17 15.42
10 CO 2Me Cl CH O 201-2 42.11 2.99 15.11 42.44 2.93 15.27
11 CO 2Me Me CH O 190-2 47.99 4.02 15.99 48.37 3.97 16.34
12 Me Me CH O 185.5-7.0 50.97 4.61 18.29 51.04 4.38 18.34
13 Me OMe CH O 192-3.5 48.44 4.38 17.38 48.63 4.55 17.64
14 Me OEt CH O 183.5-5 50.00 4.79 16.66 49.92 4.95 17.00
15 Me OPr-i CH O 174-5.6 51.42 5.18 15.99 51.40 4.92 15.70
16 Me Cl CH O 206-8 44.11 3.39 17.15 44.25 3.23 17.02
17 Me Et CH O 181-2 52.48 5.03 17.49 52.74 4.93 17.73
18 Me Pr-n CH O 183-5 53.88 5.42 16.76 54.19 5.20 17.06
19 Me Pr-i CH O 176-8 53.88 5.42 16.76 53.90 5.37 16.80
20 Cl Me CH O 191.2-2.2 44.11 3.39 17.15 44.25 3.23 17.17
21 Cl Pr-n CH O 191-3 47.39 4.26 15.79 47.34 4.18 15.86
22 Cl Pr-i CH O 186-8 47.39 4.26 15.79 47.03 4.11 15.73
23 Cl OMe CH O 209-11 42.05 3.23 16.35 42.20 3.22 16.41
24 Cl OEt CH O 164.5-6 43.76 3.67 15.70 43.93 3.97 15.96
25 Cl OPr-i CH O 187-9 45.35 4.08 15.11 45.10 4.16 15.15
26 Cl SEt CH O 193-5 41.88 3.51 15.03 41.99 3.58 15.27
27 Cl Cl CH O 205-7 38.05 2.32 16.14 38.07 2.14 16.16
28 Cl Et CH O 183-5 45.82 3.84 16.44 45.99 3.92 16.13
29 NO 2 OMe CH O 183-5 40.79 3.19 19.82 40.76 3.25 20.14
30 NO 2 SEt CH O 191-3 40.72 3.42 18.27 40.94 3.28 18.14
31 NO 2 Cl CH O 200-2 36.93 2.25 19.58 37.15 2.07 19.14
32 NO 2 Et CH O 179-80 44.44 3.73 19.17 44.68 3.97 19.60
33 NO 2 Pr-n CH O 176-8 46.02 4.14 19.17 46.00 4.03 19.08
34 NO 2 Pr-i CH O 183-5 46.02 4.14 19.17 45.97 4.15 19.07
Table 2 compound number IC 50(M) grand (contrast) 7.24 * 10 of r chlorine sulphur -70.99 1 7.96 * 10 -70.95 2 7.89 * 10 -70.97 9 2.73 * 10 -70.96 11 3.80 * 10 -70.99 12 7.12 * 10 -60.99 20 1.24 * 10 -50.93 23 4.06 * 10 -60.99 29 3.40 * 10 -60.99 annotate: 1. compound number is with table 1.2.r be linear regression coeffficient
Grand 2 S-1 T S S T-1 T S (contrast), the 12 S-1 T-1 S S-1-T T of table 3 compound dosage barnyard grass grass oat rape three-coloured amaranth clover wheat and corn numbering (gram/mu) chlorine sulphur
4 S-1 T-1 S S-1 - T T2 2 - - - - - - T
4 - - - - - - T9 2 - - - - - - T-1
4 - - - - - - T-111 2 - - - - - - T-1
4 - - - - - - T-112 5 T T-1 S T-1 - - T29 2 S T S T-1 T-1 - T
4 - - - - - - T22 2 S-1 T S T-1 T-1 - T
4------the T notes: 1. compound number is with table 1
2.S: sensitivity, S-1: in quick T: resistance, T-1: in anti-
Table 4
Compound number Long suppress (%) of rape root regular way (25ppm) root Barnyard grass grass little agar diffusion method (25ppm) Pot-culture method (20 gram/mu)
Suppress on the ground (%) Underground inhibition (%) Barnyard grass grass (list) (%) Rape (two) (%)
Chlorine sulphur swells (contrast) 78.6 * 63.2 * 78.7 * 68.0 ** 98.0 **
2 50.0 56.3 74.3 68 99.1
3 66.0 49.6 63.8 0 66.3
4 29.8 0 29.1 0 54.2
5 37.8 9.9 46.3 0 67.3
6 72.1 33.1 64.9 0 89.2
7 65.3 0 35.4 0 13.3
8 58.2 16.0 24.5 0 12.0
9 48.4 65.1 76.1 80.0 97.3
10 46.3 1.9 30.1 0 △ 83.2 △
11 42.0 66.1 75.9 89.3 97.3
13 52.1 15.7 51.4 0 △ 65.5 △
14 24.5 0 13.4 0 △ 24.8 △
15 22.3 0 29.5 5.3 43.4
16 28.7 0 11.1 0 36.3
17 59.5 0 21.5 19.3 76.8
18 34.3 0 0 0 1.2
19 41.2 0 34.6 0 0
21 50.7 0 5.9 0 7.2
22 48.3 0 39.4 8.6 14.7
23 65.3 58.1 76.2 84.2 96.3
24 23.4 0 29.7 0 △ 8.0 △
25 55.4 4.5 35.2 0 69.5
26 26.2 38.2 40.2 0 40.2
27 29.8 10.7 33.5 16.0 47.8
28 67.3 18.1 54.2 19.3 76.8
29 63.9 67.7 82.4 93.0 93.9
30 27.2 7.5 38.5 0 45.1
31 41.0 0 42.7 0 57.5
32 63.9 65.1 80.8 47.4 85.4
33 65.3 41.6 29.4 0 57.8
34 64.3 0.5 39.6 0 54.2
Annotate: 1. compound number is with table 1
2. band * person test concentrations is 2.5ppm in the table, and band △ person test concentrations is 50 gram/mus

Claims (2)

1. solsonylurea compounds with weeding activity is characterized in that its general formula is: Wherein, X is C 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Carbalkoxy or halogen; Y is C 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Alkylthio or halogen; Z is N or CH; W is O or S.
2. the application of claim 1 solsonylurea compounds is characterized in that it can impose on the farm crop field weeding of weeds.
CN94118793A 1994-12-07 1994-12-07 Sulfonylurea compound herbicide Expired - Lifetime CN1038679C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN94118793A CN1038679C (en) 1994-12-07 1994-12-07 Sulfonylurea compound herbicide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN94118793A CN1038679C (en) 1994-12-07 1994-12-07 Sulfonylurea compound herbicide

Publications (2)

Publication Number Publication Date
CN1106393A CN1106393A (en) 1995-08-09
CN1038679C true CN1038679C (en) 1998-06-10

Family

ID=5039019

Family Applications (1)

Application Number Title Priority Date Filing Date
CN94118793A Expired - Lifetime CN1038679C (en) 1994-12-07 1994-12-07 Sulfonylurea compound herbicide

Country Status (1)

Country Link
CN (1) CN1038679C (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK0964849T3 (en) * 1997-01-29 2003-08-25 Pfizer Sulfonyl-urea derivatives and their use in regulating interleukin-1 activity
CN1098633C (en) * 1998-01-21 2003-01-15 南开大学 Use of Dujiaolong (92825) In millet field
CN1311748C (en) * 2005-03-21 2007-04-25 南开大学 Herbicide composition of sulfonylurea compound water-soluble salt
CN105439970A (en) * 2015-10-16 2016-03-30 南开大学 Discovery and application of sulfonylurea novel structure with controllable soil degradation speed
CN108207983A (en) * 2016-12-22 2018-06-29 江苏龙灯化学有限公司 A kind of Synergistic herbicidal composition

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1080116A (en) * 1993-02-27 1994-01-05 南开大学 Control of maize field weed composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1080116A (en) * 1993-02-27 1994-01-05 南开大学 Control of maize field weed composition

Also Published As

Publication number Publication date
CN1106393A (en) 1995-08-09

Similar Documents

Publication Publication Date Title
UA123211C2 (en) Halogen-substituted phenoxyphenylamidines and the use thereof as fungicides
EP0878129B1 (en) Composition comprising chitosan for enhancing resistance to plant diseases
BG60302B2 (en) Herbicide and a method for unwanted vegetation control
SU1271371A3 (en) Method of producing derivatives of diphenyl ether
US3672866A (en) Use of n-(sec-butyl)-4-(t-butyl)-2,6-dinitroaniline as a selective herbicide
CA1224791B (en) Derivative of 1,2,4-triazole, process for preparing the same and herbicide containing the same
CN1038679C (en) Sulfonylurea compound herbicide
HU176545B (en) Fungicide preparation containing guanidated aliphatic polyamines and process for preparing the guanidated aliphatic polynmines applied as active materials thereof
EP0027111A1 (en) Lepidoptericidal isothiourea compounds
CN102093344A (en) N-substituted acetoxyl pyrazole compound containing thiazolidinethione or oxazolidinone, and preparation method and application thereof
US4226615A (en) Plant growth regulators
US3991116A (en) 4-Tert-butyl-N-sec-butyl-2,6-dinitroaniline
HU206433B (en) Growth-controlling synergetic compositions containing quaternairy ammoni um-salt and imidazoline derivative as active component and process for utilizing them
CN100412078C (en) Fluorine substituted phenoxy acetyl oxide alkyl phosphonate ester and salt with weeding active and preparation process thereof
RU2808337C1 (en) USE of (E)-N-(HYDROXYMETHYL)-3-(4-CHLOROPHENYL)-2-CYANOPROP-2-ENTIOAMIDE AS 2,4-D ANTIDOTE IN SUNFLOWER
Das et al. Preparation of some novel phosphonamidates, their phytotoxicity and herbicidal properties
RU2798590C1 (en) Substituted 3-(3-amino-4,6-dimethylthieno[2,3-b]pyridin-2-yl)-3-oxo-n-phenylpropanamides as 2,4-d antidotes for sunflower
RU2810585C1 (en) Use of 2-chloro-n-(4-cyano-3-cyanomethyl-1h-pyrazol-5-yl)acetamide as a 2,4-d antidote in sunflower
RU2798592C1 (en) 5-(3-amino-3-oxo-2-thiocarbamoyl-1-(furan-2-yl)propyl)-2,2-dimethyl-4-oxo-4h-1,3-dioxin-6-triethylammonium polate as an antidote 2,4-d for sunflower
RU2812590C1 (en) 6,6'-[methylenedi(imino)]bis(4-methyl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile) as a 2,4-d antidote on sunflower
US4932995A (en) Process for increasing rice crop yield
RU2799422C1 (en) Substituted esters of 6-amino-7-phenyl-3-(phenylimino)-4,7-dihydro-3h-[1,2]dithiolo[3,4-b]pyridine-5-carboxylic acid as antidotes 2,4- d in sunflower
RU2287273C1 (en) Using n-substituted 3-cyano-4,6-dimethyl-5-chloropyridyl-2-sulfonylamides as antidotes of herbicide 2,4-dichlorophenoxyacetic acid in sunflower
US4742167A (en) Biologically active N-pyrazinyl-haloacetamides
RU2719515C2 (en) N, n'-tetramethyl methylene diamine oxalic-effective water-soluble agent with growth-stimulating and fungicidal activity

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C53 Correction of patent for invention or patent application
CB03 Change of inventor or designer information

Inventor after: Li Zhengming

Inventor after: Jia Guofeng

Inventor after: Wang Lingxiu

Inventor after: Wang Suhua

Inventor after: Fan Chuanwen

Inventor after: Yang Zhao

Inventor before: Li Zhengming

Inventor before: Jia Guofeng

Inventor before: Wang Lingxiu

Inventor before: Fan Chuanwen

Inventor before: Yang Zhao

COR Change of bibliographic data

Free format text: CORRECT: INVENTOR; FROM: LI ZHENGMING; JIA GUOFENG; WANG LINGXIU; FAN ZHUANWEN; YANG TO: LI ZHENGMING; JIA GUOFENG; WANG LINGXIU; WANG SUHUA; FAN ZHUANWEN; YANG

C17 Cessation of patent right
CX01 Expiry of patent term

Expiration termination date: 20141207

Granted publication date: 19980610