CS261442B1 - - (2-alkylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazoles - Google Patents
- (2-alkylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazoles Download PDFInfo
- Publication number
- CS261442B1 CS261442B1 CS875535A CS553587A CS261442B1 CS 261442 B1 CS261442 B1 CS 261442B1 CS 875535 A CS875535 A CS 875535A CS 553587 A CS553587 A CS 553587A CS 261442 B1 CS261442 B1 CS 261442B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- dichlorophenyl
- alkylthio
- ethanol
- tetrazole
- mole
- Prior art date
Links
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
l-(2-alkyltio-6-benzoatizolylamínometyl)- -5-(3,4-dichlórfenyl)-l,2,3,4-tetrazolyl, kde alkyl znamená metyl, n-propyl, izopropyl, n- -butyl, sek-butyl, alebo n-pentyl. Syntéza uvedených zlúčenín sa uskutočňuje reakciou 5-(3,4-dichlórfenyl)-l,2,3,4-tetrazolu s formaldehydom a 2-alkyltlo-6-amínobenzotiazolmi v etanolu prí 35 až 40 °C. Zlúčeniny sú protikvasinkovo účinné, možno ich použí vat ako účinná zložku protikvasinkových prípravkov alebo ako medziprodukt pre dal šie syntézy.1-(2-alkylthio-6-benzoatoisolylaminomethyl)-5-(3,4-dichlorophenyl)-1,2,3,4-tetrazolyl, where alkyl means methyl, n-propyl, isopropyl, n-butyl, sec-butyl, or n-pentyl. The synthesis of the above compounds is carried out by the reaction of 5-(3,4-dichlorophenyl)-1,2,3,4-tetrazole with formaldehyde and 2-alkylthio-6-aminobenzothiazoles in ethanol at 35 to 40 °C. The compounds are anti-yeast active, they can be used as an active ingredient of anti-yeast preparations or as an intermediate for further syntheses.
Description
261442
Predmetom vynálezu sú l-(2-alkyltio-6--benzotiazolylamínometyl)-5-(3,4-dichlórfe-nyl)-1,2,3,4-tetrazoly. Z uvedeného radu zlú-čenín bol doteraz známy len etylový a izo-butylový derivát [Holbová, E. a Uher, M,,Chem. Zvěsti 36 254 (1982)].
Teraz sme zistili, že doteraz neznáme zlú-čeniny vzorca
kde R znamená metyl, n-propyl, izopropyl,n-butyl, sek-butyl, alebo n-pentyl, sú proti-kvasinkovo účinné. Súčasne bol zistený sposob přípravy uve-dených zlúčenín reakciou 5-(3,4-chlórfe-nyl)-l,2,3,4-tetrazolu s formaldehydom a 2--alkyltio-6-amínobenzotiazolu v etanole, pri35 až 40 °C.
Nasledujúce příklady bližšie osvetíujú, alenijako neobmedzujú přípravu a vlastnostizlúčenín podl'a vynálezu. Příklad 1 Příprava 1- (2-metyltio-6-benzotiazolylamíno-metyl) -5- (3,4-dichlórf enyl) -1,2,3,4-tetrazolu
Suspenzia 2-metyltio-6-amínobenzotiazolu(1,96 g, 0,01 mólu) a 5-(3,4-dichlórf enyl)--1,2,3,4-tetrazolu (2,15 g, 0,01 mólu] v eta-nole (60 cm3) sa za miešania zohreje na tep-lotu 35 až 40 °C. Za tejto teploty sa do roz-toku přidá 30 %-ný vodný roztok formal-dehydu (2 cm3, 0,02 mólu). Za miešaniazačne z roztoku krystalizovat: produkt reak-cie bielej farby. Po 20 minútach sa odsajea na filtri sa po kvapkách premyje etano-lom (15 cm3). Výťažok činil 3,59 g (85 %).Teplota topenia: 157 až 159 °C.
Pre C16H12S2N6CI2 (423,35) vypočítané °/o: C 45,39, I-I 2,85, N 19,85, S 15, 14, Cl 16,74zistené %: C 45,60, H 2,90, N 19,84, S 15,06, Cl 16,92 Příklad 2 Příprava l-(2-n-propyltio-6-benzotiazolylamí-nometyl) -5- (3,4-dichlórf enyl) -1,2,3,4-tetra-zolu
Suspenzia 2-n-propyltio-6-amínobenzotia-zolu (1,12 g, 0,005 mólu) a 5-(3,4-dichlór-fenyl)-1,2,3,4-tetrazolu (1,07 g, 0,005 mólu)v etanole (20 cm3) sa za miešania zohrejena teplotu 35 až 37 °C. Za tejto teploty sado roztoku přidá 30 %-ný vodný roztok for-maldehydu (1 cm3, 0,01 mólu). Za miešaniazačne po 2 minútach krystalizovat: produktreakcie bielej farby. Tento sa po 20 minú-tach odsaje a na filtri sa premyje etanolom(10 cm3). Výťažok činil 1,55 g (68,8 %).Teplota topenia: 131 až 132 °C.
Pre C18H16N6S2CI2 (451,38) vypočítané %: C 47,89, H 3,57, N 18,61, S 14,20, Cl 15,70zistené %: C 47,96, H 3,21, N 18,47, S 14,09, Cl 15,77Příklad 3 Příprava 1- (2-izopropyltio-6-benzotiazolyl-amínometyl) -5- (3,4-dichlórf enyl) -1,2,3,4--tetrazolu
Suspenzia 2-izopropyltio-6-araínobenzoiia-zolu (2,24 g, 0,01 mólu) a 5-(3,4-dichlórfe-nyl)-1,2,3,4-tetrazolu (2,15 g, 0,01 mólu) vetanole (40 cm3) sa za miešania zohreje nateplotu 35 až 37 °C. Za tejto teploty sa doroztoku přidá 30 %-ný vodný roztok for-maldehydu (2 cm3, 0,02 mólu). Po 4 minú-tach miešania začne z roztoku kryštalizovaťprodukt reakcie v tvare drobných kryštá-lov. Tento sa za odsávania premýva etanolom(15 cm3). Výťažok činil 3,20 g (70,9 %).Teplota topenia: 138 až 140 °C.
Pre Ct3HlsN6S2Cl2 (451,38) vypočítané %: C 47,89, H 3,57, N 18,61, S 14,20, Cl 15,70zistené %: C 47,65, H 3,44, N 18,18, S 14,34, Cl 15,74 Příklad 4 Příprava 1- (2-.n-butyltio-6-benzotiazolylamí-nometyl )-5-( 3,4-dichlórf enyl )-1,2,3,4--tetrazolu
Suspenzia 2-n-butyltio-6-amínobenzotia-zolu (1,19 g, 0,005 mólu) a 5-(3,4-dichlór-fenyl)-1,2,3,4-tetrazolu (1,07 g, 0,005 mólu)v etanole (20 cm3) sa za miešania zohrejena teplotu 35 až 38 °C. Za tejto teploty sado roztoku přidá 30 %-ný vodný roztok for-maldehydu (1 cm3, 0,01 mólu). Za miešaniazačne už po 1 minúte kryštalizovať pro-dukt reakcie bielej farby, který sa vo vač-šom množstve etanolu rozpusta. Preto saza odsávanie premýva na filtri po kvapkáchetanolom (7 cm3). Výťažok činil 1,62 g (70 percent).
Teplota topenia: 123 až 125 °C,
Pre C10H18N6S2CI2 (465,43) vypočítané %: C 49,03, H 3,89, N 18,05, S 13,77, Cl 15,23zistené %: C 48,69, H 3,79, N 18,06, S 13,86, Cl 15,12 Příklad 5 Příprava 1- (2-sek-butyltio-6-benzotiazolyl-amínometyl) -5- (3,4-dichlórf enyl )-1,2,3,4--tetrazolu
Suspenzia 2-sek-butyltio-6-amínobenzo-tiazolu (2,15 g, 0,01 molu) a 5-(3,4-dichlór-v etanole (40 cm3) sa za miešanla zohrejena teplotu 35 až 37 °C. Za tejto teploty safenyl )-1,2,3,4-tetrazolu (2,15 g, 0,01 molu)do' roztoku přidá 30 %-ný vodný roztok for-maldehydu (2 cm3, 0,02 mólu). Po niekol'-kých minutách miešania začne z roztokukryštalovať produkt reakcie, ktorý sa po15 až 20 minútach odsaje a na filtri sa pre-myje etanolom (10 cm3). Výlažok činil 3,62 g(78%).
Teplota topenia: 128 až 130 °C.
Pre C19HWN6S2CI2 (465,41) vypočítané %: C 49,03, H 3,89, N 18,05, S 13,77, Cl 15,23zistené %: C 48,58, H 3,80, N 17,92, S 13,59, Cl 15,29 Příklad 6 Příprava 1 - f 2-n-pentyltio-6~beuzotiazolyl-amínometyl )-5-( 3,4-dichlórf enyl )-1,2,3,4--tetrazolu
Suspenzia 2-n-pentyltio-6-amínobenzotia-zolu (1,26 g, 0,005 mólu) a 5-(3,4-dichlór-fenyl)-1,2,3,4-tetrazolu (1,07 g, 0,005-mólu)v etanole (20 cm5) sa za miešania zohrejena 35 až 37 °C. Za tejto- teploty sa ku zrnesipřidá 30 %-ný vodný roztok formaldehydu(1 cm3, 0,01 mólu). Mliečne zakalený roz-tok sa vyčíri a skoro okamžité ipo tom začnez roztoku krystalizovat produkt reakcie bie-lej farby. Po- 20 minútach sa krystalická lát-ka odsaje a na filtri sa premyje po kvap-kách etanolom (10 cm3). Výťažok činil1,69 g (70,8 %).
Teplota topenia: 122 až 123 °C.
Pre C.žoH2tiN6S2Cl2 vypočítané %: C 50,10, H 4,20, N 17,52, S 13,37, Cl 14,78zistené %: C 50,06, H 3,84, N 17,54, S 13,35, Cl 14,74 Příklad 7
Protikvasinková účinnost zlúčenín pódia vynálezu (,10“6 mol. dm-3) v porovnaní s ú-činnostou 2-merkaptobenzotiazolu (2-MBT)
Zlúčenina podl'a Candida albicans Saccharomyces cerevisae příkladu EDso ED100 EDso ED100 1 46 380 290 720 2 60 200 350 1000 3 65 200 410 760! 4 22 100 87 190 5 72 180 100 210' 6 15 100 23 51 2-MBT 360 1000 520 >1000 EDso, ED100 = koncentrácia látky, ktorá brzdí rozmnožovanie kvasinky právě na 50 %,resp. 100 % oproti kontrole; > = nepostačuje ani uvedená koucentoácia.
Pre stanovenie protikvasinkovej účinnostisa použila tekutá syntetická póda s vitamín-mi (5 cm3 v skúmavkách), kultivácia static-ká, teplota 28 °C. Látky rozpuštěné v dime-tylsulfoxide sa dávkovali do nódy, potominokulum. Rozmnožovanie kvasiniek sa sle-dovalo turbidimetricky a zo zostrojenýchrastových krivlek sa matematicko-grafickýravýpočtem získali hodnoty EDso a EDino. Tie-to sa u Candida albicans vzťahujú na 6. deňkultivácie, u Saccharomyces cerevisiae na4. deň, kedy kontroly dosiahly maximálnyrast. Významný je fakt, že všetky zlúčeniny po-dlá vynálezu sú účinneišie proti kvasinkámCandida albicans a Saccharomyces cerevi-siae ako 2-merk.aptobenzotiazol. Zvlášť vý-znamný je fakt, že zlúčenina podlá příkladu6 prejavila účinnost proti Candida albicansuž v koncentrácii 15 .10~6 mól. dm-3 a pro-ti Saccharomyces cerevisiae už v koncen-trácii 23.10_6 mól. dm-3, pričom totálně in-hibuje rozmnožovanie Candida albicans vkoncentrácii 100.10-6 mól. dm-3 a rozmno-žovanie Saccharomyces cerevisiae v kon-centrácii 51.10-6 mól. dm-3.
261442
The present invention provides 1- (2-alkylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazoles. To date, only the ethyl and isobutyl derivatives have been known [Holb, E. and Uher, M, Chem. Rumors 36,254 (1982)].
We have now found that hitherto unknown compounds of the formula
wherein R is methyl, n-propyl, isopropyl, n-butyl, sec-butyl, or n-pentyl, are anti-yeast active. At the same time, a method of preparing said compounds was found by reacting 5- (3,4-chlorophenyl) -1,2,3,4-tetrazole with formaldehyde and 2-alkylthio-6-aminobenzothiazole in ethanol at 35-40 ° C. .
The following examples illustrate, but do not limit, the preparation and properties of the compounds of the invention. Example 1 Preparation of 1- (2-methylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazole
A suspension of 2-methylthio-6-aminobenzothiazole (1.96 g, 0.01 mol) and 5- (3,4-dichlorophenyl) -1,2,3,4-tetrazole (2.15 g, 0.01) mole] in ethanol (60 cm 3) was heated to 35-40 ° C with stirring, at which temperature 30% aqueous formaldehyde solution (2 cm 3, 0.02 mole) was added to the solution. Crystallize from the solution under stirring: the white reaction product is suctioned off on the filter after 20 minutes, washed with ethanol (15 cm 3) dropwise, yield 3.59 g (85%). 159 ° C.
For C16H12S2N6Cl2 (423.35) calculated: C, 45.39; H, 2.85; N, 19.85; S, 15.14; Cl, 16.74 Found: C, 45.60; , 84, S 15.06, Cl 16.92 Example 2 Preparation of 1- (2-n-propylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4- tetra-zol
A suspension of 2-n-propylthio-6-aminobenzothiazole (1.12 g, 0.005 mol) and 5- (3,4-dichlorophenyl) -1,2,3,4-tetrazole (1.07 g, 0.005) mole) in ethanol (20 cm 3) was heated to 35-37 ° C with stirring. A 30% aqueous solution of formaldehyde (1 cm 3, 0.01 mole) is added at this temperature to the solution. With stirring, it crystallizes after 2 minutes: white product reactions. This was filtered off with suction after 20 minutes and washed with ethanol (10 cm 3). The yield was 1.55 g (68.8%) Melting point 131-132 ° C.
For C18H16N6S2Cl2 (451.38) calculated% C, 47.89; H, 3.57; N, 18.61; S, 14.20; Cl, 15.70 Found: C, 47.96; H, 3.21; , S 14.09, Cl 15.77 Example 3 Preparation of 1- (2-isopropylthio-6-benzothiazolyl-aminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazole
A suspension of 2-isopropylthio-6-araobenzothiazole (2.24 g, 0.01 mole) and 5- (3,4-dichlorophenyl) -1,2,3,4-tetrazole (2.15 g, 0%). Mole (40 cm @ 3) was heated to 35 DEG-37 DEG C. with stirring. At this temperature, a 30% aqueous solution of formaldehyde (2 cm 3, 0.02 mol) was added to the solution. After stirring for 4 minutes, the small-crystal product of the reaction starts to crystallize from the solution. This is washed with suction with ethanol (15 cm 3) under suction. The yield was 3.20 g (70.9%): mp 138-140 ° C.
H, 3.57; N, 18.61; S, 14.20; Cl, 15.7. Found: C, 47.65; H, 3.44; N, 18.18. , S 14.34, Cl 15.74 Example 4 Preparation of 1- (2-n-butylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-- tetrazole
A suspension of 2-n-butylthio-6-aminobenzothiazole (1.19 g, 0.005 mol) and 5- (3,4-dichlorophenyl) -1,2,3,4-tetrazole (1.07 g, 0.005) mole) in ethanol (20 cm 3) was heated to 35-38 ° C with stirring. A 30% aqueous solution of formaldehyde (1 cm 3, 0.01 mole) is added at this temperature to the solution. With stirring for 1 minute, the product of the white reaction crystallized, which was dissolved in all of the ethanol. Therefore, the soot is washed on the filter by dropwise addition of ethanol (7 cm 3). The yield was 1.62 g (70 percent).
Melting point: 123-125 ° C
For C10H18N6S2Cl2 (465.43) calculated% C 49.03, H 3.89, N 18.05, S 13.77, Cl 15.23 found% C, 48.69; H, 3.79; N, 18.06. , S 13.86, Cl 15.12 Example 5 Preparation of 1- (2-sec-butylthio-6-benzothiazolyl-aminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazole
A suspension of 2-sec-butylthio-6-aminobenzothiazole (2.15 g, 0.01 mol) and 5- (3,4-dichloro-ethanol (40 cm 3)) was heated to 35-37 ° C with stirring. At this temperature, safenyl) -1,2,3,4-tetrazole (2.15 g, 0.01 mol) was added to a 30% aqueous solution of formaldehyde (2 cm 3, 0.02 mol). After several minutes of stirring, the reaction product crystallizes out of the solution, which is suctioned off after 15 to 20 minutes and washed with ethanol (10 cm 3) on the filter. The yield was 3.62 g (78%).
Melting point: 128-130 ° C.
For C19H19N6S2Cl2 (465.41) calculated% C 49.03, H 3.89, N 18.05, S 13.77, Cl 15.23, found% C, 48.58; H, 3.80; N, 17.92. , S 13.59, Cl 15.29 Example 6 Preparation of 1- (2-n-pentylthio-6-beuzothiazolyl-aminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazole
A suspension of 2-n-pentylthio-6-aminobenzothiazole (1.26 g, 0.005 mol) and 5- (3,4-dichlorophenyl) -1,2,3,4-tetrazole (1.07 g, 0.005) mole) in ethanol (20 cm < 5 >) was heated with stirring at 35-37 [deg.] C. At this temperature, a 30% aqueous formaldehyde solution (1 cm 3, 0.01 mole) is added. The milky solution is clarified and the product of the white color reaction begins to crystallize almost immediately after the solution. After 20 minutes, the crystalline material is filtered off with suction and washed on the filter with ethanol (10 cm 3). The yield was 1.69 g (70.8%).
Melting point: 122-123 ° C.
% C, 50.10; H, 4.20; N, 17.52; S, 13.37; Cl, 14.78 Found: C, 50.06; H, 3.84; N, 17.54; , 35, Cl 14.74 Example 7
The anti-yeast activity of the compounds of the invention (10 < 6 > mole dm-3) compared to that of 2-mercaptobenzothiazole (2-MBT)
Candida albicans compound Saccharomyces cerevisiae example ED 50 ED100 ED 50 ED100 1 46 380 290 720 2 60 200 350 1000 3 65 200 410 760! 4 22 100 87 190 5 72 180 100 210 '6 15 100 23 51 2-MBT 360 1000 520> 1000 ED50, ED100 = concentration of the substance that inhibits the yeast multiplication to 50%, resp. 100% over control; > = even the mentioned cessation is not sufficient.
To determine the anti-yeast activity, a liquid synthetic vitamin-based stage (5 cm 3 in tubes), a static culture, a temperature of 28 ° C was used. The substances dissolved in dimethylsulphoxide were fed to the node, after the inoculum. The yeast proliferation was monitored turbidimetrically, and ED 50 and ED 50 values were obtained from mathematical-graphic calculations from the constructed curves. These are related to 6th day of cultivation in Candida albicans, in Saccharomyces cerevisiae to 4. the day the controls reached maximum growth. Of note is that all compounds of the invention are more effective against yeast Candida albicans and Saccharomyces cerevisiae than 2-mercaptobenzothiazole. Of particular importance is the fact that the compound of Example 6 exhibited activity against Candida albicansus at a concentration of 15.10-6 moles. dm-3 and for Saccharomyces cerevisiae already at the concentration of 23.10-6 mole. dm-3, whilst totally inhibiting the propagation of Candida albicans at a concentration of 100.10-6 moles. dm-3 and multiplication of Saccharomyces cerevisiae at a concentration of 51.10-6 mol. dm-3.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS875535A CS261442B1 (en) | 1987-07-22 | 1987-07-22 | - (2-alkylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazoles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS875535A CS261442B1 (en) | 1987-07-22 | 1987-07-22 | - (2-alkylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazoles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS553587A1 CS553587A1 (en) | 1988-06-15 |
| CS261442B1 true CS261442B1 (en) | 1989-02-10 |
Family
ID=5400433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS875535A CS261442B1 (en) | 1987-07-22 | 1987-07-22 | - (2-alkylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazoles |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS261442B1 (en) |
-
1987
- 1987-07-22 CS CS875535A patent/CS261442B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS553587A1 (en) | 1988-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4208521A (en) | Process for the preparation of imidazo[2,1-b]quinazolinones | |
| US3755350A (en) | Substituted 3-phenyl hydantoins useful as fungicides | |
| US4891443A (en) | N,N'-Dicyanocyclopropanecarbamidines and a process for their preparation | |
| US4315016A (en) | Heterocyclic triazolylethyl ether compounds and their use as pesticides | |
| SU567405A3 (en) | Method of preparation of heterocyclic compositions | |
| KR20110066201A (en) | Synthesis method of halogenated cyclic compound | |
| US4775762A (en) | Novel (1H-1,2,3-triazol-1-yl)pyridines | |
| US4238497A (en) | Imidazoline derivatives, salts thereof and their use as pesticides | |
| US3701784A (en) | 1,2,4-4h-triazole derivatives | |
| NO323314B1 (en) | Process for the preparation of pyrimidone derivatives with antifungal activity | |
| US4226876A (en) | Arthropodicidal imidazoline derivatives | |
| JPS62258385A (en) | Herbicide | |
| US4394380A (en) | 2-(2-Alkoxyalkyl)-1,2,4-triazole compounds and their use as fungicides | |
| PL117998B1 (en) | Process for preparing novel 2-nitroaminopyrimidones | |
| EP0455300B1 (en) | Barbituric acid derivatives having insecticidal activity | |
| CS261442B1 (en) | - (2-alkylthio-6-benzothiazolylaminomethyl) -5- (3,4-dichlorophenyl) -1,2,3,4-tetrazoles | |
| US4574155A (en) | Process for preparing 2-hydrazino-1,3-diazacycloalk-2-ene hydrohalides | |
| US4381395A (en) | Process for preparing an imidazole derivative | |
| CA1108620A (en) | Imidazolines | |
| US5359067A (en) | Process for the preparation of 5-substituted cytosines and other 4,5-disubstituted pyrimidin-2(1H)-ones, and intermediates arising in the course of this | |
| GB1592649A (en) | Imidazoline derivatives and their use as pesticides | |
| EP0019308B1 (en) | Tetrazole derivatives and a process for their preparation | |
| US5561230A (en) | Process for the preparation of aminotriazine derivatives | |
| EP0034250A1 (en) | Preparation of 5,5-dimethyl-2-hydrazino-1,4,5,6-tetrahydropyrimidine hydrohalide | |
| US4067720A (en) | Certain 2-carbamoyl-1,2,4-thiadiazole-3-one herbicides |