JPS60166601A - Herbicide - Google Patents

Abstract

PURPOSE:To provide a herbicide containing at least one compound selected from an alpha,beta-unsaturated carboxylic acid and its functional salt as an active component, exhibiting excellent herbicidal activity by the soil treatment after or before sprouting, and effective especially to broad-leaved weeds. CONSTITUTION:The objective herbicide contains, as an active component, at least one compound selected from an alpha,beta-unsaturated carboxylic acid of formula [R<1> is H, halogen, cyano, nitro, OR<9> (R<9> is H, 1-16C acyl, 1-15C hydrocarbon group, etc.), SR<9>, etc.; R<2>-R<7> are H, halogen, cyano, nitro, lower alkyl, etc.; R<8> is OR<12> (R<12> is H or 1-15C hydrocarbon group which may contain O), SR<12>, etc.; m is 0-15; n is 0-10] and its functional salt, e.g. ethylamine salt. It is used in the form of granule, wettable powder, etc. containing usually 0.1-95wt% active component.

Description

[Detailed description of the invention]

(a) Technical Field The present invention relates to a novel herbicide containing unsaturated aliphatic carboxylic acids as an active ingredient. More specifically, the present invention relates to a novel herbicide containing specific α,β-unsaturated carboxylic acids and functional salts thereof as active ingredients. (1)) Prior art Some aliphatic carboxylic acids are known to exhibit various physiological activities; for example, sorbic acid is a bactericidal agent used to prevent spoilage of foods such as cheese ( (See US Pat. No. 3,139,378) and that 3-thianic acid has cholesterol synthesis inhibitory activity (Biochemical Journal (Biochem, J-) +
147, pp. 531-539 (1975)). On the other hand, Japanese Patent Publication No. 47-41005 or Adari Cultural High-Technology Chemistry (Agrlc, Biol, Chem) + Volume 45, 2
β as seen on pages 769 to 2773 (1981)
-(N-Phenyl-N-methyl)amino-α-cyanoacrylic acid ester has been shown to have herbicidal activity and has been disclosed to have Hill reaction (optical oxygen generation reaction by free chloroplasts) inhibitory activity. . (c) Purpose The present inventors focused on the physiological activities of such carboxylic acids, and conducted intensive physiological and physicochemical research on various derivatives thereof, with the aim of obtaining herbicides with excellent activity. Surprisingly, we found that unsaturated carboxylic acids with a specific structure of triple bonds and double bonds in α and β have excellent herbicidal effects on various plants. We have arrived at the present invention by discovering that both pre-emergence treatment and post-emergence treatment of plants destroy the excellent herbicidal effect, and that pre-emergence treatment in particular shows excellent effects against broad-leaved weeds. (d) Structure of the Invention The present invention provides a herbicide containing as an active ingredient at least one selected from α, β-unsaturated carboxylic acids represented by the general formula % and functional salts thereof. . The present invention will be explained in more detail below. The α,β-unsaturated carboxylic acids in the present invention are represented by the general formula (T) above, and have 5
Carboxyl having ~20 carbon atoms and having a carboxyl group. It is composed of esters such as carboxyalkyl or acid amides. R1 in the formula (1) is a hydrogen atom, a rogen atom, a cyano group, a p group, or a group represented by the formula OR9゜sR9,Nte%::. Here, R11 is a hydrogen atom, an acyl group having 1 to 6 carbon atoms, a hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom and/or a sulfur atom, or a substituted hydrocarbon group having 1 to 15 carbon atoms. Or it is an unsubstituted sulfonyl group. 6- The acyl group having 1 to 16 carbon atoms is represented by the formula R"-Co, and R" is preferably a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. Such a hydrocarbon group having 1 to 15 carbon atoms refers to a hydrocarbon group having 1 to 15 carbon atoms.
-15 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups having 6 to J5 carbon atoms. The aliphatic hydrocarbon group having 1 to 15 carbon atoms here is
Straight chain or branched, saturated or unsaturated, for example methyl. Ethyl, various propyl, butyl, hexyl. Octyl, decyl, dodecyl, tetradecyl. Ethynyl, various propenyls, hexenyls. 7-unyl, dodecenyl, etc., or those substituted with alicyclic or aromatic hydrocarbon groups, such as cyclohexylmethyl, cyclohexyl/ruflovir, cyclohexylmethyl,
Examples include phenylethyl, among which those having a carbon number of 1 to 1° are preferred. In addition, examples of alicyclic hydrocarbon groups having 3 to 15 carbon atoms include ncro-R-ntyl, /cloxyl, various methylcyclohexyl, dimethylcyclohexyl, and diethylcyclohexyl.
Examples include qhexyl, cyclohexenyl, and various dimenalcyclohexenyl, among which those having 3 to 10 carbon atoms are preferred. Furthermore, an aromatic hydrocarbon group having 6 to 15 carbon atoms. Hydrocarbon groups include phenyl and various toluyl groups. Examples thereof include dimethylphenyl, propylphenyl, naphthyl, methylnaphthyl, diethylnaphthyl, etc. Among them, those having 6 to 10 carbon atoms are preferred. In such a hydrocarbon group, the hydrogen atom is...a rogene atom,
It may be substituted with a nitro group, hytoxy group, lower alkoxy group, lower argylthio group, etc., and specific examples thereof include trifluoromethyl and dichlorophenyl. 1 carbon number, which may contain an oxygen atom and/or a sulfur atom
~15 swelling hydrogen groups include aliphatic hydrocarbon groups having 1 to 15 carbon atoms, alicyclic hydrocarbon groups having 3 to 15 carbon atoms, aromatic hydrocarbon groups having 6 to 15 carbon atoms, and carbonization thereof. It means a hydrogen group containing an oxygen atom and/or a sulfur atom, and a hydrocarbon group having 1 to 13 carbon atoms is more preferable. Further, the hydrocarbon group may be substituted with a halogen atom, a nitro group, or the like. Note that the hydrocarbon group mentioned here that does not contain an oxygen atom or a sulfur atom can be shown in the same manner as the specific example regarding R91, so the details will be omitted. When the hydrocarbon group contains an oxygen atom and/or a sulfur atom, the total number of oxygen atoms and sulfur atoms is 1 to 5.
Preferably it is 1 to 3, such as an alkyloxyalkyl group or an aralkyloxyalkyl group. Examples include alkyloxyaralkyl groups, aralkyloxyaralkyl groups, alkyloxyγlkyloxyalkyl groups, those containing a sulfur atom instead of an oxygen atom, and heterocyclic groups, and specific examples include methoxymethyl. , methylthiomethyl, ethoxyethyl. Butoxyethyl, decyloxyethyl, phenyl, methoyaethyl, ethoxyethyl, phenoxy7methyl, l~
enoxyphenyl, benzyloxyphenyl, furyl,
Examples include pyranyl. An unsubstituted sulfonyl group is represented by the formula H5O,-, and a sulfonyl group substituted with a hydrocarbon group having 1 to 15 carbon atoms is represented by the formula R""-
8o, -. The nucleus H1llt is a hydrocarbon group having 1 to 15 carbon atoms, and more specifically, it is represented by the same formula as the formula R111 for the acyl group, and preferred examples include methyl, ethyl, and various propyl groups. Examples include hexyl, decyl, phenyl, various types of toluyl, cyclohexyl and the like having carbon atoms of 1 to 10. In addition, Rlo and R11 in the formula N)IOK are the same as -
Alternatively, it is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Hlo and R11 may cooperate with each other to form a ring. This carbon number is 1 to 1O
Examples of the hydrocarbon group include an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an alicyclic hydrocarbon group having 6 carbon atoms.
-10 aromatic hydrocarbon groups. The aliphatic hydrocarbon group having 1 to 10 carbon atoms is one having a straight chain or a branched chain, such as methyl, ethyl, various propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, etc. Al'ru group; ethynyl. Various types of probenyl, futhynyl, and pentenyl. Alkenyl groups such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, or those whose hydrogen atoms are substituted with alicyclic hydrocarbon groups or aromatic hydrocarbon groups, such as cyclohexylmethyl, cyclohexylethyl, cyclohexenylethyl, phenylmethyl , phenylethyl, etc., among which those having 1 to 5 carbon atoms are preferred. In addition, the alicyclic hydrocarbon group having 3 to 10 carbon atoms is, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclopentyl, cyclohexyl, various methylcyclohexyl, and various methylcyclohexyl; noclopentenyl. . These are unsaturated alicyclic hydrocarbon groups such as cyclohexenyl, various noblecyclohexenyl, and dimethylcyclohexenylnato. Furthermore, the aromatic hydrocarbon group having 6 to 10 carbon atoms includes, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and the like. The hydrogen atoms of these hydrocarbon groups having 1 to 10 carbon atoms are
It may be substituted with a halogen atom, a nido group, a hydroxy group, a lower alkoxy group, a lower alkylthio group, or the like. In addition, when RIG and R11 cooperate with each other to form a ring, the ring may be formed through one or more atoms selected from elemental atoms, oxygen atoms, or sulfur atoms, but if these atoms are When the number of atoms is more than 1, it is preferable to further include other hydrocarbon residues such as alkylene groups, and the total number of the atoms is preferably 1 to 5, and they may be 4- or different. The number of members forming the ring in this case is 3
-8 is preferred, and examples thereof include piperidino, piperazino, morpholino, and the like. Such RIG and R1+ are usually hydrogen atoms. Unsubstituted saturated or unsaturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups are preferably used. Further, examples of the halogen atom for R' in formula (1) include fluorine, bromine, chlorine, and iodine. Such R1 is preferably a hydrogen atom, a halogen atom, a hydroxy group, a sia/group, or the like. R", R", R', R', Rm, and R"
it, same or different, hydrogen atom, halogen atom, cyano group. A nitro group, a lower alkyl group, and the above formula OR@. It is any of the groups represented by SR' and <::'. Here, the lower alkyl group is preferably an alkyl group having a carbon 13 prime number of 1 to 5, such as methyl, ethyl, various propyl, butyl, and pentyl. m means an integer of θ to 15, preferably 0 to 1°,
Particularly preferred is θ~7. Here, R refers to the number of carbon atoms, and when m is 00, it refers to the bond represented by the formula (1). When m is 1 to 15, each Rm
, R1 may be the same or different, and R2°R3 bonded to the carbon atom adjacent to R1 is preferably a group other than the lower alkyl group defined above. n means an integer of θ to 10, preferably 0 to 8, particularly preferably 0 to 5. Here, 4 5 14- means a simple bond between carbon atoms on both sides, and n is 1 to 1.
In the case of 0, each R4 and R5 may be the same or different. Preferably, R* and R3 are a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, or the like. Also R'
, R'lR', R' and (, are as described above, but a hydrogen atom, a halogen atom, a hydroxy group, a cyan group, etc. are preferable, and especially R7 and (,' , γ) group is preferred. R8 in the formula (1'r is the formula OR1', 5Rtt
It is a group represented by IO or a group represented by the formula N/XR1. Here, Rlm is a hydrocarbon group having 1 to 15 carbon atoms that may contain a hydrogen atom or an oxygen atom and/or a sulfur atom, and the hydrocarbon group is defined in the same manner as the hydrocarbon group for R9 above. The preferred hydrocarbon group for Rlt is a saturated aliphatic or alicyclic hydrocarbon group having carbon atoms in the range of 1 to 1O. IG also relates to the formula R'
-10IG hydrocarbon group, R in the formula -N<R,
Defined similarly to lo and R11. Furthermore, in the present invention, it may be a so-called functional group that retains the herbicidal effect of the α,β-unsaturated carboxylic acid represented by the general formula (1). That machine part t! ): Salts include γ alkali metal salts, alkaline earth metal salts, ammonium salts, and salts of the carboxylic acid with an amine represented by NHCH::. Examples of the alkali metal salts include lithium salts, sodium salts, potassium salts, etc., and examples of the alkaline earth metal salts include calcium salts. Examples include magnesium salts. In addition, RH in the above formula NH- is a hydrogen atom\R or a hydrocarbon group having 1 to 20 carbon atoms, and R14
is a hydrocarbon group having 1 to 20 carbon atoms. carbon number)
The ζ1-20 hydrocarbon group refers to an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. show. Nuclear aliphatic hydrocarbon groups are linear or branched, saturated or unsaturated, such as methyl, ethyl, various propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, etc. 'L tenyl. Various types of pulvenyl, hexenyl, and nonenyl. dodecenyl, etc., or those directly substituted with alicyclic or aromatic hydrocarbon groups, such as cyclohexylmethyl,
Examples include cyclohexylpropyl, phenylmethyl, phenylethyl, etc. Among them, those having 1 to 5 carbon atoms are preferred. Examples of alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cyclopentyl, cycloΔxyl, various methylcyclohexyl, dimethylcyclohexyl, and diethyl7.
Examples include couhexyl, cyclohexenyl, and various dimethylcyclohexenyl, among which those having 3 to 15 carbon atoms are preferred. -17= Furthermore, examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl, various toluyls, diethylphenyl, naphthyl, methylnaphthyl, and the like. Preferred hydrocarbon groups as RIB and RI4 are saturated aliphatic or alicyclic hydrocarbon groups having 1 to 15 carbon atoms, and hydrogen atoms are also preferred as Rlm and R14. Function 8 of the α,β-unsaturated carboxylic acids represented by the general formula (1): Preferred as #i in the present invention in terms of herbicidal activity are alkali metal salts. Ammonium salts and salts with amines of the formula NHterR11, such as ethylamine salts, diethylamine salts, dimethylamine salts, propylamine salts, dig-pylamine salts, p-hexylamine salts, dicyclohexylamine salts . Octylamine salt, defluamine salt, dodecylamine #
X, tetradodecylamine salt, etc. Further, the unsaturated carboxylic acid derivatives of the present invention include salts, 18-acid salts, sulfates, oxalates, and sulfonates. It is sometimes used in the form of organic or inorganic acid salts, such as acetate. In the -COR' of unsaturated carboxylic acids in the present invention, those that form salts with artificial acids, acid amides, and amines are preferred, and particularly when forming esters, herbicidal activity is high. Incidentally, the unsaturated carboxylic acids may be either the cis form or the trans form, or a mixture of both. As a general method for producing α,β-unsaturated carboxylic acids represented by general formula (1) in the present invention, for example, the method described in the Journal of the American Chemical Society (J
ounal of the American Chem
icp, l 5ociety) 58 (1936) 186
1. Journal of the Chemical Society (J
nunal of the Chemical Society
ety)jL (1950) 3646, Cnmptes
[rendus] 38 (1904) 1339, etc., by Gignard reaction and hydrolysis of an acetylene derivative represented by the following formula (11), (
3) can be obtained, and further a predetermined compound (4) can be produced by Witt+g reaction. 2 5 (4) Also Tetrahedron Letters (Tetrahedron I, ettera) (1
972), 15.149], the specified compound (9) can be produced by the following reaction using the acetylene derivative (5) as a starting material. (7) R=CyoCCI%CI? -C(ICl3 C00Et-
1-÷-(8)? Et R-CyoC-C1, -CH, -C=C-Co, Et(9
1 In this formula, R means 2R'-ec+m in the above formula (H. Any other commonly used method may be used. Also, any commonly used method for producing the functional salts of unsaturated carboxylic acids may be used. When using the herbicide of the present invention, The α,β-unsaturated carboxylic acids, which are active ingredients, may be treated themselves, but they may be processed into any of the following formulations: granules, wettable powders, emulsions, fine granules, floorfuls, suspensions, etc. These herbicides in the form of formulations include talc, bentonite, clay; solid carriers such as kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, ammonium sulfate, urea; water, alcohol, dioxane, acetone, xylene; , cyclohexane,
Liquid carriers such as methylnaphthalene and dimethylformamide; alkyl sulfates, alkyl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, and poly22-oxyethylene rubitan monoalkylates. Emulsifiers such as dinaphthylmethane disulfonate. A dispersant; one or more of various auxiliary agents such as carboxymethyl cellulose and gum arabic are suitably blended with the unsaturated carboxylic acids, and produced by mixing, dissolving, or granulating. The herbicide of the present invention produced in this manner and in the form of a formulation (usually containing about 0.01 to about 99 parts by weight, preferably about 0.1 to about 95 parts by weight of the unsaturated carboxylic acid derivative) It is desirable that the unsaturated carboxylic acids be contained as an active ingredient.Also, the amount of unsaturated carboxylic acids to be used may be any amount within the range that exhibits herbicidal activity, but 10.9
/ ] Oa ~ 2 kg / 10a is preferable,
Furthermore, 50 fl / 10 a ~ 1 kg / 10 a
is preferred. When the unsaturated carboxylic acids of the invention or herbicides in the form of formulations containing said unsaturated carboxylic acids as active ingredients are used, e.g. in liquid and wettable particulate form, one or more surface additives are usually added as modifiers. The active agent may be included in an amount sufficient to readily disperse the active ingredient in water or oil. The term "surfactant" includes of course wetting agents9 dispersing agents and suspending agents. Also included are spreading agents and emulsifiers. <e)) Effects The herbicide containing the α,β-unsaturated carboxylic acids as an active ingredient in the present invention can be used in foliage treatment by absorbing the active ingredient from the leaves and stems of plants after germination, and in root and foliage treatments. Excellent herbicidal action is exhibited by any soil treatment method that allows the active ingredient to be absorbed from the soil. Furthermore, the herbicide of the present invention exhibits excellent herbicidal activity not only in post-emergence treatment but also in pre-emergence soil treatment, and is particularly effective against broad-leaved weeds such as the early weed Himedion, as well as the perennial weed Plantain. It is characterized by having a herbicidal activity. (f) Examples The present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples in any way. Furthermore, in the examples, "parts" means "parts by weight." The degree of withering, that is, the degree of withering is determined by setting 1 when the plant is healthy, 5 when the whole plant is wilted and dead, and dividing the distance by 4# to indicate the intermediate state. , using the so-called five-step method. Example 1 (1-1) [Synthesis of 4-(2-tetrahydropyranyl)oxy-2-butynal diethylacecur] 10.05 parts of metallic magnesium was added to 400 parts by volume of dry ethyl ether, and the mixture was 45.56 parts of ether bromide was added dropwise to the solution. After refluxing for 20 minutes after dropping,
3-(2-tetrahydropyranyl)oxy-propyne-1,64,5.
A solution of 25 parts of benzene (850 parts by volume) was added dropwise. The reaction mixture was further added with 68.14 parts of benzene (70 parts) of ethyl orthoformate.
After adding the solution (parts by volume), reflux for about 10 hours. A saturated aqueous solution of ammonium acetate was extracted with a small amount of ethyl ether. After drying the extracted layer over anhydrous sulfuric acid (IJ), the organic solvent was concentrated and removed under reduced pressure, and further distilled under reduced pressure to a predetermined concentration. The boiling point of this compound is 126~
b The weight was 11g. (1-2) [Synthesis of 4-hydroxy-2-butinal] Add 435 parts by volume of 0.6NHCj to 43.5 parts of diethyl acetal compound ■ synthesized in (1-1) above, and heat to 20°C.

[Stir for 5 hours. After the reaction, the organic layer was extracted with ethyl ether, and the organic layer was dried with anhydrous sulfuric acid. The ether was concentrated and removed under reduced pressure, and the ~26-predetermined compound ()10-CH,-(':=(: -CH
o ■) 14 copies were obtained. The IR and NMR spectrum data of this compound are as follows. IR, ν (Rho 1); 3400.2200, 1670°NMR (CD(M, )δ(P); 9.17(IH), 4°40(2H), 3.50(IH
) (1-3) (Ethyl-6-hydro p-xy-hex-2-
Synthesis of ene-4-inoate] 215.7 parts of the aldehyde synthesized in Example 2 was dissolved in 80 parts by volume of methylene chloride, and while cooling on ice, 65.3 parts of triphenolcarboethoxymethylenephosphorane was dissolved in methylene chloride ( 100 parts by volume) solution was added dropwise. After the dropwise addition, the mixture was stirred at room temperature overnight. After the reaction, the solvent was concentrated and removed under reduced pressure.
．． The compound (HO-CH, C
9.0 parts of C-CH=CHC0,El (su) was obtained. The spectral data of the compound "' T, R, N, M, R+Mass are as follows. 1, Rν (cm'); 3400.2200, 1700, 1620° NMR, (
CDCl, )δ (Sir): 6.83 (IH), 6.20 (IH), 4.43 (2H
). 4.2a(2t-i), a, z+(tH), t, 27(
3■ ()Mass; m/e 154 (M) Synthesis of ethyl-6-poum-hex-2-en-4-inoate 1 Synthesis using (+-3) of Example 1 (-da compound mark ) was dissolved in 77 parts by volume of dry ethyl ether, and 0.13 parts of lithium bromide and 1.83 parts of 2.4.6-collidine were added thereto. The mixture was cooled to -40°C (~-30°C, 1.5 parts of phosphorus tribromide was added and stirred. After 3 hours, 1.1 parts of phosphorus tribromide was added and the mixture was gradually warmed to room temperature overnight. Stir. After the reaction, water is added to perform ether extraction. The ether layer is washed with water and dried over anhydrous sodium sulfate. The corner is removed under reduced pressure, and the product is transferred to a silica gel column using a Kurumadograph (Wakogel C-200°). Separation and purification (-1
A given compound (Br-C)l, Cmic(I(=r711
2.2β of C(1,Et(j)) was obtained. The IR, NMR, and Mass spectrum data of the Ibi compound are as follows. IRv (z'); 2200.1710.162O NMR (CCl,) δ (Tol116); +i,
7 1 (IH), 6.17 (IH), 4.18 (2
H). 4.08 (2H), 1.26 (3H) MalIs; m/e 216,218 (M+) Example 3
(Methyl-I+-human'qgyshyhex-2-ene-
Synthesis of 4-inoate] 4.2 parts of the aldehyde synthesized in (+-2) of Example 1 was dissolved in 20 parts by volume of methylene chloride and cooled on ice.
o parts of methylene chloride (20 volumes -29 to -1 parts) solution is added dropwise. After the dropwise addition, the mixture was stirred at room temperature overnight. After the reaction, the edges were treated in the same manner as in Example 3 and further separated and purified using a silica gel column to obtain 2.1 parts of crystals of the desired compound (HOCH, CmiCC) (=CHCO2Me). m1lf+ of the compound and 1.
The R, NMR, and Mass spectrum data are as follows. m, p, 51~52°C91, Rν (bo-
I); 3400.2200, 1720, 1690.162ON
MR, (CD(J, )δ(Hayabusa): 6.76(IH), 6.13(IH), 4.41(2H
). 3.76 (3H), 2.89 (IH) Mass, 'm/e 140 (M'') Example 4 Synthesis of rmethyl-6-bromo-hex-2-en-4-inoate] In Example 3 3.15 parts of the synthesized compound (■) was dissolved in 70 parts by volume of dry ethyl ether, and 0% of lithium bromide was added to it.
．． Part 13, 2.4. Add 1.83 parts of loaf frisine. The mixture was cooled to -40 to -30-30 DEG C., and 1.77 parts of triodorid E'phosphorus was added thereto, followed by stirring. 2 hours 41 Add 0.83 parts of odorous ibirin and gradually bring the temperature to room 11, and stir overnight. After the reaction, water is added and ether extraction is performed. Wash the ether layer with water and sulfuric anhydride) +
Dry with 1 um. The ether was removed under reduced pressure, and the product was separated and purified in the same manner as in Example 4 to obtain the desired compound (BrCH,C=C-CI=(J(C(1,Me
(i) 2.0 parts of crystals of ) were obtained. m, P, of the compound;
And T, R, NMR, Mass spectrum data were as follows. m, p, 36-37°C, 1. Rν(z'); 2200.
1730.162O NMR (CC/4) δ(-); 6.73 (IH), 6.17 (IH), 4.03 (2H
). 3.73(3)1). Masa; m/e 204,202 (M+) Actual M Example 5
Synthesis of 1-ethyl-6-chloro-hex-2-en-4-inoate] 03.4 parts of the compound synthesized in (1-3) of Example 1 was dissolved in a portion of dried gothyl ether 7 (1 volume). , 0.063 part of 11thium chloride, 1.4.6-collidine.
Add 82@. The li mixture is cooled to -40°C to -30°C, and 9 parts of phosphorus trichloride () is added and stirred. After 2 hours, add 0.9 parts of phosphorus trichloride and gradually return to room temperature.
Stir overnight. After the reaction, water is added and ether extraction is performed. The L layer was washed with water and dried over anhydrous thorium sulfate. The ether was removed under reduced pressure, and the product was purified using a silica gel column column graph (Wakogel (nee 2 (10, i open solvent);
Separation and purification using benzene:ethyl acetate-20:1),
A given compound (C#-CH, CWCCH=CHCO, E
t (1.5μ of phosphorus was obtained. IR of the compound. NMR, Mass spectrum data are as follows. IRν (Pre-1); 22011.1710.162O NMR (C', CI, ) δ (p book): 6.73 (IH
), 6.17 (IH), 4.25 (2H). 4.17 (2H), l, 30 (3i (). Mass ; m/e I 60 , 158 (M+) Real Mfr example a (a thyl-6-chloro-hex-2-ene-
Synthesis of 4-inoate] Compound 4-inoate (95.0 parts) synthesized in Example 3 was dissolved in 150 parts by volume of dry ethyl ether, and this was
0.16 parts of lithium, 2.4.6-:I lysine 4.32
Add part. The mixture is cooled to -40'C to -3()C, 1.8 parts of phosphorus trichloride is added and stirred. Thereafter, the mixture was gradually warmed to room temperature and stirred overnight. After the reaction, water is added and ether extraction is performed. The goutyl layer is washed with water and dried over anhydrous sodium sulfate. The ether was removed under reduced pressure, and the product was separated and purified using a silica gel column column graph (Wakogel C-200, developing solvent benzene:ethyl acetate-20:1) to obtain the desired compound (CICHtCmiCCH-CHCOtMe).
(To)'x 3-7 parts were obtained. The I R+ NMR1Mass spectrum data of the compound is as follows. IRν (Steel 1); 2200.3720.162O NMR (CCl4) δ (9 yen); 33- 6.71 (IH), 6.13 (IH), 4.21 (2H
). 3.69 (3H) Masa; m/e 160,15B (M+) Example 7
[Synthesis of 6-but-p-mohexar-2-ene-4-inoic-and] 0.54 parts of the compound ■ synthesized in Example 2 was added to 5 parts of methanol.
0 parts by volume, dissolved in 25 parts by volume of dioxane, ]NNaO
Add 5 parts by volume of H and stir at room temperature for 3 hours. Reaction water removal 2
0 volume part was added and methanol and dioxane were removed under reduced pressure. After extracting and removing unreacted substances with ethyl ether,
The aqueous layer was acidified with hydrochloric acid and extracted with ethyl ether. The ether layer was dried with anhydrous sulfuric acid) and concentrated under reduced pressure to dryness to obtain 0.4 part of the desired compound (Br-CH,C=(nee CH=CH-C0OH).The compound The 1.R, NMR spectrum of is as follows: IRν(cR-'); 23+lO~3500, 2200, 1700, 1620
゜NMR(CDCJs) a (pllll); 3
4- 8.79 (IH), 6.89 (IH), 6.20 (IH
). 4.28 (2H) Example 8 [Synthesis of 6-bup-mohexar-2-en-4-inoic acid sodium salt] 01.89 parts of the compound synthesized in Example 7 was dissolved in lNNaOH
Dissolved in 10 parts by volume of an aqueous solution, concentrated water to dryness under reduced pressure,
2.11 parts of a predetermined compound 0φ was obtained. Example 918 Not:+mu-hex-2-ene-4-
Synthesis of inoic and isopropylamine salt] 01.89 parts of the compound synthesized in Example 7 was added to 1 liter of ethyl acetate.
Dissolve in O container and add 0.59% of isopviramine.
part and stir. After the reaction, ethyl acetate was concentrated to dryness under reduced pressure to obtain 02.48 parts of the desired compound. Example 1o [a--j rom-hex-2-ene-4-
Synthesis of inoic acid n-butylamine salt] In Example 9, 0.73 parts of n-butylamine was added instead of isopropylamine, and 2.62 parts of the desired compound was obtained in the same manner as in Example 9. Example 11 [6-brol,-hex-2-ene-4-
Synthesis of inoic acid n-hexylamine salt] In place of isopropylamine in Example 9, Ic n
-1.01 parts of hequinylamine was added and the same method as in Example 9 was carried out to obtain 62.90 parts of the desired compound. Example 12 [Synthesis of 6-poum-hex-2-en-4-inoic acid inpulpyramide] 3.7 parts of thionyl chloride was added to 01.46 parts of the compound synthesized in Example 7, and the mixture was heated at 40 to 50°C for 1.5 parts. Stir for 5 hours. Excess thionyl chloride was removed under reduced pressure, and a solution of 0.91 parts of isobutylamine in ethyl ether (5 parts by volume) was added to the mixture under water cooling. Add reaction water and perform ether extraction. The ether layer was dried over anhydrous sulfuric acid, concentrated under reduced pressure, and the product was separated and purified by silica gel column chromatography (Wakogel C-200, group Hf1j medium Hensen:ethyl acetate-1:2). , a given compound (Br CH, -C=CCH=CHCONH-CH
0.6 part of 2H:o was obtained. IR of the compound. The NMR and Mass spectra are as follows. IRν (bacteria-1); 3300.2200,1660,16]0,155ON
M R (CDCA!s) δ (solution); 6.73 (1)
1), 6.13 (IH), 4.05 (2H). 4.00 (IH), 1.13 (3H), 1.23 (3H
) Mass: m/e 229,23] (M+) 37- Example 1a Synthesis of rethyl-2-bromo-6-human t'+-xy-hex-2-en-4-inoate] Example 5 Compound (2) synthesized in (1-2) 1. a
Dissolve 4 parts in 10 parts by volume of methylene chloride and cool on ice.
A solution of 6.8 parts of triphenyl-α-bromo-carboethoxymethylenephosphorane in methylene chloride (12 parts by volume) is added dropwise. After dropping, the mixture was stirred overnight at room temperature. After the reaction, the solvent was concentrated and removed under reduced pressure, and the product was transferred to a silica gel column.
+-v) graph (Wakogel C-200, developing solvent benzene: was obtained.I, R+ NMR+M of the compound
The asa spectrum data is as follows. IRν(ciI'); 3400.2200, 1710.159ONMR(C(
J, )δ (blue); 7.30 (IH), 4.48 (IH), 4.28 (2B
). 3.59 (IH) 11.36 (:IH) = 38- Mass: m/e 232,234 (M+) Example 14
(Ethyl-2-cool-6-hydro p-xy-hex-2
-Synthesis of -ene-4-inoate] 01.04 parts of the compound synthesized in (1-2) of Example was dissolved in 10 volumes of methylene chloride and cooled on ice to prepare triphenyl-α-chloro-carboate. Part Vf/A! solution was added dropwise to 4.74 parts of quinmethylene phosphorane and 6 jugs of methylene chloride. After the dropwise addition, the solution was stirred at room temperature overnight. After the reaction, the bath medium was concentrated and removed under reduced pressure to give the product. was subjected to silica gel column chromatography (Wafugel C-200, M open fj medium benzene) to obtain 2 parts.1.R, NMR, Ma of the compound.
The ss spectrum data array is as follows. IRν(α-1); 3400.2200, 1720.159ONMR(,C
CJ, ) δ (騨): 6.96 (IH), 4.46 (2) 1), 4.26 (2
B). 3.59 (IH), 1.33 (3I () Mta@ti;
m/e 188,190 (M") Example xs [Synthesis of ethyl-2,6-dibu p mu = a-+r-2-en-4-inoate] Compound 4'94.o synthesized in Example 13 Dissolve one part in 100 volumes of dry ethyl ether and add bromide to it.
Add 0.15 parts of 1 tium and 2.08 parts of 2.4.6-collidine. The mixture was cooled to -40°C to -30°C, 2.02 parts of phosphorus tribromide was added, and the mixture was stirred. After 2 hours, 0.91 part of phosphorus iobromide was added, and the mixture was gradually warmed to room temperature and stirred overnight. After the reaction, water is added and ether extraction is performed. The ether layer is washed with water and dried over anhydrous sodium sulfate. The ether was removed under reduced pressure, and the product was subjected to silica gel column chromatography (Wakogel C-200° developing solvent: benzene:
Ethyl acetate-20:I) to 1, R, NP14R, M
The a sa spectrum is as follows. IRν (closed -1); 2200.1720.159O NMR (cc/4) δ (solution); 7.2s (+H), 4. zs(zH), 4. os(zH
). 1.33 (3B) Mass; m/e 298,296,294 (M+) Example 16 Synthesis of t-ethyl-2-bromo-6-ri p-hex-2-en-4-inoate] In Example 13 04.0 parts of the synthesized compound is dissolved in 100 parts by volume of dry ethyl ether, and 0.072 parts of lithium chloride and 2.07 parts of 2,4.6-collidine are added thereto. The mixture is cooled to -40 DEG C. to -30 DEG C., and 1.48 parts of tertiary ichlin is added and stirred. After 2.5 hours, 0.90 part of phosphorus trichloride was added, and the mixture was gradually warmed to room temperature and stirred overnight. After the reaction, water is added to perform needle extraction. The fJ ether layer is washed with water and dried over anhydrous sodium sulfate. 41- The ether was removed under reduced pressure and the product was separated and purified using Kagel C-200 (Wako Gel C-200, developing solvent benzene: ethyl acetate 20:1) to obtain the desired compound (CJ- 20 parts of CH, -C=r ■ C-CH=C-Co, Et 48) were obtained. The I, R, NMR, and Mass spectra of this compound are as shown below. ); 22υ11,1720.1119O NMR (CCj, ) a (pllll); 7.28
(IH), 4.31 (2H), 4.25 (2H). 1.35 (3H) Mass; m/e 254,252,250 (M”) Example 17r Ethyl-1-ri-p-6-bromo-hex-
Synthesis of 2ene-4-inoate] 63.65 parts of the compound synthesized in Example 14 was added to a dry filJ
, - dissolved in 100 parts by volume of ethyl ether, and to this were added 0.16 parts of lithium bromide, 1 part of lithium bromide, and 2,30 parts of 2,4.6-collidine. The mixture was heated to -40℃--30℃
2.26 parts of 1 ton of tribromide was added and stirred. 1
．． Add 1.0 part of trisodium chloride to the 5-hour incubator, gradually warm to room temperature, and stir overnight. After the reaction, water is added and ether extraction is performed. Wash the ether layer with water [- anhydrous sulfuric acid]
Dry with IIum. The chloride was removed under reduced pressure, and the product was separated and purified by silica gel column chromatography (Wafugel C-200, developing solvent benzene:ethyl acetate-20:1) to obtain the desired compound (Br-CH2C-ioC- 1 CH=C-COtEt (!l) ) 2.0 parts obtained. The I-R+NMR+Mass spectrum of this compound is as follows. IRvCcm); 2200.1720.1595°NMR (CC/4) δ (prm); a, 92 (IH), 4.25 (2ii), 4. to(
2H). 1, 33 (3H) Mass', m/e 254,252,250 (M")
Example 18 (Ethyl-2,6-diku-p-ruheki-1)-
Synthesis of 2-ene-4-inoate] Ibi compound synthesized in Example 14 @4. Part O is dissolved in 100 volumes of dry ethyl ether, and 0.089 parts of lithium chloride and 2.57 parts of 2,4.6-collidine are added thereto. The mixture was cooled to -4()°C to -3°C (1°C), and 1.79 parts of phosphorus trichloride was added thereto and stirred. After 2.5 hours, 1.10 parts of tertiary ichlin was added and gradually returned to room temperature. 1,1
Stir overnight. After the reaction, water is added and ether extraction is performed. The ether layer is washed with water and dried over anhydrous Wtm sodium. The ether was removed under reduced pressure, and the product was separated and purified by Kagel column chromatography (Wakogel C-200° developing solvent, benzene:ethyl acetate-20=1) to obtain the desired compound (C,Il-CI(, 1.5 parts of Cf=EI CCH=C-C0,Et@) were obtained.The 1, R+ NMR and Masa spectra of the compound are as follows: IRν (bacterial); 2200.1720. 1595 NMR (CCA'4) J (+'P") ; "
6.92 (IH), 7.31 (21 (), 4.28 (2
H). 1.36 (3H) Mass: m/e 210,208,206 (M") Example 19 Synthesis] 01.76 parts of the compound synthesized in (1-2) of Example 1 was dissolved in 15 parts of methylene chloride, and 8.7 parts of triphenyl-σ-bromocarbomethoxy/ethylenephosphorane was added while cooling on ice. A solution of methylene chloride (15 volumes) was added dropwise. After the dropwise addition, the mixture was stirred overnight at room temperature. After the reaction, the solvent was concentrated and removed under reduced pressure, and the product was purified by silica gel column chromatography (1 Noco-Gel C-200). , R open m solvent benzene: part is (↓). 1.R, NMR, Mass spectrum data of this compound is as follows. (C(
J4) a (ppm); 7.26 (IH), 4.4
a (2H), 3.83 (3H). 3.36 (IH) Mass l m/e 220, 218 (M
+) Example zor Synthesis of methyl-2-chloro-6-hydroxy-hex-2-en-4-inoate] Compound (6) synthesized in (1-2) of Example 1 1.2
8 parts of methylene chloride (12 parts by volume) was dissolved in 1 part of 12 volumes of Hanashiki methylene, cooled on ice, and mixed with xr-yenyl-a-chloro-carbomethquine methylenephosporan (5.61 parts of methylene chloride (12 parts by volume)).
Drop the solution. After the addition, the mixture was stirred overnight at room temperature. After the reaction, the solvent was concentrated and removed under reduced pressure, and the product was purified by silica gel column chromatography (FUCO-GEL C-2, developing solvent: benzene, 0.7 parts, m, I of the compound), 1T. , RINM
R and Mass spectral data. yl, p 50-51°C IR 1--1); 3500.2200,17]5,1690,159ON
MR (CD (JR) δ (Misaki); 6.92 (1) 1), 4.46 (2H), 3.86 (3
)1). 2.53 (IH) Mass; m/e 176, 174 (M+) Example 21 r, methyl-2,6-dypmuhegisa = 2-
Synthesis of ene-4-inoate] Example: 5.0 parts of the compound o synthesized in 9 was dissolved in 150 parts by volume of dry ethyl ether, and 0.198 parts of lithium bromide and 2.4 parts of 2,4.6-collidine were added thereto. Add 76 parts. The mixture was cooled to 0°C to -3°C (1°C), and 2.7 parts of phosphorus tribromide was added and stirred. After 1.5 hours, 1.19 parts of phosphorus tribromide was added and the mixture was gradually warmed to room temperature. Stir overnight. After the reaction, water is added to perform ether extraction. The ether layer is washed with water and dried over anhydrous sulfuric acid. The ether was removed under reduced pressure, and the product was purified by silica gel column chromatography (Wafugel C-200, developing solvent benzene:
Separation and purification using ethyl acetate (20:1) yielded 2.5 parts of the desired compound (BrCH2CyoCCH=r 2 CCOtMe@). IR of the compound. NMR and Mass spectrum data are as follows. IRν (cIn'); 2200.1720.159O NMR (CCJ4) δ (ppm); 7.30 (IH), 4.10 (2H,), 3.83 (3
H). Mass+m/e 284,282,280 (M+) Example 22 (Synthesis of methyl-2-bromo-6-chloro-hex-2-en-4-inoate) 04.0 parts of the compound synthesized in Example 19 Dissolved in 100 parts by volume of dry ethyl ether, add 0.076 parts of lithium chloride and 2.21 parts of 2,4.6-collidine.The mixture was cooled to -40°C to -30°C, Add 0.54 parts of phosphorus trichloride and stir. After 2.5 hours, add 0.61 parts of phosphorus trichloride and gradually return to room temperature and stir overnight. After the reaction, add water and perform ether extraction. Wash the ether layer with water. (7. Anhydrous M acid) Dry with II um. Ether is removed under reduced pressure, and the product is separated and purified by silica gel column chromatography (Wakogel C-200, developing solvent benzene: ethyl acetate = 20:1). 2.0 parts of a predetermined compound (CI-CH, Cff1C-Br CH=C-COtMe@) were obtained. The 1, R, NMR, and Mass spectrum data of the core compound are as follows. ); 2200.1725.159O NMR (CCJ4) δ (Sir); 7, al (IH), 4.36 (2H), 3.83 (3H
)Mass,'m/e 240,238,236(M”
) 49 Example 2: + (Methyl-2-chromium-6-brome-^
Synthesis of K-1-2-en-4-y/ate] 0.8 parts of the compound @4 synthesized in Example 20 was dissolved in 150 parts by volume of dry ethyl ether, and 0.20 parts of lithium bromide and 2.4 parts of lithium bromide were dissolved in this. . Add 2.78 parts of 6-collidine. The mixture is cooled to -408C to -30C, 2.73 parts of phosphorus tribromide is added and stirred. After 1.5 hours, 20 parts of phosphorus tribromide was added to the mixture, and the mixture was gradually warmed to room temperature and stirred overnight. Add reaction water and perform ether extraction. The ether layer is washed with water and dried over anhydrous sodium sulfate. The ether was removed under reduced pressure and the product was subjected to silica gel column chromatography (FUCO-GEL C-2 developing solvent benzene:
The mixture was separated and purified using ethyl acetate (20:1) to obtain 1.5 parts of the desired compound (Br CH, C=C-CHl written=CCOtMe m ). 1 of the compound
．． R. NMR and Mass spectrum data are as follows. 50-IRν(C111′); 2200,1725.160O NMR(CC1,′Iδ(pl”): 6.89(
IH), 4.08 (2H), 3.79 (3H) Mass
;m/e 240,238,236 (M+) Example 24
(Synthesis of ethyl-2-cyan-6-(2-tetrahydropyranyl)oxy-hex-2-en-4-inoate) 16.8 parts of 4-(2-tetrahydropyranyl)oxy-2-butinal, To a mixture of 12 parts of ethyl cyanacetate and 180 parts of benzene was added 0.1 part of benzyltrimethylammonium hydroxide dissolved in 40% methanol at 10°C.
The desired product was obtained by washing the hindlimb reaction solution with water and separating it by silica gel column chromatography using benzene as a solvent. 1. of the compound. R, NMR, spectral data are as follows: O IRν(,l+++1-'); 2200.1730.159O NMR(CCl4)δ(4); 7.18(IH), 4.86(IH), 4 .53
(2H). 4.33 (2H), 3.59 (2n), 1.66 (6n
l. 1.4f+(3H) Example 25 [Ethyl-2-cyan-6-hydroxy-
Synthesis of hexer-2-en-4-inoate] To a solution in which 0.5 parts of the compound synthesized in Example 24 was dissolved in 100 parts of methanol, 70 parts of 0.6N hydrochloric acid was added to 20 parts of 0.6N hydrochloric acid.
After addition at ℃ and treatment at the same temperature for 2 hours, methanol was removed under reduced pressure and extraction with ethyl ether yielded the target product rN (HOCH,CyoC-CH=C-Co2Et@)
2.5 parts were obtained. 1. of the compound. The R, NMR spectrum was as shown below. IRν (cm-'); 3400.2200, 1730.159ONMR (CD
Cl, )δ (Lin); 7.17 (IH), 4. 48(2)(), 4.07(
2H) 13.00 (IH), 1. 33(3H) Example 26 [Ethyl-2-cyano-6-bromo-hexer 2
Synthesis of -ene-4-inoate] Using 3.06 parts of the compound O synthesized in Example 25, 1.8 parts of phosphorus tribromide was obtained under the same conditions as in Example 15. Furthermore, m , p T , R* NMR*M of the compound
The ass spectrum data is as follows. m, p sa ~55°C IRν (Cm'); 2200.1725.159O NMR (CC14) δ (IIflll); 53- 7.26 (, IH), 4.33 (2H), 4.18 (2
H). 1.40 (3H) Mass; m/e 243,241 (M+) Example 27
[Synthesis of normal octyl-6-(2-tetrahyFl-vilanyloxy)-hex-2-en-4-inoate and normal octyl-6-hydroxy-(l-2-en-4-inoate)] Example 1 Add 43.5 parts of diethyl acetal compound (1) synthesized in (1-1) and 5 parts by volume of 5Nnc14a and stir at 10°C for 2 hours. After the reaction, extract with ethyl ether and remove the organic layer. Dry over anhydrous sodium sulfate, concentrate and remove the ether under reduced pressure, dissolve 14 parts of the obtained product in 60 parts of methylene chloride, and add 3 parts of triphenylcarbooctyloxymethylenephosporane while cooling on ice.
8.8 parts of methylene chloride (parts aO) solution is added dropwise. The mixture was stirred at room temperature for 3 hours, the solvent was concentrated and removed under reduced pressure, and the product was separated and purified by silica gel column chromatography (Wakogel C-200, developed by FljtlL; Hensen: Ethyl acetate = 20:1). , a given compound ([]-6゜□, .=(, -CH-CHCOy
CM H+ tguri, HOCH2(-ECCH=C
8 parts and 211 parts of HC0zCaH+t @ ) were obtained, respectively. The NMR spectrum data of this compound is as follows. Compound @; (CDCJ, ) δ(PIaJ 6.72 (IH), 6.13 (IH),
4.7-4, 9 (IH), 4, 36 (2
H), 3, 9-4.3 (4B), 1.1-1.9
(188). o, 9 (3H) Compound [phase]; (CDClaJ δ (Cape) 6.70 (IH), 6.13 (IH). 4.40 (2)]), 3.5-3.9 (JH) . 4.12(2)1), 1.0~z, o (1gH). n, B3tB Example 28 Synthesis of C normal octyl-6-bromo-hex-2-en-4-inoate] Synthesized in Example 27 (05.3 parts of arsenide, 0.13 parts of lithium bromide, 2 , 4. A predetermined compound (BrCH,C
xC-CH=CHC0IC, ■1. 3.2 copies of ■) were obtained. The IR and NMR spectrum data of this compound are as follows. IRν (cm-'); 220 (1,1715 NMR (CCJ4) δ (pHll); s, 7s (xH), 6.2o (zi), 4.o-4, a
(4H), 1.0-1.9 (12H), 0.90 (3H
) Example 29 [Synthesis of ethyl-6-7 ceteroxyhex-2-en-4-inoate] Ethyl-6-hydropxy-hex-2-ene-4 synthesized in (1-3) of Example 1 -inony) (3) 15
, 4 parts and 87 parts of pyridine were dehydrated with 100 parts of ethyl ether.
A solution of 7.9 parts of acetyl chloride dissolved in 20 parts of dehydrated ethyl ether was added dropwise with stirring while cooling on ice. After dropping, stir at room temperature for 2 hours, then wash with water,
After drying the organic layer, the solvent was concentrated and removed under reduced pressure, and the product was purified by silica gel column chromatography (Wakoge/l-C).
--200, developing solvent; benzene), separated and purified,
Predetermined compound (CH, C00CH2C=xC-CH=
About 14 parts of CHC0,r,t@) were obtained. 1. of the compound. R. The NMR spectrum data is as follows. TRν (1'); 2200.1750.171O NMR (CC71,) δ (11%); 6.65 (IH), 6.10 (IH), 4.70 (21
(). 4.10 (2H), 2.00 (3H,), 1.25 (3
H) = 57- Example 30 (Synthesis of ethyl-6-penzyloxy-hexyl-2-en-4-inoate) Synthesized by (1-3,) of Example 1 (7-butyl 6-hydroxy-hexyl 2-en-4-inoate ■15.4
87 parts of pyridine were dissolved in 100 parts of dehydrated ethyl ether, and a solution of 14 parts of benzoyl chloride dissolved in 20 parts of dehydrated ethyl ether was added dropwise with stirring while cooling on ice. After dropping, stir at room temperature for 2 hours, then wash with water,
After drying the organic layer, the solvent was concentrated and removed under reduced pressure, and the product was purified by silica gel column chromatography (Wakokel C,
-200, separation and purification L by developing solution @ ; H:/ -1/ :/ ), predetermined compound (CeHs C00CH
t C=CCH=CHC0,Et 2) Approximately 2 ( ) parts were obtained. 1. of the compound. The RNMR spectrum data is as follows. IRν (Rust-1); 2200.1720.1615 NMR (CCJ,) δ (Sir); 7.9-8.2 (2H) + 7-3-7, 6 (3H)
, 6.7558- (IH), 6.15 (IH), 5.02 (2H). 4.15 (2H), 1. 26 (3H) Actual Example 31 (
-r-nal-6-mena-11sulfonyloxy-hexa-
Synthesis of 2-en-4-inoate] Ethyl-6-human pgacyt synthesized in (+-3) of Example 1, 015.4 parts of x-2-en-4-inoate, l·11 ethyl γ Dissolve 1 part of 1] in dehydrated ethyl ether + LlO (1 distillate), and while cooling on ice dissolve 5 parts of salt 1'methylsulfoni/i, + 1, in 20 parts of dehydrated ethyl ether and stir the 1-solution. P1 “Garadrop”
To 1-ru. After dropping, stir at room temperature for 2 hours, then wash with water.
After drying the organic layer, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (Wako Gel C2).
00, developing solvent r benzene: ethyl acetate = lo:
1) Separated by 1-1H constant compound (CH, -8-OCH, CyoC-
About 19 parts of CH:21CH-CO2Et@) were obtained. I, R, and NMR spectral data of the compound are as follows. IRν (Pre-1); 2200.17] 5 NMR (CCl4) δ (pplN); 6.70 (IH
), 6.22 (18), 4.96 (2H). 4.18 (2H), 3.05 (3H), 1.30 (3H
) Example 32 [Synthesis of ethyl-6-(2,4-dichlorophenoxy)-hex-2-en-4-inoate] 2.4-Dichlorophenol 15lll14 Dissolved in 50 parts of dimethyl sulfoxide and hydrogenated) IIum (5
Add 5 parts of 0% oil) and stir at room temperature for 2 hours. Thereafter, compound 021. synthesized in Example 2 was added to this mixture.
A solution prepared by dissolving 7 parts in 50 parts of dimethyl sulfoxide is added dropwise at room temperature while stirring. Thereafter, the mixture was stirred overnight at room temperature, water was added, and extraction was performed with ethyl ether. The solvent was concentrated and removed from the organic layer under reduced pressure. :Ethyl acetate=10:]) to ('>CH=CT(-
Approximately 16 parts of Co, Etg) were obtained. T, R of the compound
, NMR spectrum data are as follows. IRν (--'); 2200.171O NMR (ccz, ) a (pfll); 7.34
(18), 6.95 (IH), 6.62~6°R (1(
2)+), 6, 2 o (+11),
4, 92 (2H) 4.20 (2H), 1.25 (3
H) Example 33 [Synthesis of ethyl-a-C4-(2,4-dichlorophenoxy)phenoxy]-hex-2-en-4-inoate] 4-(2,4-dichlorophenoxy)pheno-61- A mixture of 04.3 parts of the compound synthesized in Example 2, 1.4 parts of anhydrous potassium carbonate, and 200 parts of dehydrated acetone is heated under reflux for 6 hours. Thereafter, the acetone was concentrated under reduced pressure, 200 parts of ethyl ether was added, and the mixture was washed with water. The solvent was concentrated and removed from the organic layer under reduced pressure, and the product was separated and purified using silica gel column chromatography (Fuko-gel C-20+1.i opening solvent; benzene:vinegar!=-chill-10:1) CH=CH- About 4.2 parts of Co, EtD were obtained. The IR and NMR spectrum data of this compound are as follows. IRν (bacteria-'); 2200.1708 NMR (CCJ, ) δ (crime) near, 35 (1B), 6.8-7.1 (6H), 6.72
(IH), 6.13 (11 (), 4.83 (IH). 4.20 (2) 1), 1.26 (:IH) = 62- Example 34 [Ethyl-6-(4-benzyl Synthesis of oxy)phenoxy hex-2-en-4-inoate] 4.4 parts of 4-benzyloxy/phenol A mixture of 04.3 parts of the compound synthesized in Example 2, 1.4 parts of anhydrous potassium carbonate, and 200 parts of dehydrated acetone Heat to reflux for 6 hours. Concentrate the acetone under reduced pressure, add 200 parts of ethyl ether, and wash with water. The solvent was concentrated and removed from the organic layer under variable pressure, and the product was separated and purified using a Nori-Gel-based Mukp Madograph (Wakogel C-200, development 11J medium; benzene:ethyl acetate = 10:1) to obtain the desired compound 4. .0 copies were obtained. #The IR and NMR spectrum data of the compound are as follows. IRν (pot-1); 2200.171O NMR (CCl4) δ (throat); 7.05-7.30 (5H), 6.70-7.00 (4
H), 6.72 (IH), 6.06 (IH). 4.90 (21 (), 4.65 (2H), 4.10
(2)1)1.22(3H) (CH2)t OCt Hs @ and HOCH,C=
C-CH-CHCOt (CHt)20(CHt)
Synthesis of tOc*Hse] 435 parts by volume of 0.6N hydrochloric acid were added to 43.5 parts of the diethyl 7-cetal compound (1) synthesized in (]-1) of Example 1, and the mixture was stirred at 10°C for 12 hours. After the reaction, it was extracted with ethyl ether, the organic layer was dried over anhydrous sodium sulfate, the ether was concentrated and removed under reduced pressure, 14 parts of the obtained product was dissolved in 60 parts of methylene chloride, and triphenylcarpone was added while cooling on ice. (2-(2'-ethoxy)-ethoxyl-ethquine with tyrenephosphorane 38
of methylene chloride (80 parts) was added dropwise. The dropwise addition was stirred at room temperature for 3 hours, and the solvent was concentrated and removed under reduced pressure.
200, developing solvent; benzene: ninor acetate = 9:1)
Separate and purify the specified compounds @ and ■ by
I won 19 parts and 19 parts. The IR and NMR spectral data of the limb compound are similar to Gero's. Compound ■ IRν(σ-1); 22(10,1720,162O NMR(CC,1,)δ(Sir): 6.76(It(), 6.16(IH), 4.Q-4.
7 (IH), 4.33 (2H), 4.20 (2T (),
3.8-3.2(10)]), 1.8-1. 1 (6H
), 1. 16(3H) Compound [phase] rRν(fi-'); 2200.1720.162O NMR(CCl4)δ0-); 6.73(IH), 6.13(IH), 4.31(2H
)4.20(21(),3.75-3.30(,8H)
. 3.10 (I H), 1.16 (3H) 65 Example a a (BrCH, C=CC=C-CH=CH
C00(C,0(C)(,).QC,)1. Synthesis of (4?)] Performed using 5.1 parts of the compound synthesized in Example 35, 0.13 parts of lithium bromide, 1.83 parts of 2,4.6-collidine, and 2.6 parts of phosphorus tribromide. By the same method as in Example 2, 3.4 parts of the desired compound 0 was obtained by reaction and post-treatment. The IR and NMR spectral data of this compound are as follows. IRy (cML'); 2200.1720.162O NMR (CCl4) δ (Sir); a, 75 (lH), a, 2o11t), 4. a~4.0
(2)i), 4.03 (2H), 3.30 to 3.75 (
8H), 1.16 (3H) Example 37 0.05 part of the compound ■ synthesized in Example 2 was added to a mixed solution of 12.5 parts of water and 12.5 parts of acetone, and then added as a spreading agent to 5ORPOL 2a8o. ('Ml Japan Chemical) 0.
A mixture containing 0.013 parts was sprayed on the stems and leaves of 66-Himedione and Lamina japonica, which had been cultivated in advance, in an amount equivalent to 500.9/1゜a, and the cultivation was continued.Furthermore, the withering condition of each plant was observed with the naked eye. We conducted an experiment. In addition, Table 1 shows the degree of withering one week after treatment as ζM? ! *It's L. Example 38 = 48 0.05 part of each of the compounds synthesized in Examples 4, 13 to 18, 2] to 23 and 26 was mixed with 12.5 parts of water and 1 part of acetone.
In addition to 25 parts of the mixed solution, 5ORPO was added as a spreading agent.
Himedion was grown in a mixture containing 0.033 parts of L 2680 (Toho Chemical System). The ridges were sprayed three times in about 1.5 hours on the stems and leaves of crabgrass.
Furthermore, following the cultivation, a withering experiment was conducted by visually observing the degree of withering of each plant. One week after treatment, the degree of mortality was 8.
Listed in Table 1 (-) Examples 49 to 62 Compounds synthesized in Examples 1, 3.5 to 12.19, 20, 24.25 ■, ■, (7), (θ), ■ ,@,
411. The results of a withering experiment conducted in the same manner as in Example 3B using @0, 0, 0, @, O are shown in the second column. 1 Table 69 - Table 2 - 70 = Examples 63 to 74 Table 3 shows the results of a withering experiment conducted in the same manner as in Examples using the compound O- [strain] synthesized in Examples 27 to 36. It was shown to. Reference example 1 Add 5ORP to a mixed solution of 12.5 parts of water and 12.5 parts of acetone.
A blight experiment similar to that in Example 37 was conducted using a mixed solution to which 0.013 parts of flL and 2680 were added. As a result, the degree of death of all weeds was 1. ls3 Table Example 75.76 Compounds synthesized in Examples 2 and 15 ■, ■ each 0
, 2 parts of Of+, acetone o, oos container, SO
Add to RPOT, 26800.0032 and dilute with 20 parts of water. On the other hand, fill a pot with a diameter of 10 and a depth of 10α with soil, sow the seeds of Himedion and Plantain, cover with soil to the extent that the seeds are covered, and apply 25 minutes of the prepared liquid on the soil surface.
The seeds were sprayed at a rate equivalent to 0 μ/10 alC, and the number of germinated seeds and growth status were observed. As a result, compound (j), Q
7) In both cases, even after two weeks, himedione,
Seeds of plantain also did not germinate, showing a germination inhibiting effect of 100%. Reference example 2 Acetone o, oog container, 5ORPOL 26810
．． A mixed solution of 32 parts of 0O and 20 parts of water was applied in the same manner as in Example 75, and the germination status of the seeds of Himedion and Plantain was observed.All seeds germinated and remained healthy within two weeks of contact. 73- 72-

Claims (1)

[Scope of Claims] A herbicide containing at least one type of functional salt selected from the general formula % as an active ingredient.