WO1989002595A1 - Bioassay analysis of sulfonylurea herbicide soil - Google Patents

Bioassay analysis of sulfonylurea herbicide soil Download PDF

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Publication number
WO1989002595A1
WO1989002595A1 PCT/US1988/002668 US8802668W WO8902595A1 WO 1989002595 A1 WO1989002595 A1 WO 1989002595A1 US 8802668 W US8802668 W US 8802668W WO 8902595 A1 WO8902595 A1 WO 8902595A1
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Prior art keywords
amino
sulfonylurea
methyl
carbonyl
sulfonyl
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PCT/US1988/002668
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French (fr)
Inventor
Charles John Peter
Original Assignee
E.I. Du Pont De Nemours And Company
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Publication of WO1989002595A1 publication Critical patent/WO1989002595A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/24—Earth materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/5005—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving human or animal cells

Definitions

  • This invention relates to the accurate measurement of the presence of sulfonylurea herbicide residuals in soil by making use of the effects of such sulfonylureas on lentil plants.
  • Fully controlled conditions are necessary to accurately make such measurements and such conditions are critical to the instant invention.
  • the soil temperature in which the lentils are planted must be maintained at about 15 to 25oC.
  • the measurements of the effects must be made at temperatures within about 1 to 2°C for consistency. Otherwise, there will be variation which will mask the affect of the damage itself.
  • the measurements themselves are also critical and must be taken as follows.
  • Measurements are confined to the extent of damage to the secondary and tertiary root growth of the plant.
  • the measurements are usually taken visually by ones skilled in the art, but other means for taking such measurements would be readily apparent and they include well-known computerized techniques.
  • the damage itself may be in more than one form. For instance, one may see stunting of the secondary or tertiary root growth and in some more extreme cases, there would be complete absence of the secondary and tertiary root growth which would serve as a warning that considerable residual sulfonylurea is present.
  • fewer secondary and tertiary roots will form, thereby reflecting the presence of damage caused by the presence of the sulfonylurea residual.
  • sulfonylurea herbicide one generally means the following compounds:
  • Q is O, S, S(O), S(O) 2 or C(O);
  • R 1 is F, Cl, Br, NO 2 , C 1 -C 3 alkyl, cyclopropyl,
  • R 2 is H, F, Cl, Br. NO 2 , CN, C 1 -C 3 alkyl, CF 3 , C 1 -C 4 alkoxy, OCF 2 H, C 2 -C 3 haloalkoxy or C 1 -C 4 alkylthio;
  • R 3 is NO 2 , CO 2 CH 3 , CO 2 CH 2 CH 3 , S(O) 2 N(CH 3 ) 2 ,
  • R 4 is H, F, Cl, Br, C 1 -C 3 alkyl, C 1 -C 2 haloalkyl,
  • R 5 is F, Cl, Br, C 1 -C 3 alkyl, C 1 -C 2 haloalkyl,
  • R 7 is F, Cl, Br, C 1 -C 3 alkyl, C 1 -C 2 alkoxy, CF 3 , C 2 -C 3 haloalkenylcut CO 2 R a , C(O)NR b R c , S(O) 2 NR d R e ,
  • R 8 is H, F, Cl or CH 3 ;
  • R 9 is H or C 1 -C 2 alkyl;
  • R 10 is F, Cl, Br, C 1 -C 3 alkyl, C 2 -C 3 haloalkenyl, C 1 -C 2 alkoxy, OCF 2 H, NO 2 , CO 2 R a , C(O)NR b R c ,
  • R 11 is H, Cl, F. Br, C 1 -C 3 alkyl or C 1 -C 2 alkoxy;
  • R 12 is H or C 1 -C 2 alkyl
  • R 13 is H or CH 3 ;
  • R 14 is H, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkoxyalkyl or C 4 -C 6 cycloalkylalkyl;
  • R 15 is H, F, Cl, Br, CH 3 , OCH 3 or SCH 3 ; n is 0, 1 or 2; R a is C 1 -C 3 alkyl optionally substituted by halogen, C 1 -C 2 alkoxy or CN, cyclopropylmethyl, allyl or propargyl;
  • R b is H, C 1 -C 3 alkyl or C 1 -C 2 alkoxy
  • R c is C 1 -C 2 alkyl
  • R d is H, C 1 -C 4 alkyl, C 1 -C 2 alkoxy, allyl or cyclopropyl
  • R e is H or C 1 -C 2 alkyl
  • R f is C 1 -C 3 alkyl, C 1 -C 2 haloalkyl, allyl or propargyl;
  • R g is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 3 -C 5 alkyl;
  • R h is H or CH 3 ;
  • R i is H or CH 3 ;
  • R j is H, CH 3 or CH 2 CH 3 ;
  • R k is H. CH 3 , CH 2 CH 3 , OCH 3 , OCH 2 CH 3 , SCH 3 or
  • R m is H. CH 3 or CH 2 CH 3 ;
  • R n is H or CH 3 ;
  • X is CH 3 , OCH 3 , OC 2 H 5 , OCF 2 H or Cl; Y is C 1 -C 2 alkyl, C 1 -C 2 alkoxy, OCF 2 H, OCH 2 CF 3 , NHCH 3 or N(CH 3 ) 2 ; and Z is CH or N provided that
  • R 2 when J is J-1 and R 2 is CN, C 2 -C 4 alkoxy, OCF 2 H, C 2 -C 3 haloalkoxy or C 1 -C 4 alkylthio, then R 2 is restricted to the position para to the R 1 substituent on the phenyl ring and R 1 is CO 2 R a ;
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl”, denotes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl isomers.
  • Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butyloxy isomers.
  • Alkenyl denotes straight chain or branched alkenes, e.g., vinyl, 1-propenyl, 2-propenyl and 3-propenyl.
  • Alkylthio denotes methylthio, ethylthio and the different propylthio and butylthio isomers.
  • Cycloalkyl denotes cyclopropyl. cyclobutyl and cyclopentyl.
  • C 1 -C 6 cycloalkylalkyl means cyclopropylmethyl through cyclopropylpropyl or cyclopentylmethyl.
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl” said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH 2 CH 2 F, CF 2 CF 3 and CH 2 CHFCl.
  • haloalkenyl is defined analogously to the term “haloalkyl”.
  • C i -C j The total number of carbon atoms in a substituent group is indicated by the C i -C j prefix where i and j are numbers from 1 to 6.
  • C 1 -C 3 alkylthio would designate methylthio through propylthio
  • C 2 alkoxyalkoxy would designate OCH 2 OCH 3
  • C 3 alkoxyalkoxy would designate the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 3 carbon atoms, examples including OCH 2 OCH 2 CH 3 ,
  • C 2 alkoxyalkyl would designate CH 2 OCH 3 and C 4 alkoxyalkyl would designate the various isomers of an alkyl group substituted with an alkoxy group containing a total of 4 carbon atoms, such as
  • non-sulfonyl ⁇ reas may be discovered by the technique of the instant invention.
  • Such non-sulfonylureas would include the following:
  • Ar is R a is C 1 -C 4 alkyl , F , Cl , Br , I , NO 2 , S (O) p R d ,
  • R b is H, F, Cl, Br, I, C 1 -C 4 alkyl or COOR e ;
  • R c is H, C 1 -C 4 alkyl, F, Cl, Br, I, CH 2 OR d , phenyl, NO 2 or COOR e ;
  • R d is C 1 -C 4 alkyl
  • R e is C 1 -C 4 alkyl, C 1 -C 4 alkenyl, C 1 -C 4 alkynyl, or 2-ethoxyethyl
  • V is H, C 1 -C 3 alkyl, allyl, propargyl, benzyl or C 1 -C 3 alkcylcarbonyl;
  • X 1 , Y 1 , and Z 1 are independently H, F , Cl , Br , I , C 1 -C 4 alkyl , C 1 -C 2 alkylthio or C 1 -C 4 alkoxy; and p is O, 1 or 2.
  • R f is C 1 -C 4 alkyl
  • R g is C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl
  • a 1 is COOR i , CH 2 OH or CHO
  • R i is H; C 1 -C 12 alkyl optionally substituted by C 1 -C 3 alkyl, C 3 -C 6 cycloalkyl or phenyl; C 3 -C 5 alkenyl optionally substituted by phenyl or 1-2 C 1 -C 3 alkyl, F, Cl, Br or I; or C 3 -C 5 alkynyl optionally substituted by phenyl or 1-2 C 1 -C 3 alkyl, F, Cl, Br or I; B is H; C(O)C 1 -C 6 alkyl or C(O)phenyl optionally substituted by Cl, NO or OCH 3 ;
  • X 2 is H, F, Cl, Br, I, OH or CH 3 ;
  • Y 2 and Z 2 are independently H, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, F, Cl, Br, I, phenyl, NO 2 , CN, CF 3 or SO 2 CH 3 ;
  • X 3 is H, C 1 -C 3 alkyl, F, Cl, Br, I or NO 2 ;
  • L, M, Q and R h are independently H, F, Cl, Br, I, CH 3 , OCH 3 , NO 2 , CF 3 , CN, N(CH 3 ) 2 , NH 2 , SCH 3 or
  • M or Q may be a substituent other than H, F, Cl, Br, I, CH or OCH 3 .
  • the sulfonylurea residual is typically present in the amount of about 10 parts per trillion up to about 100 parts per billion.
  • the amount of sulfonylurea present is not critical to the invention but is relevant only for the effect it would have on subsequent plantings of crops such as sugar beets. Utilizing the instant technique, one skilled in the art would be aware that certain crops which are extremely sensitive to sulfonylureas, such as sugar beets, should not be planted until the residual level is lower.
  • Lentil plants are planted in soil containing sulfonylurea. The planting is typically done with lentil seed but more mature plants could also be utilized depending on the individual situation. Other plant species can also be used. such as sorghum, corn, alfafa. cotton, rice, peas, barley, flax, oats, tomatoes and tobacco.
  • a soil temperature selected from the range of about 15 to 25°C is held constant to within a variation of less than ⁇ 2°C, preferably ⁇ 1°C by any of the numerous methods known to one skilled in the art. For instance, this may be done by heating or cooling the soil or by maintaining the temperature within a given range over the soil itself.
  • the soil temperature should be selected from the range of about 16 to 20°C, most preferably about 18oC.
  • the soil temperature sho ⁇ ld be within 2°C, preferably 1°C of one another, if not, the growth will be variable from measurement to measurement and a useful comparison of the residual damage will not be achieved.
  • the measurements are made three to four weeks after the seeds are planted. By this time, secondary and tertiary root growth has taken place and one will visually observe differences in the secondary and tertiary root growth of plants growing in soil with sulfonylurea residual when compared to plants growing in a controlled environment where there is no such residual.
  • Knowing the extent of the sulfonylurea presence can assist one in determining which crops he intends to plant in the soil.

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Abstract

The presence of residual sulfonylurea herbicide in soil is determined by measuring the effect of such residual on lentils planted in the soil. This must take place at a temperature within 1 or 2°C of one another and the soil must be maintained at about 15 to 25°C for such measurement.

Description

Title BIOASSAY ANALYSIS OF SULFONYLUREA HERBICIDE SOIL BACKGROUND OF THE INVENTION
Many techniques for measuring the presence of residual chemicals are known in the art. Recently, attempts have been made to measure the residue of sulfonylurea herbicides remaining after the growing season has ended. This has proven to be a difficult task because of the high activity of such sulfonylurea herbicides . Thus , mo st conventional techniques would not be effective for measuring sulfonylurea herbicides in soil since they are not sensitive enough to detect minute quantities. This presents a difficult problem because of the potency of the herbicides. Consequently, a method is needed to accurately measure the presence of such residual sulfonylurea herbicides in the soil so that one can then determine which crops can be planted in the soil; certain crops are damaged by small amounts of such sulfonylurea herbicides.
According to this invention, it has unexpectedly been found that such a method is possible to achieve.
SUMMARY OF THE INVENTION This invention relates to the accurate measurement of the presence of sulfonylurea herbicide residuals in soil by making use of the effects of such sulfonylureas on lentil plants. Fully controlled conditions are necessary to accurately make such measurements and such conditions are critical to the instant invention. For instance, the soil temperature in which the lentils are planted must be maintained at about 15 to 25ºC. The measurements of the effects must be made at temperatures within about 1 to 2°C for consistency. Otherwise, there will be variation which will mask the affect of the damage itself. The measurements themselves are also critical and must be taken as follows.
Measurements are confined to the extent of damage to the secondary and tertiary root growth of the plant. The measurements are usually taken visually by ones skilled in the art, but other means for taking such measurements would be readily apparent and they include well-known computerized techniques. The damage itself may be in more than one form. For instance, one may see stunting of the secondary or tertiary root growth and in some more extreme cases, there would be complete absence of the secondary and tertiary root growth which would serve as a warning that considerable residual sulfonylurea is present. In addition, on occasion, fewer secondary and tertiary roots will form, thereby reflecting the presence of damage caused by the presence of the sulfonylurea residual.
Typically, three to four weeks after planting. one will observe the above-mentioned changes in the secondary and tertiary root growth. Needless to say. in individual instances shorter and longer periods may be necessary and they too will be obvious to one skilled in the art.
DETAILED DESCRIPTION OF THE INVENTION By sulfonylurea herbicide, one generally means the following compounds:
Figure imgf000006_0010
Figure imgf000006_0001
Figure imgf000006_0002
Figure imgf000006_0003
Figure imgf000006_0004
Figure imgf000006_0005
Figure imgf000006_0006
Figure imgf000006_0007
Figure imgf000006_0008
Figure imgf000006_0009
Figure imgf000007_0001
Figure imgf000007_0002
Figure imgf000007_0003
Figure imgf000007_0004
Figure imgf000007_0005
Figure imgf000007_0006
Figure imgf000007_0007
Figure imgf000007_0008
Figure imgf000007_0009
Q is O, S, S(O), S(O)2 or C(O);
R1 is F, Cl, Br, NO2 , C1-C3 alkyl, cyclopropyl,
C1-C3 haloalkyl, C2-C3 haloalkehyl, C1-C4 alkoxy, C1-C3 haloalkoxy, C2-C3 alkoxyalkoxy,
CO2Ra, C(O)NRbRc, S(O)2NRdRe, S(O)nRf,
C(O)Rg, CH2CN or L;
R2 is H, F, Cl, Br. NO2, CN, C1-C3 alkyl, CF3, C1-C4 alkoxy, OCF2H, C2-C3 haloalkoxy or C1-C4 alkylthio;
R3 is NO2, CO2CH3, CO2CH2CH3, S(O)2N(CH3)2,
S(O)2CH3 or S(O)2CH2CH3;
R4 is H, F, Cl, Br, C1-C3 alkyl, C1-C2 haloalkyl,
C2-C3 haloalkenyl, C1-C2 alkoxy, NO2, CO2Ra,
C(O)NRbRc, S(O)2NRdRe, S(O)nRf, C(O)Rg or L;
R5 is F, Cl, Br, C1-C3 alkyl, C1-C2 haloalkyl,
C2-C3 haloalkenyl, C1-C2 alkoxy, NO2, CO2Ra, C(O)NRbRc, S(O)2 NRdRe, S(O)nRf, C(O)Rg or L; R6 is H, F, Cl, Br or CH ;
R7 is F, Cl, Br, C1-C3 alkyl, C1-C2 alkoxy, CF3, C2-C3 haloalkenyl„ CO 2Ra, C(O)NRbRc, S(O)2NRdRe,
S(O)nRf, C(O)Rg or L; R8 is H, F, Cl or CH3; R9 is H or C1-C2 alkyl; R10 is F, Cl, Br, C1-C3 alkyl, C2-C3 haloalkenyl, C1-C2 alkoxy, OCF2H, NO2, CO2Ra, C(O)NRbRc,
S(O)2NRdRe, S(O)nRf, C(O)Rg or L;
R11 is H, Cl, F. Br, C1-C3 alkyl or C1-C2 alkoxy;
R12 is H or C1-C2 alkyl;
R13 is H or CH3;
R14 is H, C1-C6 alkyl, C1-C4 haloalkyl, C2-C4 alkoxyalkyl or C4-C6 cycloalkylalkyl;
R15 is H, F, Cl, Br, CH 3, OCH3 or SCH3; n is 0, 1 or 2; Ra is C1-C3 alkyl optionally substituted by halogen, C1-C2 alkoxy or CN, cyclopropylmethyl, allyl or propargyl;
Rb is H, C1-C3 alkyl or C1-C2 alkoxy;
Rc is C1-C2 alkyl; Rd is H, C1-C4 alkyl, C1-C2 alkoxy, allyl or cyclopropyl; Re is H or C1-C2 alkyl;
Rf is C1-C3 alkyl, C1-C2 haloalkyl, allyl or propargyl;
Rg is C1-C4 alkyl, C1-C4 haloalkyl or C3-C5 alkyl;
Figure imgf000009_0001
Figure imgf000009_0002
Figure imgf000009_0003
Figure imgf000009_0004
Figure imgf000009_0005
Figure imgf000009_0007
Figure imgf000009_0006
Figure imgf000009_0009
Figure imgf000009_0008
Figure imgf000009_0011
Figure imgf000009_0012
Figure imgf000009_0010
Figure imgf000009_0013
Figure imgf000009_0014
Figure imgf000009_0015
Figure imgf000009_0016
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
Figure imgf000010_0004
Figure imgf000010_0005
Figure imgf000010_0006
Figure imgf000010_0007
Figure imgf000010_0008
Figure imgf000010_0009
Figure imgf000010_0010
Figure imgf000010_0011
Figure imgf000010_0012
or
Figure imgf000010_0013
Rh is H or CH3 ;
Ri is H or CH3 ;
Rj is H, CH3 or CH2CH3;
Rk is H. CH3, CH2CH3, OCH3, OCH2CH3, SCH3 or
SCH2CH3
Rm is H. CH3 or CH2CH3;
Rn is H or CH3 ;
B is
Figure imgf000010_0014
X is CH3, OCH3, OC2H5, OCF2H or Cl; Y is C1-C2 alkyl, C1-C2 alkoxy, OCF2H, OCH2CF3, NHCH3 or N(CH3)2; and Z is CH or N provided that
(1) when J is J-1 and R2 is NO2, C2-C3 alkyl or CF3, then R2 is restricted to the position para to the R1 substituent on the phenyl ring and R1 is
CO2Ra or S(O)2NRdRe;
(2) when J is J-1 and R2 is CN, C2-C4 alkoxy, OCF2H, C2-C3 haloalkoxy or C1-C4 alkylthio, then R2 is restricted to the position para to the R1 substituent on the phenyl ring and R1 is CO2Ra;
(3) when X is Cl, then Z is CH and Y is C1-C2 alkoxy and
(4) when X or Y is OCF2H, then Z is CH.
In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl", denotes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl isomers.
Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butyloxy isomers.
Alkenyl denotes straight chain or branched alkenes, e.g., vinyl, 1-propenyl, 2-propenyl and 3-propenyl.
Alkylthio denotes methylthio, ethylthio and the different propylthio and butylthio isomers. Cycloalkyl denotes cyclopropyl. cyclobutyl and cyclopentyl. C1-C6 cycloalkylalkyl means cyclopropylmethyl through cyclopropylpropyl or cyclopentylmethyl.
The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH2CH2F, CF2CF3 and CH2CHFCl. The term "haloalkenyl" is defined analogously to the term "haloalkyl".
The total number of carbon atoms in a substituent group is indicated by the Ci-Cj prefix where i and j are numbers from 1 to 6. For example, C1-C3 alkylthio would designate methylthio through propylthio; C2 alkoxyalkoxy would designate OCH2OCH3; C3 alkoxyalkoxy would designate the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 3 carbon atoms, examples including OCH2OCH2CH3,
OCH(CH3)OCH3 and OCH2CH2OCH3; as a further example C2 alkoxyalkyl would designate CH2OCH3 and C4 alkoxyalkyl would designate the various isomers of an alkyl group substituted with an alkoxy group containing a total of 4 carbon atoms, such as
CH2OCH2CH2CH3. CH2OCH(CH3)2, CH2CH2OCH2CH3.
CH2CH2CH2OCH3, CH(CH2CH3)OCH3 and C(CH3)2OCH3.
More specifically, the following individual sulfonylureas would be relevant to the instant invention: • 2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2- yl)amino]carbonyl]benzenesulfonamide (chlorsulfuron);
• 2-(2-chloroethoxy)-N-[[(6-methoxy-4-roethyl-1,3,5- triazin-2-yl)amino]carbonyl]benzenesulfonamide (trisulfuron); • methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin- 2-yl)amino]carbonyl]amino]sulfonyl]benzoate (metsulfuron methyl);
• methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin- 2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate (thiametυron methyl);
• methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5- triazin-2-yl)-N-methylamino]carbonyl]amino]- sulfonyl]benzoate;
• ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)- amino]carbonyl]amino]sulfonyl]benzoate
(chlorimuron ethyl);
• 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]- carbonyl]amino]sulfonyl]-N,N-dimethyl-3- pyridinecarboxamide; • N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]- carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide;
• ethyl 2-[[[[(4,6-dimethoxy-1,3,5-triazin- 2-yl)amino]carbonyl]amino]sulfonyl]-4- (2,2,2-trifluoroethoxy)benzoate;
• methyl 2-[[[[(4-ethoxy-6-methylamino-1,3,5- triazin-2-yl)amino]carbonyl]amino]- sulfonyl]benzoate;
• methyl 2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)- amino]carbonyl]amino]suIfonyl]methyl]benzoate
(benzsulfuron methyl); • ethyl 5-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-methyl-1Hpyrazole-4-carboxylate; and
• methyl 2-[[[[(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate (sulfometuron methyl).
In addition, it is thought that residuals from non-sulfonylυreas may be discovered by the technique of the instant invention. Such non-sulfonylureas would include the following:
TRIAZOLOPYRIMIDINE SULFONAMIDES
wherein
Figure imgf000014_0001
Ar is
Figure imgf000014_0002
Ra is C1-C4 alkyl , F , Cl , Br , I , NO2, S (O)pRd ,
COORe or CF3 ;
Rb is H, F, Cl, Br, I, C1-C4 alkyl or COORe;
Rc is H, C1-C4 alkyl, F, Cl, Br, I, CH2ORd, phenyl, NO2 or COORe;
Rd is C1-C4 alkyl; Re is C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, or 2-ethoxyethyl;
V is H, C1-C3 alkyl, allyl, propargyl, benzyl or C1-C3 alkcylcarbonyl;
X1, Y1 , and Z1 , are independently H, F , Cl , Br , I , C1-C4 alkyl , C1-C2 alkylthio or C1-C4 alkoxy; and p is O, 1 or 2. IMIDAZOLINONES
Figure imgf000015_0001
wherein
Figure imgf000015_0002
Figure imgf000015_0003
Rf is C1-C4 alkyl;
Rg is C1-C4 alkyl or C3-C6 cycloalkyl;
A1 is COORi, CH2OH or CHO;
Ri is H; C1-C12 alkyl optionally substituted by C 1-C3 alkyl, C3-C6 cycloalkyl or phenyl; C3-C5 alkenyl optionally substituted by phenyl or 1-2 C1-C3 alkyl, F, Cl, Br or I; or C3-C5 alkynyl optionally substituted by phenyl or 1-2 C1-C3 alkyl, F, Cl, Br or I; B is H; C(O)C1-C6 alkyl or C(O)phenyl optionally substituted by Cl, NO or OCH3 ;
X2 is H, F, Cl, Br, I, OH or CH3;
Y 2 and Z2 are independently H, C1-C6 alkyl, C1-C6 alkoxy, F, Cl, Br, I, phenyl, NO2, CN, CF3 or SO2CH3; X3 is H, C1-C3 alkyl, F, Cl, Br, I or NO2; and L, M, Q and Rh are independently H, F, Cl, Br, I, CH3, OCH3, NO2, CF3, CN, N(CH3)2, NH2, SCH3 or
SO2CH provided that only one of M or Q may be a substituent other than H, F, Cl, Br, I, CH or OCH3.
More specifically, the following individual imidazolinones would be relevant to the instant invention:
• 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)- 5-oxo-1H-imidazol-2-yl]-3-pyridinecarboxylic acid (imazapyr);
• 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)- 5-oxo-1H-imidazol-2-yl]-5-ethyl-3-pyridinecarboxylic acid (imazethapyr); • 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)- 5-oxo-1H-imidazol-2-yl]-3-quinolinecarboxylic acid (imazaquin);
• methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-y1]-4-methylbenzoate; and
• methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-y1]-5-methylbenzoate.
The sulfonylurea residual is typically present in the amount of about 10 parts per trillion up to about 100 parts per billion. The amount of sulfonylurea present is not critical to the invention but is relevant only for the effect it would have on subsequent plantings of crops such as sugar beets. Utilizing the instant technique, one skilled in the art would be aware that certain crops which are extremely sensitive to sulfonylureas, such as sugar beets, should not be planted until the residual level is lower.
Lentil plants are planted in soil containing sulfonylurea. The planting is typically done with lentil seed but more mature plants could also be utilized depending on the individual situation. Other plant species can also be used. such as sorghum, corn, alfafa. cotton, rice, peas, barley, flax, oats, tomatoes and tobacco. A soil temperature selected from the range of about 15 to 25°C is held constant to within a variation of less than ± 2°C, preferably ± 1°C by any of the numerous methods known to one skilled in the art. For instance, this may be done by heating or cooling the soil or by maintaining the temperature within a given range over the soil itself. Preferably, for greater sensitivity the soil temperature should be selected from the range of about 16 to 20°C, most preferably about 18ºC. For repeated measurements, the soil temperature shoυld be within 2°C, preferably 1°C of one another, if not, the growth will be variable from measurement to measurement and a useful comparison of the residual damage will not be achieved. Typically, the measurements are made three to four weeks after the seeds are planted. By this time, secondary and tertiary root growth has taken place and one will visually observe differences in the secondary and tertiary root growth of plants growing in soil with sulfonylurea residual when compared to plants growing in a controlled environment where there is no such residual. By the extent of the damage, one can get an accurate picture of the presence of the sulfonylurea. That is to say, if there is considerable stunting of the secondary and tertiary root growth, one would be aware of a high sulfonylurea presence relatively speaking. Conversely, little damage would mean a low presence. If in fact secondary and tertiary root growth are inhibited, this would also indicate a high sulfonylurea presence.
Knowing the extent of the sulfonylurea presence can assist one in determining which crops he intends to plant in the soil.
EXAMPLE In a typical situation utilizing the instant invention soil has been exposed to Glean® (chlorsulfuron). A sample of the soil is taken and Chilean lentils planted. After a period of three to four weeks, the lentils have germinated and secondary and tertiary root growth is observed. At the same time as the original planting, a control soil which has not been exposed to sulfonylurea is implanted with lentil seeds. At the end of the period of growth, the damage is compared and one observes considerable stunting of the secondary and tertiary root growth in the soil exposed to the sulfonylurea. The control soil contains plants which have no evidence of secondary and tertiary stunting of the roots. Thus, one is aware that he could not plant sugarbeets at that time in the soil which contains the sulfonylurea (Glean®) residual.

Claims

WHAT IS CLAIMED:
1. A method for measuring the presence of sulfonylureas in soil which comprises planting lentils in a sulfonylurea containing soil, maintalning the temperature in such soil at between about 15 and 25°C with a variation of less than about 2°C and measuring the effect of the sulfonylurea on the second and tertiary root systems of such lentils.
2. The method of Claim 1 wherein several lentil plants are planted and the temperature of the soil for such plantings is maintained within about 1 to 2°C of one another.
3. The method of Claim 1 wherein the lentils are planted from seed.
4. The method of Claim 3 wherein the measurement is taken visually at least three weeks after planting.
5. The method of Claim 1 wherein the sulfonylurea is 2-chloro-N-[[(4-methoxy-6-methyl-1,3,5- triazin-2-yl)amino]carbonyl]benzenesυlfonamide.
6. The method of Claim 1 wherein the sulfonylurea is 2-(2-chloroethoxy)-N-[[(6-methoxy-4-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide.
7. The method of Claim 1 wherein the sulfonylurea is methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate.
8. The method of Claim 1 wherein the sulfonylurea is methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate.
9. The method of Claim 1 wherein the sulfonylurea is methyl-2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]- sulfonyl]benzoate.
10. The method of Claim 1 wherein the sulfonylurea is ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate.
11. The method of Claim 1 wherein the sulfonylurea is 2-[[[[(4,6-diraethoxy-2-pyrimidinyl)-amino]carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridinecarboxamide.
12. The method of Claim 1 wherein the sulfonylurea is N-[[(4,6-dimethoxy-2-pyrimidinyl)-amino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide.
13. The method of Claim 1 wherein the sulfonylurea is ethyl 2-[[[[(4.6-dimethoxy-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-4-(2,2,2-trifluoroethoxy)benzoate.
14. The method of Claim 1 wherein the sulfonylurea is methyl 2-[[[[(4-ethoxy-6-methylamino-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-benzoate.
15. The method of Claim 1 wherein the sulfonylurea is methyl 2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)aminocarbonyl]amino]sulfonyl]methyl]benzoate.
16. The method of Claim 1 wherein the sulfonylurea is ethyl 5-[[[[(4.6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-methyl-1H-pyrazole-4-carboxylate.
17. The method of Claim 1 wherein the sulfonylurea is methyl 2-[[[[(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-benzoate.
PCT/US1988/002668 1987-09-14 1988-08-10 Bioassay analysis of sulfonylurea herbicide soil WO1989002595A1 (en)

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CN106770932A (en) * 2016-11-29 2017-05-31 河南省农业科学院植物保护研究所 A kind of determination methods of the crop rotation safety interval of pedo relict bensulfuron-methyl

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Cited By (6)

* Cited by examiner, † Cited by third party
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EP0476403A1 (en) * 1990-09-18 1992-03-25 BASF Aktiengesellschaft Herbicidal(((1,3,5-triazine-2-yl)aminocarbonyl)aminosulfonyl)benzoeacidesters, method for their preparation and their use
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CN102283232A (en) * 2011-06-25 2011-12-21 陕西韦尔奇作物保护有限公司 Weeding composition containing rimsulfuron and clopyralid
CN106770932A (en) * 2016-11-29 2017-05-31 河南省农业科学院植物保护研究所 A kind of determination methods of the crop rotation safety interval of pedo relict bensulfuron-methyl

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