JPS606677A - (e) or (z)-5-substituted-2-phenylthio-2,4-pentadien-4-olide and its preparation - Google Patents

Abstract

NEW MATERIAL:An (E) or (Z)-5-substituted-2-phenylthio-2,4-pentadien-4-olide shown by the formula I or formula II (R is phenyl or benzyl which may have substituent group selected from the group consisting of 1-10C alkyl, halogen and lower alkyl group). EXAMPLE:(E) or (Z)-5-Pheny1-2-phenylthio-2,4-pentadien-4-olide. USE:A physiologically active compound useful as an antibacterial agent, fungicide, insecticide, etc. in a medical field, agricultural and horticultural field, etc., and useful as an intermediate for synthesis in the same fields. PREPARATION:A 2-phenylthio-5-hydroxy-5-substituted-2-penten-4-olide shown by the formula III is brought into contact with an organic base catalyst, dehydrated in the molecule, to give a compound shown by the formula I . The compound shown by the formula III is synthesized from lithium salt of 2- phenylthio-2- buten-4-olide and a compound shown by the formula RCHO.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides V) a raw site foil injection compound I which is useful as an anti-destruction agent, a -1 windcide, etc. in the field of docking, agriculture, etc.; or (Z)-, which is expected to be useful as a synthetic intermediate, etc.
5-m; + Central-2-phenylthio 2,4-pentadiene-4-olide and its production method.

More specifically, the present invention is expressed by the following formula (1)% formula % () where R is CI<,. gills from the group consisting of alkyl groups, halodane and low acid alkyl groups rL 7t i
4. Phenyl group which may have 4 threads.

The present invention relates to (E) or (Z) -5-i1q-2-phenylthio-2,4-pentadiene-4-olide (4) and six methods thereof, which can be translated as:

For example, the following formula (1) k1 1 where R is defined in the above formula (1)'.

2-phenylthio-5-hydroxy-5- coated with
1M-2-pentene-4-olide is known to be a basic medium, and Wta is used to cause an intramolecular dehydration reaction.
And it can be made in different ways.

The invention also relates to the process.

The parable is - Article division, Imaginary - Art part%l
2, Handa, Bo, Jakuhai Wholesale J, etc., the menstruation of the shoulder is a sexual compound, and the history is rI: So, 8, as a middle isomer m')
)Ifx2-7! Synthesis 4I7 of nyl-2-1 ten-4-oli r-based chemical reaction was investigated, but this time, the above formula (1
(E) or (Z
)-5-Phenylthio-2°4-pentadiene/-4-olides have been found to be easily synthesized by simple means.

According to the research of the duds, if νif, the above formula (II
), by the intramolecular dehydration reaction of 2-phenylthio-5-hydroxy-5-7a-substituted-2-penten-4-olide h1, the sweetener of the formula C1 can be easily and favorably prepared. It was discovered that it could be produced with high yield.

Therefore, one feature of the present invention is to provide protection against the aforementioned formula (1).

*, JA Ming's other purposes are to cultivate (1) Chu "Rising Rise" 14
To provide the first manufacturing method.

From the following description, the advantage of nu's 1:II, which is based on the above observations and findings of Part 1, will be -N1.

In the ifMe formula (1) compound, the alkyl group of H in formula 1 is methyl, ethyl, propyl (n+, 1
so-), buti Jl/(n-, 1so-, 5ea-.

tart-L pliers A/(n-, iso-), hexykc n-, 1ao-), hedechikc n-t, 1
so-).

octyl (n-, 1so-), nonyl, decyl, etc. can be represented by the alkyl ratio of @C (-C1゜).Also, the face which the phenyl group of R in formula 1 may have, Examples of the chivalry group include halodane atoms such as salt purple, bromine, fluorine, methyl, ethyl, propyl, etc., and lower alkyl i such as the C3 to C4 alkyl group in the alkyl i shown in -1 above. can.

It can be produced, for example, by molecular circle dehydration of the compound of formula (1), as described above. Nucleic acid compounds are %2-
Phenylthio 2-1 ten-4-olide O! Jf”)A
It can be obtained by reacting rm with an aldehyde compound represented by RCBO [wherein R#'i formula (1), [same meaning as]. Furthermore, the 2-phenylthio-2
-Butene-4-olide is a publicly known product, for example:
It can be easily sweetened from r-1 tyrolactone. Specifics of R in the 2RCHO aldehyde compound 1
As 1, t can be exemplified by the same groups R as already exemplified for R in the compound of formula (1).

Taking the present defense formula (j) compound 'IJ of the above-mentioned f-f tyrolactone ρ1 as an example, 1. The manufacturing process 8 of the present invention formula (1) compound is shown as the following formula. Can be done.

OO ゛(■) (■) O0 (V) (mV) H (dish) Q 0 1) body (z) body (1) In the example of substitution shown in the above formula, enter iFh J”t 7r
Formula (→r-1 from tyrolactone 1 e.g. literature = ICo
Iwai, -11, Kossgi, H, Uda, M
, Kawai, Hull, Cham.

Soc, Jpn, 50, 242 (1977
1 set (M), (V') and (■] according to the method described in )
The compound LI can be converted into the above formula [melon] to form a proboscis. According to this /p, g3 vc, the above formula [■] γ-butyrolactone is also presented: Org, 5yn
th, Co11. Vol.

According to the method of 5.255 #) in the presence of % phosphorus, n11 is 80
When fermented with the same amount of juice at 31% °C, the above formula [VI] can be obtained at a yield of, for example, 55%.

For example, when this is reacted with thiophenol sodium salt in the dark in an ethanol solvent, the above formula [V]
2-phenylthio-γ-butyrolactone with a yield of 90%. Next, [v] compound? For example, the four-shallow-restored rabbit-bath medium-ko, the sulfuryl pentoxide and 2:1 at 0°C.
When the hi1 reaction is carried out, the above formula % tyrolactone is converted into %U, which is further reacted with, for example, tetrahydrofuran (THF), 26-centered lithium, carbon i
React with lithium under flowing water for 30 minutes to obtain the above formula % formula % lido? You can get it with a good profit of 90chi.

A': Formula (II) 2-phenylthio-5
-Hydroxy-5-benzene-2-pentene-4-olide] is the formula (II) 2-phenylthio-2-butene-4-olide which can be obtained as described above. Lithium salt and aldehyde of 2RCHO
It can be easily obtained by reacting the compound.

The reaction between the compound of formula (1) and the 2RCIiO aldehyde (baboon) is, for example, in a suitable non-commercial medium.

In the presence of a suitable lithium amide, in the presence of an inert gas; h', the compound of formula (lI) and the formula it
This can be carried out by carrying out a ligation reaction δ with c, uo aldehyde compounds.

Examples of the above-mentioned lithium amides include secondary amines such as zoethylamine, noisoprobylamine, cyclohexylamine, and sozolobyl cyclohexylamine.
Hf”HA-liquid and e.g. methyllithium.

Lithium dialkylamides, such as lower alkylamides, can be prepared by mixing, for example, equivalent moles of alkyllithium such as ethyllithium, propyllithium, butyllithium, etc. in hexane solution.
j1 can be shown. Examples of the above-mentioned solid gases include solid gases such as argon gas and argon gas. Furthermore, an example of 1 meter of waste used in the reaction is tetrahydrofuran (THE").

Somethoxyethane, ethyl ether% etc., suitable mixture of ether, inert, double refrigerant? I can give an example.

Preferably, the reaction is carried out under comparative Eta low temperature conditions.

For example, it is possible to show a temperature range of 9Jl such as fJ-'20°C to about -70'C. The amount of lithium amide used in the reaction can be selected as appropriate;

A single amount, such as about 1 to about 1.2 moles, can be added to the compound of formula (1). In addition, the use of 2RCHO aldehyde name compound can be selected as appropriate, and the amount of i! is about 1 to about 1.5 moles based on the compound of formula (1). An example of this is 1 history Mml. In addition, 113μ is added to the solvent's δ.
It can be selected over a range of about 20 to about 80 times based on the compound of formula (It).
can be shown.

Above formula 1 (III) @! To give a more detailed example of Kazusho where the compound of formula (1) is formed from the proboscis and the second RCHO aldehyde compound, for example, 'l'fiF' of the formula (1/) 2-phenylthio-2-laten-1-olide Bath liquid 1 Example: Diisopropylamine 1' in bath liquid Kelgon air stream
For example, a mixed M solution of HF I solution and loop til lithium in a hexane bath was mixed with M solution cooled to -50°C, so that it could be mixed with υ11. For example, R in the above formula (1) is a phenyl group. When trying to obtain the ratio-8-compound, R is phenyl and the formula RCfiO is converted to benzaldehyde-T H
F The molten layer is washed away, for example, ilt'J for 40 minutes, -
The reaction formula for 51 at 50℃ is the formula (1) where R is phenyl.
I can smell the kiss. The same procedure can be applied to compounds in which R is expressed in other ways by using the formula gcHo, in which R is expressed in other ways. Next, the ether bath is neutralized with, for example, 10% ester, extracted with ether, and the ether bath liquid is dehydrated with, for example, free magnesium, and then transferred to a silica gel column (for example, with 1 G of ether). , 1) Separate in the mixed bath ψ and 1jII
2-phenylthio-5-human sexy 5-phenyl-2-pentene- in the formula (II) where R is phenyl
4-Olido f,? C. can be obtained in good yields such as 7B'%.

According to the present method, the formula (11) 2-phenylthio-5-hydroxy-5 can be prepared as described above.
-m-$-2-Penten-4-olide is brought into contact with a shoulder group and subjected to an intramolecular dehydration reaction to produce (b') or (z)-5- of formula (1). It can be converted to 9-2-phenylthio-2,4-pentadiene-4-meridine.

Reaction is 0 For example, m proper inert M Hakuzokujochu・shou 1 or 11, for example, Muzuitei Am, Trifluoro Marshal H I, etc.@
1) Groups such as anhydride and triethylamine, pyridine
For example, 4-dimethylaminopyridine, 4-dimethylaminopyridine, etc.
- Pyrodinovirison, 4-morpholinopyridone can be performed.

As an example of an inert M medium to be used, -r may be tf,
methylene chloride, chloroform, 4j1 charcoal purple.

The presence of halodanized hydrocarbon yarns such as U-ethylene
Tower A can be exemplified.

The reaction occurs smoothly at a certain temperature and does not require any particular rhythm or heating, but the temperature range may be, for example, from about 0' to about 30°C. During the reaction, r- can be freely selected,
For example, υ:I can be expressed as 11jl at a reaction time of about 30 minutes to tJ2.

The reaction vc I can be selected from the complex type of the tertiary amine base to be used, and the details can be selected as follows.
I) In the compound, 1.5 to 4.0 mol, preferably about 25 mol to about &0 mol, can be exemplified. Also, regarding the 41 parts of traditional traces (for example, Anhydrous Yaba), one can choose as desired, but for example, based on the compound of formula (1), about 1 to 5 moles, more preferably about 1.5 to about An example of 25 moles of free salt is shown below. Also, for example, 4-
Dimethylaminopyridine's 1 history can also be selected based on the formula (II) compound and prevention of about 0.5 to about 5 11-
It is possible to show about 0.8 to about 1.5 ri]1 for sake such as denchu. Also, the value used for ζ) can be freely selected, and if i>-i, formula (1) shows about 5 to about 30 tani hT, and the double Okawa 1i- is vj1. I can do it. Reaction end value 1 For example, salt is removed with a short column, and then separated by column chromatography.
It is possible to do 1f14◎Formula (II) above @'! 4
fllJ t-Intramolecular dehydration reaction/Histome expression (summer) @
To give a more specific example of how to produce VTL, for example, 2-phenyl-5-hydroxy-5-[73-2-pentene-4 which is substituted with 1 in the above formula (1)
-Olido'Af7j For example, the dust obtained by reacting with 1, e.g., triethylamine, anhydrous solids, and 4-trimethylaminopyridine in methylene chloride under stirring at room temperature for 1 hour under a short column. After removing the barrier, using silica gel column chromatography and separating with a mixed solvent of 1 petroleum ether and benzene (3:2), L'u was prepared (E) or C.
2) To -5-1:? A-2-phenykf-o-2e4-pentadiene-4-olide pongee can be produced in high yield.

Below, several examples of the Laughing Mountain side's Reimei method will be illustrated in more detail.

Reference Example 1. Sweet acid of 2-phenylthio 5-human xy-5-phenyl-2-penten-4-olide [formula (■); R=phenyl].

Diisopropylamine o, sos, 9 under argon stream
(5 mmol) dissolved in wTtiFs- and 15%
n-butyllithium (hex f”j47it) a 2
Add d (5 mmol), cool to -50'C, and add 2-phenylthio-2-1-4 by hand.
-d-IJ I'0.960.9 (5 mm% le) J-T
: The bath solution dissolved in F8- is gradually moved south. After stirring at -50℃ for about 20 minutes, add 0 benzaldehyde to the solution.
．． 795g (7.5 mmol) in 1'H/”8tnl
The layered liquid containing Vc dissolved in f was moved south for 10 minutes, and stirred in the direction and direction for 40 minutes at -50"C to allow the reaction to rise.
Neutralize with 0chi salt and take out the helmet with ether. The ether-soluble gauze was dehydrated with Yanshui Feishu magnesium to remove the ether, and the remaining residue was purified using column chromatography with a benzene-ether (10:1) mixed solvent. + tree folds. Eye 1 (9 rostrum q2-phenylthio-5-hyVroxy5-phenyl-2-pentene-4
- oride 1.162. u (78%) Lee Suta.

Its physics is shown in Table 1.

Mochi example 2 ~ & 2-phenylthio-5-hydroxy-2
-Octene-4-olide [Formula (I); Norpropyl] and 2-phenylthio-5-hydroxy-2-dodecene-
Sweet acid of 4-olide [formula (I) 'i A' thegetyl].

Formula (ml) compound? I2-phenylthio 2-butene-4
- Instead of benzaldehyde (R: phenyl) to be reacted with 7-tanal (Rt propyl) or octanal (R: heptyl), it was carried out according to the method of Reference Example 1, and the compounds shown in Table 1 below were used. was gotten. I
tI! I Prisoner Data Book - This is shown at the beginning.

Synthesis of (Z)-5-phenyl-2-phenylthio-2,4-pentadien-4-olide (R:phenyl) -5
-Phenyl-2-penten-4-oliFO,532,9
(L?9 mmol) to cyclized methylene 101,
To this was added triethylamine 0.505.9 (5.0 mmol), anhydrous vinegar, 264# (2.6 mmol), and 4-dimethylaminopyridine as a catalyst needle, and the mixture was reacted with stirring at room temperature for L hours. I do. After the reaction was completed, 1 reaction solution was desalted using a short column, and 1 petroleum ether benzene (1) was extracted using silica gel column chromatography.
3:2) Minutes with mixed solvent! ! If you have curly hair (A')-5-7
enyl-2-phenylthio-2,4-pentadiene-4
-tlJ is 0.0841 (17%), 1) -5-phenyl-2-phenylthio-2,4-pentadiene-4-
Oride was obtained at 0.345.9 (69 degrees).

The +VIJ h'4i data about 4i'e are shown in 2.

Examples 2-9 Preparation of RI phenyl of compound of formula (1) 8 Substitute for Qffl.

Except for using the compound @ shown in Table 2 below, which is R.

The procedure was carried out according to the method of Example 1, and the compound shown in Example 2 below was obtained.

The 'e1m data is also shown in Fuki 2.

Claims (1)

[Claims] 1. The following formula (1) % Formula % (1) However, Narita, 17 is a C8 to C1o alkyl group, halogen, and an alkyl group.
M'jlh group may be rearranged. or penzuruo; expressed as (E) or (Z) -5-ffh:
2-phenylthio-2,4-pentadiene-4-olide. or 2-phenylthio-5-hydroxy-5- represented by benzyl base tube.
The following formula (I) RH CE) body (2) body -- -(1) However, in the formula, it has the same meaning as defined on Ra. Followed by name (Ao) or (Z)-s-Naokiichi 2-
Treatment of phenylthio 2,4-pentadiene-4-olide tumors.