JPS62175456A - 5-arenesulfonylalkanamide derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is alkyl, alkenyl or aryl; R<2> and R<3> are H or alkyl; R<4> is aryl; R<5> is acyl; R<6> is monoalkylamino, dialkylamino, 1-pyrrolidinyl or piperidino). EXAMPLE:4-Acetoxy-5-(benzenesulfonyl)decanoic acid piperazinamide. USE:A synthetic intermediate for (2E,4E)-dienamide, e.g. pellitorine, trichonine, etc., having insecticidal activity. PREPARATION:An arenesulfonic acid derivative expressed by formula II is reacted with a base in an inert solvent at -78-+50 deg.C and the resultant product is then reacted with a formylamide derivative expressed by formula III at -48-0 deg.C to give a hydroxyamide derivative expressed by formula IV. The resultant compound expressed by formula IV is further reacted with an acid halide expressed by the formula R<5>X (X is halogen) or an acid anhydride expressed by the formula (R<5>)2O in the presence of an organic amine at -20-+100 deg.C to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is based on the general formula (wherein R1 is an alkyl group which may have a substituent,
Represents an alkenyl group or an aryl group H2 and R8 are the same or different and each represents a hydrogen atom or a lower alkyl group H4 represents an aryl group and R6 represents a haacyl group R6 represents a monoalkylamino group, dialkylamino group, 1-pyrrolidinyl or piperidino group. ) The present invention relates to a 5-arenesulfonylalkanamide derivative represented by:

The arenesulfonyl alkanamide derivatives represented by the general formula (1) provided by the present invention are E,E-N-inbutyl-2,4-decadienamide (pelitrin), E,E-2, (2E, 4E) such as 4-eicosadienoic acid pyrrolidine amino)' (trichonine)
-Useful as a synthetic intermediate for dienamide.

[Conventional technology]

Conventionally, (2E, 4E) such as E,E-N-inbutyl-2,4-decadienamide (Peritrin), E,E-2,4-eicosadienoic acid pyrrolidineamide (Triconine), etc.
- Dienamide is known to be produced by the following method. How to make Tetrahedron Letters (Tetrahedron Letters)
Letters) 1979, No. 1043-104
Page 4 (2) Wizteich (Wi) of aldehyde and 3-(piperidinocarbonyl)allylphosphonium salt
t t ig) [Tetrahed
ron) Volume 39 (1983), Nos. 123-128
See page] (8) 4-7 syloxy-2-alkenamide or 4-
A method using decarboxylic acid reaction of acyloxy-2-alkenoic acid ester [The Journal of Organic C
hemistry) Volume 47 (1982), No. 110
See pages 1 to 1106 [Letters) 1983, pages 4525 to 4528] [Problems to be solved by the invention] In the above conventional method, % (2E, 4E)-dienamide or its precursor is (2E, 4E)-dienamide or its precursor. In the reaction to produce (2E, 4Z)-diene amide or (2E, 4Z)-diene acid ester, a large amount of by-product (, (2E, 4g)-diene amide or (2E, 4
E) The stereoselectivity to dienoic acid ester is not sufficiently high, and the yield is not necessarily satisfactory.

Therefore, it is an object of the present invention to provide a bicarbonate 4 (2E#4) which can be easily produced with good yield from readily available industrial raw materials.
The object of the present invention is to provide a novel compound which has a high stereoselectivity to E)-dienamide and can be easily synthesized in a good yield.

[Means for solving problems]

According to the present invention, the above object is achieved by providing a 5-arenesulfonylalkanamide derivative represented by the general formula (1).

R1, kt2, R3, R4 according to the above general formula (1) by 2σ
, R6 and R6 will be explained in detail. kc1F! Methyl group, ethyl group, propyl group, isopropyl group, butyl group,
Alkyl groups such as inbutyl group, pentyl group, hexyl group, hexadecyl group; vinyl group, allyl group, 1-flobenyl group, isopropenyl group, 2-)fk-1-7"ropenyl □M, 1-pentenyl group, 1 -'7 Ndecenyl M, 2
．． 6-dimethyl-1,5-hebutagenyl group, 2,6.
10-) Represents an alkenyl group such as dimethyl-1,5,9-undecatrienyl group; or an alkenyl group such as 7-enyl group, tolyl group, cumenyl group, xylyl group, naphthyl group, etc. The alkyl group, alkenyl group, or aryl group may have a radical such as a methyl group, a methylenedioxy group, an ethylenedioxy group, or a 2-tetrahydropyranyloxy group. R2 and R3 are the same or different), a hydrogen atom; or a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an inpropyl group, a butyl group, and H4 is a phenyl group, a tolyl group, a cumenyl group, a medium silyl group, Represents a 7-aryl group such as a naphthyl group.

R5 represents an acyl group such as an acetyl group, a globionyl group, a butyryl group, or a benzoyl group, and R11 represents a monoalkylamino group such as a methylamino group, an ethylamine group, a glopylamino group, an isopropylamino group, a butylamino group, or an octadecylamino group; 7 group, dialkylamino group such as diethylamino group, dibutylamino group, dibutylamino group; 1-pyrrolidinyl group; or piperidino group.

The 5-7-lensulfonylalkanamide derivative represented by the general formula (1) can be easily produced, for example, by the following method.

(■) (■)
(In the formula, 11.R2, R+!, R4, R' and R' u
It is the same as 'Nm' above, and X represents a halogen atom.

) That is, the arenesulfone derivative represented by the general formula (II) has a concentration of about 0.
Organolithium compounds such as butyl lithium and phenyl lithatum with a concentration of 5 to 1.2 mol; ethyl magnesium bromide,
A base such as a Grignard reagent such as methylmagnesium chloride is mixed in an inert solvent such as an ether solvent such as tetrahydrofuran, diethyl ether, or dimethophythane; or a carbonized ice cream solvent such as toluene or hexyphne at a temperature in the range of about -78°C to 50°C. of the general formula (Ill.
) of the formylamide derivative shown at approximately -78°C to 0°C.
It works at temperatures in the range of . The hydroxyamide derivative represented by the general formula (■) thus obtained and the acid halide represented by the general formula (V) or the general formula (Vl) in an amount of about 1 to 5 molar equivalents to the hydroxyamide derivative The indicated acid anhydride is reacted with the hydroxyamide derivative in the presence of an organic amine such as triethylamine or pyridine in an amount of about 1 molar equivalent or more with respect to the hydroxyamide derivative at a temperature in the range of about -20°C to 100°C. By this, it is possible to produce a 5-are-7 sulfonylalkanamide visiting conductor represented by the general formula (1).

The 5-arenesulfonylalkanamide derivative represented by the general formula (1) can be obtained, for example, by the following method with high stereoselectivity and good yield (2E, 4
E) - converted to dienamide.

(In the formula, R1, HJa, R4, R5 and R6 are as defined above.) That is, the 5-arenesulfonylalkanamide derivative represented by the general formula (1) is converted into % t-butoxypotassium, methoxypotassium, The amount of the C base to be used to obtain the (2E, 4g)-dienamide represented by the general formula (■) by treatment with a base such as an alkali metal alcoholade or hydroxide such as potassium hydroxide is The amount is preferably about 2 to 20 molar equivalents relative to the 5-7 monosulfonyl alkane amide derivative shown in 1). This reaction is preferably carried out in an inert solvent, and examples of such inert solvents include alcohol solvents such as t-butyl alcohol; carbonized ice cream solvents such as toluene and cyclohexipne. It is also preferred that the reaction be carried out at a temperature in the range of about θ to 80°C.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.
2.56 J (6 mmol of butyl lithium) of a hexane bath solution of butyl lithium with a concentration of 15 F/100 R1 was added dropwise at -30°C to a solution consisting of 5 mmol of tetrahydrofuran and 1 OMI of tetrahydrofuran, and after 1 hour, the reaction mixture was ℃
4-oxobutyric acid piperidinamide o, 85
A solution consisting of f (smmol) and tetrahydrofuran was added dropwise. After the completion of the dropwise addition, an additional 0.5% solution was added at -78°C.
After continued stirring for an hour, the reaction mixture was poured into dilute hydrochloric acid and extracted with diethyl ether.

The ether extract was washed with saturated brine, dried over anhydrous sulfuric acid, and then low-boiling components were distilled off under reduced pressure to obtain crude piperazine 5-(benzenesulfonyl)-4-hydroxydecanoate. Obtained amide.

mutLftm 5- (benzenesulfonyl)-4-
Hydroxydecanoic acid piperazinamide was dissolved in pyridine 10, 0.62 t (6 mmol) of acetic anhydride was added, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into water and extracted with diethyl ether. The extract was washed successively with dilute hydrochloric acid, aqueous sodium chloride solution and saturated brine, and then dried over anhydrous magnesium sulfate. After distilling off the low boiling point substances under reduced pressure, the resulting residual liquid was purified by silica gel column chromatography to obtain the following NMR
The spectrum shows +4-acetoxy-5-(benzenesulfonyl)decanoic acid piperazine amide at 1.46F (3,
35 mmol)? I ft- (67% yield based on the hexyl phenyl sulfone used) O NML x pect h (60 MHz) δTMS.

Cα4゜0.87 (br, t, 3H); 1.03~
2.60 (m, 18H); 1.69, 1.76 (8
, 3H); 2.77-3.68 (m, 5) 1); 4.9
1-5.28 (m, IH); 7.27-7.94 (m,
5H) In the actual MiflJ1, 5 mmol of an arrene sulfone derivative in which R1 or R4 in the general formula (It) is a phenyl group is used instead of hexyl72nylsulfone, and R in the general formula (l[I) in place of 4-oxobutyric acid piperidinamide.
2 and R3 are hydrogen atoms, and R6 is a group shown in Table 1.The same operation is carried out except that s mmol of formylamide conductor is used, and the corresponding general formula (1) is obtained.
A 5-7 resin sulfonyl alkane amide derivative represented by the following formula was obtained. Table 1 shows the yield (yield based on the arenesulfone derivative used) and NMR spectrum of the obtained 5-7 sulfonyl alkanamide spinner.

Table 1 7.13-7.80 (m, 5H) Examples 8-12 In Example I, R1 and R4 are each shown in Table 2 in the general formula (ff) instead of hexyl phenyl sulfone. 5 mmol of arenesulfone derivative which is a group
Using 4-okynebutyric acid piperidinamide, a formylamide collar conductor of general formula (Ill) in which R', R' and R6 are groups shown in Table 2, respectively, was prepared.
mol, and 2 in general formula (V) instead of acetic anhydride.
The same operation was carried out except that 6 mmol of an acid halide in which R5 was a group shown in Table 2, and The yield of the obtained 5-7-lensulfonylalkanamide fatty conductor (
Yield based on the arenesulfone derivative used) and F
D mass spectra are shown in Table 2.

Reference Example 4-7 Setoxy 5-(benzenesulfonyl)-5-(3,4-methylenedioxyphenyl)valeric acid piperidinamide 0.974F (2mm
ol) was dissolved in t-butoxypotassium 0.672f (6 mmol).
was added, and the mixture was stirred at room temperature for 12 hours. The resulting reaction mixture was poured into water and extracted with diethyl ether. The extract was washed with saturated brine and dried over anhydrous sodium sulfate. After distilling off the low boiling point substances under reduced pressure, the residue was By separating the seeds by alumina column chromatography, 5-(3,4-methylenedioxyphenyl)-2
, 4-pentadienoic acid piperidinamide was obtained as a mixture of geometric isomers at 488"lF (melting point 130-131-
C).

As a result of measuring the NMR spectrum, the purity of E, E-5-(3,4-methylenedioxyphenyl)-2,4-pentadienoic acid piperidinamide (piperine) in the competitive isomer mixture was 90 % (:E
, E-5-(3,4-methylenedioxyphenyl)-2
, 4-Pentadienoic acid piperidinamide formation i 1.
54 mmol (77% yield)].

]E, E-5-3,4-methylenedioxyphenyl)-
The NMR spectrum of 2,4-pentadienoic acid piperidinamide is as follows1) 1.49 (br, s, 6H); 3.11-3.55 (
m, 4H); 5.69 (s, 2H); 5.8
4-6.83 (m, 6H); 6.83-7.23
(m, IH) [Effects of the invention] Kanatooshi can be easily produced in good yield from readily available industrial raw materials. Further, as shown in the 5-arene sulfo represented by the general formula (1) of the present invention, it can be easily applied to K(214g)-dienamide with high stereoselectivity and good yield.

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R^1 represents an alkyl group, alkenyl group, or aryl group that may have a substituent, and R^2 and R
^3 are the same or different and each represents a hydrogen atom or a lower alkyl group, R^4 represents an aryl group, and R^5
represents an acyl group, R^6 is a monoalkylamino group,
Represents a dialkylamino group, 1-pyrrolidinyl group or piperidino group. ) A 5-arenesulfonylalkanamide derivative represented by: