CA1251219A

CA1251219A - Cyclohexenone derivatives

Info

Publication number: CA1251219A
Application number: CA000418709A
Authority: CA
Inventors: Isao Iwataki; Akira Nakayama; Minoru Kaeriyama; Hisao Ishikawa; Hideo Hosaka; Kenichi Kohara
Original assignee: Nippon Soda Co Ltd
Current assignee: Nippon Soda Co Ltd
Priority date: 1981-12-29
Filing date: 1982-12-29
Publication date: 1989-03-14
Also published as: GB2116544B; IT8249771A0; IT1158045B; GB2116544A; DE3248554A1; DE3248554C2

Abstract

Abstract A compound having the general formula wherein R1 is alkyl having 1-3 carbon atoms;
R2 is alkyl having 1-3 carbon atoms, allyl, propargyl or haloalkenyl; and A is selected from the group consisting of wherein R3 is -SO2R6 group, group or group; R4 is hydrogen, alkyl having 1-6 carbon atoms; phenyl or halophenyl; R5 is alkyl having 1-3 carbon atoms; X is oxygen or sulfur; and n is 0 or 1; wherein R6 is alkyl having 1-6 carbon atoms, haloalkyl having 1-6 carbon atoms or propenyl;
R7 is hydrogen or alkyl having 1-4 carbon atoms; R9 is hydrogen, alkyl having 1-6 carbon atoms, propenyl or methoxy; R9 is hydrogen, alkyl having 1-8 carbon atoms, haloalkyl having 1-3 carbon atoms, alkoxy having 1-6 carbon atoms, propenyl or phenyl substituted with methyl; and Y and Z are oxygen or sulfur;
and a metal salt or a quaternary ammonium salt of a compound defined herein above.

The compound is useful as a herbicide.

Description

~s~z~g S P E C I F I C A T I O N

Cyclohexenone Derivatives The present invention relates to cyclohexenone derivatives, to a process for the preparation thereof and their uses as selectlve herbicides.

According to the present invention, there are provided a compound of the formula OH
A {~ IC=NOR2 o wherein Rl is alkyl having 1-3 carbon atoms;
R2 is alkyl having 1-3 carbon atoms, allyl, propargyl or haloalkenyl; and A is selected from the group consisting of R3NH ~ group, R4X~ ~ group, R5S(O)n ~ group -CN'~R7 Z
wherein R3 is -SO2R6 group, R8 group or -C-R9 group; R4 is hydrogen, alkyl having 1-6 carbon atoms, phenyl or halophenyl; R5 is alkyl having 1-3 carbon atoms; X is oxygen or sulfur; and n is 0 or 1;
wherein R6 is alkyl having 1-6 carbon atoms, haloalkyl having 1-6 carbon atoms or propenyl;
R7 is hydrogen or alkyl having 1-4 carbon atoms;
R8 is hydrogen, alkyl having 1-6 carbon atoms, propenyl or methoxy;
Rg is hydrogen, alkyl having 1-8 carbon atoms, haloalkyl having 1-3 carbon atoms, alkoxy having 1-6 carbon atoms, propenyl or phenyl substituted with methyl; and Y and Z are oxygen or sulfur;
and a metal salt or a quaternary ammonium salt of a compound defined herein above.

It is disclosed in United States Patent ~os. 3,950,420 and 4,011,256 some cyclohexenone derivatives give excellent control of grassy weeds. The above compounds also cause heavy damage to gramineous crops. Thus we con ducted further investigation to find out new compounds which provide no phytotoxicity against gramineous crops. As the result, we found that 2~
ethoxyimino)-propyl3-5-(substituted phenyl)-3-hydroxy-2-cyclohexene-1-one showed a slightly weak action on wheat. ~Advances in Pesticide Science Part

2 235 (1979)]. They are relatively selective at the lower stage of grass weeds and wheat in post-emergence treatment. However, the bigger they grow, the higher the dose is needed. Thus, using higher rate of active ingredient, more herbicidal activity against grassy weeds is obtained and at the same time heavier damage is caused on wheat. On the other hand, decreasing the dosage to the rate which gives no phytotoxicity toward wheat, herbicidal activity is less effective. Thus the optimum dose range for giving a good selectivity is limited. To improve these adverse properties and to obtain more active and more selective compounds we conducted further studies.

We have found that the compounds having the formula [I] show higher activity and/or remarkably higher selectivity against gramineous crops such as corn, wheat, barley and rice compared with the known compounds.
That is;
the compounds having R3NH ~ group (wherein R3) is as previously defined) show only a slightly weak action toward gramineous crops such as corn, wheat and barley, especially corn, and a high herbicidal activity on grassy weeds, especially wild oat.

3~2~ 9 The compounds having R4XC ~ group (wherein R4 and X are as previ-ously defined) show not only higher activity on grassy weeds but also higher selectivity between wheat and wild oat.

Further, the compounds having RsS(O)n ~ (wherein Rs and n are as - previously defined) increase significantly in activity against grass weeds ..
compared with the known compounds containing phenyl substituted with methoxy or methylsulfonyl, though both compounds are almost equal selectivity.
All the compounds of this invention are active against gramineous weeds in both pre- and post-e~ergence treatment. Higher activities can be expected in post-emergence treatment than in pre-emergence treatment.

The compounds of this invention can be prepared in accordance with the following equation:
OH ~H
A ~ CORI + R20NH2 ~ A ~ C-NOR2 wherein Rl, R2 and A are as previously defined.

The above reaction can be conducted in an inert solvent.

As an inert solvent, methanol, ethanol, diethyl ether, benzene, toluene and chloroforrn may be used.
, The reaction temperature may be from -10C to the boiling point of the reaction solution, preferably from lO to 60C, and the reaction may be carried out from half an hour to several hours or longer.

.
, ~2~5~2~

After the reaction has been completed, the solvent is, if necessary, removed and the reaction mixture is then extracted with an alkaline solution.
lhe solution is acidified with hydrochloric acid and the crude product is iso-lated from the acid mixture by extraction or by filtration.

If the product is crystalline, the crude product can be purified by recry-stallization, and if the product is an only substance, the crude product can be purified by distillation or column chromatography.

A chemical formula for the resulting purified compound can be assigned by means of an elemental analysis, NMR spectrum, MASS spectrum and IR spectrum.

The sodium and potassium salts may be prepared by treating a compound of formula [I] with sodium or potassium hydroxide in aqueous solution or in an organic solvent such as acetone, methanol, ethanol or dimethylformamide. The salts may be isolated by filtration or by evaporation of resulting solution.

The calcium, barium manganese, copper, zinc, nickel, cobalt, iron and silver salts may be prepared from the sodium or potassium salt by treatment with the appropriate inorganic metal salt, e.g. calcium chloride, barium chlo-ride, copper sulfate, zinc chloride, nickel chloride and cobalt nitrate.

The calcium salt may also be prepared by treating a compound of the for-formula [I] with calcium hydroxide.

Some metal salts produced by above-mentioned process may undergo a chemical change or decomposition at a high temperature, and therefore not show a clear melting point. By applying infrared absorption spectroscopy to the starting material and reaction product, the formation of the metal salt is evidenced by transference of absorption bands and a change of absorption intensity. Thus, the starting material having the formula [I] has the ~5~LZ~9 - absorption due to the carbonyl group at wavelengths 1605 cm I and 1655 cm 1, whereas the corresponding metal salt shows the absorption at longer wavelengths.

Further, an anion such as OH may be simultaneously coordinated with a metal atom of some ~etal salts mentioned above.

- The structure of the metal salt may be shown as follows:
., O

A ~ C-NOR2-M
O
wherein M+ is me~al ion such as Na , 1/2 Ca2 or 1/2 CuZ .

Ammonium salts of this invention may be shown as same as the metal salts, namely, O
:- J
10A ~ \~ C=NOR N(r) 4 O Rl wherein N (r)4 is quaternary a~monium ion and r is same or different substi-tuent selected from alkyl and benzil. The ammonium salt can be prepared by the reaction of the compound of the formula [I] with ammol~lum hydroxide [N(L)40H] in the same manner as in the preparation of sodium salt.

It is expected that the compounds represented by the formula [I] exist in the following tautomeric forms:

A ~ ~ NO 2 ~ RNlHOR2 : (I) ~
~\ ,_4 /1./
A- ~ R 2 ~;~51;2~9 .. - 6 -.
The starting material of the formula [II3 can be prepared in accordance with the following equation:

(1) In case of the co~pounds having R3NH ~ glOUp;

CH3CONH ~ CHO (CH3)2CO ~ CH3CONH ~ CH=CHcocH3 CH2(COOC2Hs)2>

OH OH
CH3CONH ~ ~ RlCOCQ~ CH3CONH ~ $
COOC2Hs OCOOC2Hs O
OHOH
CH3CONH ~'~/ ~ COR~NH2 ~ COR
O
OH
R~S02CQ, Rg - NCO or RsCCQ~ R NH ~ COR

(2) In case of the compounds having R4XC ~ group;

NC ~ CHO (CH3)2CO~ NC ~ CH=CHCOCH3 CH2(COOC2Hs)2>

OH OH OH
10C ~ RlCOCQ NC ~ ~ ~ CORl -~ HOOC ~ ~ ~ COR
COOC2Hs O O

CQOC ~ ~ COR R4XNa R XC ~ ~ COR
O O

~2~

(3) In case of the compounds having RsS(O)n ~ group;

RsS(O)n ~ CHO (CH3)2CO R S(O) ~ CH=CHcocH3 CH2(COOC2Hs) OH OH
RsS(O~n ~ RlCOC~ RsS(O)n~ )/ ~ COR
COOC2 s COOC2Hs OH
RsS(O)n ~ ~ ~ COR
o The following Exa~ples illustrate the invention:

~5~9 : - 8 -' ~
Example 1 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(4-methanesulfonamido-phenyl)-2-cyclohexen-1-one:

Into 10 ml of tetrahydrofuran was dissolved 1.5 g of 3-hydroxy-5-(4-metha-nesulfonamidophenyl)-2-propionyl-2-cyclohexen-l-one and to the solution was added 0.5 g of ethoxyamine. The mixture was kept at room temperature for 15 hours and poured into ice water. And then the mixture was acidified with hydrochloric acid and it was extracted with chloroform. The chloroform solution was washed with water and extracted with 15 ml of an aqueous solution containing 5% of sodium hydroxide. The solution was acidified with hydrochloric acid and the crystal sedimented was extracted with chloroform and the solution was washed with water and it was dried with magnesium sulfate. Then, it was distilled off under a reduced pressure and thus, 1.4 g of the objective compound was obtained.
It was colorless crystals having a melting point of 115-116C.
'' Example 2 2-[1-(allyloxyimino)propyl]-5-(4-methanesulfonamidophenyl)-3-hydroxy-2-cyclohexen-1-one:

Into 10 ml of tetrahydrofuran was dissolved 1.0 g of 5-(4-methanesulfon-amidophenyl)-3-hydroxy-2-propionyl-2-cyclohexen-1-one and to the solution was added 0.5 g of allyoxyamine. The mixturezwas kept at room temperature for 15 hours and then it was treated with similar to Example 1. Thus, 0.8 g of the objective compound was obtained. It was colorless crystals having a melting point of 134-135C.
' Example 3 2-[l-(methoxyimino)propyl]-5-(4-methanesulfonamidophenyl)-3-hydroxy-2-cyclohexen-1-one:

Into ]0 ml of tetrahydrofuran was dissolved 1.2 g of 3-hydroxy-5-(4-me~llane-sulfonamidophenyl)-2-propiollyl-2-cyclohexen--1-one and to the so]ution were added 0.6 g of me~lloxyamille hydrocholorate salt and 1.4 g oF metll!llol con~ainillg 28~

~S:~L2:~.9 _ 9 _ of sodium methylate. Then> the mixture was ~ept for 15 hours at room tempera-ture and an insoluble material was filtered off from it and the resulting filtrate solution was concentrated under reduced pressure. Its residue was dissolved in chlorform and the solution was washed with a dilute hydrochloric acid solution and water, and it was dried with anhydrous magnesium sulfate.
The chlorform was distilled off from it under a reduced pressure and ethyl ether was add in it. Thus, the crystal sedimented is collected with a filter-ing step and 1.2 g of the objective compound which was colorless crystal having a melting point of 150-151C was obtained.

Example 4 2-[1-(3-chloroallyloxyimino)propyl]-3-hydroxy-5-(4-methanesul-fonamidophenyl)-2-cyclohexen-1-one:

Into 40 ml of mixture solvent of ethanol - chloroform (1:1) was dissolved 2 g of 3-hydroxy-5-(4-methanesulfonamidophenyl)-2-propionyl-2-cyclohexen-1-one and to the solution was added 10 ml of ethanol containing 10% of 3-chloroallyl-oxyamine at room temperature. The mixture was kept for 3 hours and it was poured into ice water. The mixture was acidified with hydrochloric acid and the oil separated was extracted with chloroform. The chloroform solution was dried with anhydrous magnesium sulfate and the chloroform was removed from it under reduced pressure and 1.5 g of objective crude compound was obtained.
It was purified by column chromatography and trans-cis mixture which was pale pink crystal having a melting point of 125-127C was obtained.
:
Example 5 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-[4-(3,3-dimet}lylurado) phenyl]-2-cyclohexen-1-one:

Into 6 ml of ethallol was dissolved 1.0 g of 3-hydroxy-5-[4-(3,3-dimethylu-rade)phenyl]-2-propionyl-2-cyclohexen-1-one and to the solution was added 0.5 g of ethoxyamine. The mixture was kept for 3 hours at room temperature and it ~L2Sl~ ~ 9 was poured into ice water. Then, the mixture was acidified with a dilute hydrochloric acid solution and it was extracted with chloroform. The chloroform solution was washed with water and extracted with 10 ml of aqueous solution containing 5% of sodium hydroxide. To the alkaline solution was add a dilute hydrochloric acid solution and the crystal sedimented was extracted with chloro-form. The chloroform solution was washed with water and dried with anhydrous magnesium sulfate. The chloroform was distilled off from it under a reduced pressure and ethyl ether was added in the residue. Thus, the crystal sedimented was collected with a filtering step and 0.9 g of the objective compound which was colorless crystal having a melting point of 77-79C was obtained.

Example 6 2-[1-(ethoxyimino)propyl]-5-~4-[3-(ethyl)thioureido]phenyl}-3-hydroxy-2-cyclohexen-1-one:

Into 10 ml of chloroform was dissolved 1.4 g of 5-{4-[3-(ethyl)thioureido]
phenyl}-3-hydroxy-2-propionyl-2-cyclohexen-1-one and to the solution was added - 1.0 g of ethoxyamine. The mixture was kept for 15 hours at room temperature and the reacting mixture was washed with a dilute hydrochloric acid solution and water. The solution was dried with anhydrous magnesium sulfate and the chloroform was distilled off from it under reduced pressure and 1.4 g of the objective compound was obtained. It was colorless crystal having a decomposition point of 116-118C.

Example 7 5-(4-acetamidephenyl)-2-[1-(ethoxyimino)propyl]-3-hydroxy-2-cyclohexen-l-one:

Into 10 ml of tetrahydrofuran was dissolved 2.0 g of 5-(4-acetamidephenyl)-2-propionyl-3-hydroxy-2-cyclohexen-1-one and to the solution was added 1.0 g of aqueous so]uLion containing 50% of ethoxyamine. The mix~ure was kept for 15 hours at room temperature and it was poured into ice water and the crystal ~2SlZ~43 .
sedimented was collected with a filtering step. The crystal was dissolved in 20 ml of chloroform and the solution was washed with water and extracted with 15 ml of aqueous solution containing 5% of sodium hydroxide. To the alkaline solution was added a dilute hydrochloric acid solution and the crystal sedimented was extracted with chloroform. The solution was washed with water and dried with anhydrous magnesium sulfate and the chloroform was distilled off from it under reduced pressure. Thus 1.4 g of the objective compound was obtained.
It was pale yellow crystals having a melting point of 135-136C.

Example 8 2-[1-(ethoxyimino)propyl]-5-(4-formamidophenyl)-3-hydroxy-2-cyclohexen-l-one:

Into 25 ml of chloroform was dissolved 1.3 g of 5-(4-formamidophenyl)-3-hydroxy-2-propionyl-2-cyclohexen-1-one and to the solution were added 1.0 g of ethoxyamine and 5 ml og ethanol. The mixture was kept for 3 hours in a water bath having 40C and the reacting solution was washed with a dilute hydrochoric acid solution and water. The solution was extracted with 15 ml of aqueous solution containing 5~ of sodium hydroxide and to the alkaline solution was added a dilute hydrochloric acid solution and the-crystal sedimented was ex-tracted with chloroform. The solution was washed with water and to the solution were added anhydrous magnesium sulfate and a small amount of active carbon.
And then, the mixture was agitated and filtered and the filtrate solution was concentrated. Ethyl etner was added in the residue and the crystal sedimented was collected with a filtering step and 1.0 g of objective compound was obtained.
It was colorless crystal having a melting point of 111-113.5C.

Example 9 2-[1-(ethoxyimino)propyl]-5-[4-(2-methylbenzamido)phenyl]-3-hy(lroxy-2-cyclohexen-1-one:

Into 30 ml oL cl-loroEorm was dissolved 1.6 g of 5-[4-(2-methylbenzamido) ~S~L2~

phenyl]-2-propionyl-3-hydroxy-2-cyclohexen-1-one and to the solution was added 0.4 g of ethoxyamine. The mixture was kept for 15 hours at 40C and the react-ing solution was washed with water and a surplus amount of ethoxyamine was removed from it. After dried, the chloroform was distilled off from it and ethyl ether was added in the residue. The crystal sedimented was collected with a filtering step and 1.0 g of objective compound was obtained. It was colorless crystal having a melting point of 139-140C.

Example 10 2-[1-(ethoxyimino)propyl]-5-[4-(methoxycarbonylamino)phenyl]-3-hydroxy-2-cyclohexen-1-one:

Into 30 ml of chloroform was dissolved 1.8 g of 5-[4-(methoxycarbonyl-amino)phenyl]-2-propionyl-3-hydroxy-2-cyclohexen-1-one and to the solution was added 0.5 g of ethoxyamine. The mixture was agitated for 15 hours at ~0C and the chloroform containing produced water and a surplus amount of ethoxyamine was distilled off from it under a recuded pressure. And then, the ethyl ether was added in the residue and the crystal sedimented was collected with a fil-tering step and 1.2 g of objective compound was obtained. It was colorless crystal having a melting point of 160-161~C.

Example 11 Sodium 2-[1-(ethoxyimino)propyl]-5-(4-methansulfonamidephenyl)-3-oxo-1-cyclohexenolate:

Into 10 ml of methanol was dissolved 1.9 g of 2-[1-(ethoxyimino)propyl]-5-(4-methansulfonamidephenyl)-3-hydroxy-2-cyclohexen-1-one and to the methanol solution was added 20 ml of methanol containg 0.27 g of sodium methylate.
Then, the solvent was removed under a reduced pressure and the residue was recrystallized with acetonitrile. Thus, 1.8 g of the objective compound which was a colorless crystal havillg a decoml)ositioll point of 165-170C was obtained.

~25~

,.
. Example 12 Calcium 2-[1-(ethoxyimino)propyl]-5-(4-methanesulfonamidophenyl)-- 3-oxo-1-cyclohexenolate:

Into 20 ml of an aqueous solution containg 2% of sodium hydroxide wad dissolved 1.9 g of 2-[1-(ethoxyimino)propyl]-5-(4-methanesulfonamidophenyl)-3-hydroxy-2-cyclohexen-1-one and to the solution was added 3cc of an aqueous solution containg 10~ of calcium chloride at room temperature. The water was - removed under a reduced pressure and the residue was dissolved in ethanol and an insolble sodium chloride was separated with a filtering step. The ethanol was distilled off under reduced pressure and 1.5 g of white powder havi.ng a melting point of 250C or more was obtained.
.
Example 13 Benziltrimethylammonium 2-[1-(ethoxyimino)propyl]-5-(4-butyl-amidephenyl)-.-oxo-l-cyclohexenolate:

~ Into 30 ml of methanol was dissolved 1.9 g of 2-[1-(ethoxyimino)propyl]-- 5-(4-butylamidephenyl)-3-hydroxy-2-cyclohexen-1-one and to the solution was : added 2.2 g of methanol containing 40% of benziltrimethylammonium hydroxide .;. at room temperature. The methanol was distilled off from it under reduced pressure and 2.7 g of colorless hygroscopic crystal having a melting point of 65-66~C was obtained.

.
: Example 14 - 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(4-methoxycarbonylphenyl)-Z-cyclohexen-l-one:

Into 20 ml of methanol was dissolved 2.5 g of 3-hydroxy-5-(4-methoxycar-~ bonylphenyl)-2-propionyl-2-cyclohexen-1-one and to the solu~ion was addcd 0.7 g - of ethoxyamine. The mixture was kept for 15 hours at room temperature and it was poured into ice water. The crystal sedimented was collected with a filter-ing step and recrystallized wiLh mixture solvent of methanol-water. Tlll-s, 1.9 g of rhe objectivc compoulld whicll was colorless crystals having a melting point oi 75-7~C ~ ol~Lc~ e(l~

~25~ 9 ., Example 15 2-[1-(ethoxyimino)butyl]-3-hydroxy-5-[4-(methylthio)carbonyl-phenyl]-2-cyclohexen-1-one:

Into 20 ml of tetrahydrofuran was dissolved 2 g of 2-butyryl-3-hydroxy-5-[4-(methylthio)carbonylphenyl]-2-cyclohexen-1-one and to the solution was added 0.6 g of ethoxyamine. The mixture was kept for 15 hours at room tempe-rature and the solvent was distilled off from it under reduced pressure.
Then, the residue was recrystallized with mixture solvent of benzene-ligroin and 1.8 g of colorless objective crystals having a melting point of 75-77C
was obtained.

Example 16 3-hydroxy-5-[4-(methylthio)carbonylphenyl]-2-[1-(propargyloxy-imino)butyl]-2-cyclohexen-1-one:

Into 20 ml of tetrahydrofuran was dissolved 2 g of 2-butyryl-3-hydroxy-5-[4-(methylthio)carbonylphenyl]-2-cyclohexen-1-one and to the solution was added 0.7 g of propargyloxyamine. The mixture was kept for 15 hours at room temperature and the solvent was distilled off from it under reduced pressure.
Then, the residue was recrystallized with mixture solvent of benzene-ligroin and 1.6 g of colorless objective crystals having a melting point of 95-96C was obtained.

Example 17 2-[1-(allyloxyimino)butyl]-5-[4-(ethylthio)carbonylphenyl]-3-hydroxy-2-cyclohexen-1-one:

Into 20 ml og tetrahydrofuran was dissolved 2 g of 2-butyryl-5-[4-(ethyl-thio)carbonylphenyl]-3-hydroxy-2-cyclohexen-1-one and to the solution was added 0.8 g of allyloxyamine. The mixture was kept for 15 hours at room temperature and the solvent was clistilled off from it under reduced prossure. Then, the resiclue was rec~ystallizcd with mixture of berlzene-ligroill a;l(l 0 ~ g of color-less objective crystals havi,ng a melting point of 72-75C was obtained.

~2s~ g Example 18 Sodium 2-[1-(ethoxyimino)propyl]-5-(4-methoxycarbonylphenyl)-3-oxo-1-cyclohexenolate:

Into 10.8 g of methanol containing 2.5% of sodium methoxide was dissolved 1.7 g of 2-~1-(ethoxyimino)propyl]-3-hydroxy--5-(4-methoxycarbonylphenyl)-2-cyclohexen-l-one and the solvent was removed from it under reduced pressure.
Thus, 1,8 g of colorless objective crystals was obtained.

Example 19 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(4-methylthiophenyl)-2-cyclohexen-1-one:

Into 20 ml of ethanol was dissolved 2.9 g of 3-hydroxy-5-(4-methylthio-phenyl)-2-propionyl-2-cyclohexen-1-one and to ~he solution was added 0.8 g of ethoxyamine. The mixture was kept for 15 hours at room temperature and it was poured into ice water. The crystal sedimented was collected with a fil-tering step and recrystallized with methanol. Thus, 3.1 g of colorless objective crystals having a melting point of 83-84C was obtained.

Example 20 2-[1-(allyloxyimino)butyl]-3-hydroxy-5-(4-methylthiophenyl)-2-cyclohexen-1-one:

Into 20 ml of ethanol was dissolved 1.5 g of 2-butyryl-3-hydroxy-5-~4-methylthiophenyl)-2-cyclohexen-1-one and to the solution was added 0.5 g of allyloxyamine. The mixture was kept for 15 hours at room temperature and it was poured into ice water. The crystal sedimented was collected with a filter-ing step and recrystallized with methanol. Thus, 1.4 g of colorless objectivecrystals having a melting point o~ 72--74C was obtained.

ExaMple 21 2-[1--(ethoxyimillo)butyl]-3-hydroxy-5-(4-metllylsulfinylpllellyl)-2-cycl~hexe:l-]-one:

~-~S~ 9 Into 20 ml of ethanol was dissolved 1.6 g of 2-butyryl-3-hydroxy-5-(4-methylsulfinylphenyl)-2-cyclohexen-1-one and to the solution was added 0.5 g of ethoxyamine. The mixture was kept for 15 hours at room temperature and it was poured into ice ~ater. The crystal sedimented was collected with a fil-tering step and recrystallized with methanol. Thus, 1.3 g of colorless objective - crystals having a melting point of 72-74C was obtained.
In addition to the above-mentioned compounds, some typical compound are listed in Table 1.

.
'i .. ....

~ ~7~ 9 Table ' _ _ _ _ Compound R6~02NH ~ \ C=NOR2 Physical Constant No. O Rl [m-p-] C

R6 Rl R2 -1 -CH3 -C2Hs -C2Hs [115-116]
2 -C2Hs -C2Hs -C2Hs [119-120]
:- . 3 -C3~7 -C2Hs -C2Hs [111-112]

4 -C4Hg -C2Hs -C2Hs [118-119]
:- 5 2 -C2Hs -C2Hs [142-143]
6 1 -CH3 -C2Hs -CH2CH=CH2 [134-135]
1 7 ' -CH3 -C2Hs -CH3 [150-151]
8 -CH3 -C3H7 -C2Hs [117-119]
. 9 ~ -CH3 1-C3H7 -CH2CH=CH2 [100-101]
~ -CH2CR I-C2Hs -CH2CH=CH2 [138-140]
11 1 -CH2C~ I-C3H7 -C2Hs [102-104]
12 -CH2CQ -C3H7 ¦ -CH2CH=CH2 [134-135]
13 i -CHzCH=CH2 -C2Hs ¦ -C2Hs [ 98-100]
14 ¦ -CH2CH=CH2 -C2Hs ¦ -CH2CH=CH2 [ 90- 92]
lS I -CF3 -C2Hs I -C2Hs [124-126]
16 L -CH3 -C2Hs ~ -CH2CH=CHCQ [125-127 __ __ ___ __ _____ ____ .. _ .. .. ._ .

~5~9 - ].8 -____ -~ r -: R7 N-C-NH ~ C ~ ~ $ C-NOR2 , Physical ,. Compound Rs/ ~ Rl i constant No. l l O ; [m.p.] C
y I R7 I Rs ~ ~ . I

17 O 1. -H I -H -C2Hs -C2Hs ~ [115-116]
18 S I -H -C2Hs -C2Hs -C2Hs , [116-lld8]
19 O ¦ -CH3 -CH3 l -CzHs -C2Hs ¦ [ 77- 79]
O I -H -CH3 , -C2Hs -C2Hs [139-141]
21 O -CH3 -CH3 -C3H7 -C2Hs [132-134]
. 22 O ~ -H -CH3 -C2Hs-CH2CH=CH2 : [131-133]
. 23 O I -CH3 --OCH3 -C2Hs¦ -C2Hs , [128-131]
24 S I -H -CH3 -C2Hs¦ -C2Hs [113-114]
i S ¦ -H -CH2CH=CH2 -c2Hs ¦ -C2Hs , [112-lld4]
. 26 1 ! -H -C2Hs -C2Hs -C2Hs [142-144]
27 ' O ¦ -C2Hs -C2Hs -C2Hs I -C2Hs [ 92- 93]
. 28 ~, O , -H -CH(CH3)2 . -C2Hs i -C2Hs [144-146]
29 I S ¦ -H -CH2CH(CH3)z -C2Hs -C2Hs [108-110]
1 0 ¦ -H -C4Hg -C2Hs -C2Hs , [143-144]
31 1 0 ¦ -CH3 -CH3 -C2Hs -CH2CH=CH2 , [ 63- 64]
32 1 0 , -CH3 -CH3 -C3H7 ¦ -CH2CH=CH2 ~ [ 80- 82]
. 33 ¦ S ¦ -H -H -C2Hs ¦ -C2Hs , [140-150]
34 ¦ O ¦ -~i -t-C4Hg -C2Hs ¦ -C2Hs i [133-134]

:
' ;'' .9 Compound : Rg-CNH ~ C-NOR2 Physical constant : No. l o Rl[m.p.] ~C
: I Z ¦ Rg R1 R2 _ . ~
-CH3 -C2Hs -C2Hs[135-136]
36 0 -C2Hs -C2Hs -C2Hs[147-149]
37 ' -C3~17 -C2Hs -C2Hs [144-145]
33 ¦ 0 -OC2Hs -C2Hs -C2Hs [159-160]
: 39 1 0 CH3 -C2Hs -C2Hs [139-140] ~1' ~

. 40 , 0 1 -C3H7 -C2Hs -CH2CH=CH2 [114-116]
41 li S ! -oc2Hs -C2Hs -C2Hs ¦ [129-132]
¦ 42 0 1 -CH=CH-CH3-C2Hs -C2Hs [153-154]
! 43 0 ¦ -H -C2Hs -C2Hs [111-113.5]
44 1 0 1 -i-C3H7 -C2Hs -CzHs [131-132]
1 45 , 0 ¦ -t-C4Hg -C2Hs -C2Hs I [124-125]
¦ 46 1 0 ¦ -CH3 -C2Hs -CH2CH=CH2 ¦ [127-129]
¦ 47 , 0 ¦ -H -C2Hs I -CH2CH=CH2 ' [ 79-81]
48 , 0 ¦ -CH2CQ -C2Hs -C2Hs I [177-178]
49 ' 0 ¦ -CH3 -C3H7 -C2Hs ¦ [130-131]
, 0 1 -CH3 -C3H7 -CH2CH=CH2 [112-114]
51 , 0 ~ -H -C3H7 -C2Hs [116-117]
52 0 -H -C3H7 -CH2CH=CH2 I nD2 1.5988 ¦53 -(CH2)7CH3-C2Hs -C2Hs ~ [104-105]
54 0 -O(CH2)7CH3 -C2Hs -C2Hs I [ 87- 90]
1 -CF3 -C2Hs -C2Hs 1 dec.
.. ... .. .. I . _ . . ...... _ _ _ I

~25~L2.~3 56 ¦ O --CF3 ¦ -C2~1s -CH2CH=CH2 [159-16l]
57 ~ CU3 1 -C~Hs ~ - U2 ]H=CU~ 1l03-lO5 sa o CU3 -C~H7 ~ - ~Hs ~ [152-153]

S9 ~ O ~C3H7 ~ - UzCII=CH~ ~ ~130-131]

l, O -OCH3 -C2Hs -C2Hs [160-161]
61 ¦ O -OCH2CH=CH2 -C2Hs -C2Hs [132-133]
62 ¦ O -OCH3 -C2Hs -CH2CH=CH2 [113-114]
63 ¦ O -OCH3 -C3H7 -C2Hs [149-150]
64 i O -OCH3 -C3H7 -CHzCH=CH2 ¦ [119-121]
¦ O -OC2Hs -C3H7 -C2Hs ¦ [142-143]
66 ¦ O ~ -OC2Hs -C3H7 2CH=CUz L [122-123] L
'', . .

25~ 9 __ _ 1-4 0 Physical Compound ~ ~ Rl constant No. O [m.p.] C
- R} Rl R2 M
- I r 67 -SO2CH3 -C2Hs -C2Hs Na ¦ dec 68 1 -S02CH3 C2Hs -C2Hs 1/2 Ca ~ [250]up 69 ' -COC3H7 -C2Hs -C2Hs Na ~ [183]dec.
, -COC3H7 1-C2Hs -C2Hs 1/2 Sn l [144-ld6]
71 -COC3H7 1-C2Hs -C2Hs [ 65- 66]
N(CH3)3 72 -COC3H7 1-C2Hs -CH2CH=CH2 Na , [200] up 73 -SO2CH3 1-C3H7 -C2Hs Na I [142-145]
74 -SO2CH3 ¦-C3H7 ' -CH2CH=CH2 , Na , hygroscopic -SO2CH2CH=CHz 1 -C2Hs -C2Hs I Na i [ 85- 88]
76 -CON(CH3)2 ', -C7Hs -C2Hs i Na I [180-182]
~ I I dec 77 , -CONHCH3 i-C2Hs , -C2Hs Na I [183-185]
78 i -CONHCH3 I-C2Hs I -C2Hs ~ 1/3 Fe I [147-149]
79 -CONHCH3 ,-C2Hs I -C2Hs ~ 1/2 Ba , [188-189]
1 -COCH3 1-C3H7 , -CH2CH=CH2I Na , [163-167]
81 , -CHO I-C2Hs , -C2~5 Na ', [165-170]

82 I CH3\ 1-C2Hs -C2Hs I Na ; [177]dec.
-C~

83 1 -COOCH3 1-C2Hs I -C2Hs Na [ 62- 65]
84 1 -COOC2Hs 1 -C3H7~ 1 -C2Hs I Na []70]dec.
1 -COCF3 1 -C2Hs 1 -C2Hs I Na j [186-188]
86 1 -COCF3 1-C2Hs l - Cll 7 CH-- CH 2 ! _ . . . ¦ - - -- -------~25~'3 ,, _ ____ _ ___ __ . _ ___ ._~_ 1-5 0 ~ OH Physical Compound Rl,XC ~ C-NORz constant No. O
R4 X R~ _ _ _ 87 ~ H O-C2Hs -C2Hs [178-179]
. 1 88 1 -CH3 O-C2Hs -C2Hs [ 75- 76]
¦ 89 1 -CH3 S-C2Hs -C2Hs [ 98-100]
1 -CH3 1 -C2Hs -CH3 [110-111]
91 ' -CH3 ~ S-C2Hs -CH2CH=CH2 [ 87- 89]
¦ 92 , -CH3 -C3H7 -C2Hs [ 75- 77]
¦ 93 , -CH3 ' S-C3H7 -CH2C--CH [ 95- 96]
1. 10 1 94 l, -CH3 I S-C3H7 -CH2CH=CH2 [ 81- 82]
I 95 , -CH3 1 0-C3H7 -C2Hs [ 47- 49]
96 -CH3 . O-C3H7 -CH2CH=CH2 1 [ 54- 56] ¦
97 -CH3 O-C3H7 j -CH2C-CH I [ 81- 83] ¦
. 98 . -C2Hs ' O-C2Hs 1 -CzHs ¦ [ 77- 78]
: 99 -C2Hs I O-C2Hs I -CH2CH=CH2 1 [ 53- 54]
100 . C2Hs i OC2Hs ¦ CH3 , [113-115]
101 C2Hs I C3H7 I C2Hs ' [ 46- 48]
.~ ¦ 102 ~ C2Hs I OC3H7 ¦ CH2CH=CH2 j [ 54- 56]
103 I C2Hs SC2Hs ¦ C2Hs 'I [ 88- 90]
104 , C2Hs S¦ C2Hs ¦ CH2CH=CH2 1 [ 58- 60]
105 ~ C2Hs 'I S C2Hs CH3 ~ [109-llO]
106 , C2Hs SC3H7 C2Hs , [ 60- 61 107 C2Hs I C3H7 CH2CH=CH2 , [ 72- 75] 1 108 CH(CH3)2 ~ C2Hs C2Hs I [ 65- 67] j L log -CH(CH3)2 S C7Hs I -C2Hs I 69- 7l] ¦
, ., . . . _ , , . . , . , . .. . _ .... ..

~s~ 9 110 -C3H7 ¦ S -C~Hs r -C2H [ 78- 80]
111 -C4Hs I 0 -C2Hs ¦ -C2Hs [ 61- 62]
112 -C4Hgn I S -C2Hs -C2Hs [ 61- 62]
113 -CH2CH(CH3)2 S -C2Hs -C2Hs [ 45- 46]
114 ~ 0 -C2Hs --C2Hs [112-114]

115 ~ S -C2Hs -C2Hs [127-128]

116 ~ CQ S -C2Hs -C2Hs [132-134]

117 H 0 -C2Hs -C2Hs 2Na salt 118 -CH3 0 -C2Hs ~ -C2Hs [230-233]
_ _ I l [200] up ...., _ _ _ _ I 1-6 OH _ Compoond ~sS(O)n ~ C-NOR2 m.p.~ C

Rs ! n Rl R2 - , , . ! ~ _ I
119 -CH3 0 C2Hs C2Hs [83-84]
120 -CH3 0 C2Hs CH2CH=CH2 nD 1.6026 121 -CH3 1 C2Hs C2Hs [107-109]
122 -CH3 1 C2Hs CH2CH=CH2 nD3 1.5900 123 -CH3 , 0 C3H7 C2Hs [82-85]
124 1 -CH3 1 0 C3H2 CH2CH=CH2 [72-74]
125 1 -CH3 1 1 C3H7 C2Hs [72-74]
126 ¦ -CH3 ~ 1 C3H7 ~H2CH=CH2 ¦ nD2 1.5862 127 1 -CH3 1 0 C2Hs . C2Hs ¦ . (Na salt) 128 ~ -CH3 0 C2Hs CH2CH=CHCQ nD4 1.5998 129 1 -CH3 1 0 C3H7 I CH2CH=CHCQ nD4 1.5972 130 -CH3 j 0 C2Hs ! CH~CH=CHCQ [57-59]
l I (trans form) 131 -CH3 0 C3H7 C3H7 [80-81]
1 132 1 -CH3 1 0 C3H7 I CH3 1 [60-61]
! 133 ¦-C2Hs I O ¦ C2Hs ¦ C2Hs I [77-78]
¦ 134 1-C2Hs ' 1 ¦ C2Hs ¦ C2Hs l [89-90]
L 135 ¦-C3H7 i L C2Hs 1 C2Hs [63-64]

~;~5~ 9 As mentioned previously, the compounds possess superior herbicidal acti-vity. The compounds may be applied directly to the soil as pre-emergence treatment or to plant foliage as post-emergence treatment, or they can be mixed intimately with soil. The preferred treatment is post-emergence treat-ment and the compounds may be applied to soil or to plant foliage in amount of

5 g or more per 10 are.

A herbicidal composition having a compound of this invention as its active ingredient may be formulated by mixing suitable carriers in a form generally used in agricultural chemicals, such as wettable powder, water soluble powder, emulsifiable concentrate and flowable. As solid carriers, talc, white carbon, bentonite, clay, diatomaceous earth or the like may be used. As liquid carriers, water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclo-hexanone, dimethylformamide or the like may be used. A surface active agent may, if necessary, be added in order to give a homogeneous and stable formulation.

m~ompounds can also be applied admixed with other chemicals, which are used in agronomic and horticultural management and which are compatible with such compounds. Such chemicals can be, but are not restricted to, the classes of chemical commonly known as fungicides, insecticides, acaricides, herbicides and plant growth regulators. In particular, by mixing it with the other herbi-cides, its using chemical amount and manpower can be decreased and furthermore, the higher effect of synergetic function with both chemicals can be expected.
1, For admixture of the compound with known herbicides, the use is recom-mended of triazine derivatives such as simazine, atrazine and terbutryne, urea derivatives such as ipuron and tribunyl, heterocyclic compounds such as benta-zone, phenoxyalkane carboxilic acid derivatives sucl- as 2,4-D and MCPP, benzonirile derivatives such as ioxynil, and sulfoneainide derivatives such as chlorosulfuron.

~25~ 9 The concentration of the active ingredient in a herbicidal composition may vary according to type of formulation, and the concentration is, for example, in the range of 5 - 80 weight percent, preferably 30 - 60 weight percent, in wettable powder; 70 - 95 weight percent, preferably 80 - 90 weight percent, in water soluble powder; 5 - 70 weight percent, preferably 20 - 40 weight per-cent, in emulsifiable concentrate; 10 - 70 weight percent, preferably 20 - 50 weight percent, in flowable.

A wettable powder, a water soluble powder or an emulsifiable concentrate thus produced may be diluted with water to a aspecified concentration and used 10 as a liquid suspension or a liquid emulsion for treating soils or plant foliage.
Further, a flowable may be directly used for soil or foliage treatment, other-- wise, it may be diluted with water to a specified concentration and used as a liquid suspension for treating soils or plant foliage.

Non-limiting examples of herbicidal composition are illustrated by the following tests:

: Example 22 Wettable powder parts by weight Compound No. 1 50 - White carbon 12 Diatomaceous earth 30 Sodium alkylsulfate 8 These are mixed homogeneously and reduced to fine particles to provide a wettable powder containing 50% of active ingredient. In use, it is diluted to a desired concentration with water, and is sprayed as suspension.

~51~ ~9 Example 23 Water soluble powder parts by weight Compound No. 118 90 Dialkylsulfosuccinate 10 These are mixed homogeneously and reduced to fine particles to provide a water soluble powder containing 90% of active ingredient.

Example 24 Emulsifiable concentrate parts by weight Compound No. 120 20 ~ylene 40 Dimethylformamide 30 Polyoxyethylene phenyl ether 10 These are mixed and dissolved to provide an emulsifiable concentrate containing 20% of active ingredient. In use, it is diluted to a desired concentration with water, and sprayed as an emulsion.

: Example 25 Flowable parts by weight Compound No. 82 30 Sun spray-7N ~commercial product of Sun Oil Co., Ltd.) 60 Polyoxyethylene alkylether 5 Sorbitan alkylate 5 These are mixed homogeneously to provide a flowable containing 30% of active ingredient.
j /l u s tf ~ tr~r~
The herbicidal effects of colllpounds are ill~strQctcd by the following tests:
3~
~ e~n~Jt r k ~5~

Test Seeds of wild oat and corn were planted in each pot having a surface area of 100 cm2 and kept in a green house. When t:he plants were grown to 2-2.5 leaves and 2-3 leaves stage respectively, aqueous suspensions, prepared by diluting an emulsifiable concentrate with water to specified concentration containing 400 ppm and 200 ppm of active ingredient were sprayed on the foliage ; of the test plants at a rate of 100 Q/10 are, and the pots were kept in a green house. Twenty eight days after spraying, the degree of damage to each plant was observed and evaluated on the scale of value of 0-10, which has the following meanings:
Degree of Damage ' O : O %
2 : 20 - 29 %
4 : 40 - 49 %

6 : 60 - 69 %
8 : 80 - 89 %
. 10 :. 100 %
1, 3, 5, 7 and 9 mean the intermediate degree between 0 and 2, 2 and 4, 4 and 6, 6 and 8, and 8 and 10 respectively.

The results are shown in Table 2.

,:

~5~ g ., - 29 -- Table 2 : Application Rate Degree of Damage . Compound No.
.~ . (g/10 are)wild oat corn . l 240 10

7 420 98 41

8 42o 10 42 ' 20 9 240 10 .. lO 420 18 4 11 42o 10 4 14 _ 20 '3 42 L~ _ _ ___ 5 ~ L9 s ~ -- 42o 1 lo - ` - 3 - 17 42o 1 lo 8 20 ~ 6 o

9 40 lo 2 9 ~ o ~ lo 20 40 9 :` 21 420 lo 3 22 40 lo , 3 6 . o 23 40 lo 1 9 o 24 ~ 40 1 9 : 25 1 40 ~ 8 2 I 20 1 7 o 1 40 1 lo ~ 4 1 20 1 lo ; 27 1 40 1 lo 3 - 1 20 1 8 o 28 1 40 1 lo 1 2 ' 9 1 1 i 40 lo I o : ' I 20 1 7 1 o 31 1 40 ! 9 1 4 - 30 1 1 20 ~ 7 3 32 1 40 j lo 3 ; 1 20 7 j 2 ~ ..... . . . . . .. . . . . .. I . . ... . .. ...... . .. . .... ... L

~2~ 9 - 31 - .

; 34 ~ 40 1-0 - 2 ~

. 38 40 10 5 39 ~lO lO 4 24o 78 o . 1 4'2 40 1 9 ~ l . 44 40 1 10 1 2 ', 9 1 ~ ...... . . .. . . . _ ~

~251~C~

,. _. _ _ 51 42o 170 3 68 42o ~ 10 2 1 69 ~ 40 ~ 9 71 ~ 42o 1 ~

72 42o ~ 86 ~_. .. _. _.. __._ . . . .. . _ .. . ... .. . ... . . . _ __. _ . _ . . _ _.. _.. .. _ .

~51~:q!19 _ -- __ ~, 76 420 10 2 ~` ~ 81 40 9 ~ 3 : 20 8 2 . 83 40 10 3 ', . 20 8 0 ; 84 40 10 2 _ _ ___,_ , Comparative 40 9 lO
compound A 20 7 7 Comparative 40 10 10 : compound B 20 Comparative Compound A: 2-[l-(ethoxyimino)propyl]-3-hydroxy-S-phenyl-2-; cyclohexen-l-one B: 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(4-methoxy-. phenyl)-2-cyclohexen-1-one .

Test 2 Seeds of wild oat and wheat were planted in each pot having a surface area of 100 cm2 and kept in a green house. When the plants were grown to 2-3 leaves stage respectively, aqueous suspensions, prepared by diluting .: an emulsifiable concentrate, with water to specified concentration contain-ing 400 ppm and 200 ppm of active ingredient were sprayed on the foliage of the test plants at a rate of 100 ~/10 are, and the pots were kept in a green house. Twenty eight days after spraying, the degree of damage to each plant was observed and evaluated on the same scale in Test 1.

The results are shown in Table 3.
-Table 3 _____ _l Application Rate Degree of Damage Compound No.
(g/10 are)wild oat wheat ,.. ~ . _ _ _ _ __ 87 42o 5 : 20 8 0 . 20 91 42o 6 1 0 .~ 1 92 40 10 1 o g3 42o 5 1 O

., . ~ ... . ... . 10 .. I

~2'j~LZ~l 9 _ _ 1 10 o , 8 0 : 1 20 10 1 0 97 1 40 ` 9 1 0 . 1 20 3 0 . 98 1 40 , 10 0 . 20 1 7 1 0 ', 5 1 0 101 1 40 1 10 1 o . 1 20 10 0 . 102 j 40 i 10 'I 7 0 ~ 1 104 1 40 ~ 10 2 - I ! 20 I 10 .: 1 106 40 1 10 0 2Q l 20 1 10 0 -. 108 40 1 10 1 0 109 40 j 9 0 . I 20 1 6 0 : 110 40 10 o . . ,. .. _ ,. , .. ... , .. ,,, . ~ ., .. . O

~25~ 9 I _ ___ ~_ _ _ _., ,.. . _ _ _, 114 24o 86 117 42o 10 0 _ 20 _ _ _ 8 _ Comparative 40 10 4 compound C 20 6 0 Comparative 40 9 5 compound A 20 4 3 __ __ .__ . _ .__,._. . _ .

Comparative compound C: 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(4-methyl-phenyl)-2-cyclohexen-1-one A: The same in Test 1.
'' .
Test 3 Seeds of wild oat and wheat were planted in each pot having a surface area .~ of 100 cm2 and kept in a green house. When the plants were grown to 3-4 leaves stage respectively, aqueous suspensions, prepared by diluting an emulsifiable concentrate with water to specified concentration containing 400 ppm and 200 ppm of active ingredient were sprayed on the foliage of the test plants at a rate of 100 Q/10 are, and the pots were kept in a green house. Twenty eight days after spraying, the degree of damage to each plant was observed and eva-luated on the same scale in Test 1.

The results are shown in Table 4.

~25~2~'~
. - 37 -'~
.. Table 4 Application Rate Degree of Damage . Compound No.
. (g/10 are) wild oat wheat . 119 40 10 5 ,; 121 40 10 3 .. 20 10 122 42o 10 41 . 123 40 10 3 .. i 20 10 2 _ 20 10 4 ... 125 40 10 3 .: 20 10 1 ' 10 2 .. 20 10 . 133 40 10 4 .- 20 10 3 135 20 10 _ ~ . _ _ ____ __ ~251~:~9 Comparative 40 10 : compound D 20 8 5 Comparative 40 9 3 . compound B 20 6 :- Comparative 40 9 2 compound C 20 ~ 0 Comparative compound D: 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(4-methane-sulfonylphenyl)-2-cyclohexen-1-one B: The same in Test 1 C: The same in Test 2 Test 4 Seeds of wild oat, crabgrass, wheat and barley were planted in each pot having a surface area of 100 cm2 and kept in a green house. When the wild oat and crabgrass were grown to the tillering stage (20-30 cm of shoot length) and wheat and barley were grown to the stage of 30-35 cm of shoot length res-pectively, aqueous suspensions, prepared by diluting a wettable powder with water to specified concentration containing 750 ppm, 500 ppm, 250 ppm and 125 ppm of active ingredient were sprayed on the foliage of the test plants at a rate of 100 Q/10 are, and the pots were kept in a green house. Twenty eight days after spraying, the degree of damage to each plant was observed - and evaluated on the same scale in Test 1.

The results are shown in Table 5.

~25~ 3 Table S
, I _ . Application Rate ¦ Degree of ~amage .. Compound No. _ . _ . (g/10 are) wild oat crabgrass wheat barley .. 75 10 10 5 5 : S0 10 10 2 3 .. 12.5 . 7 0 0 . 75 10 10 43 52 : 10 121 25 10 10 1 2 . 12.5 6 4 0 0 ' 123 25 10 10 2 12.5 6 - 5 . 0 0

- 10 8 3 -4 Comparative 50 9 6 3 3 compound C 25 5 4 1 _ 12.5 4 1 0 0 Comparative compound C: The same in Test 2.
.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR PRIVILEGE
IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound having the general formula wherein R1 is alkyl having 1-3 carbon atoms;
R2 is alkyl having 1-3 carbon atoms, allyl, propargyl or haloalkenyl; and A is selected from the group consisting of group, and group, wherein R3 is -SO2R6 group, group or group; R4 is hydrogen, alkyl having 1-6 carbon atoms, phenyl or halophenyl;

X is oxygen or sulfur; wherein R6 is alkyl having 1-6 carbon atoms, haloalkyl having 1-6 carbon atoms or propenyl; R7 is hydrogen or alkyl having 1-4 carbon atoms, R8 is hydrogen, alkyl having 1-6 carbon atoms, propenyl or methoxy, R9 is hydrogen, alkyl having 1-8 carbon atoms, haloalkyl having 1-3 carbon atoms, alkoxy having 1-6 carbon atoms, propenyl or phenyl substituted with methyl; and Y and Z are oxygen or sulfur;
and a herbicidally acceptable metal salt or quarternary ammonium salt of a compound defined herein above.

2. A compound according to claim 1, wherein A is group;

wherein R3 is -SO2R6 group, group or group.

3. A compound according to claim 2, wherein R3 is -SO2R6 group.

4. A compound according to claim 2, wherein R3 is group.

5. A compound according to claim 2, wherein R3 is group.

6. A compound according to claim 1, wherein A is group.

7. A process for the preparation of a compound having the general formula which comprises reacting a compound of the formula with a compound or the formula wherein R1 is alkyl having 1-3 carbon atoms;
R2 is alkyl having 1-3 carbon atoms, allyl, propargyl or haloalkenyl; and A is selected from the group consisting of group, group, and wherein R3 is -SO2R6 group, group or group; R4 is hydrogen, alkyl having 1-6 carbon atoms, phenyl or halophenyl;
X is oxygen or sulfur; wherein R6 is alkyl having 1-6 carbon atoms, haloalkyl having 1-6 carbon atoms or propenyl; R7 is hydrogen or alkyl having 1-4 carbon atoms; R8 is hydrogen, alkyl having 1-6 carbon atoms, propenyl or methoxy; R9 is hydrogen having 1-8 carbon atoms, haloalkyl having 1-3 carbon atoms, alkoxy having 1-6 carbon atoms, propenyl or phenyl substituted with methyl; and Y and Z are oxygen or sulfur.