JPH06256354A - Novel tetrazole compound and process for producing the same - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as an agricultural germicide. CONSTITUTION:A compound of formula I (Z is hydroxyl group-protecting group for benzyl, benzoyl, acetyl group, etc.), e.g. (7R,8S,9S-10R)-8,9,10-tribenzyloxy-7- benzyloxymethyl-6-oxa-1,5pentamethylene tetrazole. This compound of formula I can be obtained by dissolving a compound of formula II in an inert solvent such as benzene or toluene followed by either heating or irradiation using e.g. a mercury-vapor lamp. The compound of formula II can be obtained by reaction of a compound of formula III with an azidating agent (e.g. trimethylsilyl azide) in the presence of a Lewis acid (e.g. anhydrous aluminum chloride) in a solvent (e.g. dichloromethane).

Description

Detailed Description of the Invention

[0001]

The present invention relates to general formula (I) having bactericidal activity for agriculture;

[Chemical 6] (In the formula, Z represents a hydroxyl group-protecting group such as a benzyl group, a substituted benzyl group, a benzoyl group, a substituted benzoyl group, and an acetyl group), a production method thereof, and a production method of an intermediate thereof.

[0002]

BACKGROUND OF THE INVENTION Various agricultural fungicides are known, but more effective ones are always required.

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies as to a novel agricultural fungicide, and as a result, a tetrazole compound represented by the general formula (I), which has not been described in the literature, has an agricultural fungicidal activity. That is, the present invention has been completed.

The compound represented by the general formula (I) can be synthesized, for example, by the method shown below.

[Chemical 7] (In the formula, Z is the same as above)

That is, the compound represented by the general formula (I) is
It can be synthesized by dissolving the compound represented by the general formula (II) in an inert solvent such as benzene or toluene and heating or irradiating with light from a mercury lamp or the like. The reaction time depends on the reaction temperature,
Although it varies depending on the reaction scale, it may be appropriately selected from the range of 0.5 to 48 hours.

The compound represented by the general formula (II) is obtained by reacting the compound represented by the general formula (III) with an inert solvent such as dichloromethane or tetrahydrofuran as shown by the following formula.
It can be obtained by reacting with an excess amount (preferably twice the molar amount) of trimethylsilylazide, silver azide, sodium azide and the like in the presence of a Lewis acid such as anhydrous aluminum chloride and titanium tetrachloride. The Lewis acid is used in an equimolar amount with respect to the compound represented by the general formula (III). Reaction temperature is 50
It may be appropriately selected from the range of ℃ to 200 ℃. The reaction time varies depending on the reaction temperature and the reaction scale, but may be appropriately selected from the range of 0.5 to 48 hours.

[0007]

[Chemical 8] (In the formula, Z is the same as above)

The compound represented by the general formula (III) used in this reaction is described in J. Am. Chem. Soc. 104 , 4976 (1982), J. Am.
Chem. Soc. Chem. Commun. 431 (1990), Tetrahedron L
It can be prepared according to the method described in etter 31 , 4441, (1990). Next, representative examples of the compound represented by the general formula (I) are shown in Table 1, but the present invention is not limited thereto.

[0009]

[Table 1]

The physical properties (NMR) of the compounds in the table are shown below. Compound 1 ¹ H-NMR (400MHz, CDCl ₃ ): δ3.86 (d, 2H, C H ₂ OBn, J ₇ , CH ₂ OBn
= 2.93Hz), 3.99 (dd, 1H, H-9, J ₉ , ₁₀ = 4.58Hz, J _8,9 = 1.28Hz,
4.15 (dd, 1H, H-8, J _8,9 = 1.28Hz, J _7,8 = 10.26Hz), 4.24 (d, 2
H, C H ₂ Ph, J _gem = 12.27Hz), 4.31 (d, 2H, CH ₂ Ph, J _gem = 12.28H
z), 4.441 (d, 2H, C H ₂ Ph, J _gem = 11.54Hz), 4.46 (d, 2H, C H ₂ Ph,
J _gem = 11.54Hz), 4.58 (d, 2H, C H ₂ Ph, J _gem = 12.09Hz), 4.66
(d, 2H, C H ₂ Ph, J _gem = 12.28Hz), 4.67 (d, 2H, C H ₂ Ph, J _gem = 12.
09Hz), 4.83 (d, 2H, C H ₂ Ph, J _gem = 12.27Hz), 4.96 (dd, 1H, H-
7, J _7,8 = 10.26Hz, J ₇ , CH ₂ OBn = 2.93Hz), 5.83 (d, 1H, H-10, J
_9,10 = 4.58Hz), 7.00-7.02 (m, 2H, Ph), 7.20-7.37 (m, 18H, P
h), ¹³ C-NMR (100.40MHz, CDCl ₃ ): δ68.7 ( C H ₂ OBn), 71.5,7
2.1,72.8,73.7 (Ph C H ₂ × 4), 76.9,77.4,83.6,84.4 (C-7,8,
9,10), 127.8-128.6 (Ph), 135.5,136.2,137.1,137.7 (ipso
CofPh × 4), 162.4 (C-5), IR (neat) 3000 (Ph), 2850cm ^-1 (C
H); MSm / z (FAB), 579 (M + 1) ⁺ .

Compound 2 ¹ H-NMR (500 MHz, CDCl ₃ ): δ3.68 (dd, 1H, C H ₂ OBn, J ₇ , CH ₂ OB
n = 5.23Hz, J _gem = 11.55Hz), 3.78 (dd, 1H, C H ₂ OBn, J ₇ , CH ₂ OBn
= 2.75Hz, J _gem = 11.55Hz), 3.91 (dd, 1H, H-8, J _8,9 = 6.60Hz, J
_7,8 = 6.87Hz), 4.12 (dd, 1H, H-9, J _9,10 = 6.60Hz, J _8,9 = 6.60H
z), 4.42 (d, 2H, C H ₂ Ph, J _gem = 11.27Hz), 4.49 (s, 2H, C H ₂ Ph),
4.57 (d, 2H, C H ₂ Ph, J _gem = 11.27Hz), 4.61 (m, 1H, H-8), 4.65-
4.68 (m, 6H, C H ₂ Ph x 3), 4.86 (d, 2H, C H ₂ Ph, J _gem = 11.80H
z), 5.04 (d, 1H, H-10, J _9,10 = 6.60Hz), 7.12-7.36 (m, 20H, P
h), ¹³ C-NMR (100.40MHz, CDCl ₃ ): δ60.4 (CH ₂ OBn), 67.4,7
2.6,73.6,74.1 (PhCH ₂ × 4), 71.5,76.7,78.9,89.4 (C-7,8,
9,10), 127.5-128.5 (Ph), 136.4,137.0,137.1,137.2 (ipso
CofPh × 4), 146.4 (C-5), IR (neat) 3000 (Ph), 2840cm ^-1 (C
H); MSm / z (FAB), 579 (M + 1) ⁺ .

Compound 3 ¹ H-NMR (500 MHz, CDCl ₃ ): δ3.63 (dd, 1H, C H ₂ OBn, J ₇ , CH ₂ OB
n = 8.40Hz, J _gem = 11.95Hz), 3.85 (dd, 1H, C H ₂ OBn, J ₇ , CH ₂ OBn
= 3.16Hz, J _gem = 11.95Hz), 4.07 (dd, 1H, H-9, J ₉ , ₁₀ = 4.67Hz,
J _7,8 = 3.00Hz), 4.33 (dd, 1H, H-8, J _8,9 = 3.00Hz, J _7,8 = 4.12H
z), 4.43-4.73 (m, 8H, PhC H ₂ × 4), 4.93 (m, 1H, H-7), 5.74
(d, 1H, H-10-, J _9,10 = 4.67Hz), 7.04-7.06 (m, 2H, Ph), 7.17-
7.40 (m, 18H, Ph), ¹³ C-NMR (100.40MHz, CDCl ₃ ): δ67.4 (CH ₂
OBn), 71.5,73.0,73.6,73.8 (PhCH ₂ × 4), 75.6,75.7,84.1,
84.3 (C-7,8,9,10), 127.8-128.7 (Ph), 135.1,136.4,137.
0,137.7 (ipso CofPh × 4), 160.5 (C-5), IR (neat) 3000 (P
h), 2850cm ^-1 (CH); MSm / z (FAB), 579 (M + 1) ⁺ .

Compound 4 ¹ H-NMR (500 MHz, CDCl ₃ ): δ3.32 (dd, 1H, C H ₂ OBn, J ₇ , CH ₂ OB
n = 3.11Hz, J _gem = 9.08Hz), 3.70 (dd, 1H, C H ₂ OBn, J ₇ , CH ₂ Ph =
5.47Hz, J _gem = 9.08Hz), 4.19 (dd, 1H, H-9, J ₉ , ₈ = 2.15Hz), 4.
38 (d, 2H, C H ₂ PH, J _gem = 11.73Hz), 4.47 (dd, 1H, H-8, J _7,8 = 7.
09Hz, J _8,9 = 2.15Hz), 4.51-4.63 (m, 6H, C H ₂ Ph × 3), 4.82 (d
dd, 1H, H-7, J _7,8 = 7.09Hz, J ₇ , OCH ₂ Ph = 3.11,5.49Hz), 5.06
(d, 1H, H-10, J _9,10 = 6.04Hz), 7.15-7.36 (m, 20H, Ph × 4),
¹³ C-NMR (100.40 MHz, CDCl ₃ ): δ65.0 (CH ₂ OBn), 67.7, 72.3,
73.6,73.7 (PhCH ₂ × 4), 76.4,78.3,80.2,80.5 (C-7,8,9,1
0), 126.5-128.6 (Ph), 136.2,136.9,136.9,137.5 (ipso Co
fPh × 4), 147.4 (C-5), IR (neat) 3000 (Ph), 2840cm ^-1 (CH);
Found: m / z (FAB), 579.2605.C ₃₄ H ₃₅ O ₅ M ₄ (M + 1) ⁺ requires m
/ z 579.2609.

[0014]

EXAMPLES Examples of the compounds of the present invention are shown below, but the present invention is not limited to these.

Example 1 [(7R, 8S, 9S, 10R) -8,9,10-tribenzyloxy-7-benzyloxymethyl-6-oxa-
Synthesis of 1,5-pentamethylenetetrazole (Compound 1)

[Chemical 9] Under an argon stream, 2,3,4,6-tetra-O-benzyl-D-gluconolactone 5 0.323 g (0.599 mmol) was dissolved in 5 ml of dry dichloromethane and trimethylsilylazide 0.5 ml (3.77 mmol) was added. The mixture was stirred at room temperature for 0.5 hours. To this, boron trifluoride-ether complex 0.15 ml
(1.22 mmol) was added dropwise over 5 minutes, and the mixture was stirred at room temperature for 13 hours. The reaction solution was purified by silica gel column chromatography and 1-C-azido-2,3,4,6-tetrakis-O-
(Phenylmethyl) -D-glucopyranosyl azide 6
To give 0.156 g (oil, yield 44.1%). Then, under argon flow, 0.173 g (0.233 mmol) of compound 6 was added to the o.
-Dissolved in 3 ml of xylene and heated under reflux for 17 hours. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography to obtain 0.135 g of Compound 1 (yield 100%).

Example 2 [(7R, 8S, 9S, 10R) -8,9,10-tribenzyloxy-7-benzyloxymethyl-6-oxa-
1,5-Pentamethylenetetrazole (Compound 1) and [(7R, 8S, 9S, 10R) -8,9,10-Tribenzyloxy-7-benzyloxymethyl-6-oxa-
Synthesis of 1,5-pentamethylenetetrazole (Compound 2)

[Chemical 10] Under an argon stream, 0.0688 g (0.093 mmol) of compound 6 was dissolved in 7 ml of benzene and irradiated with a 400 W high pressure mercury lamp for 2 hours. After distilling off benzene under reduced pressure, the reaction product was purified by silica gel column chromatography to obtain 33.3 mg of Compound 1.
(Yield 62%) and 12.8 mg of compound 2 (yield 23%) were obtained.

Example 3 [(7R, 8S, 9S, 10R) -8,9,10-tribenzyloxy-7-benzyloxymethyl-6-oxa-
Synthesis of 1,5-pentamethylenetetrazole (Compound 3)

[Chemical 11] 0.63 g (1.280 mmol) of 2,3,4,6-tetra-O-benzyl-D-galactolactone (Compound 7 ) was dissolved in 5 ml of dry dichloromethane, and 1.1 ml (8.33 mmol) of trimethylsilylazide was added under a stream of argon. And add at room temperature for 15
Stir for hours. The reaction solution was purified by silica gel column chromatography to give 0.292 g of 1-C-azido-2,3,4,6-tetrakis-O- (phenylmethyl) -D-galactopyranosyl azide (Compound 8 ) as an oil. (Yield 37.6%) was obtained. Then, under argon flow, compound 8
0.290 g (0.48 mmol) was dissolved in 5 ml of o-xylene,
The mixture was heated under reflux for 20 hours. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to obtain Compound 3 as an oily substance (0.150 g, yield 86%).

Example 4 [(7R, 8R, 9S, 10R) -8,9,10-tribenzyloxy-7-benzyloxymethyl-6-oxa-
1,5-Pentamethylenetetrazole (Compound 3) and [(7R, 8R, 9S, 10R) -8,9,10-Tribenzyloxy-7-benzyloxymethyl-6-oxa-
Synthesis of 1,5-pentamethylenetetrazole (Compound 4)

[Chemical 12] Under an argon stream, 0.103 g (0.169 mmol) of compound 8 was dissolved in 12 ml of tetrahydrofuran and irradiated in a quartz tube at 30 ° C. with a 15 W low-pressure mercury lamp for 3 hours. The reaction solution was dried under reduced pressure,
Compound purified by silica gel column chromatography
As an oily substance, 0.0285 g (yield 29%) of Compound 3 and 0.0369 mg (yield 38%) of Compound 4 were obtained.

Reference Example A 200 ppm chemical solution containing the compound of the present invention as an active ingredient was sprayed at the 4th leaf stage of tomato planting, and one day later, Phytophtho
ra infestans) was spray-inoculated with a zoospore suspension. After inoculation, after infecting in a humid chamber at 25 ° C. for 1 day and in a greenhouse for 6 days, the degree of lesions on each leaf was investigated, and the effect was judged based on the following criteria in comparison with the untreated plot. The test results are shown in Table 2. A: Control value 100-95% B: Control value 94-80% C: Control value 79-60% D: Control value 59-0%

[0020]

[Table 2] Table 2 ───────────────────── Test compound Control value ──────────────────── ── 1 A 2 D 3 D 4 D ──────────────────────

[0021]

The tetrazole compound of the present invention is useful as an agricultural fungicide.

Claims (3)

[Claims] 1. A compound represented by the general formula (I): (In the formula, Z represents a hydroxyl protecting group such as a benzyl group, a substituted benzyl group, a benzoyl group, a substituted benzoyl group, and an acetyl group). 2. A compound represented by the general formula (II): (Wherein Z represents a hydroxyl group-protecting group such as a benzyl group, a substituted benzyl group, a benzoyl group, a substituted benzoyl group and an acetyl group), which is heated in an inert solvent or irradiated with light. General formula (I); (In the formula, Z is the same as defined above). 3. A compound represented by the general formula (III): (Wherein Z represents a hydroxyl group-protecting group such as a benzyl group, a substituted benzyl group, a benzoyl group, a substituted benzoyl group, and an acetyl group), and a compound represented by the general formula ( II); (In the formula, Z is the same as defined above).