JPS59193852A - Optically active nitric acid ester and its preparation - Google Patents

Abstract

NEW MATERIAL:A nitric acid ester of formula I (R1 is H, lower alkyl; R2 is lower alkyl, lower alkenyl, lower alkinyl). EXAMPLE:(R)-3-Methyl-4-nitroxy-2-(2-propinyl)-2-cyclopentene-1-one. USE:It is useful as an intermediate of agricultural chemicals. PREPARATION:The nitration of a cyclopentenolone of formula II gives the compound of formula I . As a nitration reagent, is used nitric acid, a mixture of nitric acid and acetic anhydride, nitronium tetrafluoroborate. The amount of the reagent used is an equimolar or excessive amount based on the cyclopentenolone. In the above nitration, a solvent such as dichloromethane or chloroform may be used. The reaction temperature is -40-+30 deg.C, preferably -30 deg.C-+5 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a nitric acid ester and a method for producing the same.
, ) and a method for producing the same.

1 [In the formula, R1 represents a hydrogen atom or a lower alkyl group, & represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group. ] General formula (II) R+ [In the formula, R1 and R2 have the same meanings as above. Cyclopentenolone represented by [ is known as an important acrylate component of a group of carboxylic acid ester compounds called synthetic pyrethroids, which have excellent insecticidal activity. Since cyclopentenolone has an asymmetric carbon at the 4-position, two types of optical isomers exist, and the insecticidal activity of these carboxylic acid esters is usually determined by It is also known that (R) is several times superior to that of a single unit (for example, Matsuo et al., Pe5tic, Sci.
,.

11, 202 (1980)).

Therefore, there is a desire to develop a method for producing cyclopentenolone represented by the above formula (II) containing (S), and such a method involves converting the racemic form of cyclopentenolone into a half ester of phthalic acid. A method of resolution using an optically active amine (for example, JP-A No. 56-2929), a method of biochemically optically resolving the racemic form of cyclopentenolone using an esterase as an organic carbonic acid ester (JP-A No. 51-1988) -47495) and the like are known.

However, in all of these methods, along with the target monolithic (S) cyclopentenolone, approximately the same amount of the enantiomer, i.e., monolithic or enriched (R) cyclopentenolone, is produced. .

As mentioned above, (R) monolithic or enriched cyclopentenolones have corresponding (S) activity as esters.
Because it is inferior to cyclopentenolone monomer or cyclopentenol enriched in cyclopentenol or racemic form, and because the amount of cyclopentenolone is extremely large especially when carrying out optical resolution on an industrial scale, it is difficult to use the optical resolution technique described above industrially. In order to make more effective use of these (R1-integrated or R1-enriched cyclopentenolone), a technique is required to effectively utilize these (R1-integrated or R1-rich cyclopentenolone) by some method.

Under these circumstances, the present inventors developed the optically active formula (1
While investigating various methods for isomerizing cyclopentenolone shown in 1), it was found that by introducing the cyclopentenolone into a nitrate ester and then hydrolyzing this, the asymmetric center is inverted, and therefore the efficiency is improved. isomerization often occurs,
In this method, the inventors discovered that the nitric acid ester represented by the general formula (II) is an extremely useful intermediate, and completed the present invention.

That is, the present invention provides an optically active nitrate ester represented by the general formula (II) and a method for producing the same.
The present invention provides a production method by nitration of cyclopentenolone shown in the following.

By red-whitening the nitrate ester of the present invention, the optically active cyclopentenolone represented by the general formula (W) can be converted into the corresponding enantiomer at low cost and efficiently. In the resolution method, the cyclopentenolone represented by the general formula (B) monomer or enriched with (R) is also converted directly into a more useful (51-isomer or the general formula enriched with (II)
Since it is converted to cyclopentenolone shown by
It is extremely efficient, and combined with the optical resolution technology of cyclopentenolone represented by the general formula (b) above,
(S) The cyclopentenolone represented by the general formula (II) can be produced very advantageously even on an industrial scale.

The present invention will be explained in detail below.

When producing the nitrate ester of the present invention by nitrating the optically active cyclopentenolone represented by the general formula (Acetyl nitrate is a substantial nitrating agent.), nitronium butrafluoroborate, nitronium trifluoromethanesulfonate, N-nitrocollidinium tetrafluoroborate, and the like.

The amount used is not particularly limited, but it is usually used in an amount equal to or more than 1 mole of cyclopentenolone as a raw material.

In the nitration reaction, the use of a reaction solvent is not essential, but an inert organic solvent may be used if necessary. Such solvents include dichloromethane, dichloroethane, chloroform, carbon tetrachloride, etc. Examples include halogenated hydrocarbons, nonitroalkanes such as nitromethane and nitroethane, and lower aliphatic carboxylic acids such as acetic acid and propionic acid.

In addition, the reaction temperature of the nitration reaction is usually -40° to +
It is carried out at between 30°C, preferably between -30° and +5°C.

The nitric acid ester of the present invention obtained as described above can be subjected to hydrolysis as it is without purification to obtain cyclopentenron with an inverted asymmetric center, but if necessary, it can be subjected to column chromatography. It can be purified by means such as photography.

EXAMPLES The present invention will be explained in more detail below using Examples and Reference Examples, but the present invention is not limited thereto.

In Examples and V Examples below, the chemical purity is the value measured by gas chromatography, and the optical isomer ratio of 00 monomer and (S) monomer is the value measured by high performance liquid chromatography using an optically active stationary phase.

Example 1 Add (R
1-4-hydroxy-08-methyl-2-(2-7'0
vinyl)-2-cyclopenten-1-one ([α] sweetened-19.5° (C=tg6.chloroform), (
R) Integral/(S) Integral; 96.7/8.8) 6 y
was added dropwise at -6 to 10°C. After stirring at the same temperature for 80 forces, the reaction solution was poured into 200 m ice water and extracted with toluene. The toluene layer was sequentially washed with a 5% aqueous sodium bicarbonate solution and water, dried over anhydrous magnesium sulfate, and condensed to give Japanese tRl-8-methyl-4-nitroxy-2-(2-propynyl)-2-. Cyclopenten-1one 7,56P was obtained.

1.24 y of the crude product was chromatographed on a silica gel column (eluent: hexane/acetic acid nylon = 7).
/ 3), purified product i, t4 having the following characteristics
I got y.

Refractive index, n D-1,5188 Specific rotation; [α] 0.103° (C-1,41, chloroform) JR spectrum (film, characteristic absorption Lyn) 829
0.2120, 1715, 1650°1630.128
O NMR spectrum (CDCl3.TMS) 2,04
ppm (t,,1=3H2,LH)2.26 pp
m (s, 3H) 2,48 ppm (dd, J=2, 18Hz,
]LH 8,06ppm (dd, J=6, 18Hz, I
H) 3,19 ppm (d, J=8I-1z, 2H)
5.90 ppm (br, d, J-611z.

LH) Example (R1-4-hydroxy-8-methyl-2-(2-propynyl)-2-cyclopenten-1-one ([002 Knee 19.5° (C=1.86° chloroform), (
R) Integral/(S) Integral-967/8.8) 1. ．． 5
0 y of methylene chloride (15,/) solution ((-5-5~
Gradually add 10 y of fuming nitric acid at 10°C. After stirring at the same temperature for 2 hours, the reaction solution was poured into ice water and the methylene chloride layer was separated. The methylene chloride layer was washed, dried and concentrated in the same manner as in Example 1.

The Iv et al. 41 concentrate was purified by silica gel column chromatography, and the Ikunomi 9 Naruto 1 obtained in Example 1 was purified by silica gel column chromatography.
(R1-3-methyl-4-2-
Roquin-2-(2-propynyl)=2-enclopenoten--one 055y was obtained.

Reference Example 1 Crude fRl-3-methyl-4- obtained in Example 1
Nitroxy-2-(2-propynyl)-2-cyclopenten-■-one 1.95y.

A mixture of 1.00 F calcium carbonate and 3 Q me of water is stirred at 80-85° C. for 5 hours. The reaction solution was cooled and filtered through Celite to remove insoluble materials, and the aqueous layer was saturated with sodium chloride, followed by extraction with methyl isobutyl ketone. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give (Sl-4-hydroxy-3-methyl-2-(
2-propynyl)-2-cyclopenten-1-one1.
28y (chemical purity: 901%, [α)9: +15.0°
(C=LOG, chloroform), (R) unitary/(S) unitary = 11.6/88, -4) was obtained.

The product is similar to the starting material of Example 1 (k)-4-hydroxy-3-methyl-2- in properties such as IR, NMR spectra and retention time in gas chromatography, except for optical rotation. (2-propynyl)-2-
Completely consistent with cyclopentethyl-1-one.

Reference Example 2 The crude (R1-8-methyl-4-nitroxy-2-(2-propynyl) product obtained in Example 1 was heated at 85 to 90°C.
Stir for 4 hours. Thereafter, by the same operation as in Reference Example 1, (Sl-4-hydroxy-3-methyl-2-(2-
Flobinyl)-2-cyclobenzon-1-one 1.01
y (chemical fineness: 935%, [α]ゎ, l 4., 2゜ (C = 1.09.chloroform), (R) unitary / (S)
Total = 12.2/87.8) was obtained.

The product is the starting material of Example 1 (R)-4- in terms of properties such as IR, NMR spectrum and gas chromatographic retention time, except for optical rotation.
Hydroxy-3-methyl-2-(2-propynyl)-2
-Cyclopenten-1-one.

Reference Example 3 A mixture of 1.95P of the crude (R1-8-methyl-4-nitroxy-2-(2-furopinyl)-2-cyclopenten-■-one obtained in Example 1) and water 3Q me, Stir at 85-90°C for 4 hours. Thereafter, by the same operation as in Reference Example 1, (S)-4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentene/-
1-on 1. g5r (chemical purity: 90.2%, [α]o
, ±18.1' (C=1.07.

chloroform), (R1 unitary/(S) unitary = 16.2/
88.8) was obtained.

The product is the starting material of Example 1 (R1-4-hydroxy-3-methyl-2- (2-7'ropinyl)-2
Example 8 Solution 1c of a mixture of fuming nitric acid 8y and acetic anhydride 249, (
S) -4-hydroxy-3-methyl-2-(2-)0
benyl)-2-cyclopenten-1-one ([α]2δ
: +10.8° (c=1.17.chloroform), (R
) Integral / (S) Integral = 15.7/84.8 ) 6 y
is added dropwise at 15 to 0°C. Thereafter, the same procedure as in Example 1 was carried out to obtain crude (St-8-methyl-4-nitroxy-2-(2-7'lopenyl)-2-cyclopenten-1-one 7,56y).

A part of the crude product was purified by silica gel column chromatography in the same manner as in Example 1 to obtain a purified product having the following characteristics.

Refractive index; n2%5: 1.5084 Specific rotation; [α) 24I55: +65.4° (C=
1.06. Chloroform) JR spectrum (film, n-type absorption c, ) 171
5.1650.16:30°1280.915 NMR spectrum (CDC, #3.TMS) 2.1
2ppm (S, 8H) 2.48pl)m (dd, J=2.18Hz, IH
)2.96ppm (dd, J=6.18Hz, LH
)8, O8ppm (d, J=6Hz, 2H)4.8
0 to 6.20 ppm (m, 4H) Reference Example 4 Purified (Sl-3-mef-4-nitroxy-2-(2-7'lopenyl)-2- obtained in Example 8)
A mixture of 0.99y of cyclopenten-1-one, 050y of calcium carbonate and 3011C of water was heated at 85-90°C.
Stir for 2 hours.

Thereafter, by the same operation as in Reference Example 1, (R) -4-
Hydroxy-3-methyl-2-(2-propenyl)-2
-Cyclopenten-1-one 0.72y (chemical purity: 9
4.2%, [α]2 also knee 6.64° (C=1.18
．． chloroform).

(R) integral/(Sl integral = 76.2/28.8) was obtained.

The product was found to be similar to the starting material of Example 3 (S)-4-hydroxy-3-methyl-2-(2 -propenyl)-2-cyclopenten-■-one.

Example 4 (R
)-4-hydroxy-3-methyl-2-(2-7'ropenyl)-2-cyclopenten-1-one (tolJD,
-7,810 (C=1.07.chloroform), (R1
One piece/(S) one piece=77.4/22.6) 6y is added dropwise at -5 to 10°C. Thereafter, by the same operation as in Example 1, crude (R)-8-methyl-4-nitroxy-
2-(2-7'Lopenyl)-2-cyclopentene-1
-on 7,50 y was obtained.

A part of the crude product was purified by silica gel column chromatography in the same manner as in Example 1 to obtain a purified product having the following characteristics.

Refractive index; nゎ"5: 1.5076 Specific rotation; [03%; 52. I 0 (C=1.
40. Note that the NMR spectrum was similar to that of the (S) monomer obtained in Example 3.

Reference Example 5 Crude (R)-3-methyl-4- obtained in Example 4
Nitrokidi-2-(2-propenyl)~2-cyclopenten-1-one L, 9'ly, calcium carbonate 0.20
y, water 1brnI! and dioxane 15- is stirred at 85-90° C. for 5 hours. Hereinafter, reference example 1
Perform the same operation as above, and then perform silica gel column chromatography (eluent: hexane/ethyl acetate = 6/4).
(Sl-4-hydroxy-3-methyl-2-(2-propenyl-2-cyclopentene-1-
On 0.5 q y <Chemical purity: 98.9%, [α]
Father-in-law; 10a, so.

(C=1.28.chloroform), -(R) unitary/(
S) Unity = 35.8764. 'l) was obtained.

The product was found to be similar to the starting material of Example 4 (R)-4-hydroxy-3-methyl-2-(2 -propenyl)-2-cyclopenten-1-one.

Procedural amendment (voluntary) t Indication of the case 1982 Patent application No. 1) 7s-bg No. 2 Title of the invention Optically active nitrate esters and their manufacturing method 3 Relationship with the case by the person making the amendment Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka City Name (
209) Sumitomo Chemical Co., Ltd. Representative Hijikata
Osamu Takefu Address Sumitomo Chemical Co., Ltd., 5-15 Kitahama, Higashi-ku, Osaka Name Patent Attorney (8597) Mitsuhiro Moroishi'l'EL (061220-34045, detailed description of the invention in the specification subject to amendment) Column 6, Contents of amendment (1) The following is added after the bottom line of page 1 of the procedural amendment (written specification) dated May 2z, 1988.

“Example 5 In a solution of 5.5 f of fuming nitric acid and 222 g of acetic anhydride,
Fl-4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopenten-1-one ([α]25-14.9° (C=1.19.chloroform), unit)/ (S) Total = 99°270.8) Drop 4 f at -5 to 10°C. Thereafter, by the same operation as in Example 1, crude (1'L)-3-methyl-4-nitroxy-2-(2-propenyl)-2-cyclopentene-1
-on 5.022 was obtained.

A part of the crude product was purified by silica gel column chromatography in the same manner as in Example 1 to obtain a purified product having the following characteristics.

24.5, - Refractive index; n, 1° 5068 Specific rotation; [α): -94,7° (c=1.
20. (Chloroform) Note that the NMR spectrum was similar to that of the 31 monomer obtained in Example 3.

Reference Example 6 Purified t)-3-methyl-4- obtained in Example 5
Nitroxy-2-(2-propenyl)-2-cyclopenten-1-one 1.97F, calcium carbonate 0.20
A mixture of F and 30 rnl of water is stirred at 85-90° C. for 3 hours. Thereafter, by the same operation as in Reference Example 1, (R
)-4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopenten-1-one 1.20F (chemical purity; 93.6%, [α);': +11.2°(C
=1.23. Chloroform), one) one / (S) one =
14.8/85.2).

The product differs from the starting material of Example 5, P)-4-hydroxy-3-methyl-2-(2- It completely matched with propenyl)-2-cyclopenten-1-one. ” Written amendment to the above procedure (white) January 2, 1925 Dear Commissioner of the Japan Patent Office, Shukasumi 1, Indication of the case, Showa date, Patent Application No. 2/Evening 2? - No. 2, Relation to the case of the person making the amendment to the name of the invention and the "Mutual Manufacturer Law 3" Patent applicant Sumitomo Chemical, 5-15 Kitahama, Higashi-ku, Osaka (209) Representative of Kogyo Co., Ltd. Takeshi Hijikata 46 Agent 5-15 Kitahama, Higashi-ku, Osaka Patent attorney at Sumitomo Chemical Co., Ltd. (8597) Mitsuteru Moroishi, 轡聡-=r+, t”:+, 2d”3qo<329 −

Claims (1)

[Claims] +1+ Optically active general formula] In the formula C, R represents a hydrogen atom or a lower alkyl group, and R2 represents a lower alkyl group, a lower alkenyl group, or a lower argini/14. ] Nitrate esters shown in (2) Optically active general formula [wherein R1 represents a hydrogen atom or a lower alkyl group, and R2 represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group. [In the formula, R1 and R2 have the same meanings as above. ] A method for producing nitric acid esters.