JPS5925302A - Herbicide - Google Patents

Abstract

PURPOSE:To prepare a herbicide effective to the broad-leaved weeds such as annual fleabane, broad-leaved plantain, etc. and narrow-leaved weeds such as manna-grass, nutgrass, etc. especially by foliar treatment, by using a specific cyclohexenone derivative as an active component. CONSTITUTION:The objective herbicide contains the cyclohexenone derivative of formula I (R is OH, lower alkoxy, lower alkoxycarbonyl, lower alkylcarboxy, hydroxycarbonyl, their salts, etc.; n is 0-5), e.g. phyllosinol (=5,6-epoxy-4- hydroxy-2-hydroxymethyl-2-cyclohexenone) as a main active component, preferably at a concentration of >=5X10<-3>wt%. The herbicide has the characteristics of both water-soluble and oil-soluble. The compound of formula I can be prepared easily, e.g. by oxidizing the hydroquinone derivative of formula II, epoxidizing the resultant guinone derivative of formula III with a peroxide, and reducing the product with NaBH4.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel herbicide containing cyclohexenone as a main active ingredient.

It has been reported that cyclohexhynone compounds have certain physiologically active effects of yuzu.

For example, 1 Grit Rural Bio μ Dical Chemistry
(Agricultural
Former o1oglcal Cbamistry)
+38, 163 (1974) is the following formula (1■
) to υII has inhibitory action, antibiotic action/11
．． It has also been described that it has a root growth promoting effect on plants. In addition, the above formula (
11) The compound promotes the germination of ttrt seedlings and the root development 41J
It has been shown to have a promoting effect.

From the above, it can be seen that the compound h' IW 'JJ1 of f.a. has some kind of physiologically active effect on animals and plants. It wasn't made clear.

The present inventors have conducted intensive physiological and physicochemical research on various cyclohexenone compounds, which are thought to have this interesting physiologically active effect. , Schiff 11 not shown in the present invention
The present inventors have discovered that Fuhexen/aC derivatives have extremely excellent herbicidal effects on various plants, and that these derivatives have particularly excellent herbicidal effects even in foliage treatments.

That is, the present invention provides +1 ridge 4 from cyclohexenone compounds represented by the following general formula (I).
) Contains at least 14M as the main active ingredient.
The object of the present invention is to provide an insect repellent characterized by the following.

The present invention will be explained in more detail below.

The cyclohexenone derivative in the present invention is pre-fiiE
It is represented by the formula (1), but the deceased (R in 11 is a hydroxy group: lower flukoxy I!
I": lower alkoxycarbonylnor; lower furkylcarboxyjk; hydrocarboxy group; hydroxycarbonyl, its metal salt, or a hydrogen atom or lower alkyl h (with no exception) The carbamoyl formula shown is used.

The most desirable lower alkoxy group is an alkoxy group having 6 or less carbon atoms, which is -()I? R4 represented by ' is methylno1 (, ethyl group, Meishin f+ 7
'μ-pyl group, various Zunar+) (IL, cyclopentyl/l;, cyclohexyl group, vilanyl group, (, piperidyl, piperazine/1 group, 7)1 holinyl group, etc., '17FK preferred lower a11. Examples of xinol include metquin group, ethoxy group, and bu-μ boxy group.

In addition, as a preferable example of the lower alkoxycarbonyl, 'C is a fluorocarbonyl group having 6 or less carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, and a buppoquincarbonyl group with one each. 1, Nyl group, each (
111's carbonyl group is mentioned, and 1:1:1. , <Keme] xycarbonite h';
, =c toxic small nyl group, fluoroxycarbonyl 4 (bamboo).

In addition, the lower furkylcarboxy group of 1j11 is preferably one having a carbon number of 6 or less, such as methylcarboxyl/toboxyl, ethylcarboxo group, various propyl carboxyl groups (y is various 7° methylcarboxy J162q Ka J
7.1), particularly preferred or methyl nonorbo1. ″
These include cy group, ethylcarboxybo・\' cy group, etc.

Furthermore, 611 B self-hydroxyl, +5 nyl group gold 1
If h is preferable for g and [5 is, for example, lithium I
UK.

Na;lium j2, -4lium Jsu1 -1gnesium salt.

Monovalent or divalent gold A/11 salts such as calcium salts, l[h
Preferred examples include lithium salts, lithium salts, potassium salts, etc. 1. -, 7/7nium Jj. of hydroxycarbonyl group at +1. [)1. Then, the following formula (seal) N@“(■ζ゛), ・・・・・・・・・
... (1)! Dimensioned to 11 or non-li1'
Salts of ammonium io:7 are used, and preferred examples thereof and L'C are ammonium salt, ethylammonium salt, diethylammonium salt, isopropylammonium salt, and di-ammonium salt. .

, Il+ more l! IIJR Self-〇〇N, 8. In the carbamoyl group represented by ``It', R'' means the same or different hydrogen atoms or lower alkyl groups, and preferable examples thereof include a hydrocarbon atom or a flukyl group having 5 or less carbon atoms, that is, methyl 11 ( , Ethylno ((.

Examples include various propyl groups, various nofol groups, and the like.

Furthermore, n in 111 general formula (1) is 0 to 50I
A&! ! , means. However, when n is 00, it is assumed that the carbons Klt at the 2nd position forming a monkey are connected by 10 points. With the preferred n-Ci, t, and Q, a 3-way alignment is achieved.

Preferred examples of the cyclohexenone conductors in the present invention include those in which R in the general formula (1) is a hydroxy group, a lower fulkylcarboxy group, a cyclohexenone group, or the like. It will be done.

The herbicide of the present invention is a cyclohexenone PA conductor represented by the general formula (1)! At least 1 selected from lJ′1
It contains seeds as an active ingredient, and it is preferably 5 x 10-31i lz1 or more, and I
X l O-double printing≠ is particularly preferred. However, if two or more kinds of nuclear fermentation conductors are included in 1 ton, the content in the row dt Jll shall be determined.

Is the iC okei 1 herbicide of the present invention an IIA herbicide? It is preferable that the active ingredient cyclohexenone [1] is contained in
♂Conductor knowledge θ) From the outside, it can be anything.

Examples of additives that can be included in the herbicide of the present invention include inert diluents, 411 molluscs, 411 or l
Examples include t1.11 regulating agents.

The n5 additive and the cyclo-, ki)=non-accumulating substance represented by the above general formula (+) are mixed and prepared in the form of, for example, finely divided particulate solids, granules (1 vent), solution (1) dispersant, or emulsion. The herbicide of the present invention can be produced. That is, the cyclohexenone derivative is a quadrant, such as a finely divided granular solid.

Liquids of organic origin, water, wetting agents, dispersants, emulsifiers, etc., or any of these in combination, g+, i
%2 and the herbicide of the present invention.

16. Use in the herbicide of the invention 7. Typical finely divided solid bodies and inert solid enhancers include, for example, Merck, natural and synthetic clays such as kaolinite and heptadol guides.

Pumice, glue, 8 ingredients (calcium and magnesium 11ate, silica earth 1 quartz, Fuller's earth, salt, powdered cork, powdered water + 4. crushed l Umo I7 Koshiho '1111 + walnuts), -f-Yoke, Charcoal, volcanic ash.

From cotton fire, flour, thick D-powder 1 j + poly (sandy lime) O [the throat is scorched. Norihari-like 1. Examples of cirk body diluents include water or i, r, petroleum moieties such as Kelsene, hexa/l/l/n, benzene, diesel oil, toluene, acetone, ethylene diglycolide, stondart solvent, al: Pools such as purpanol, glycol, etc.

In the camellia removal process of the present invention, the liquid and wettable particles are usually one or more of the surface t1'i
I! It contains enough nl to easily dissolve its components in water or oil. A5 here! Of course, for serum +11, agent use, 1) 1 lubrication.

Also included are hk shavings, turbid shavings, dispensing agents, and emulsifiers.

In addition, the herbicide has a negative impact (・(Oi C Insecticides generally used as pesticides 2. Auxiliary C 1).

Other C removal 4 (contains deletion, etc.)

1j II of the present invention A cyclohexynone derivative represented by general formula (1) 2. One horizontal tI! l! As a dragon (Kei,
In general, even if you get a train in the direction of 1f/) direction θ: no.

Below, if you like. ) As shown in the formula (OV), the idoto\non derivative is converted into 1 (by converting it into quinone of the formula (IV); The cyclohexenone derivative of the general formula (I) can be obtained by epoxidizing it with NaB1 (IK) and then reducing it with NaB1 (IK). Some are, for example, Tetrahedron Letters.
ters) + 4231 (+974) As noted in @, 611i-dimethylfulpene is added to penzoqui7 as shown in the following formula, f=1 is added, this is epoxidized with peroxide, and then formylated, ^1~ Decomposition 6: Ij77J can also be obtained by processing q+n.

The agent of the present invention containing the Schiff 1I/Se/no derivative as an active ingredient is the Schiff 1. Since the 1-heptinone derivative has both water-soluble and oily properties, it can be used to treat grass leaves by absorbing the active +41 component from the leaves and stems of plants, and to absorb it from fields. It has the characteristic that it exhibits a herbicidal effect that is not affected by any soil treatment that absorbs the active ingredient. ! What is unique about this herbicide is that it has an extremely excellent IA removal effect in negative treatment of stems.

Furthermore, the MA herbicide of the present invention can be applied to, for example, broad-leaved weeds such as hymedion, halzion, and plantain;
It exhibits an extremely excellent herbicidal effect on a wide variety of plants such as crabgrass, Japanese turmeric, and narrow-leaved grasses such as hackberry.

Another advantage is that the cyclohexenone derivative, which is the active ingredient of the herbicide of the present invention, can be easily produced industrially.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to the Examples in any way.

Incidentally, "Part 1 of Examples" means "Serious introduction part."

1 Example 1 [Phyllo-7nol (5,6-evogycy-4-hydroquine-2-hydroxymethyl-2-cyclohexyl-1,-non)
Synthesis] Dissolve 16 parts of rosebenzoquinone in 100 parts of ethanol IW
Then, 32 parts of 6,6-dimethylfulvene was added dropwise with stirring at 5°C, and the mixture was left at 5°C for 48 hours. The reaction mixture was condensed under reduced pressure 1:1 and cooled to obtain 30 parts of pale yellow crystals.

30 parts of the crystals of Otsu were dissolved in 100 parts of tetrahydrofuran, and 50 parts of +o% hydrogen peroxide solution was added to a solution of 8.5 parts of carbonate sorter dissolved in 100 parts of water under water-cooled stirring. Drop - around. Then spread the width of the chamber for 1 hour.
l'L, 28 parts of crystals are obtained by benzene extraction.

28 parts of the crystals were dissolved in 460 parts of dry tetrahydrofuran, and while cooling with water, 21 parts of 1 lium of borohydride was added in small portions, stirred for 1 hour, and after 1 filtration, the tetrahydrofuran was concentrated. After adding water and extracting with ether, 23 parts of the product was obtained by removing the ether, and this was subjected to chromatography using solica gel to obtain 21 parts of the product.
Part of the product is obtained. 21 parts of this product were dissolved in 50 parts of tetrahydrofuran, 11 parts of 37% formalin and 1 part of 37% formalin.
, 14 parts of 8-diazabicyclo(5,4,0)undeceno 7 were added, stirred overnight at an ambient temperature, the reaction solution was concentrated and subjected to needle extraction, and the residue obtained by distilling off the needle was separated on a silica gel column. 23 parts of product are obtained. 23 ttll of this product was added to 500 parts of engineered ethylene glycol dimethyl ether, and after refluxing in a steam atmosphere for 1.5 hours, the ly, li=, rlA compound was dried under reduced pressure to form the remaining liI.
：'a・Silica gel force, separation a) by 1]
target '・(1,+10.5 parts of sinol are obtained.

The analytical results for the obtained phyllosonol are shown below.

Summer □, p, 82.5~8: L5°C 11t v c=0 1 680 (711v
32+(0,3350(:m-”H N kl It δp +1111 (CI) (J!
3) 3.45 (Ill), 3.58 (11 (),
3.75 (III).

4.0-4.5 (2H), 4. ss(+IN, 4.95
(IH).

6.65 (I II) λ1haa Flll++1 = 1 57 Example 2 20III g of the fiber p seal obtained in Example 1 was added to 50 g of water.
m1, and the spreading agent Full Soap 3 () o,
+m/ was added and i was also self-dissolved, and then the stems of crabgrass, Oibako, and Japanese red mullet:A were planted in pots in advance.
After spraying once for about 15 hours, a withering experiment was conducted by observing each plant with the naked eye. As a result, crabgrass and plantain are 48
Parts begin to discolor over time, and within 72 hours the entire area has discolored.
It completely died within 6 hours. Red mullet A) completely changed color and partially shriveled in 48 hours, and completely died in 72 hours.

Example Example bm The filocil 200119 obtained in Example 1 was dissolved in water so
Dissolved in me and further spreader full soap 30 o, zn
The mixed and dissolved mixture was carried out in the same manner as in Reli 2 (we conducted a withering experiment targeting the Japanese aphrodisiacs, Japanese amberjacks, plantains, and common sedges. Withering 1; Experiment 6
The condition fI14 after 48 hours was expressed in terms of withering degree and shown in No. 1k. Here, the degree of withering indicates the degree of withering, and the plant is still alive and well! Condition I
d1 is ・], Ill, the whole withered state (141 withered and withered is set as 5, and the space between them is divided into 1 equal parts (,,) is a method of displaying the intermediate state, the so-called 5-stage IJ: 4- method. It is something that

1st v Reference Example 1 ゛50cc of water and 30% of full soap. l'cc is the melting angle i
The 11° solution was prepared in the same manner as in Example 2.3 - C411qf4
pkoi! l' (The payment of the ticket) Even after the pilgrimage, there was no change at all.
; Grows to 114 I, 2.

7hri・Applicant Teijin Ltd.

Claims (1)

[Scope of Claims] 1. An agent containing at least one selected from cyclohexenone Rfj conductors represented by the following general formula (I) as a main active ingredient. 2. The cyclohexenone Rfj conductor represented by the following general formula (I) Senon Attraction 2! Classification 5 X 1.0
-Special 1t'F crystalline category 1 containing at a concentration of 3% by weight or more
1tl The herbicide according to item 1.