JPH05213899A - New halogenated cycloalkenecarboxylic acid derivative and herbicide comprising the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain the subject new derivative, a halogenated cycloalkenecarboxylic acid compound having a nitrogen-containing heterocyclic group bonded by sulfide group, useful for herbicide, etc., having a wide herbicidal spectrum, high herbicidal effects and excellent safety to crops. CONSTITUTION:A halogenated cycloalkanone derivative (e.g. ethyl 1-fluoro-2- mercapto-2-cyclohexanecarboxylate) of formula I [W is halogen; X is lower alkoxy, lower alkenoxy, (substituted) aryloxy, hydroxy, amino, etc.; (n) is 0 or 1] is reacted with a compound (e.g. 4-chloro-6-methoxy-2- methylsulfonylpyrimidine) of formula II (W' is halogen, alkylsulfonyl, etc.; Y and Z are N or methine; R<1> and R<2> are halogen, lower alkyl, lower alkoxy, etc.) in a solventless state or in the presence of a proper solvent by using a proper base in the temperature range of -78 deg.C to the boiling point of the solvent to give the objective compound of formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel halogenated cycloalkenecarboxylic acid derivative not described in the literature, and a herbicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 2-85262 describes an alkanoic acid containing a pyrimidine ring or a triazine ring and a herbicide containing the same.

[0003]

However, the compounds described in the above-mentioned documents have many points to be improved in terms of herbicidal spectrum, dosage amount, selectivity and the like.

The present inventors have conducted extensive studies to develop a compound having a broad herbicidal spectrum, a high herbicidal effect, and excellent safety against crops. As a result, the halogenated cycloalkenecarboxylic acid moiety and a specific substituent are bonded to each other. The halogenated cycloalkenecarboxylic acid derivative of the present invention having a structure in which the pyrimidine ring or triazine ring portion thereof is condensed via a sulfur atom is novel, and this compound is an excellent herbicide against not only annual but also perennial weeds. In addition to showing the effect, they have found that they have high safety against certain kinds of crops, and have completed the present invention.

[0005]

The compound of the present invention has the following general formula (I):

[0006]

[Chemical 3]

[In the formula, W represents a halogen atom. X is a lower alkoxy group, a lower alkenoxy group, a lower alkynoxy group, an optionally substituted aryloxy group, a di-substituted amino group which may form a ring structure by combining mono or two substituents, a hydroxy group and An agriculturally acceptable salt thereof, an amino group, a hydroxyamino group, a lower alkoxyamino group, a lower alkenoxyamino group, a lower alkynoxyamino group, an optionally substituted aryloxyamino group, or a benzyloxy group. Indicates. In Y and Z, when Y is a nitrogen atom, Z represents a nitrogen atom or a methine group, and when Y is a methine group, Z represents a nitrogen atom. R ¹ and R ² are each independently a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, or a mono- or two-substituents bonded to each other to form a ring structure. A substituted amino group or a lower alkylthio group is shown. n represents 0 or 1. ] The novel halogenated cycloalkenecarboxylic acid derivative represented by

In the above general formula (I), W represents a halogen atom, preferably a fluorine atom or a chlorine atom,
Particularly, a fluorine atom is preferable. X is a lower alkoxy group, a lower alkenoxy group, a lower alkynoxy group, an optionally substituted aryloxy group, a mono- or two-substituent may be bonded to form a di-substituted amino group or a hydroxy group. And its agriculturally acceptable salts,
Amino group, hydroxyamino group, lower alkoxyamino group, lower alkenoxyamino group, lower alkynoxyamino group, optionally substituted aryloxyamino group,
Alternatively, a benzyloxy group is shown, and among these, a methoxy group, an ethoxy group, a hydroxy group, an allyloxy group, a propargyloxy group, or an ammonium salt is preferable.

R ¹ and R ² independently of each other form a ring structure in which a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, a mono- or two substituents are bonded to each other. Optionally substituted di-substituted amino group or lower alkylthio group, among them, methyl group, methoxy group, difluoromethoxy group, ethoxy group, propoxy group, chlorine atom, fluorine atom, dimethylamino group, or methylthio group Is desirable.

In the above general formula (I), W, X, R ¹
Specific examples of each group and atom in the definition of R ² and R ² are shown below.

Halogen atom ; for example, fluorine, chlorine, bromine, or iodine lower alkyl group ; for example, methyl, ethyl, propyl,
Lower alkenyl groups such as isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and hexyl, heptyl, octyl, or isomers thereof ; for example, lower alkynyl groups such as vinyl, allyl, or propenyl. A lower alkoxy group such as ethynyl or propargyl; a lower alkoxy group substituted with a halogen atom such as methoxy, ethoxy, propoxy, butoxy, isopropoxy, isobutoxy, secondary butoxy or tertiary butoxy;
Lower alkylthio group such as monofluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, or 2,2,2-trifluoroethoxy; for example, methylthio, ethylthio, propylthio, or isopropylthio, etc. The above general formula (I) The compound of the present invention represented by
An example is shown in the table.

[0012]

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3]

The compound of the present invention can be produced, for example, by the method shown below.

[0016]

[Chemical 4]

[Wherein W, X, Y, Z, R ¹ , R ² and n have the same meanings as described above, and W'represents a halogen atom, a lower alkylsulfonyl group or an arylalkylsulfonyl group. In the above reaction scheme, the compound represented by the formula (I) is obtained by reacting the halogenated cycloalkene thiol derivative of the formula (II) with or without a suitable base in the presence of a suitable base at -78 ° C. To the boiling point of the solvent, it can be produced by reacting with the substituted pyrimidine or triazine of the above formula (III) for 1 to 24 hours.

When a solvent is used in this reaction, examples thereof include hydrocarbon solvents such as benzene, toluene and xylene; halogenated hydrocarbon solvents such as dichloromethane and chloroform; diethyl ether, diisopropyl ether, tetrahydrofuran. , 1,4-
Ether solvents such as dioxane; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as methyl acetate and ethyl acetate; aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide; acetonitrile, water, etc. You can

As the base, carbonates such as sodium carbonate and potassium carbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal alkoxides such as sodium methoxide and sodium ethoxide; sodium hydride, Alkyl metal hydrides such as potassium hydride; lithium amides such as lithium diethylamide, lithium diisopropylamide and lithium bistrimethylsilylamide can be mentioned.

[0020]

EXAMPLES Next, synthetic examples of the compounds belonging to the above formula (I) of the present invention will be explained with reference to Examples. Example 1 1-Fluoro-2- (4-chloro-6-methoxypyrimi
Dinyl-2-thio) -2-cyclohexenecarboxylic acid
Production of Chill (Compound No. 15) First, Tetrahedron Letters, Vol. 27, No. 37, 4
Ethyl 1-fluoro-2-oxocyclohexanecarboxylate was produced from ethyl 2-oxocyclohexanecarboxylate with reference to the method described on pages 465 to 4468 (1986).

This ethyl 1-fluorocyclohexanecarboxylate was reacted with Lawesson's reagent in a toluene solvent at 60 ° C. to obtain ethyl 1-fluoro-2-mercapto-2-cyclohexenecarboxylate.

1.03 g (5 mmol) of ethyl 1-fluoro-2-mercaptocyclohexenecarboxylate and 0.84 g of 2,4-dichloro-6-methoxypyrimidine
(5 mmol) was dissolved in 30 ml of tetrahydrofuran, and 240 mg (6 mmol) of sodium hydride was added thereto.
Was added and the mixture was stirred at 0 ° C. for 5 hours. The reaction solution was poured into 100 ml of water, extracted three times with 50 ml of ethyl acetate, the obtained organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 1.3 g of a crude product. This is subjected to silica gel chromatography (developing solvent:
Purify with hexane / ethyl acetate = 9/1) to obtain the desired 1
1.12 g (yield: 65%) of ethyl 2-fluoro-2- (4-chloro-6-methoxypyrimidinyl-2-thio) -2-cyclohexenecarboxylate was obtained.

¹ H-NMR (CDCl ₃ ) δ; 6.88
(M, 1H), 6.31 (s, 1H), 4.27 (q,
2H, 7Hz), 3.97 (s, 6H), 1.75 ~
2.61 (m, 6H), 1.31 (t, 3H, 7Hz)
ppm Example 2 1-Fluoro-2- (4,6-dimethoxypyrimidinyl
Methyl-2-thio) -2-cyclohexenecarboxylate
Production of (Compound No. 1) 1-fluoro-2- (4-chloro-6-obtained in Example 1
Ethyl methoxypyrimidinyl-2-thio) -2-cyclohexenecarboxylate is reacted with sodium methoxide in a methanol solvent to give the desired 1-fluoro-2-
(4,6-dimethoxypyrimidinyl-2-thio) -2-
Methyl cyclohexenecarboxylate was obtained. Example 3 1-Fluoro-2- (6-chloro-2-methoxypyrimi
Dinyl-4-thio) -2-cyclohexenecarboxylic acid
Preparation of chill (Compound No. 28) According to the method described in Example 1, the target 1-fluoro-
Obtained ethyl 2- (6-chloro-2-methoxypyrimidinyl-4-thio) -2-cyclohexenecarboxylate.

¹ H-NMR (CDCl ₃ ) δ; 6.92
(1H, m), 6.88 (1H, s), 4.27 (2
H, d, J = 7 Hz), 3.98 (3H, s), 1.8
0 to 2.58 (6H, m), 1.31 (3H, t, J =
7 Hz) ppm Example 4 1-Fluoro-2- (2,6-dimethoxypyrimidinyl)
-4-Thio) -2-cyclohexenecarboxylic acid methyl ester
Preparation of (Compound No. 29) 1-Fluoro-2- (6-chloro-2- ) obtained in Example 3.
Ethyl methoxypyrimidinyl-4-thio) -2-cyclohexenecarboxylate is reacted with sodium methoxide in methanol solvent to give the desired 1-fluoro-2-
(2,6-dimethoxypyrimidinyl-4-thio) -2-
Methyl cyclohexenecarboxylate was obtained.

¹ H-NMR (CDCl ₃ ) δ; 6.94
(1H, m), 6.58 (1H, s), 3.97 (3
H, s), 3.80 (3H, s), 1.83 to 2.60.
(6H, m) ppm The herbicide of the present invention contains a novel halogenated cycloalkenecarboxylic acid (I) which is a compound of the present invention as an active ingredient.

When the compound of the present invention is used as a herbicide, it is mixed with a carrier or a diluent, an additive, an auxiliary agent and the like by a known method to prepare a formulation form usually used as an agricultural chemical, for example, powder, granules, It is prepared and used as a wettable powder, an emulsion, a water solvent, a sol, etc. Further, it can be used in combination or in combination with other agricultural chemicals such as fungicides, insecticides, acaricides, other herbicides, plant growth regulators and fertilizers, soil conditioners and the like. In particular, when used in combination with other herbicides, it not only reduces the amount of the drug used and saves labor, but it is also expected that the synergistic action of both drugs will broaden the herbicidal spectrum and further enhance the synergistic effect. .

As the carrier or diluent, a generally used solid or liquid carrier is used. As solid carriers, kaolinite group, clays represented by montmorillonite group or polygloskite group, etc., specifically, pyroflight, attapulgite, sepiolite, kaolinite, bentonite, vermiculite,
Talc, mica, etc .; gypsum, calcium carbonate, dolomite,
Other inorganic substances such as diatomaceous earth, magnesium lime, apatite, zeolite, anhydrous silicic acid, and synthetic calcium silicate; soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose and other plant organic substances Substances: coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum,
Examples thereof include synthetic or natural polymer compounds such as cobal gum and dammal gum; waxes such as carnauba wax and beeswax, and urea. Suitable liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene and methylnaphthalene; chloroform, trichloroethylene, monochlorobenzene, Chlorinated hydrocarbons such as orthochlorotoluene; ethers of dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate , Esters such as diethyl succinate;
Methanol, n-hexanol, ethylene glycol,
Examples thereof include alcohols such as diethylene glycol, cyclohexanol, and benzyl alcohol; ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide; and water.

In addition, a surfactant or other auxiliary agent is used for the purpose of emulsification, dispersion, wetting, spreading, binding, control of disintegration, stabilization of active ingredient, improvement of fluidity, rust prevention and the like of the compound of the present invention. You can also As examples of the surfactant used, nonionic, anionic, cationic and zwitterionic compounds may be used, but usually nonionic and / or anionic compounds are used. A compound is used. Suitable nonionic surfactants include, for example, compounds obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; compounds obtained by polymerizing addition of ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Compounds obtained by polymerizing addition of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Compounds obtained by polymerizing addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid; higher fatty acid esters of polyhydric alcohols such as sorbitan and Examples thereof include compounds obtained by polymerizing addition of ethylene oxide; compounds obtained by block-polymerizing addition of ethylene oxide and propylene oxide.

Suitable anionic surfactants include, for example, alkyl sulphate salts such as sodium lauryl sulphate, oleyl alcohol sulphate amine salts; alkyls such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulphonate. Sulfonates; aryl sulfonates such as sodium isopropyl naphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, sodium dodecylbenzene sulfonate, and the like.

Further, the herbicide of the present invention is a polymer such as casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and polyvinyl alcohol for the purpose of improving the properties of the preparation and enhancing the herbicidal effect. Compounds and other auxiliary agents can also be used in combination.

The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the application scene and the like.

The content of the compound (active ingredient) of the present invention in the various dosage forms thus obtained varies depending on the dosage form, but is usually 0.1 to 99% by weight, and particularly preferably 1-80 weight% is preferable.

In the case of powders, for example, the active ingredient compound is usually contained in an amount of 1 to 25% by weight, and the balance is a solid carrier.

In the case of a wettable powder, for example, the active ingredient compound is usually contained in an amount of 25 to 90% by weight, and the balance is a solid carrier and a dispersion wetting agent, and if necessary, a protective colloid agent, a defoaming agent and the like are added. Be done.

In the case of granules, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the balance is mostly a solid carrier. The active ingredient compound is either uniformly mixed with the solid carrier or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm.

In the case of an emulsion, for example, the active ingredient compound is usually contained in an amount of 5 to 30% by weight, to which about 5 to 2% is added.
It contains 0% by weight of an emulsifier, the balance being a liquid carrier, optionally with a rust inhibitor.

In the case of a flowable agent, for example, the active ingredient compound is usually contained in an amount of 5 to 50%, and 3 to 1 is added thereto.
The dispersion wetting agent is contained in an amount of 0% by weight, and the balance is water, and a protective colloid agent, a preservative, an antifoaming agent and the like are added if necessary.

The novel halogenated cycloalkenecarboxylic acid derivative of the present invention can be applied as it is to the compound of the general formula (I) or in any preparation form as described above.

The herbicide of the present invention can be applied to the control or control of various weeds growing in paddy fields and upland fields from the pre-emergence stage to the growing season. The application rate is 0.01 to 5k per ha as the amount of the compound represented by the general formula (I) (the amount of active ingredient).
It is about g, preferably about 0.01 to 1 kg, and can be appropriately selected and changed depending on the kind of the target weed, the growth stage, the application place, the application time, the weather and the like.

Next, several embodiments of formulation examples using the compound of the present invention will be shown. "Parts" in the following formulation examples are based on weight.

Formulation Example 1 (Granule) Compound No. 1 5 parts Bentonite 50 parts Talc 40 parts Sodium dodecylbenzene sulfonate 2 parts Sodium lignin sulfonate 2 parts Polyoxyethylene alkylphenyl ether 1 part After thoroughly mixing the above, An appropriate amount of water was added and kneaded, and granulated using a granulator to obtain 100 parts of granules.

Formulation Example 2 (wettable powder) Compound No. 15 20 parts Diatomaceous earth 60 parts White carbon 15 parts Sodium lignin sulfonate 3 parts Sodium dodecylbenzene sulfonate 2 parts The above components are mixed and uniformly pulverized with a kneader. Wettable powder 1
I got 00 parts.

Formulation Example 3 (Emulsion) Compound No. 28 30 parts Xylene 55 parts Cyclohexanone 10 parts Calcium dodecylbenzene sulfonate 3 parts Polyoxyethylene alkylphenyl ether 2 parts The above components were uniformly mixed and dissolved to obtain 100 parts of an emulsion.

Drugs using the compound of the present invention could be prepared according to the above-mentioned preparation examples.

[0045]

The effect of the present invention is represented by the above general formula (I),
The halogenated cycloalkenecarboxylic acid derivative is a novel compound described in the end of the literature. The general formula (I) of the present invention
The compound represented by has a structure in which a structurally extremely simple halogenated cycloalkenecarboxylic acid moiety and a pyrimidine ring or triazine ring moiety to which a specific substituent is bonded are bonded via an oxygen atom. It is considered that the excellent herbicidal action is exhibited due to its structural characteristics.

The compounds and herbicides of the present invention can control various weeds that grow on agricultural land from the pre-emergence stage to the growing season. For example, paddy weeds such as Nobie, Firefly, Mizuhigai, Konagi, Azaena, Mizohabe, Kishigusa, Matsubayai, Urikawa, etc., and Crabgrass, Enocorogusa, Ohishiba, Suzunohie, Suzunotsutsupou, Azaleas japonicus, Acacia serrata, Acacia serrata, Acacia serrata, Acacia, It is possible to control weeds such as morning glory, morning glory, ragweed, ragweed, herb, rapeweed, sengangusa, yaemgra and buckwheat vine. In addition to paddy fields and fields, orchards, mulberry fields,
It can also be used on lawns and non-cultivated lands.

Moreover, the compound of the present invention has selectivity for certain cultivated crops, and particularly excellent for crops such as cotton, soybean and corn.

Next, the herbicidal effect will be described with reference to test examples.

Test Example 1 (Treatment of Upland Field Leaves) A square pot (30 × 30 × 12 cm) was filled with upland soil, and various crops and various weed seeds shown in Table 2 were sown in fixed amounts, and each plant had 1 The plants were grown in a greenhouse until the stage of 5 to 3 leaves. The compound of the present invention shown in Table 2 was used in Formulation Example 2
A water-dispersible powder was prepared according to the above procedure, and the water-diluted solution was evenly sprayed onto the foliage of each plant in an amount corresponding to the spraying amount of 5001 / ha so that the active ingredient amount shown in Table 2 was obtained. Twenty-one days after spraying the chemicals, the herbicidal effect on various weeds and the degree of phytotoxicity on various crops were determined according to the following criteria. The result is the second
Shown in the table.

[0050] Test Example 2 (Soil Treatment Before Germination of Upland Field) A square pot (30 × 30 × 12 cm) was filled with upland soil, and various crops and various weed seeds shown in Table 3 were sown in fixed amounts, and then covered with 1 cm of soil. did. The compound of the present invention shown in Table 3 was prepared as a wettable powder according to Formulation Example 2, and the diluted solution was adjusted to 5001 so that the amount of active ingredient shown in Table 3 was obtained.
/ Ha was sprayed evenly in the soil direction at an amount equivalent to the sprayed amount. Twenty-one days after the chemical spraying, the herbicidal effect on various weeds and the degree of phytotoxicity on various crops were determined according to the criteria of Test Example 1. The results are shown in Table 3.

[0051]

[Table 4]

[0052]

[Table 5]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C07D 239/56 8615-4C 239/60 8615-4C 251/38 (72) Inventor Keiji Endo Ibaraki 8-3-3 Chuo, Ami-cho, Inashiki-gun, Sanryo Yuka Co., Ltd. Tsukuba Research Institute (72) Inventor Shinji Kawaguchi 8-3-1, Chuo, Ami-cho, Inashiki-gun, Ibaraki Sanryo Yuka Tsukuba Co., Ltd. Inside the General Research Institute (72) Inventor Rika Higurashi 8-3-1, Chuo, Ami-machi, Inashiki-gun, Ibaraki Sanryo Yuka Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the general formula (I): [In formula, W shows a halogen atom. X is a lower alkoxy group, a lower alkenoxy group, a lower alkynoxy group, an optionally substituted aryloxy group, a di-substituted amino group which may form a ring structure by binding of mono or two substituents, a hydroxy group and Its agronomically acceptable salt,
Amino group, hydroxyamino group, lower alkoxyamino group, lower alkenoxyamino group, lower alkynoxyamino group, optionally substituted aryloxyamino group,
Alternatively, it represents a benzyloxy group. Y and Z are, when Y is a nitrogen atom, Z is a nitrogen atom or a methine group,
When Y is a methine group, Z represents a nitrogen atom. R ¹ and R ² are each independently a halogen atom, a lower alkyl group,
A lower alkoxy group, a lower alkoxy group substituted with a halogen atom, a di-substituted amino group which may form a ring structure by combining mono- or two substituents, or a lower alkylthio group is shown. n represents 0 or 1. ] The novel halogenated cycloalkene carboxylic acid derivative represented by these. 2. A compound represented by the general formula (I): [In formula, W shows a halogen atom. X is a lower alkoxy group, a lower alkenoxy group, a lower alkynoxy group, an optionally substituted aryloxy group, a di-substituted amino group which may form a ring structure by binding of mono or two substituents, a hydroxy group and Its agronomically acceptable salt,
Amino group, hydroxyamino group, lower alkoxyamino group, lower alkenoxyamino group, lower alkynoxyamino group, optionally substituted aryloxyamino group,
Alternatively, it represents a benzyloxy group. Y and Z are, when Y is a nitrogen atom, Z is a nitrogen atom or a methine group,
When Y is a methine group, Z represents a nitrogen atom. R ¹ and R ² are each independently a halogen atom, a lower alkyl group,
A lower alkoxy group, a lower alkoxy group substituted with a halogen atom, a di-substituted amino group which may form a ring structure by combining mono- or two substituents, or a lower alkylthio group is shown. n represents 0 or 1. ] A herbicide containing a novel halogenated cycloalkenecarboxylic acid derivative represented by the following as an active ingredient.