JPH02229171A - Cyclopenta(1,2-c)-3-pyrazolecarboxylic acid derivative - Google Patents

Abstract

NEW MATERIAL:A cyclopenta[1,2-C]-3-pyrazolecarboxylic acid derivative shown by formula I (R<1> is 1-4C alkyl; R<2> is H or 1-3C alkyl; R<3> is H or methyl; R4 is R or 1-4C alkyl with the proviso that when R<1> is methyl or ethyl and both R<2> and R<3> are H, R<4> is 2-4C alkyl). EXAMPLE:2,6-Dimethylcyclopenta[1,2-C]-3-pyrazolecarboxylic acid ethyl ester. USE:An intermediate for drugs, agricultural chemicals, especially insecticides, acaricides and fungicides. PREPARATION:For example, a compound shown by formula II (Z is 1-4C alkyl) is reacted with a hydrazine compound to give a compound shown by formula Ia, one of compounds shown by formula I. Then this compound is hydrolyzed with an alkali to give a compound shown by formula Ib, one of compounds shown by formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel cyclopenta[/. The present invention relates to 2-Cl-3-pyrazolecarboxylic acid and its esters. In particular, it relates to compounds useful as intermediates for medicines, agricultural chemicals, especially insecticides, acaricides, and fungicides.

[Problems to be solved by conventional technology and invention]

Pyrazole compounds are useful compounds as medicines and agricultural chemicals, and their excellent medicinal efficacy has attracted attention in recent years. In particular, it is difficult to produce virazole compounds whose medicinal efficacy can be improved by introducing various substituents into the virazole ring, and the compounds that have been manufactured or used for this purpose are , little known.

[Failure to solve the problem]

In view of the above-mentioned problems, the present inventors conducted extensive studies and as a result discovered a virazole carboxylic acid derivative which is a useful new intermediate and completed the present invention.

That is, the gist of the present invention is to provide cyclopenta [8. 2-C]-3-pyrazolecarboxylic acid derivatives.

R1 (In the above formula, R1 represents a C, to C4 alkyl group, R
2 represents a hydrogen atom or a C1-C3 alkyl group; R3
represents a hydrogen atom or a methyl group, and R4 represents a hydrogen atom or an alkyl group of 01 to cl. However, when R1 is a methyl group or an ethyl group, and R2 and R3 both represent a hydrogen atom, R4 represents a C2-q alkyl group.

) The present invention will be explained in detail below.

In the general formula CI), R1 is a methyl group, an ethyl group, an n-
C1 to C4 of probyl group, isobrobyl group, n-butyl group, inbutyl group, sec-butyl group, t-butyl group, etc.
represents a straight-chain or branched alkyl group. R2 hydrogen atom; represents a C1 to C3 straight or branched alkyl group such as a methyl group, an ethyl group, an n-furopyl group, or an isoprobyl group. R3 represents a hydrogen atom or a methyl group. R4 is a hydrogen atom; C, ~c4 straight or branched alkyl group such as methyl group, ethyl group, n~probyl group, isobrobyl group, n-butyl group, inbutyl group, sec-butyl group, t-butyl group, etc. shows. However, if R1 is a methyl group or an ethyl group, and R2 and R3 are both hydrogen atoms, the preference is an ethyl group, n-probyl group, inglovir group, n-butyl group, inbutyl group. It is a C2 to C4 straight chain or branched alkyl group such as a sec-butyl group or a t-butyl group.

Among the compounds of the present invention represented by the general formula (1), esters (Ia) and carboxylic acids (Ib) can be produced, for example, according to the following reaction formula.

= 3 - - 4 - (in the above reaction formula, LR' L R2 and R3 are as defined in the above general formula (I), Z represents an alkyl group of C1 to q)] That is, the above general formula The above general formula (
Compound Ia) can be easily obtained.

Alternatively, the ester represented by the general formula (Ia) may be mixed in water, in an alcohol such as methanol or ethanol, or in a mixed solvent of alcohol and water in the presence of an alkali.
By hydrolyzing at 20 to /θθ°C, carboxylic acids represented by the above general formula (Ib) can be obtained.

As the alkali, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. are used.

The compound represented by the above general formula (Ia) can also be produced according to the following reaction formula.

Rl (Ia) (In the Doki anti-shin formula, R'.R2 and R3 are the above general formula C
p as defined in I), Z represents a C, -C4 alkyl group. That is, the compound of the above general formula (II,) and hydrazine hydrate are mixed with water or methanol, ethanol, ingropanol, etc. In alcoholic solvent, O-. By reacting at 5'θ°C, preferably 70 to 30°C), a compound represented by the above general formula (III,) can be obtained. The obtained compound represented by the above general formula (II-f) and an alkylating agent are mixed with halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and 81-dichloroethane; aromatic compounds such as benzene, toluene, and xylene. Hydrocarbon; N,
In a solvent such as N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, or without a solvent /0
The compound represented by the above general formula (Ia) can be easily obtained by reacting at ~/00°C, preferably 10~SO°C. Examples of the alkylating agent include dimethynole sulfate, diethyl sulfate, diglopyr sulfate, dibutynole sulfate, methyl bromide, ethyl bromide, provinole bromide, butyl bromide, methyl iodide, ethynole iodide, probyl iodide, butyl iodide, Methyl chloride, ethyl chloride, probyl chloride, butyl chloride, etc. can be used.

In addition, the compound represented by the above general formula (■) is the compound represented by Org.
Syntli. , u, jf 3 /.

〔Example〕

Next, the present invention will be explained in more detail, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example/-] Preparation of λ,A-dimethylcyclopenta[8a-C:]-3-pyrazolecarboxylic acid ethyl ester Coketocyclobentylglyoxalic acid ethyl ester 41 g. /g ethanol! λO~.00ml solution. 2
Methylhydrazine/2.7 at 5℃? was added dropwise, stirred at the same degree of rot for S hours, and concentrated under reduced pressure. Next, it was extracted with toluene and washed with water. Concentrate the toluene layer and add hexane/
The mixture was cooled to 0° C., and the by-product precipitated crystals were separated from P. After concentrating the filtrate, it is distilled to a temperature of 3 to 5 degrees C/θ. 7m
Compounds listed in Table 1 of mHfl (Ban 3). 2g. Got 2 on the left. NMR of the obtained compound. & and the IR spectrum are shown below. , [・'H-NI'viR(CDCI3)δppm;
/． 29(d)3H. /． 3? (t)3H. /． g
~3, 3(m)3H, lI-/j(s)3H+ Arc 3
3(q)2HIR(NaCI); /7 2
0B 'Example λ co,A-dimethylcyclobenta[/. 2-C) -3-
Production of pyrazole carboxylic acid, dimethylcyclopenta:/, 2-C)-3-
Pyrazole carboxylic acid ethyl ester/L? 62 and sodium hydroxide g. A yoml aqueous solution of 01 was heated to reflux for 1 hour. After cooling to room temperature, the mixture was acidified with hydrochloric acid and the precipitate was collected. Dry at 0°C under reduced pressure and prepare the compound listed in the table (Banyu).
/ 5. / ? ,mp! 7/~/73°C was obtained. The NMR and IR spectra of the obtained compound are shown below.

'H-NMR (CDCI3) δpIJm; /-
2! rcd)3H. /． 9! (m) IH. 2.47
~3.0(m)3H. 3. /． ! t(m)/H,
+! ．． /&(S). ? HIR(KBr); ikuiocrn'Example 3! -Methylcyclopenta[/, CoC]-3-Pyrazolecarboxylic acid ethyl ester production Coketocyclobentylglyoxalic acid ethyl ester ig. Hydrazine hydrate in qta ethanol iooml solution! ;． 0
? was added dropwise, and after stirring for 7 hours, the precipitate was separated. After concentrating the slurry, the residue was extracted with toluene and washed with water. Toluene was distilled off under reduced pressure to obtain an oily substance. Next, 3.27 g of dimethyl sulfate was added dropwise to the oil at 70°C.

After stirring at 0 to 50°C for 3 hours, the mixture was cooled to room temperature, poured into ice water, and sodium carbonate was added to adjust the pH to g to 9. The oil was extracted with ethyl acetate, washed with water, and then concentrated. The residue was purified by silica gel lambda chromatography, and the compounds listed in Table 1 (A/) 90g, mpg~ke9
℃ was obtained. The NMR and IR spectra of the obtained compound are shown below.

'H-NMR (CDC13) δppm; /.
35(t)3■{, ;1.3 ~2.9 & (m,
Otsu H). g, /(S, +3HI g.y.ff(
q) JHIR (KBr); / 7 / 0 (B
[Example J] - Compounds listed in Table 1 were obtained in the same manner as in Examples 1 to 3.

Table/111-112 For some compounds listed in Table 1/, their NM
The R and IR spectra are shown below.

A Gu'H NMR (CDCI-s) δppm;
/． /-/. A(m) 9H+. 2. / ~. 2.3
(m) ,! H. 2.6 ~. 3. 'l (m) 2
H. 'I. / (s) 3H. Goo 35 (q)
λH IR (NaCI); / 7 / OcIrL-g 1H NMR (CC14) δppH1; /. ．． 2~/
．． 5(m) Otsu I7. 2. 'l (m). 2H. 2.
7 (m,) &H, ll-. 2 5 (q).
2H. q. G5 (q) JH IR (NaCl, ); / 7.20C:rn' flat
Ta1H NMR (CDC13) δppm; /. 3! ;(m,)9H. ．． 2. / 3 ~ 2.9 0 (m,) Otsu H,'1.3
(q,)2H. 5.5 (m)/HIR(NaCl)
; /70ACa' / 0'H-NMR (CDCi3) δpprn ; /J
(d+ Otsu■li, 2.3 ~.2.9 !i(m)
Otsu H,! ．． 'l 3 (m,) / H, g. 0
Left (bs,) /HIR (KBr); /70
/. 0(
t). 3H. /． 2! (d) 3H. /J ~. 2. /
(m) JH. 2. ? ~． 2.9 (m) 3H. ．． 7.
/ Left (m) / H, Ku. /j-(S)3H. 4'-+2
Ct)2HIR(NaCI); /720(B'
j! 6//' H NMR (CJ)CI3)δppm
; θ. 9(t)3H/J~/. Ta (m+). 2H.
．． 2. ．． 2~. 2.9 (m) 6H. 'AI! ;-
4. A (rn)Ll{IR(NaC].); /
7 no 6cm'/. 4t (m) Evening H, I6/6'H NMR (CDCIs) δppm; Human,
l ~/. lI(H1)deH,/. 7 ~. 2. ．． ? (
m)/H, r. 3~. 2.9(m,)3H. ．． ? ．． i!
; (m)/H. 'I. / (s). ? H, 3.
/! r (m) /HIR(NaCI); /7
/OCrn'A. / 2'H-NMR (CDCI3) δppm +, θ9
! (t). ? H/. / ~2.0 (m)4tI{.
．． 2. ．． 3 ~3.0 (m) Otsu H, 41. ! ; (
t). xH, 7J (bs)/H IR (KBr); / 7/ 9 (B'A/7'H-NMR (CC1.4) δppm; 0.9!
;(t)3H. /． ．． 2(d). ? Hi. / ~. 2.
/ (m). rH, 2. Otsu! ; (m). ? H,
3. Oj (m,)/H, 4t. 0 left (s) 31-
{． ! ．． ．． 2(t). 21-1IR (NaCl)
; / 7 2 0crn' / 3 NMR (CDC13) δppm: / evening (t) JH /. Otsu (6)yH 3.05~. 2. ．． (In) Otsu H. G. G left (q
．． )λHIR(NaC1); /7 25cm'
l5 A/g'H-NMR (CC14) δppm; 0-9
! r(t)3H. /． /3 ~/. 4t(m) Otsu H,
/． lI~u. 2 (m,) 3H. 2. ．． 2 ~2.
g 5 (m). 3H. ．． 3-0 3 (m) /H
, 4t. 0 3 (s). ? H evening. Ta left (+11.
/H) I R (NaCl;y7/!cm' flat /9'H-NMR C CCI4,lδTJpm;
/． ．． 2(d). ? H, /J(s)taH/. 9
(ro) / H, 2. ．． 3 ~. 2.7! r (
m) 3H. 3.0 (m) /H,g. 0(S)JH IR(NaC1); /? /OCTL' [Effects of the Invention] The cyclopenta[/,110]-3-pyrazolecarboxylic acid derivative of the present invention is useful as an intermediate for villazonole insecticides, acaricides, and fungicides, and is suitable for industrial use. The value is high.

Sender: Mitsubishi Kasei Corporation Representative Patent Attorney Hase J Others/names

Claims (1)

[Claims] (1) Cyclopenta [1] represented by the following general formula (I)
,2-C]-3-pyrazolecarboxylic acid derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the above formula, R^1 represents an alkyl group of C_1 to C_4, R^2 represents a hydrogen atom or an alkyl group of C_1 to C_3, R^3 represents a hydrogen atom or a methyl group, and R
^4 represents a hydrogen atom or an alkyl group of C_1 to C_4. However, R^1 is a methyl group or an ethyl group,
And when R^2 and R^3 are both hydrogen atoms, R^4
represents a C_2 to C_4 alkyl group. )