Cyclohexane-1,3-dione derivatives, process for their preparation and their use in combating the growth of undesirable plants

The invention relates to cyclohexane-1,3-dione derivatives, processes for their preparation and herbicides which contain these compounds as active ingredients.

It is known to use cyclohexane-1,3-dione derivatives to control unwanted grasses in broadleaved crops. Active ingredients with furyl or thienyl substituents show a relatively weak effect (DE-OS 24 39 104). In addition, EP-OS 0071707 discloses heterocyclic-substituted cyclohexane-1,3-dione derivatives with good herbicidal activity against plants from the grass family.

It has been found that new cyclohexane-1,3-dione derivatives which carry certain heterocyclic substituents in the 5-position have a significantly stronger herbicidal action against a number of grass types (wild and crop species) than the active ingredients belonging to the prior art. These compounds show excellent tolerance both for broad-leaved crops and for monocot crops that do not belong to the grass family. In addition, some of these compounds, despite their good activity against grasses, are at the same time compatible with cereals in wheat at certain dosages.

The new cyclohexane-1,3-dione derivatives have the formula<chemistry id="chem0001" num="0001"><img file="EP0142741A2_D0001.tif" /></chemistry>in the

A tetrahydropyran-4-yl, 3-methyltetrahydropyran-4-yl, 1,4-dioxanyl, 5,5 - dimethyl-1,3-dioxan-2-yl, 2,5-dimethyl-l, 4-dioxane 3-yl, 2,6-dimethyl-1,4-dioxan-3-yl, 2-methyl-l, 3-dithiolan-2-yl, 2,6-dimethyltetrahydro-thiopyran-3-yl, 2-methyl 1,3-dithian-2-yl or 1,3-dioxepan-5-yl optionally substituted by alkyl having 1 to 8 carbon atoms, alkylene having 4 or 5 carbon atoms or optionally methyl-substituted cycloalkyl or bicycloalkyl having 6 to 12 carbon atoms,<ul id="ul0001" list-style="none"><li>R is hydrogen or methoxycarbonyl,</li><li>_R² Alkyl of 1 to 4 carbon atoms and</li><li>R³ Alkyl with 1 to 4 carbon atoms, alkenyl with 3 or 4 carbon atoms, haloalkenyl with 3 or 4 carbon atoms and 1 to 3 halogen substituents or propargyl.</li></ul>

The compounds of formula I can occur in several forms, all of which are encompassed by the claim:<chemistry id="chem0002" num="0002"><img file="EP0142741A2_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP0142741A2_D0003.tif" /></chemistry>The 1,3-dioxepan-5-yl radicals for A in formula I can be replaced by unbranched or branched alkyl radicals having 1 to 8 carbon atoms, such as methyl, ethyl, i-propyl, t-butyl, 1,2-dimethyl-4-butyl, 1-ethyl-n-pentyl or by cycloalkyl or bicycloalkyl having 6 with 12 carbon atoms, such as cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, bicycloheptyl, for example bicyclo [3.1.1] heptyl. The cycloalkyl and bicycloalkyl radicals can also carry one or more methyl substituents. Furthermore, the 1,3-dioxepan-5-yl radicals can be substituted by an alkylene chain having 4 or 5 carbon atoms, ie tetramethylene or pentamethylene, so that, for example, spiro compounds are formed.

R² in formula I stands for unbranched or branched alkyl radicals with 1 to 4 carbon atoms, ie for methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, tert-butyl.

Leftovers for R³ in formula I are propargyl, alkyl with 1 to 4 carbon atoms, alkenyl with 3 or 4 carbon atoms or haloalkenyl with 3 or 4 carbon atoms, which can contain up to three halogen substituents, for example chlorine, bromine, fluorine, for example methyl, Ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, i-butyl, tert.-butyl, allyl, 1-chloroprop-1-en-3-yl, 2-chloroprop-l-en- 3-yl, 1,3-dichloroprop-1-en-3-yl, 1,2,3-trichloroprop-l-en-3-yl.

Preferred cyclohexane-1,3-dione derivatives of the formula I are those in which R¹ Means hydrogen, and those in which R² Alkyl with 2 or 3 carbon atoms means. Preferred radicals for A are tetrahydropyran-4-yl, 2,6-dimethyl-tetrahydrothiopyran-3-yl or optionally by alkyl having 1 to 8 carbon atoms, in particular 1 to 4 carbon atoms, alkylene having 4 or 5 carbon atoms or optionally methyl-substituted cycloalkyl or bicycloalkyl 1,3-dioxepan-5-yl radicals substituted with 7 to 12 carbon atoms, in particular 1,3-dioxepan-5-yl or 1,3-dioxepan-5-yl radicals substituted by unbranched or branched alkyl radicals having 1 to 4 carbon atoms.

Examples of salts of the compounds of the formula I are the alkali metal salts, in particular the potassium or sodium salts, alkaline earth metal salts, in particular calcium, magnesium or barium salts, and also manganese, copper, zinc or iron salts and ammonium and phosphonium salts, for example alkylammonium, Dialkylammonium, trialkyl or tetraalkylammonium salts, benzyltrialkylammonium salts, triphenylphosphonium salts, trialkylsulfonium salts or trialkylsulfoxonium salts.

The compound of formula I can by reacting compounds of formula<chemistry id="chem0004" num="0004"><img file="EP0142741A2_D0004.tif" /></chemistry>in the A, R¹ and R² have the meanings given above, with hydroxylamine derivatives R³O-NH₃Y, in the R³ has the meanings given above and Y represents an anion can be obtained.

The reaction is expediently carried out in a heterogeneous phase in an inert diluent at a temperature between 0 and 80 ° C. or between 0 ° C. and the boiling point of the reaction mixture in the presence of a base. Suitable bases are, for example, carbonates, hydrogen carbonates, acetates, alcoholates, hydroxides or oxides of alkali or alkaline earth metals, in particular of sodium, potassium, magnesium, calcium. Organic bases such as pyridine or tertiary amines can also be used.

Examples of suitable solvents are dimethyl sulfoxide, alcohols, such as methanol, ethanol, isopropanol, benzene, optionally chlorinated hydrocarbons, such as chloroform, dichloroethane, hexane, cyclohexane, esters, such as ethyl acetate, ethers, such as dioxane, tetrahydrofuran.

The reaction is complete after a few hours, the reaction product can then be isolated by concentrating the mixture, adding water and extracting with a non-polar solvent such as methylene chloride and distilling off the solvent under reduced pressure.

The compound of formula I can also by reacting the compounds of formula II with hydroxylamines of formula R.³0-NH₂, in the R³ has the meanings given above, can be obtained in inert diluents at a temperature between 0'C and the boiling point of the reaction mixture, in particular between 15 and 70 ° C. If appropriate, the hydroxylamine can be used as an aqueous solution.

Suitable solvents for this reaction are, for example, alcohols, such as methanol, ethanol, isopropanol, cyclohexanol, optionally chlorinated hydrocarbons, such as hexane, cyclohexane, methylene chloride, toluene, dichloroethane, esters, such as ethyl acetate, nitriles, such as acetonitrile, cyclic ethers, such as tetrahydrofuran.

The alkali metal salts of the compounds of formula I can be obtained by treating these compounds with sodium or potassium hydroxide in aqueous solution or in an organic solvent such as methanol, ethanol, acetone. Sodium and potassium alcoholates can also serve as bases.

The other metal salts, e.g. B. the manganese, copper, zinc, iron, calcium, magnesium and barium salts can be prepared from the sodium salts by reaction with the corresponding metal chlorides in aqueous solution. Ammonium, sulfonium, sulfoxonium and phosphonium salts can be prepared by reacting compounds of the formula I with ammonium, phosphonium, sulfonium and sulfoxonium hydroxides, optionally in aqueous solution.

The compounds of the formula II can be obtained from cyclohexane-1,3-diones of the formula III, which may also be present in the tautomeric formulas IIIa and IIIb<chemistry id="chem0005" num="0005"><img file="EP0142741A2_D0005.tif" /></chemistry> according to methods known from the literature (Tetrahedron Letters, 29, 2491 (1975)).

It is also possible to prepare compounds of the formula II via the intermediate stage of the enol esters, which may be obtained as isomer mixtures in the reaction of compounds of the formula III and are rearranged in the presence of imidazole or pyridine derivatives (JP-OS 79/063052).

The compounds of the formula III are obtained by methods known from the literature, as can be seen from the following scheme:<chemistry id="chem0006" num="0006"><img file="EP0142741A2_D0006.tif" /></chemistry>Aldehydes of the general formula A-CHO are obtained by processes known from the literature, for example by oxidation of corresponding alcohols, reduction of carboxylic acid derivatives, hydroformylation of oleic acids.

The following examples explain the preparation of the cyclohexane-1,3-dione derivatives of the formula I. In the examples, parts by weight relate to parts by volume like kilograms to liters.

The ¹H-NMR spectra were recorded in deuterochloroform as a solvent with tetramethylsilane as the internal standard. The¹H chemical shifts are given in δ [ppm]. The following abbreviations were used for the signal structure:<ul id="ul0002" list-style="none"><li>s - singlet, d = doublet, t - triplet, q = quartet, m - multiplet, strongest signal</li></ul>

example 1

6.5 parts by weight of 2-butyryl-5- (2-isopropyl-1,3-dioxepan-5-yl) cyclohexane-1,3-dione, 2.1 parts by weight of ethoxyammonium chloride and 1.8 parts by weight of sodium hydrogen carbonate are mixed in 80 parts by volume Methanol stirred for 16 hours at room temperature. The solvent is distilled off under reduced pressure, the residue is stirred with 50 parts by volume of water and dichloromethane, the organic phase is separated off, the aqueous phase is extracted once with 50 parts by volume of dichloromethane, the combined organic phases are dried over sodium sulfate, and the solvent is removed under reduced pressure distilled off. 6.2 parts by weight of 2- (1-ethoxyamino-n-butylidene) -5- (2-isopropyl-1,3-dioxepan-5-yl) cyclohexan-1,3-dione are obtained as an oil. (Active ingredient No. 1) n²⁶_D: 1,5₁4 ¹H-NMR spectrum: δ = 0.90 (d), 1.18 (t), 2.45 (q), 4.15 (q)

Example 2

14.0 parts by weight of 2-butyryl-5- (tetrahydropyran-4-yl) cyclohexane-1,3-dione and 4.2 parts by weight of allyloxyamine are stirred in 100 parts by volume of methanol at room temperature for 16 hours. The solvent is distilled off under reduced pressure, the residue is dissolved in dichloromethane, the solution is then washed with 5% hydrochloric acid and water and dried over sodium sulfate. After the solvent has been stripped off under reduced pressure, 12.9 parts by weight of 2- (1-allyloxyamino-n-butylidene) -5- (tetrahydropyran-4-yl) -cyclohexane-1., 3-dione as a solid. (Active ingredient No. 2) Mp 55-56 ° C ¹H-NMR spectrum δ = 0.95 (t), 2.85 (t), 3.40 (t), 4.55 (d)

The following compounds can be obtained in the same way:<tables id="tabl0001" num="0001"><img file="EP0142741A2_D0007.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0142741A2_D0008.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0142741A2_D0009.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0142741A2_D0010.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0142741A2_D0011.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP0142741A2_D0012.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP0142741A2_D0013.tif" /></tables>

The cyclohexane-1,3-dione derivatives of the formula I and their salts can, for example, in the form of directly sprayable solutions, powders, suspensions, also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules Spraying, atomizing, dusting, scattering or pouring can be used. The application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils etc., as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, xylene, are used to produce directly sprayable solutions, emulsions, pastes or oil dispersions , Paraffin, tetrahydronaphthalene alkylated naphthalenes or their derivatives, for example Methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, into consideration.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, wetting agents, adhesives, dispersants or emulsifiers, and possibly solvents or oil, can also be prepared from active substance and are suitable for dilution with water.

Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, fatty acid alkali and alkaline earth metal salts, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ether, Condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or the naphthalenesulfonic acids with phenol and formaldehyde, Polyoxyethylenoctylphenoläther, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, Laurylalkoholpolyglykoletheracetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth. Calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as corn flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations contain between 0.1 and 95 percent by weight, preferably between 0.5 and 90 percent by weight, of active ingredient.

Examples of formulations are:<ul id="ul0003" list-style="none"><li>I. 90 parts by weight of compound no. 2 are mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone and a solution is obtained which is suitable for use in the form of tiny drops.</li><li>II. 20 parts by weight of compound no. 3 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.</li><li>III. 20 parts by weight of compound no. 1 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.</li><li>IV. 20 parts by weight of active ingredient No. 17 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280⁰C and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.</li><li>V. 20 parts by weight of active ingredient No. 12 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1 percent by weight of the active ingredient.</li><li>VI. 3 parts by weight of active ingredient No. 52 are mixed with 97 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 3 percent by weight of the active ingredient.</li><li>VII. 30 parts by weight of active ingredient no. 67 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, a preparation of the active ingredient with good adhesiveness is obtained.</li><li>VIII. 20 parts of active ingredient No. 6 are intimately mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.</li></ul>

The application can be done pre-emergence or post-emergence. If the active ingredients are less compatible with certain crop plants when used post-emergence, application techniques can also be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit as far as possible, while the active ingredients are applied to the leaves underneath growing unwanted plants or the uncovered floor area (post-directed, lay-by).

Depending on the season, the target plants and the growth stage, the active compound application rates are 0.025 to 3 kg / ha, preferably 0.05 to 0.5 kg / ha. The herbicidal activity of the cyclohexane-1,3-dione derivatives of the formula I can be demonstrated by greenhouse tests:<ul id="ul0004" list-style="none"><li>Plastic flower pots with 300 cm serve as culture vessels³ Content and loamy sand with about 1.5% humus as a substrate. The seeds of the test plants are sown flat according to species.</li></ul>

In pre-emergence treatment, the active ingredients are applied to the earth's surface immediately afterwards. For this purpose, they are suspended or emulsified in water as a distribution medium and sprayed by means of finely distributing nozzles. With this application method, the application rates are 3.0 kg of active ingredient / ha.

After the application of the agents, the vessels are lightly sprinkled to start germination and growth. Then cover the containers with transparent plastic covers until the plants have grown. This cover causes the test plants to germinate evenly, unless this is affected by the active ingredients.

For the purpose of post-emergence treatment, depending on the growth habit, the test plants are first grown to a height of 3 to 15 cm and then treated. The soybean plants are grown in a substrate enriched with peat. For post-emergence treatment, either plants that have been sown directly and grown in the same containers are selected, or those that are only grown separately as seedlings and transplanted into the test containers a few days before the treatment. The application rates for post-emergence treatment vary between 0.03 and 0.25 kg of active ingredient / ha. There is no cover during post-emergence treatment.

The test vessels are set up in the greenhouse, warmer areas (20 to 35 ° C.) for heat-loving species and 10 to 25 ° C. for those with moderate climates are preferred. The trial period spans 2 to 4 weeks. During this time, the plants are cared for and their response to the individual treatments is evaluated. It is rated on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts.

The plants used in the greenhouse experiments consist of the following types:<ul id="ul0005" list-style="none"><li>Alopecurus myosuroides (arctic foxtail), Avena fatua (airport oat), Avena sativa (oat), Beta vulgaris (sugar beet), Bromus inermis (common</li></ul> grizzled brim), Bromus spp. (Trespe), Digitaria sanguinalis (blood millet), Echinochloa crus-galli (chicken millet), Glycine max (soybeans), Hordeum vulgare (barley), Lolium multiflorum (Italian Raygras), Oryza sa_tiva (rice), Setaria italica (millet), Sinapis alba (white mustard), Triticum aestivum (wheat), Zea mays (corn), sorghum halepense (Sudan grass).

The following cyclohexane-1,3-dione derivatives known from EP-OS 0071707 are used as comparison means:<chemistry id="chem0007" num="0007"><img file="EP0142741A2_D0014.tif" /></chemistry><tables id="tabl0008" num="0008"><img file="EP0142741A2_D0015.tif" /></tables>

The application rates correspond to those of the compound according to the invention to be compared in each case.

Pre-emergence application: In pre-emergence application, for example, the compounds Nos. 7, 53, 2, 1, 17, 54, 10, 12, 20, 23, 29, 57, 59, 60 prove to be effective at a rate of 3.0 kg of active ingredient / ha herbicidally active against plants from the grass family. Sinapis alba remains undamaged as a broad-leaved test plant.

Post-emergence application:<ul id="ul0006" list-style="none"><li>With post-emergence application of 0.25 kg of active ingredient / ha, for example of compounds Nos. 1, 11, 12, 13 and 17, certain grass-like undesirable plants or crop plants from the grass family, insofar as they are undesirable at certain locations, are better controlled than with the comparative agents I and III. Soybeans as an example of broad-leaved crops are not harmed. Connection no. 14 with 0.25 kg of active ingredient / ha, an effect against Sorghum halepense superior to comparative VI with full tolerance for soybean plants.</li></ul>

Compounds Nos. 2 and 3, for example, with 0.125 kg of active ingredient / ha, have a very good herbicidal activity against Gramineae, such as wheat (as wheat) and Bromus spp. The agents are selective in sugar beets. Compounds No. 52 and 53 also control very well with 0.125 kg of active ingredient / ha of grass. With this application rate, the compounds no. 26, 29 and 55 have a good effect against grasses and do not cause damage to wheat, which suffers significant damage from comparative agent I. With compound no. 7, millet can be combated as an undesirable type of grass in rice, the crop plant, in contrast to the use of comparative agent I, likewise not being damaged.

In addition to selectivity in broadleaved crops, compound no. 6 shows a considerable action against grasses at a low application rate and does not cause damage to wheat. Comparative agent II severely damages this cultivated grass. Also at low application rates, compound no. 67 can be used to combat undesirable types of grass from a wide variety of vegetation zones - including crops from the Gramineae family. The herbicidal activity of compound no. 67 is clearly superior to that of comparative agent IV.

In view of the compatibility and the large number of application methods, the compounds according to the invention can also be used in a further number of crop plants for eliminating unwanted wild grasses or grass-like crop plants, provided that they are undesirable in certain locations. For example, the following crops can be considered:<tables id="tabl0009" num="0009"><img file="EP0142741A2_D0016.tif" /></tables><tables id="tabl0010" num="0010"><img file="EP0142741A2_D0017.tif" /></tables> To broaden the spectrum of activity and to achieve synergistic effects, the cyclohexane-1,3-dione derivatives of the formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl carbamates, thiol carbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3- dione derivatives of other structure and other herbicidal active substances into consideration.

It may also be useful to apply the new compounds, alone or in combination with other herbicides, together with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to combat nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.