JPS60166642A - Hex-2-en-4-ynecarboxylic acid - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R<1> is H, CN, NO2, OR<6> (R<6> is H, 1-16C acyl, etc.), SR<6> or formula II (R<7> and R<8> are H, 1-10C hydrocarbon group, etc.); R<2> and R<3> are H, halogen, CN, NO2, OR<6>, SR<6> or formula II; R<4> is H, halogen, CN, NO2, lower alkyl, OR<6>, SR<6> or formula II; R<5> is OR<9> (R<9> is H or 1-15C hydrocarbon group which may contain O or S), SR<6> or formula II] and a salt thereof. EXAMPLE:Ethyl 6-bromo-hex-2-en-4-ynoate. USE:An agricultural chemical such as herbicide, plant growth regulator, germicide, insecticide, etc. and a medicine such as a physiologically active agent, e.g. having inhibitory activity for synthesis of cholesterol. PREPARATION:A compound expressed by formula III is reacted with a compound expressed by formula IV to give a compound expressed by formula V, which is then hydrolyzed to afford a compound expressed by formula VI. The resultant compound expressed by formula VI and a compound expressed by formula VII are subjected to the Wittig reaction to give the aimed compound expressed by formula I .

Description

Detailed Description of the Invention (a) Technical Field The present invention provides novel α, β
-Relating to unsaturated carboxylic acids.

More specifically, it relates to hex-2-en-4-ynecarboxylic acids and functional salts thereof.

佽）Prior art Some of the aliphatic carboxylic acids are known to exhibit physiological activities such as fl[. (Refer to US N% Permit No. 3139378) and 3-
Decinoic acid synthesizes consterol! 11 Having harmful activity (Biochem, J
), Vol. +147, pp. 531-539 (1975)). On the other hand, hour 1ifi47-
Publication No. 41005 or Agricultural Biop
Dical Chemistry (Agrjc, Biol, C
hem)+45, pp. 2769-2773 (1981)K β-(N-phenyl-N-methyl)
It has been disclosed that amino-α-cyanoacrylic acid ester exhibits herbicidal activity and has Hill reaction (photochemical oxygen generation reaction by free chloroplasts) llI11 harmful activity.

(e) Purpose The present inventors focused on the physiological activities of such carboxylic acids, and conducted physiological and physicochemical studies on various derivatives thereof, with the aim of obtaining excellent physiologically active substances such as medicines and agricultural chemicals. As a result of intensive research, it was surprisingly discovered that hex-2-en-3-ynecarboxylic acids, unsaturated carboxylic acids with a specific structure, have excellent physiological activities such as inhibiting the germination of plant seeds and herbicidal effects. The present invention was achieved based on the discovery that the present invention has physiological activity against plants and against pests, microorganisms, and animals.

(d) Structure of the Invention The present invention is based on the following general formula (wherein R1 is a hydrogen atom, a 7-cya group, a nitro group,
OR' (where R6 is a hydrogen atom, an acyl group having 1 to 16 carbon atoms, an oxygen atom and/or a hydrocarbon group having 1 to 15 carbon atoms which may contain a sulfur atom, or a hydrocarbon group having 1 to 15 carbon atoms) (substituted or unsubstituted sulfonyl group),
A group represented by SR' (however, the definition is different as above, it is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may cooperate with each other to form a ring); R',
R" are the same or different, and are a hydrogen atom, a halogen atom, a cyano group, a nido ρ group, the above O", and a group shown above; R1 is OR' (However, R9 is a hydrogen atom or an oxygen atom and/or a sulfur atom The number of carbon atoms that may contain atoms is 1 to 150
), SR' (wherein R1 is an open group as above) or a functional salt thereof, hexa-2
-En-4-ynecarboxylic acids.

5- The present invention will be explained in more detail below.

The hex-2-en-4-ynecarboxylic acids in the present invention are those represented by the above general formula (I), but have six carbon strands in the upper chain and a terminal end having a carboxyl group. is composed of an ester such as carboxyl or carboxyalkyl, or an acid amide.

R1 in the formula (I) is a hydrogen atom or a sulfur group. Here, W is a hydrogen atom, an acyl group having 1 to 16 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 or substituted hydrocarbon group having 1 to 15 carbon atoms. It is an unsubstituted sulfonyl group.

The acyl group having 1 to 16 carbon atoms is represented by 2R"-Co, where #Rel is a hydrogen atom,
A hydrocarbon group having 1 to 15 carbon atoms is preferred.

Such a hydrocarbon group having 1 to 15 carbon atoms and 6- is an aliphatic hydrocarbon group having 1 to 15 carbon atoms.

Alicyclic hydrocarbon group having 3 to 15 carbon atoms and 6 to 15 carbon atoms
15 aromatic hydrocarbon groups are shown.

Here, the aliphatic hydrocarbon group having 1 to 15 carbon atoms is
Straight chain or branched, saturated or unsaturated, eg methyl.

Ethyl, various propyl, butyl, hexyl.

Olytyl, decyl, dodecyl, tetradecyl.

Ethynyl, various purvenyls, hexenyls.

Examples include nonenyl, dodecenyl, etc., or those substituted with an alicyclic or aromatic hydrocarbon group, such as cyclohexylmethyl, cyclohexylmethyl, phenylmethyl, phenylethyl, etc. Among them, those having 1 to 10 carbon atoms are preferred. .

Examples of alicyclic hydrocarbon groups having 3 to 15 carbon atoms include cyclopentyl, cyclohexyl, various types of methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, cyclohexenyl, and various types of dimethylcyclohexenyl. is preferably 3 to 10.

Further, examples of aromatic hydrocarbon groups having 6 to +5 carbon atoms include phenyl and various types of toluyl.

Examples thereof include dimethylphenyl, propylphenyl, naphthyl, methylnaphthyl, diethylnaphthyl, etc. Among them, those having 6 to 10 carbon atoms are preferred.

Such a hydrocarbon group is such that its hydrogen atom is
2) It may be substituted with a +' group, a hydroxy group, a lower alkoxy group, a lower furkylthio group, etc., and specific examples thereof include trifluoromethyl and dimethylphenyl.

A hydrocarbon group having 1 to 15 carbon atoms that may contain a sulfur atom is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, or an alicyclic hydrocarbon group having 3 to 15 carbon atoms. group, an aromatic hydrocarbon group having 6 to 15 carbon atoms, and a group containing an acid Xi atom and/or a sulfur atom in these hydrocarbon groups, and a hydrocarbon group having an R prime number of 1 to 13 is more preferable. .

Further, one hydrocarbon group may be substituted with a no-p gene atom, a nitro group, etc. Note that the hydrocarbon group that does not contain an oxygen atom and a sulfur atom mentioned here can be shown in the same manner as the specific example regarding R'' above, so details will be omitted. As for those containing such oxygen atoms and sulfur atoms, the argument number is 1 to 5.
, preferably 1 to 3, such as an alkyloxyalkyl group or an aralkyloxyalkyl group.

Examples include alkyloxyaralkyl groups, aralkyloxyaralkyl groups, alkyloxyfurkyloxyargyl groups, those containing a sulfur atom instead of an oxygen atom, and complex alkyl groups. Specific examples thereof include methoxymethyl, methylthio Methyl, ethoxyethyl.

7') Xyethyl, decyloxyethyl, phenylmethoxyethyl, ethoxyphenyl, phenoxymethyl, phenoxyphenyl, pen 9-zyloxyphenyl, furyl, pyranyl and the like.

An unsubstituted sulfonyl group is represented by the formula H8O,-, and a sulfonyl group substituted with a hydrocarbon group having 1 to 15 carbon atoms is represented by the formula R62S.
It is indicated by Ox-.

m R62 is a hydrocarbon group having 1 to 15 carbon atoms, and more specifically, it is shown in the same way as the above-mentioned ``R'' regarding the acyl group, and preferable examples thereof include methyl, ethyl, various propylhexyl, Decyl, phenyl, various toluyl, cyclohexyl, etc. with 1 carbon number I G
I can give you something.

Also, R in the above formula Ng%? and R8 are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R7 and R'' may cooperate with each other to form a lump. The number of carbon atoms is 1 to !0 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 aromatic hydrocarbon group having 6 to 10 carbon atoms.

-10= The aliphatic hydrocarbon group having 1 to 10 carbon atoms is a linear or branched group, such as methyl, ethyl, various types of propyl, butyl, pentyl, hexyl, heptyl, octyl, Alkyl groups such as nonyl: ethynyl.

Various propenyl, butenyl, and pentenyl.

Alkenyl groups such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, or those whose hydrogen atoms are substituted with alicyclic hydrocarbon groups, aromatic hydrocarbon groups, such as cyclohexylmethyl, cyclohexylmethyl, cyclohexenylethyl, phenylmethyl, Examples include phenylethyl, among which those having 1 to 5 carbon atoms are preferred.

Also, an alicyclic swollen hydrogen group having 3 to 10 carbon atoms! : is a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclopentyl, cyclohexyl, various types of methylcyclohexyl, and various types of dimethylcyclohexyl; cyclopentenyl.

These are unsaturated alicyclic hydrocarbon groups such as cyclohexenyl, various types of methylcyclohexenyl, and dimethylcyclohexylnato.

Further, aromatic hydrocarbon groups having 6 to 10 carbon atoms include, for example, phenyl, tolyl, xylyl, ethylphenyl, and thick phthyl.

The hydrogen atom of these hydrocarbon groups having 1 to 10 carbon atoms may be substituted with a hapogen atom, a nitro group, a hydroxy group, a lower alkoxy group, a lower alkylthio group, or the like.

In addition, when R7 and Il'' cooperate with each other to form a ring, the ring may be formed through one or more atoms selected from nitrogen atoms, oxygen atoms, or sulfur atoms, but if these atoms In the case of more than 1, it is preferable to further include other bulky hydrocarbon residues such as alkylene groups, and the total number of Ojihara groups is preferably 1 to 5, and they may be the same or different. The number of members of the ring forming the ring is 3~
8 is preferred, and examples thereof include piperidino, piperazino, morpholif, and the like.

Such R7 and Ra are usually hydrogen atoms.

Unsubstituted saturated or unsaturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups are preferably used.

Such R1 is preferably a hydrogen atom, a human-oxy group, a cyano group, or the like.

Bt and R1 are the same or different, and represent a hydrogen atom, a halogen atom, a cyano group, a nido rz group, and a fluorine atom in the invention.

Examples include bromine, chlorine, and iodine.

Preferred examples of R'' and R'' include a hydrogen atom, a hydrogen atom, a hydroxy group, and a cyano group. Here, the lower furkyl group is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, various propyl, butyl, and pentyl. Such R4 is a hydrogen atom.

13- /% f3 Gun atom, cyano group, etc. are preferred.

671 Formula (I) K OR W is the formula OR' +
SR"C where R9 is a hydrogen atom or an oxygen atom and/or
Alternatively, it is a hydrocarbon group having 1 to 15 carbon atoms which may contain a sulfur atom, and the skeleton hydrocarbon group is defined in the same manner as the hydrocarbon group corresponding to 1 with respect to R6.

A preferable hydrocarbon group as such RQ is a saturated aliphatic group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group.

It is something that can be done.

Furthermore, the function of hex-2-en-4-ynecarboxylic acid represented by the general formula (I) in the present invention+! ! Examples of the salt include alkali metal salts, alkaline earth metal salts, and ammonia of nuclear carboxylic acids.

Here, examples of the alkali metal salt include lithium 14-rum salt, sodium salt, potassium salt, etc., and examples of the alkaline earth metal ring include calcium salt.

Magnesium salts etc. are blocked.

Further, R"° in the above formula NHζ7:τ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R" is a hydrocarbon group having 1 to 20 carbon atoms.

The hydrocarbon group having 1 to 20 carbon atoms refers to a hydrocarbon group having 1 to 2 carbon atoms.
0 aliphatic hydrocarbon group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms.

#Aliphatic swollen hydrogen group is ijr#A or branched and saturated or unsaturated, such as methyl, ethyl, various types of propyl, butyl, hexyl, octyl,
Decyl, dodecyl, tetradecyl, octadecyl, ethynyl.

Examples include various pulvenyl, hexenyl l/ne=/Ll dodecenyl, etc., or those substituted with alicyclic or aromatic hydrogenated groups, such as cyclohexylmethyl, cyclohexylpropyl, phenylmethyl, phenylethyl, etc. Those having 1 to 15 carbon atoms are preferred.

Examples of alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cyclopentyl, cyclohexyl, various types of methylcyclohexyl, dimethylschiff-cohexyl, diethylcyclohexyl, cyclohexenyl, and various types of dimethylcyclohexenyl. ga; 4-15
Preferably.

Further, as aromatic hydrocarbon groups having 6 to 20 carbon atoms, phenyl, various toluyls, gelphenyls, naphthyls,
Examples include methylnaphthyl.

Preferred hydrocarbon groups as RIolR'' are saturated aliphatic or alicyclic hydrocarbon groups having 1 to 15 carbon atoms, and hydrogen atoms are also preferable as R'' and R'.

α represented by general formula (1) in the present invention.

As a general method for producing β-unsaturated carboxylic acids, for example, Journal of American Chemical Science 7
Tay (Journal of the America
nChemical 5ociety )s s (I
9a s) 1s a s.

Journal Opsa Chemical Nzaiatei (Jo
unal of the Chemical 5oci
ety) 4 (1950) 3646 + Complete
s rendus 138 (1904) 1339, etc., a Grignard reaction and hydrolysis of an acetylene derivative represented by the following formula (1) yields a compound (31), and a WjtHg reaction yields a predetermined compound (4). ) can be manufactured.

+11 121 17 The hex-2-en-4-ynecarboxylic acid represented by the formula (I) in the present invention is not limited to the production method described above, but may be produced by other commonly used methods.

Furthermore, any commonly used method may be used for producing the functional salts of nuclear unsaturated carboxylic acids.

(e) Effects The hex-2-en-4-ynecarboxylic acids of the present invention exhibit significant physiological activity toward living organisms and are useful as Ilk drugs and pharmaceuticals. In other words, agricultural chemicals include herbicides targeted at plants, plant growth regulating circuits, germicidal circuits aimed at killing or inhibiting the growth of microorganisms, and insecticides targeting pests. Examples include physiologically active pathways such as cholesterol synthesis inhibitory activity.

To further describe the usefulness as a herbicide among these physiological activities, the carbonic acids of the present invention not only exhibit excellent herbicidal activity in both the foliage treatment of plants after germination and the soil treatment. It also shows excellent herbicidal effects in soil treatment for germinated plants.

(f) Examples The present invention will be further explained with reference to Examples below, but the present invention is not limited to these Examples in any way.

Furthermore, in the examples, "part" means "one lid part".

Example 1 (1-1) (Synthesis of 4-(2-tetrahydropyranyl)oxy-2-butynal diethyl acetal) 10.05 parts of metallic magnesium was added to 400 parts by volume of dried ethyl ether to form a nuclear crystal compound. to ethyl bromide 4
Add 5.56 parts dropwise. After refluxing for 20 minutes after the dropwise addition, the bath solution containing 64.5 parts of 3-(2-tetrahydropyranyl)oxy-propyne-1, 64.5 parts of benzene (85° noodles) was cooled and the temperature was maintained at 10 to 15°C. drip. A solution of 68.14 parts of ethyl orungate in benzene (70 volumes, 1 part) is further added to the nuclear reaction mixture, and the mixture is refluxed for about 10 hours.

After the reaction, a saturated aqueous solution of ammonium acetate was added and extracted with ethyl ether. After drying the extracted layer with thorium borosulfate anhydride, +14! Concentrate and remove the thf6 medium under reduced pressure,
Further, the desired compound was obtained by distillation under reduced pressure. The boiling point of the compound is 126-127°C 73 mmI
It was Ig.

(1-2) [Synthesis of 4-human p-q-2-butinal] The above (
Diethyl 7-cetal compound synthesized in 1-1) ■43,
To 5 parts, 1435 parts by volume of 6NHC was added and stirred at 20°C for 5 hours. After the reaction, extraction was carried out with ethyl needles, the organic layer was dried over anhydrous sodium sulfate, and the ether was concentrated and removed under reduced pressure to obtain the desired compound (HO-CH, -C-C-
14 parts of CH0■) were obtained.

The IR and NMR spectra of this compound are as follows.

IR, ν(α); 3400+ 2200+ 1670+ Deka (CD(J,) δ(solution): 9.17(111)+ 4.40(2H)y 3.50
(IIF()(1-a) [Synthesis of ethyl-6-hydro px-hex-2-en-4-inoate] 15.7 parts of altehyde 2 synthesized in Example 2 was dissolved in 80 parts by volume of methylene chloride. 65.3 parts of triphenylcarfoethoxymethylenephosphorane and 100 parts by volume of methylene chloride are added dropwise while cooling on ice. After the addition, the mixture is stirred overnight at room temperature.

=21- After the reaction, the solution was concentrated and removed under reduced pressure, and the product was separated and purified using a silica gel column coomadography (Noco-Glu C-200, developing solvent: benzene: ethyl acetate - 20:1), and the product was purified to the specified concentration. Compound (HO-CI(ICCI-CH
=CHC0,Et■) 9.0 parts were obtained. 1 of the compound,
The spectral data of R, N, M, and tL Mass are as follows.

1, Rν(cIR'); 34(10,2200,1700,162ONMR,(
CDC4, ) δ (pp+); 6.83 (IH), 6.
2o (IH) + 4.43 (2B) 14.23 (2HL
3.24 (IH) + 1.27 (3H) Mass;
m/e 154 (M+) Example 2 (-x-+ /l=-6-riμmuheki9--2-
Synthesis of ene-4-inoate] 3.4 parts of the compound (1) synthesized in Example 1 (1-3) was dissolved in 77 parts by volume of dry ethyl ether, and 0.13 parts of lithium bromide was added thereto. 2,4.6=
Add 1.83 parts of collidine. The mixture was heated to -40℃~-
Cool to 30°C, add 1.5 parts of phosphorus tribromide, and stir.

After 3 hours, 1.1 parts of phosphorus tribromide was added, and the mixture was gradually warmed to room temperature and stirred overnight.8 Reaction water was added to perform needle 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 purified using a silica gel column (Wako Glu C-200 + developing solvent;
Separation and purification using Hensen: ethyl acetate = 20:1),
Predetermined compound (Br-CH, C=CCH=CHC0,E
2.2 g of t■) was obtained. IR, NMR, M of the compound
, +ss spectrum theta is as follows.

IRν (113+'); 2200, 1710.162O NMR (CD (J,) δ (Sir): 6.73 (IH) 16.17 (IHL 4, 18 (2H)
), 4.08 (2H) 11.26 (3H) Mass; m/e 216,218 (M+) Example 3 [Synthesis of methyl-6-hydro px-hex-2-en-4-inoate] Implementation 04.2 parts of the aldehyde synthesized in (1-2) of Example 1 was dissolved in 20 parts by volume of methylene chloride, and while cooling on ice, 10.0 parts of triphenylcarpomethoxymethylenephosphorane was dissolved.
A solution of 20 parts methylene chloride (20 parts by volume) is added dropwise. After dropping, stir overnight at room temperature. After the reaction, post-treatment was carried out in the same manner as in Example 3, and further separation and purification was carried out using a silica gel column column chromatograph to obtain a predetermined compound (HOCH, C=CCH=
2.1 parts of crystals of CHC0*Me)■ were obtained. rn, p, and 1. of the compound. R, NMR.

The Ma　s　s spectrum data is as follows.

m, p, 51-52°C 1, Rp (cIn); 3400, 2200.1720.1690.162ON
MR, (CI) C4s) δ (solution); 6.76 (IH) + 6.13 (IH), 4.41 (2
H) 13.76 (3H) + 2.89 (IH) Mass
: m/e 140 (M+) Example 4 [Synthesis of methyl-6-sp-mohexar-2-en-4-inoate] 70 parts by volume of ethyl ether obtained by drying 3.15 parts of the compound ■ synthesized in Example 3 and add 0 lithium bromide to it.
．． Add 13 parts and 71.83 parts of 2,4.6-Colidi.

The mixture was cooled to -40~30°C and phosphorus tribromide 1.
Add 77 parts and stir. After Zhr, add 0.0% phosphorus tribromide.
Add 83 parts, gradually warm to room temperature, and stir overnight.

Add reaction water and perform ether extraction. Wash the limb ether layer with water, dilute with anhydrous sulfuric acid, and dry with IJum. 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 (B rCH, C=C-C
2.0 parts of crystals of H=CHCO,Me■) were obtained. The m, p, and 25-T-R9 NMR and Mass spectrometry of the compound were as follows.

m, p, 36-37℃ T, Ru (cm) p 2200, +730.1620゜NMR (CC1,) δ (blue): 6.73 (IH), 6.17 (IHL 4.03 (2)
H) 1a, 7a (aH) Mass; m/'e 204, 202 (M'-)
Example 5 [Ethyl-6-chlorohe? Synthesis of Sar-2-2-4-inoate] 3.4 parts of the compound (1) synthesized in Example 1 (1-3) was dissolved in 70 parts by volume of dry ethyl ether, and 0.063 parts of lithium chloride was added thereto.

2.4. Add 1.82 parts of 6-collidine. The mixture was cooled to 0° C. to −30° C., and 9 parts of phosphorus trichloride was added and stirred. After 2 hours, 0.9 part of phosphorus trichloride was further added, and the mixture was gradually returned to room temperature = 26 = 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 separated and purified using a silica gel column column graph (Fuko-gel C-2oo, developing solvent: benzene:ethyl acetate = 20-21) to obtain a predetermined compound (C/'- Cl, C4:CCH=CHC
0, Et■) was obtained at 1.59. #IR of compound.

NMR, Maaa spectrum booter is as follows.

IRν(cIR).

2200, 1710.162O NMR (CCI, ) a(ppi); 6.7a(l
H), 6.17 (+H) + 4.25 (2H) + 4.
17 (2HL t, 3oc3io.

Example 6 [Synthesis of methyl-6-ri p-hex-2-en-4-inoate] 05.0 parts of the compound synthesized in Example 3 was poured into dry ethyl ether + 50 parts by volume, and Lithium chloride 0
．． Add 16 parts and 4.32 parts of 2,4.6-collidine. The mixture is cooled to -40°C to -30°C, 1.8 parts of phosphorus trihydride is added and stirred. Gradually return the ridge to room temperature,
Stir overnight. Add reaction water and perform ether extraction. The ether layer is washed with water and dried over anhydrous tutria sulfate. The ether was removed under reduced pressure, and the product was separated using a silica gel column column graph (Fuco-Glu C-2oO + developing solvent: benzene:ethyl acetate -20:1), and the predetermined compound (CJ-Cl, - CmiC-CH=CH
3.7 parts of Co, Me■) were obtained. IR of the compound.

The N M R+ Mass spectral data is as follows.

1, Rν (α-ri: 2200, 1720.1620°NMR (CC4) δ(p); 6.71 (IH) + 6.13 (IH) + 4.2
1 (2H) + 3.69 (3H) Masa; m/e
1so, +ss (M”) Example 7 [Synthesis of 6-p-p-mohexar-2-en-4-inoic acid] 00.54 parts of the compound synthesized in Example 2 was dissolved in 5 parts of methanol.
Dissolve in 0 volume i part diogysan 25 volume parts, I N Na
Add 5 parts of OH and stir at room temperature for 3 hours. Add a 20-capacity lid for reaction water and remove methanol and dioxane under reduced pressure.

After extracting and removing unreacted substances with ethyl ether, the mixture is acidified with hydrochloric acid and extracted with ethyl ether. The ether layer was dried over anhydrous sodium sulfate, concentrated to dryness under reduced pressure, and a predetermined compound (Br-CH, -C=C-CH=C
0.4 part of H-COOH■) was obtained. 1. of the compound. R,
The NMR spectrum is as follows.

1, Rv(1).

2300~3500.2200.1700.162ON
MR (CDC4) J (pps); 29- 8.79 (IH,), 6.89 (J) i), 6.20 (
JH), 4.28 (2H) Example 8 [Synthesis of 6-from-hex-2-en-4-ynoic acid sodium salt] 01.89 parts of the compound synthesized in Example 7 was added to IN Na
The mixture was dissolved in 10 volume parts of an OH water bath solution, and the water was concentrated to dryness under reduced pressure to obtain 2.11 parts of the desired compound [phase].

Example 9 (Synthesis of 6-7cy muhex-2-en-4-inoitusquacidimpylamine salt) 01.89 parts of the compound synthesized in Example 7 was dissolved in 1 part by volume of ethyl acetate. 0.59 parts of isopropylamine was added to this and stirred. After the reaction, ethyl acetate was concentrated to dryness under reduced pressure to obtain 02.48 parts of the desired compound.

30- Example 10 [Synthesis of 6-p-p-mohexar-2-en-4-inoic acid n-butylamine salt] In Example 9, 0.73 parts of Kn-butyl 7mine was added instead of inpropylamine, and Example 9 and four different methods - (Wr constant compound @
2.62 parts were obtained. Example 11 [Synthesis of 6-bup-hexar-2-ene-4-ynoic acid n-hexylamine salt] In Example 9, Kn-hexylamine was substituted for isopropylamine 71.0
．． 1 part of the specified compound ■ in the same manner as in Example 9.
2.90 parts were obtained.

Example I2 [Synthesis of 6-tulomuhexa-2-2-2-4-inoink 7cypine-bu-pvir 7mid] To 01.46 parts of the compound synthesized in Example 7, 3.7 parts of tincanyl chloride was added. 40-5
Stir at 0°C for 1.5 hours. Remove excess thionyl chloride under reduced pressure, and add a solution of 0.91 parts of isopropylamine in ethyl ether (5 parts by volume) under water cooling6.
Add reaction water and perform ether extraction. After drying the ether layer with anhydrous thorium sulfate, it was condensed under reduced pressure,
The product was separated and purified using a silica gel column column graph (Fuco-gel C-2oo+=]:2) to obtain 0.6 parts of the desired compound. I R + NMR + Mass of the compound
The spectrum is as shown below.

1, R ν(σ-1); 3300, 2200, 1660. 1610. 1
55ONMR (CDC7,) J(pIm);
6, 73 (IB), 6.13 (IH), 4.05 (
2H) + 4.00 (IH) 11, 13 (3H), 1
．． 23(3H)hlaas ;rn/e 2 2 9
, 2 3 1 (M+) Example 13 [Normal octyl-6-(2-tetrahydropyranyloxy)-Hekey I7--2-! -4-inoate and normal octyl-6-hyl'qxy-hex-2
-Synthesis of -ene-4-inoate] To 43.5 parts of the diethyl 7-secure compound (1) synthesized in Example 1 (1-1), a volumetric part of 0.6NHC1435 was added, and the mixture was stirred at 10°C for 2 hours. After the reaction, it was extracted with ethyl ether, the organic layer was dried over anhydrous sodium sulfate, and the ether was concentrated and removed under reduced pressure.
1 part was dissolved in 60 parts of methylene chloride, and while cooling with water, 38 parts of triphenyl fluorophoctyloxymethylene phosphorane was dissolved.
．． A methylene chloride (Bull) solution of 8111 is added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, the solvent was concentrated and removed under reduced pressure, and the product was transferred to a silica gel column using a silica gel column.
Gel C-200, solvent bath medium; benzene: ethyl acetate = 2
0:1) From Ic, 8 parts and 21 parts of IIN 33-17 and the specified compound were obtained, respectively. # The spectrum spectrum of the compound is as follows.

Compound [phase]; (CD(J.) δ(胛) 6.72(IB), 6.13(IHL 4
．． 7~4.9 (IH) 14, 36 (2H) 1 3.9~
4.3(4)i).

1,1-1.9(18H)IO. 9(3H) compound ■; (CD(Js) δ(suite) 6.70(IB)1 6.13(IH)+
4.40 (2H) + 3, 5 ~”, 9 (IHL 4.12
(2H)+1, 0~2.0(+2H), 0.9(3)
i) Example I4 [Normal octyl-6-7' q moohexer 2
5.3 parts of the compound synthesized in Example n, 0.13 parts of lithium bromide. 2,4.6-collidine 1.83 34
A predetermined compound (Br
3.2 parts of CH, C=C-CH=CHC0, C mountain 7■) were obtained. The IR and NMR spectra of this compound are as follows.

IR, ν (cm).

2200, 1715 NMR (CC/4) δ (solution); 6.75 (III), 6.20 (II-1), 4.
0-4.3 (4HL1.0-1.9 (12H), 0.
90(3H) Example 15 [Ethyl-6-7cetyloxyhex-2-ene-4
-Total μ of inoate] 15.4 parts of ethyl-6-hydro-pxy-hex-2-en-4-inoate synthesized in (l-3) of Example 1,
87 parts of pyridine is bathed in 100 parts of dehydrated ethyl ether, and while cooling with ice, a solution of 7.9 parts of acetyl chloride dissolved in 20 parts of dehydrated ethyl ether is added dropwise with stirring.

After the dropwise addition, the mixture was stirred for 2 hours at a room temperature, then washed with water, and the organic layer was dried. The solvent was removed by condensation under reduced pressure. benzene) in minutes and the given compound (CH,C00C)1. C=C-CH=CHC0,
About 14 parts of EtQ'') were obtained.1.R,N of the compound
The MR spectrum data is as follows.

rtt, ν(c+++).

2200.1750.171O NMR (CCA', ) am); 6.65 (IH), 6.10 (IH) 14.70 (2
H) +4.10 (2H) 12.00 (3H) 11.25
(3H) Example 16 [Ethyl-6-benzyloxy-hex-2-ene-4
-Synthesis of inoate] Ethyl-6-hydro px-hex-2-en-4-y/x-t synthesized in (1-3) of Example M Example 1 15.4
87 parts of pyridine are 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 is added dropwise while cooling with ice while stirring. After the dropwise addition, the mixture was stirred for 2 hours at a room temperature, then washed with water, and the organic layer was dried. The solvent was concentrated and removed under reduced pressure.
1N solvent; benzene) to separate and purify the desired compound (caH, coocH, c=c-cH=cHco, Et
(i□) About 20 parts were obtained. 1. of the compound. R+NMR
The spectral data of is as follows.

IR, ν(a).

2200.1720.1615 NMR (CCA',) δ (scale); 7.9-8.2 (2HL 7.3-7.6 (3H)1
6.75 (IH) + 6.15 (IH) 15.02 (2
H), 4.15(2)().

1+26(3H) Example 17 [Synthesis of ethyl-6-methylsulfonyloxy-37-x-2-en-4-ynonite] Example 1 (
1-3) Ethyl-6-hydroxy poxy-hex-
15.4 parts of 2-ene-4-inoate ■ and 11.1 parts of triethylamine were dissolved in 100 parts of dehydrated ethyl ether, and a solution of 11.5 parts of methylsulfonyl chloride dissolved in 20 parts of dehydrated ethyl ether was stirred while cooling with water. While dripping. After the dropwise addition, the mixture was stirred for 2 hours at a room temperature, then washed with water, and the organic layer was dried. The solvent was concentrated and removed under reduced pressure.
200, solvent bath medium; benzene:ethyl acetate=lO:1)
The product was separated and purified to obtain about 19 parts of the desired compound. 1. of the compound. The R and NMR spectrum data are as follows.

IR+y (cIn'); 2200.1715 NMR (CCJ, ) δ (4); 38- 6.70 (IH), 6.22 (IH), 4.96 (2H
L4.18 (2H), 3-05 (3H), 1.30 (:
DI) Implementation fP1118 [Synthesis of ethyl-6-(2,4-dichlorophenoxy)-hex-2-en-4-inoate] 18 parts of 2,4-dichlorophenol was dissolved in 50 parts of dimethyl sulfoxide, and hydrogen Add 5 parts of sodium chloride (50 thioyl) and stir at room temperature for 2 hours. Thereafter, a solution prepared by dissolving 021.7 parts of the compound synthesized in Example 2 in 50 parts of dimethyl sulfoxide is added dropwise to this mixture at room temperature while stirring. Thereafter, the mixture was stirred overnight at room temperature, water was added and extracted with ethyl ether, and the solvent was concentrated and removed from the organic layer under reduced pressure.
Approximately 16 parts of separated eluent==c'n-Co, Et) was obtained by 1o:t). 1. of the compound. R, NMR spectrum data (see below).

1, R+ b (m); 2200.171O NMR (CCI,) δ (pp); 7.34 (IH), 6.95 (IH) 1 6.62
~6.60 (2H) + 6.20 (ITi) + 4.92
(2HL 4.20(2H)+ 1.25(3)I) Example 19 [ethyl-6-(4-(2',4'-dichlorophenoxy]fe/xy]-hex-2-ene- Synthesis of 4-inoate] 5.0 parts of 4-(2'14'-dichlorophenoxy)phenol, 4.3 parts of compound ■ synthesized in Example 2, 1.4 parts of anhydrous potassium carbonate, and 200 parts of dehydrated acetone. The mixture is heated to reflux for 6 hours.

Thereafter, the acetone was concentrated under reduced pressure, and 20% of ethyl ether was added.
Add 0 parts and wash with water. The solvent was concentrated and removed from the organic layer under reduced pressure, and the product was separated by silica gel column chromatography (Wakoglu (:'-2001 developed medium; benzene: ethyl acetate = tO: 1), and the product was purified using a predetermined chemical formula). Approximately 4
．． Got 2 copies. The I'R and NMR spectrum data of this compound are as follows.

IR, p (trust).

2200.1708 NMR (CCAI4) δ (narrow) near, 35 (IH) + 6.8-7.1 (6H), 6.
72 (1) 1) 6.13 (1! () + 4.83 (2H
) + 4.20 (2H) + 1.26 (3) 1) Example 20 [Synthesis of ethyl-6-(4-be/zyloxy)fluorocarbon/xy-hex-2-en-4-ynony F] 4 - 4.4 parts of bendioloxyphenol 4.3 parts of the compound synthesized in Example 2, 41 parts of anhydrous acid - 6 parts of a mixture of 1.4 parts of potassium and 200 parts of dehydrated acetone
Heat to reflux for an hour. 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 removed from the organic layer by S line under reduced pressure, and the product was separated and purified by silica gel column chromatography (Fuko-gel C-200, developing solvent: benzene:ethyl acetate-10:1), and the desired compound (αCH ,O1-OCR,C-EC-CH=C
Approximately 4.0 parts of HCO, Et [phase]) were obtained. Compound I
R, NMR spectrum data are as follows.

IR, p (cm).

2200.171O NMR (C(J4)δ (Hayabusa); 7.05-7.30 (5H), 6.70-7.00 (
4H) 16.72 (IH), 6.06 (IH), 4
．． 90 (2H) 14.65 (2H) 14.10 (21 (
) + 1.22 (3H) Example 2I and HOCHIC=iiC-CH=C11-CO, (
Synthesis of CH,),0(CL''),QC,H,@] To 43.5 parts of the diethyl 7-secure compound ■ synthesized in (1-1) of Example 1, 435 parts by volume of 0.6N hydrochloric acid was added. Add and stir at 10°C for 2 hours. After the reaction, extract with ethyl ether and dry the 41st layer with anhydrous sulfuric acid.
The ether was concentrated and removed under reduced pressure, and the resulting product 14
of triphenylcarbo-(2-(2'-ethoxy)-ethoxy]-ethoxymethylenephosphorane was added dropwise to a bath solution of 38 parts of methylene chloride (80 parts) while cooling on ice. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, the solvent was concentrated and removed under reduced pressure, and the product was separated using a silica gel column chroma graph (Wako Glu C200 + kHz bath solvent: ethyl acetate - 9:1) Ic. , 10 parts and 19 parts of the given compounds @ and @ were obtained, respectively.

The IR and NMR spectral data of the compound are as follows.

Compound 0 I R + b (cm).

2200. 1720. 162O NMR, (CC4)δ(PIM); 6.76(IH)+6.16(IH)+4.9~4
．． 7 (IH) 14.33 (2HL 4.20 (2H),
3.8-3.2 (IOH).

1.8-1.1 (6H), 1.16 (3) 1) Compound O I R+ p (cm); 2200, I 720,] 62ONMR, (CC
/4) δ (blue); 6.73 (IH), 6.13 (IHL 4.31 (2)
HL4.20(2H)+ 3.75-3. ao(gH)
, 3.10 (IH) + 1.16 (3H) Example 22 (BrCH=C=C-CH=CHCOO(CH,), 0
Synthesis of (CH, ), 0CIH, @] 5.1 parts of the compound synthesized in Example 21, 0.13 parts of lithium bromide, 1.83 parts of 2,4.6-collidine,
By using 2.6 parts of phosphorus tribromide and performing reaction and post-treatment in the same manner as in Example 244-, 3.4 parts of the desired compound O was obtained.

The IR and NMR spectral data of the core compound are as follows.

IR, ν(a).

2200.1720.162O NMR, (CC/4) δ (solution); 6.750) (L 6.20 (lu) 14.3-4.0
(211) 14.03 (2H) 13.75-3.30
(811) 11.16 (3H) Example 23 Compound synthesized in Example 2 (io, 05 parts in water 12.5 parts
In addition to a mixed solution of 12.5 parts of acetone and 12.5 parts of acetone, 5ORPOL 26s o (Toho Chemical 1!ri0.
After spraying the mixture to which 013 parts was added three times in about 1.5 hours to the stems of previously cultivated Himedion and Lamina, we continued the cultivation and conducted a withering experiment by observing the degree of withering of each with the naked eye. went. The degree of mortality after one week of treatment is shown in Table IK. The degree of withering, that is, the degree of withering is expressed as a 45-indicator: 1 indicates that the plant is healthy, 5 indicates that the whole plant is wilted and dead, and the intermediate state is indicated by dividing it into 4 parts. It was expressed using the so-called five-step method.

Reference example 1 5 ott in a mixed solution of 12.5 parts of water and 12.5 parts of acetone
i) Using a mixed solution to which 0.013 parts of oI and 26so were added, the same test for withering as in Example 23 was carried out.

The results are also shown in Table 1.

Example 24 0,002 parts of the compound ■ synthesized in Example 2 was added to 0,002 parts of acetone by volume + 5 ORPOL 2680 0
．． 0032 parts and diluted with 20 parts of water. On the other hand, fill a pot with a diameter of 100 tn + depth lOG, and sow the seeds of Himedion and Plantain, cover with soil to the extent that the seeds are covered, and sprinkle the above prepared solution on the soil surface to determine the number of germination of seeds. The growth status was observed. As a result, even after two weeks, none of the yuzu from Himeji 46 Ion and Plantain yuzu had germinated, showing a germination inhibiting effect of 100 Chi.

Reference example 1 Acetone 0.008 volume: 11 parts, 80RPOL 26
A mixed solution of 800.0032 parts and 20 parts of water was sprayed in the same manner as in Example 24, and the germination status of Himedion and Plantain yuzu was observed. As a result, all of them germinated and were healthy after two weeks. Ta.

Table-1 47- Continuation of page 1

Claims (1)

[Claims] General formula [wherein R1 is a hydrogen atom, a Schiff group, a nido μ group,
OR' (where R6 is a hydrogen atom, an acyl group having 1 to 16 carbon atoms, a hydrocarbon group having 1 to 15 carbon atoms which may contain an oxygen atom and/or a sulfur atom, or a hydrocarbon group having 1 to 15 carbon atoms) (substituted or unsubstituted sulfonyl group). A group represented by SR& (where R is defined as above) or a hydrocarbon group having 1 to 10 child or leg primes, which may cooperate with each other to form a ring;
+R” are the same or different, hydrogen atom, hapgun atom,
Cyano group, 2) +-&. 7 The group represented by the above OR', the above SR' or the above N~ is a group represented by the above N::H:: R1 is OR'(
However, RQ is a hydrogen atom or an oxygen atom, and / is a hydrocarbon group having 1 to 15 carbon atoms that may contain a sulfur atom.)
, SR'' ((B and R1' are defined as above) or the above N(H?) -2-en-4-ynecarboxylic acids.