JPH03151386A - New tetracyclic condensed heterocyclic compound and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [A is formula II (R1 is H or lower alkyl); R2 is H or lower alkyl; R3 to R6 are H, halogen or lower alkyl; m and n are 0 or 1, provided that m and n are not simultaneously 0 or 1; all the R3 to R6 are not simultaneously H when R1 and R2 are H and n is 1]. EXAMPLE:13,13a-Dihydro-11-methyl-8H-isoquino[2,1-g][1,6]naphthyridine- 8,9(12H)- dione expressed by formula III. USE:A herbicide. PREPARATION:A compound (e.g. 13,13a-dihydro-11-methyl-8H,9H- benzo[a]pyrano[3,2-g]quinolizine-8,9-dione) expressed by formula IV is reacted with a compound expressed by the formula R1-NH2 (e.g. aqueous ammonia), as necessary, in an inert solvent preferably in the presence of a base (e.g. triethylamine) at a temperature within the rang of cooling with ice to 120 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a group of novel compounds belonging to the tetracyclic fused heterocyclic compounds. The present invention also relates to a herbicide containing a tetracyclic fused heterocyclic compound as an active ingredient.

(Prior Art) Conventionally, compounds belonging to tetracyclic fused heterocyclic compounds have been described in Pharmaceutical Journal, Vol. 84, p. 874 (1964-), Vol. 87, p. 597 (1967) and Pharmaceutical Journal, Vol. 10
The compound described in Vol. It was not known that these compounds, including ring compounds, have herbicidal activity.

The present invention provides a herbicide containing as an active ingredient at least one of a group of novel compounds belonging to the fused tetracyclic fused heterocyclic compounds and the fused tetracyclic fused heterocyclic compounds.

(Structure of the Invention) The present invention provides a compound represented by the following formula (I).

R2 is a hydrogen atom or a lower alkyl group;
R3, R4, R5 and dog are the same or different and represent a hydrogen atom, a halogen atom or a lower alkyl group; m and n represent O or 1; However, m or n is O at the same time.
Or, if R1 and R2 are hydrogen atoms and n is 1, then R3, R4, R5 and dog cannot all be the same at the same time. ] Here, the lower alkyl group means a group containing 01 to C6 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, impentyl, hexyl, isohexyl, and the like.

Halogen atoms include chlorine, bromine, fluorine, and iodine.

The compound represented by formula (E) of the present invention can be produced by the following method.

Production 1 of a compound where A=-N- [wherein R1, R2, Ra, R4, R5, R6 are the formula (
Same as the definition of I')] This method applies to formula (IV) produced by the above method a or b.
This is carried out by reacting a compound represented by formula (V) without a solvent or in an inert solvent. The reaction temperature is preferably in the range from water cooling to about 120°C. The compound of formula (V) is preferably used in an amount equal to or more than the amount of the compound of formula (IV). At this time, triethylamine, pyridine,
The reaction proceeds smoothly when an organic or inorganic base such as sodium carbonate or sodium hydroxide is added.

The present invention provides a herbicide containing at least one compound represented by formula (E) as an active ingredient.

In the herbicide of the present invention, the active ingredient compound represented by the above formula (E) may be used as is, but in general, depending on the purpose of use, solid carriers, liquid carriers, surfactants, and other formulation auxiliaries are used. It is formulated into wettable powders, granules, emulsions, etc. by mixing with the drug.

These preparations contain the compound as an active ingredient, 10-80% for wettable powders, 1-10% for granules, and 10% for emulsions.
~50% (all percentages by weight are not shown).

Solid carriers used in formulations include fine powders or granules such as kaolin, bentonite, clays, talc, diatomaceous earth, gicrite, zeolite, pyrophyllite, synthetic hydrous silicon oxide, and calcium carbonate, and liquid carriers. Aromatic hydrocarbons such as xylene and methylnaphthalene,
Ethanol, isopropanol, ethylene glycol,
Examples include alcohols such as methyl cellosolve, ketones such as acetone, isophorone, and cyclohexanone, vegetable oils such as soybean oil and cottonseed oil, dimethylformamide, dimethyl sulfoxide, acetonitrile, and water.

Surfactants used for emulsification, dispersion, wet carbonization, etc. include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Examples include nonionic surfactants such as ethylene polyoxypropylene block polymers, anionic surfactants such as alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, and polyoxyethylene alkyl sulfate salts.

Formulation adjuvants include lignin sulfonates, alginates, polyacrylates, polyvinyl alcohol, vegetable gums, carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), and the like.

(Example) Next, the present invention will be explained by referring to an example. In addition to the compounds shown in the examples, the following compounds may be included as interesting compounds included in the present invention. (Table 1) (Synthesis example) Synthesis example 1 13.13a-dihydro-11-methyl-8H,9H-
benzo[a]pyrano[3,2-g1 quinolidine-8,9
-Production of dione (compound Nα7).

5 ml of diketene was added dropwise to a solution of 2.50 g of isoquinoline and 3 ml of benzene over about 15 minutes while cooling with water. After the dropwise addition was completed, the mixture was heated and refluxed for 4 hours. The reaction mixture was cooled, and the precipitated crystals were filtered and dried to obtain 1.89 g of the compound mentioned above.

Melting point 220-221°C Synthesis example 2 6a,7-sihydro9-methyl-1LH,12H-benzo[0pyrano[2,3-bl quinolidine-11,12
-Production of dione (compound Nα5).

Quinoline 5. 15 ml of diketene was added to a solution of OOg and 7.5 ml of benzene, and the mixture was refluxed for 4 hours. The reaction mixture was cooled, the precipitated crystals were filtered and dried, and the compound was reduced to 6.0
I got 4g.

Melting point: 225-231°C Similarly, the following compounds were obtained from the respective reacting quinolines.

Nα6) Melting point 221; 5°C (decomposed) 3-chloro-6a, 7 dihydro 9-methyl-11H,
12H-benzo[f1 pyrano[2,3-bl quinolidine-11,12-dione (compound Nα9) Melting point 251-252°C (decomposed) IR (KBr disk): 855, 1168, 1
318, 1445.

1690cm-1 Synthesis example 3 13.13a-dihydro gl [L6] Naftiri Manufacture of rod 1).

rho-11-methyl-8H-isoquino(2,1-dine-8
,9(12H)-dione (compound 13.13a-dihydro-11-methyl-8H,9H-benzo[alpyrano[
3,2-g1 quinolidine-8,9-dione 1. OOg,
A mixture of 0.39 ml of concentrated ammonia water and 30 ml of water was stirred at 45°C for 15 hours. After cooling the reaction mixture, the precipitated crystals were treated with silica gel column chromatography and further recrystallized from a mixture of ethyl acetate and methylene chloride to obtain the compound 382m
I got g.

Melting point 186~18'15°C IR (KBr disk): 785, 1250, 1
465, 1598.

16401650 cm' NMR (CDC13) δ value: 2.48 (s, 3H), 3.10-4.00 (
m, 2H), 5.26(q, IH).

5.95 (d, IH), 6.61 (s, I
H), 6.80-7.50 (m, 5H).

12.57(s, IH) Synthesis Example 4 6a,7-sihydro9-methyl-11H-quino[1,
2-gl[L6]su6a,7-sihydro9-methyl-
A mixture of 1.50 g of 1LH,12H-benzo[0pyrano[2,3-bl quinolidine-11,12-dione, 0.43 ml of concentrated aqueous ammonia and 30 ml of water] was prepared at 55°C.
It was stirred for 3 hours. After cooling the reaction mixture, the precipitated crystals were treated with silica gel column chromatography and further recrystallized from a mixture of ethyl acetate and l.xane to obtain 332 mg of the compound ε1-.

Melting point: 162.5-164°C Similarly, the following compounds were obtained from the corresponding raw materials.

Note that in the production of compound Nα8, a 40% methylamine aqueous solution is used instead of aqueous ammonia.

3-chloro-6a,7-sihydro-9-methyl-11H
-quino[1,2-gl[L6]naphthyridine-11,1
2(8H)-dione (compound 3).

Melting point 186.5-188.5°C IR (KBr disk): 1200, 1260,
1380, 1482.

1605 1652 cm' NMR (CDC1a) δ value: 2.4.6 (s, 3H), 3.30 (d,
2H), 4.50-5.00 (m, LH).

5.85 (q, IH), 6.42 (q, I
H), 6.97-7.33 (m, 2H).

8.07 (d, LH), 8.50-12.00
(br, IH) 6a,7-cyhydro5,9-dimethyl-11H-quino[1,2-gl[1,6]naphthyridine-11,12-(8H)-dione (compound tooth 4).

Melting point 138.5-140.5°C IR (KBr disk): 1208, 1443,
1485, 1580.

1650 cm' NMR (CDC13) δ value: 2.00-2.22 (m, 3H), 2.39 (
s, 3H), 2.90-3.80 (m.

2H), 4.40-4.90 (m, IH),
5.60-5.85 (m, IH).

6.63 (s, IH), 7.00-8.20 (
m, 4H) 6a,7-sihydro8,9-dimethyl-11H-quino[1,2-gl[1,6]naphthyridine-11,12(8H)-dione (compound Nα8) melting point
IR above 300°C (KBr disk): 782, 852, 11
90, 1275.

1358, 1483, 1555, 1625.

1675 cm-1 (Test example) Plant physiological activity test Talc (50 parts by weight), bentonite (25 parts by weight),
A carrier was prepared by mixing Tsurupol-9047 (manufactured by Toho Chemical Co., Ltd., 2 parts by weight) and Tsurupol-5039 (manufactured by Toho Chemical Co., Ltd., 3 parts by weight). 50 parts by weight of each of the test compounds and 200 parts by weight of the carrier were mixed to prepare a 20% permanent agent. This hydrating powder was dispersed in pure water to obtain a hydrating powder dispersion having a predetermined concentration. Separately, prepare a petri dish containing germinated rice, wildflower, Japanese radish, and firefly seeds, add the above-mentioned hydrating agent fraction, and grow the seedlings for 7 days in a constant temperature warehouse with lighting at 25°C. It was evaluated according to the standards, and the results are shown in Table 2.

Claims (2)

[Claims] (1) Formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼(R_
1 is a hydrogen atom or a lower alkyl group); R_2 is a hydrogen atom or a lower alkyl group; R_3, R_4, R_5
and R_6 are the same or different and represent a hydrogen atom, a halogen atom, or a lower alkyl group; m and n represent 0 or 1; However, m or n will never become 0 or 1 at the same time, and if R_1 and R_2 are hydrogen atoms and n is 1, R_3, R_4, R_5, and R_6 will never become all at the same time. ] A novel tetracyclic fused heterocyclic compound. (2) Formula (I'): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A is an oxygen atom or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1 is a hydrogen atom or a lower alkyl group); R_2 is a hydrogen atom or a lower alkyl group; R_3
, R_4, R_5 and R_6 are the same or different hydrogen atom, halogen atom or lower alkyl group; m and n
indicates 0 or 1. However, m or n cannot be 0 or 1 at the same time. ] A herbicide characterized by containing at least one type of tetracyclic fused heterocyclic compound represented by the following as an active ingredient.