JPS58103351A - Novel chloroacetanilide derivative and herbicide for paddy field - Google Patents

Abstract

NEW MATERIAL:A 2',6'-diethyl-N-[(cis-alkenyloxy)methyl]-2-chloroacetanilide shown by the formula (R is cis-form 4C or 5C alkenyl). EXAMPLE:2',6'-Diethyl-N-[(2-cis-butenoxy)methyl]2-chloroacetanilide. USE:A herbicide for paddy field. Having improved herbicidal effect on Echinochloa crus-galli Beauv. var. praticola Ohwi, a strongly harmful weed in cultivation of a paddy-rice plant especially by application into water before germination of weeds. Exerting no influence on rice plant independent of high or low temperature, having low toxicity. PROCESS:2',6'-Diethyl-N-chloromethyl-2-chloroacetanilide is reacted with a cis- alkenol in the presence or absence of an acid binder, to give a compound shown by the formula.

Description

[Detailed description of the invention] Regarding paddy field herbicides containing as.

More specifically, R represents a cis-type FiS alkenyl group having IIt carbon atoms. , 6'-diethyl-N-((cis-alkenyloxy)methyl)-1-a acetanilide (hereinafter referred to as the compound of the present invention) and at least seven types of compounds of the present invention as active ingredients. Regarding paddy field herbicides.

The object of the present invention is to obtain a paddy field herbicide industrially and to provide a paddy herbicide that is extremely effective in aquarium cultivation compared to related compounds.

Many haloacetanilide derivatives that have herbicidal activity are already known, and among them, N-alcomethyl derivatives? However, it is known in the literature.

For example, Tokuko Shoda Zaichi IIS Koda No. 37g-0, U.S. Patent No. 3, Dada 2.9$j and U.S. Patent No. 3.5
1I ri, 6ko θ, etc. are known.

In particular, the above-mentioned Japanese Patent Publication No. Ig-37g Co. No. 0 describes a test example of the pre-emergence phytotoxic activity of 100 liu of haloacetanilide derivatives including N-alkenoxymethyl derivatives.

Which of these derivatives are actually commercially available? , 6'-diethyl-N-methoxymethyl-Coke G!
roacetanilide, J,A'-diethyl-N-toxymethyl-cochloroacetanilide, in which R in the above general formula is changed to an alkyl group, and the former #'iC,
, the latter indicates 04.

Among the haloacetanilide derivatives, 1, especially 2'. A'-diethyl-N-alkoxymethyl-cochloroacetanilide is considered to be an excellent herbicide with nine efficacy, but in reality, even if it is the same N-alkoxymethyl substituted product, it is N-methoxymethyl substituted product. (R=
C,) is mainly used as a herbicide for fields such as corn, soybeans, cotton, and sugar cane, whereas the N-methoxymethyl substituted product (R=04) is used as a herbicide for paddy rice, wheat, sugar, and radish. ], the difference in alkyl groups has an extremely large effect on plants. In fact, Tokuko Shoda g-37gaO
According to Table 1 (test table) of the issue, N-methoxymethyl substituted products and N-ethoxymethyl substituted products inhibit the growth of rice, whereas N-zoro4xymethyl substituted products and N-ethoxymethyl substituted products
Results show that -methoxymethyl substitutions do not inhibit growth (see Compound No. 3, g%lt and col).

Even if the number of carbon atoms in the group R is the same, whether it is saturated or unsaturated has a large effect. For example, N-proloxymethyl substituted products do not inhibit the growth of rice, whereas N-glo(nyloxymethyl substituted products) and N-f a hynyloxymethyl substituted products have been shown to inhibit growth (see Table 7 above).
See compound nos. 9, 11 and 21).

Therefore, according to the knowledge of such prior art, among related compounds, compounds in which R has 3 or more carbon atoms and a saturated alkoxy group have efficacy as paddy herbicides,
On the other hand, in the case of alkenyloxy groups, even if the number of carbon atoms in R is 3 or more, it is found that the alkenyloxy group has a growth inhibiting effect on rice.

However, as a result of intensive study by the present inventors on the properties of these related compounds from the viewpoint of their effects on rice, which is required for the paddy field herbicide KllI, and their monocidal properties against Japanese field grass, a typical harmful weed, we found that In the case of alkenyloxy groups having a carbon atom number of t to S, there is little growth inhibition on rice;
Of the stereoisomers, compounds with a trans-alkenyloxy group are slightly less effective than commercially available compounds with a butoxy group; however, in the case of compounds with a cis-alkenyloxy group, It was found that the trans isomer has a remarkable improvement effect in terms of herbicidal effect under paddy field conditions, phytotoxicity to paddy rice (especially at high temperatures)', and fishability, even when compared with commercially available products. .

That is, the compound of the present invention, in mirror culture of paddy rice, especially when applied to the water surface before the germination of weeds, helps the harmful weeds, weeds, and -
Shows strong herbicidal effect against annual and rod weeds, -1
It has a selective herbicidal effect on rice that has almost no effect on rice at any stage before or after transplanting, regardless of temperature, and is also highly safe for fish. It was confirmed.

The compounds of the present invention include...! , 6'-diethyl-N-(C2-cis-butenoxy)methyl]-cochloroacetanilide +21 , r, b' -? xfk-N-((J-shix
--4-tenoxy)methyl]-cochloroacetanilide 131 2e b'-NXfk-14-((3-1'J
-47teno-methyl]-cochloroacetanily
Do 42', A'-diethyl-N-[(/-methyl-1-
cis-butenoxy)methyl]-cok-aloacetanilide. Among them, the compounds of ... and Minoru ν will be awarded the prize.

The compounds of the present invention are all characterized by being cis-forms, and therefore are preferably as pure as possible, but as long as they do not essentially impair the effects of the present invention, they may be used as by-products. May contain trans isomer. However, as the amount of the trans isomer increases, the effect of the present invention gradually decreases, so it is appropriate to set the cis linkage to 0 or more, preferably qos or more.

Further, it is essential that the compound of the present invention has a carbon number of 5 to 5, and compounds having 6 or more carbon atoms are not preferred because their herbicidal activity is extremely poor.

The compounds of the present invention can be produced by various methods. Preferably,
! It can be prepared by reacting ',A'-diethyl-N-chloromethyl-cochloroacetairide with cis-alkenoxy in the presence or absence of an acid binder. All of these raw materials are known substances. The former is ko,
6-dinitylaniline and formalin or formaldehyde low polymer are reacted to form an azomethine compound,
Then, by reacting this with chloroacetyl chloride, a product is obtained. The latter can also be obtained by partial hydrogenation of alkynols in the presence of a Lindlar catalyst.

Another method is to first react 2,6-diethylaniline with cis-alkenyl ÷ halomethyl ether to obtain N-(cis-alkenoxy)methyl-,6-diethylaniline, and then react this product with chloroacetyl chloride. Alternatively, it can also be produced by reacting N-chloroacetyl-co#6-dinitylaniline and cis-alknyl halomethyl ether in the presence of an acid binder.

By appropriately combining more than one species of the compounds of the present invention, it is also possible to provide a mixed herbicide that is effective against many grass species.

Next The present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example/ ! , 61-diethyl-N- [(kosi soup tenoxy)
Methyl]-cochloroacetanilide...
...(In a 3θOal flask, add 2, 30 A-diethylaniline.
．． 31.31% Hokwsu 73S, /II, Benzenda S
I and refluxed on an oil bath for 1 hour. Next, the water layer is removed and the oil layer is subjected to condensation dehydration. 3. /l of N-co,6-ethylphenyl-N-methyleneimine was obtained. Benzene 3. θIK This material was dissolved, and a solution of chloroacetyl chloride and Sf was added to the solution at 0°C.

After the addition, the temperature was returned to room temperature, stirred for 30 minutes, and concentrated using the evaporation residue to give 311. . Y-T coarse! , 6'-diethyl-N-chloromethyl-2-chlorogastric acetanilide was obtained.

Penzenko OPK Dissolve this and prepare -1 cysuittenol (cis ratio 9 days)/1. -f was added, stirred at room temperature for q hours, and after 90 reactions, -〇〇- water and -001 ethyl ether were added and stirred well. The oil layer was further washed with water, and i
i! Dry with magnesium acid and evaporate the ether.

10. The target object is a dark yellow oil. ．． I got 2f. Crude yield v
4I*.

Historically, when refined copper was purified using a silica dull column using pentane as an eluent, 3. ．． A 3f pale zeta-brown oil was obtained.

This oil was then subjected to elemental analysis, IR, NMR and C-
As a result of NMR analysis, this oily substance! , 6'-diethyl-N-([2-cis-butenoxy)methyl]--chloroacetanilide (pure f5?q-), and it is certain that it contains the trans isomer as a by-product. It was done.

Elemental analysis value: C,,824No,CtCHN
C1 Calculated value (Feed: A!;, 9θ ri, g/'1.!;
Ko //, Dada actual value (lt): 45.4 Hiro 7.9
Zada, deco //, 71I IR (m-'): N, 10 (-^-C-5), 10
1010(-0-)H-N: ri, 04'(jH,
m),! ;@39 (,2H,m),'F,*za/ (
2H*s)e, 15L2H,d)1. ? ,,! tlh(
koH-sr, 2-34 (4'H1Q)/, 6θ(38
, d), /, -〇 (AH, t) Refractive index (no): /
,! ;2! Note that the ratio of cis to trans in the product was determined using lc-NMR. ' ``C-NM
In the measurement of R, first, the chemical shift values were qualitatively determined using cosis- and trans-butynol as model compounds, and then r-
The fiNOE effect t# was removed by dead decagri/da, and the simole ratio was determined by the areal weight method.

Example! , 6'-diethyl-N-[(cocissupentenoxy)methyl]---chloroacetanilide...
・・・・・・・・・(2) Confirmation system 1 in Example 1
By carrying out the same procedure using cosi-superpentenol (99% cis-M)/-f instead of tenol, an amber oil was obtained. This oily substance was analyzed in the same manner as in Example 1, and it was found that it was J, A'-diethyl-N-((cocis-(tenoxy)methyl)-Coke I loacetanilide (cis ratio Tade-).
- was done.

Elemental analysis value: C1°824No, Cj CHN C1 calculated value (*): 61ri6 g, 09 11. ．． 3J
10.9! Actual value (-): 44.5? g, J
Oda, 4/ //, 331 1R (m-): /410 (-N-C-), 101
10 (-0-)H-NMR: Ri, , 20 (3H, m)
,s,tis<koH#m),Hiroshi,? ? L2H#d)
3,g(,2H,s),J,jko(lI+,q),ko,05(-H,m)8-2(/sH,t),0. m3H
, t) Refractive index (np'): /asco/6 Comparative Example 1 Confirmation When the procedure was repeated in the same manner as in Example/, using n-butanol in place of cysutinol, an amber oily substance was formed. Obtained. When this oily substance was analyzed in the same manner as in Example 1, it was confirmed to be J',A'-diethyl-N-toxymethyl-cochloroaltanilide (^).

COMPARATIVE EXAMPLE Confirmation of transsuit tenol J) Using K-1 transsuit tenol (trans ratio 93%), the procedure was repeated in the same manner as in Example 1 to obtain a yellow oily substance S and KF. It was done. As a result of analyzing this oil in the same manner as in Example 1, it was found that J',A'-diethyl-N-1cotrans-butenoxy)methyl]---chloroacetanilide (8)
() Rance percentage? 4All) was confirmed as a friend.

Elemental analysis values: C,, H, 4No, C1CHN
C1 1tlL(i(kai', 1.!;, 90'Z, t/
e, S, 2 //, 1111 column value (1):
bk,! ;g Ri, 9 Ko, Ri A ii, t
rco1 1R(aa-'):/1-75 (-N-C-), 10
90 (-0-), 9Aj () Lance) H-NMR: ri, 20 (JH, m), 3.40 (koH@
rn)% 4'e gko(koH9$) Hiro, OS<
koH*d)% J-Aff(2H*”)%ko, Aj(4
4H, q) 1, Otsu, ? (3H, d), /, ko2 (AH,
t)i Refractive index (no): /, ffcoit To use the compound of the present invention as a herbicide, it must be mixed with various auxiliaries, such as diluents, solvents, and surfactants, and then used as a herbicide. It is used in formulations such as wettable powders, powders, and granules.

It may be appropriate to add other herbicides to reduce spraying effort or to broaden the range of grass species that can be effectively controlled.

Examples of drugs that can be added include the following four.

Ko, Derzikuro■ Phenoxyacetic acid, its salt 1 ester and alkylamine salt; Confirmation Methyl-derchlorophenoxyacetic acid, its salts and esters; λ-Methyl-tei-chlorophenoxybutyric acid, its salts and esters; (4I-chloro-O-tolyluo)-tetrapionic acid, salts and esters thereof; octanoic acid-cyanocyano, 6-diiodophenyl; lI# A-) +7 chlorophenyl router'
-nitrophenyl ether; J a'll-8'chlorophenyl! - theta'-nitro, phenyl ether in met; Nitro Aeniru! , y-xylin ether; hexahydro-/H-ayabin-/-cal-5-ethyl thioate; 3.4L-dicyclotetraglobionanilide; z, b'--
,yethyl-N-(butoxymethyl)-confirmed chloroacetanilide; ,? , A'-diethyl-N-(n-zoloxyethyl)
-cochloroacetanilide; 12'#A'-diethyl-N-(butoxymethyl)-confirmation chloroacetanilide; /-(α,a-dimethylbenzyl) -,3-P-)lyl w; co, Derpis (ethyl amino)-6-methylthio-i,
, y, s-triazine; confirmation ethylaminoder isoglobylamino-6-methylthio/, 3.3-triazine; s-triazine; diazoline-kone; co,6-cyclobe/zonitrile; 2,6-cyclothiobenzamide; core ξ-no-3-chloro-7, dana-7 toquinone; 5.
4-nato-2hydrophthalimide; , 2,47-dichlorophenyl-! -ethoxyethoxyethoxytil-nitrophenyl ether; N-(/
-ethylpropyl)-co,6-sinitro3. 01O-diinoprobyl-co(benzenesulfonamide) ethylene dithiophosphate; 3, ? '-Dimethyl-dermethoxypenzophenone;α-(cornaphthoxy)globionanilito; θ-ethyl-〇-(3-methyl-6-nitrophenyl) N-5ec-butylphosphorothioamidate; 3-inonolopyruco# /
# 3--4 ndzothiadiazinone-(+')-2, codeioxide and its salts; S-(J-,,l methyl-/-,'peridyl car is nylmethyl)-0,0-sea n- Propyldithiophosphate; S-benzyl-N,N-dimethylthiocarbamate.

Formulation examples of the compound of the present invention will be described below, but the types and blending ratios of the compounds and additives are not limited to these formulation examples, and can be varied within a wide range. Parts in each example mean parts by weight.

Formulation example / Wettable powder The compound of the present invention (20 parts of 11, 3 parts of silica, talc tiom, 3 parts of sodium lignin sulfonate, and 2 parts of sodium dodecylbenzenesulfonate are mixed and crushed to form an irrigation agent. do.

Formulation Example - Granules 5 parts of the compound (2) of the present invention, 1S part of bentonite, 1 part of Tal! r 2- S ms 25 parts of clay, some λ part of lignin sulfonic acid, and 0.5 part of sodium dodecylbenzenesulfonate were uniformly mixed and ground, water was added, the mixture was made into P granules using an extrusion granulator, and dried and sieved. Take the form of granules.

Formulation Example 3 Emulsion The compound (1) of the present invention is prepared by uniformly dissolving 3 parts of Silenc, boroxyethylene alkyl ether svm, and ylkyl penzene sulfonic acid calcium salt Jll in -0s% to prepare an emulsion.

Next, the effects of the compounds of the present invention will be explained using test examples, and these results show that the compounds of the present invention have superior medicinal efficacy compared to compound ^, and also have reduced phytotoxicity to water 11. That is clear.

Test Example 1 Novie pest control test in direct sowing by flooding //! ! 0
After filling 4 pieces of 00 are Hugner with 1K of rice paddies and puddling them, 20 rice seeds (variety: Nipponbare) and 50 wildflower seeds were added to %IIl. When paddy rice seeds and wild field seeds germinate, and when they reach θ day 1 (one-leaf stage) after sowing, the watering method is set to 3 cm, and the compound of the present invention is made into granules according to the formulation example, and a predetermined amount Measure it out and apply it evenly on the water surface.

The herbicidal effect and influence on rice plants were investigated on the vkllI day of chemical treatment, and the results shown in Table 1 were obtained.

Table 7 (#Ik indicates the live weight ratio to the non-treatment area,
) Test example Soil treatment test on paddy leather //! ;0
Fill a 00 are Wagner pot with paddy soil and grow paddy rice seedlings (variety: Nipponbare>ttII) at the -leaf stage (plant height 10m).
! I transplanted the first B book.

Spread the soil containing a large amount of seeds of field weeds and major paddy weeds evenly within the surface layer. However, when the 1ik3 wound was flooded and the novies grew around the /If stage.

An emulsion of the compound of the present invention prepared according to Formulation Example 3 was diluted with a predetermined amount of water, spread uniformly, and stored at an average temperature of 2 g°C. The herbicidal effect and chemical damage to paddy rice were evaluated after S days of chemical dispersion.The results are shown in Table 3.Efficacy and chemical damage to paddy rice were evaluated in the following six stages.

S: l for untreated area! 1 revolution rate zaO- or more (Rice damage rate for untreated area) 4t = Weed killing rate for untreated area 10 to 7 days attack (Rice damage rate for untreated area) 3: Weed killing rate for untreated area 4tiθ~ 39% (Rice damage rate compared to untreated area) Weed killing rate compared to Koni untreated area 20-39- (Rice damage rate compared to untreated area) l: λO-F() 0: Same test as completely untreated area Example 3 Mixing ratio and herbicidal effect test of Compound 01 and Compound (provided) Novel grass is grown in i and ss stages (1 year old broad-leaved weeds are in the early stage of true leaf development, fireflies are in the 2-leaf stage)
Each leaf agent was applied at a predetermined concentration on the following day, and the herbicidal effect was investigated after -0 days. The evaluation method was performed according to the test example. The results are shown in Table 3.

Koi (current year) Noriza time-based half-lethal-K (TLM)
But it's a ratio mulberry agent ^. , 6ρρm, the compound of the present invention (1
) showed a TLM value of / ppm, and was confirmed to be completely safe for fish.

Claims (1)

[Claims] (General formula 11: In the formula, R represents a cis-type alkenyl group with a number of carbon atoms of lIt or S, represented by!, 6'-diethyl-N-[(cis-alkenyloxy ) Methyl]---Chloroacetanilide. (Ill General formula: In the formula, R represents an alkenyl group in which the number of carbon atoms in the cis form is S, and contains at least seven types of compounds represented by the following as active ingredients. Paddy field herbicide.