CS264978B1 - 2,5,6-Trisubstituted-4-pyrones and processes for their preparation - Google Patents

Abstract

The solution concerns new, fungicidally effective 2,5,6-trisubstituted 4-pyrones of the general formula I, which can be prepared by reacting 2-chloromethyl-5,6-disubstituted 4-pyrone of the general formula VI with a compound containing the substituent R^ in an organic solvent environment at a temperature of 20 to 120°C.

Description

(57) The invention relates to novel, fungicidally active 2,5,6-trisubstituted 4-pyrones of the formula I, which can be prepared by reacting a 2-chloromethyl-5,6-disubstituted 4-pyrone of the formula VI with a compound storing an R 1 substituent. in an organic diluent at ~ 20 to 120 ° C.

CS 264 978 B1

The invention relates to 2,5,6-trisubstituted 4-pyrones as well as a process for their preparation. The compounds are fungicidally active.

2- [N- (2'-cyanoethylthiocarbamidosulfenylmethyl)] - 5-hydroxy-4-pyrone and its complexes with Zn and Ni as fungicides are known in the literature [US Patent 799,945, CA 80,146,018 (1974)], further, 2-hydroxymethyl-5-hydroxy-5- [N, N-dialkylthiocarbamosulfenylmethyl-4-pyrone (DOS 2,625,823). Organophosphorus compounds of the general formula (XI) are also known.

12 (XI) wherein R ⁸ is hydrogen, alkyl, alkenyl, R ⁹ is alkyl, alkenyl, R ¹ is alkyl, R 12 is cycloalkyl, R hydrogen, alkyl, alkenyl, R is hydrogen, haloalkyl, Y is oxygen or Sulfur, which are effective as insecticides and miticites (JP JP 6 229 593, CA 107, 780 79 (1987)).

We have now found 2,5,6-trissubstituted 4-pyrones of formula I

CH-R wherein R is hydrogen, chloro, bromo, R ⁷ is a group of formula II, III, IV or V

-S-CII p

<'(II) ii * or ⁶ (III)

-SCOR ⁷ (IV)

II p

(IN)

4 wherein R and R are the same or different alkyl of 1 to 4 carbon atoms, optionally together with the nitrogen atom, form a six-membered heterocyclic ring, which can, as a further heteroatom oxygen-R® is ethyl or a group R ³ X ^8, wherein X ³ is O or s and R ⁸ is alkyl of 1 to 8 carbon atoms or phenyl, X ³ is O or s, R® is C 1 -C 4 alkyl or phenyl, R is alkyl of 1 to 4 carbon atoms, allyl, and 2

R is hydrogen, methyl or chloroacetyl.

At the same time, a process for the preparation of compounds of formula I by reacting 2-chloromethyl-5,6-disubstituted pyrone of formula VI ch ₂ ci

(VI), wherein R and R are as defined above, with a compound of formula VII, VIII, IX or X

7 MS-CN II ⁴ r R ⁵ (VIII (VII) ^ms_p IL & ΠΓ ^ ΟΕ ⁶ MS-C-OR ⁷ (IX) \ J. (X)

II \ = N

WITH

Wherein R and R are as previously described, M is sodium, potassium or NH 4 in an organic diluent such as ethyl alcohol, acetic acid nitrile, methyl ketone, ethyl acetate, dimethylformamide, and the like. at 20 to 120 ° C.

The following examples illustrate but do not limit the scope of the invention.

Example 1

2 / N, N-dimetyltiokarbamosulfenylmetyl / 5-hydroxy-4-pyrone

A mixture of 0.25 mol of 2-chloromethyl-5-hydroxy-4-pyrone and 0.3 mol of sodium Ν, Ν-dimethyldithiocarbamate in 300 ml of acetone was stirred at reflux for 4 h. After completion of the reaction and cooling, the precipitated solid was filtered off, dried, triturated with water in a mortar and dried again.

54.2 g of white solid, m.p. 170-173 ° C, IR in CHCl 3: v / c = 0/1 ^cm v _{/ 0} . _{H /} 3420 cm ¹

Analysis for C 9 H 15 N ₂ O ₂ S (M = 245.29)

Calculated. found: 4 S 26.14 / 25.98; 4 N 5.71 / 5.78;

Example 2

2/0-metyltiokarbsulfenylmetyl / 5-hydroxy-4-pyrone

From 0.1 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.11 mole of sodium O-methylxanthate in 150 ml of methanol, 14 g of a white solid were prepared as in Example 1. mp 108.0 ° C.

Analysis for C 8 H 8 O ₂ S ₂ (M = 232.26)

Calculated. found:% S 26.30 / 25.98

Example 3

Ethylene-bis-2 / tiokarbamosulfenylmetyl / 5-hydroxy-4-pyrone

From 0.1 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.05 mole of sodium ethylene-bis-dithiocarbamidate in 100 ml of methyl ethyl ketone, 14.8 g of a yellow-brown solid was prepared as in Example 1. . t. m.p. to 183 ° C.

Analysis for ^c 14 ^H 16 ^N 2 ° 6 ^S 4 (M = 460.53)

PDF. / Check. % S 27.84 / 27.62; % N 6.10 / 5.81;

Example 4

2- / 0,0-dimetyltiofosforylsulfenylmetyl / 5-methoxy-4-pyrone

A mixture of 0.05 mole of 2-chloromethyl-5-methoxy-4-pyrone and 0.05 mole of 1,2,4-triazole sodium salt in 80 ml of acetonitrile was stirred at boiling point for 6 h, charcoal was added, filtered off, the solvent was removed under reduced pressure. 6.7 g of a viscous liquid were obtained.

Analysis for C 8 H 9 N 3 O 3 (M = 207.10)

Off. (Found:% C 49.22 / 49.48; 1H 4.38 / 4.40;% N 20.28 / 20.12)

Example 5

2 / N, N-dimetyltiokarbamosulfenylmetyl / 5-methoxy-4-pyrone

From 0.05 mole of 2-chloromethyl-5-methoxy-4-pyrone, 0.065 mole of N, N-dimethyldithiocarbamic acid sodium salt and 80 ml of acetonitrile, 7.1 g of a white solid were prepared as in Example 4. t. 188.5 ° C.

IR in CHC1 ₃ ·. vi _{c = 0} 1 1642 cm ^-1

Analysis for C 6 H 11 N ₃ O ₂ S ₂ (M = 259, 32) calcd, found:% S 24.72 / 25.26; % N 5.40 / 5.43

Example 6

2/0, O-dietyltiofosforylsulfenylmetyl / 5-methoxy-4-pyrone

6.5 g of a viscous liquid were prepared from 0.05 mole of 2-chloromethyl-5-methoxy-4-pyrone and 0.04 mole of Ο, Ο-diethyldithiophosphoric acid sodium salt in 60 ml of acetonitrile.

Analysis for C ₃₃ H ₃ O 6 O ₂ PS ₂ (M = 324.33)

Off. %:% P 9.55 / 9.88; % S 19.76 / 20.17

Example 7

2- / 0,0-Dimethylphosphorylsulphenylmethyll-5-hydroxy-4-pyrone

12.5 g of a viscous liquid were prepared from 0.04 mol of 2-chloromethyl-5-hydroxy and 0.044 mol of sodium O, O-diamildithiophosphoric acid in 60 ml of acetonitrile as described in Example 4.

Analysis for ^C 18 ^H 27 ^{R 5 S} 2 (M = 394.46)

Off. found:% P 7.85 / 8.02; % S 16.26 / 16.51

Example 8

2/0-ethyl S-etylfosforylsulfenylmetyl / 5-hydroxy-4-pyrone

From 0.04 mol of 2-chloromethyl-5-hydroxy-4-pyrone, 0.044 mol of 0.5-diethyldithiophosphoric acid sodium salt and 70 ml of methyl ethyl ketone, 4.9 g of a white solid was prepared as in Example 4. t. 149.1 ° C.

Analysis for C ₃ H ₃₃ O ₃ PS ₂ (M = 310.31)

Off. found:% P 9.99 / 9.69; 4 S 20.68 / 21.09

Example 9

2- (O-ethyl-O-isopropylphosphorylsulfenylmethyl) -5-hydroxy-4-pyrone from 0.04 moles of 2-chloromethyl-5-hydroxy-4-pyrone, 0.044 moles of O-ethyl-S-isopropylthiophosphoric acid sodium salt and 80 ml of methyl ethyl ketone was prepared as in Example 4 to give 9.8 g of a viscous liquid.

IR in CHCl₃: in _which y ^ 1 1 720 cm 360 cm 430 cm N 3 ¹

Analysis for C- ^H ^OgPS (M = 308.27)

Off. (found: P 10.04 / 10.28;% S 10.40 / 10.61

Example 10

2- / 0,0-difenyltiofosforylsulfenylmetyl / 5-hydroxy-4-pyrone

From 0.03 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.033 mole of O, O-diphenyldithophosphoric acid potassium salt in 60 ml of acetonitrile, 8.3 g of a white crystalline solid were obtained as in Example 4. mp 124.1 ° c.

Analysis for ^c 18 ^H 15 ^O 5 ^p S 2 (M = 406.29)

Off. (found:% P 7.62 / 7.78;% S 15.77 / 16.18

Example 11

2 / O-etyletyltiofosforylsulfenylmetyl / 5-hydroxy-4-pyrone

From 0.03 mol of 2-chloromethyl-5-hydroxy-4-pyrone and 0.033 mol of O-ethyl-ethyldithiophosphoric acid potassium salt in 60 ml of methyl ethyl ketone, 6.2 g of white solid was prepared as in Example 4. t. 110.3 ° C.

Analysis for ^c 10 ^H 15 ^O 4 ^PS 2 (M = 294.31)

Off. found:% P 10.52 / .10.95% S 21.78 / 22.18

Example 12

2/0, O-dimetyltiofosforylsulfenylmetyl / 5-hydroxy-4-pyrone

From 0.03 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.033 mole of O, O-dimethyldithiophosphoric acid sodium salt in 60 ml of acetonitrile, 6 g of a white crystalline solid was obtained as in Example 4. t. 165.4 ° C.

IR in CHC1 _3: ^I / _{C = ^0/1} 640 cm ^{"1; in} / QH / ^{3420 cm @ -1}

Analysis for C 9 H ₃₃ 0gPS ₂ (M = 282.25)

Off. found:% P 10.97 / 10.70; % S 22.72 / 21.92

Example 13

2- / O, O-diethylphosphorus lsul bitches lime -5-hydroxy-4-pyrone

From 0.02 mole of 2-chloromethyl-5-hydroxy-4-pyrone, 0.022 mole of Ο, Ο-diethyldithiophosphoric acid sodium salt, and 60 ml of acetone, 5.4 g of a white crystalline solid were obtained as in Example 4. t. 109.0 ° C.

Analysis for C ₁₀ H ₁₅ O ₅ PS ₂ (M - 310.31)

Off. found:% P 9.98 / 10.24; % S 20.66 / 20.86

Example 14

2 / N, N-dietyltiokarbamosulfenylmetyl / 5-hydroxy-4-pyrone

From 0.02 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.022 mole of N, N-diethyldithiocarbamic acid sodium salt in 60 ml of acetone, 2.6 g of a white crystalline solid was obtained as in Example 4. t. 116.2 ° C.

Analysis for (M - 273,45)

Off. found: N 5.12 / 5.08; «S 23.45 / 23.74

Example 15

2- / 1,2,4-triazolylmethyl / 5-methoxy-4-pyrone

From 0.05 mole of 2-chloromethyl-5-methoxy-4-pyrone and 0.05 mole of 1,2,4-thiazole sodium salt in 80 ml of acetonitrile, 4.2 g of white crystalline solid was prepared as in Example 4, m.p. t. 12.6 ° C.

Analysis for C 8 H 9 N 6 O 3 (M = 207.19)

Off. found: C 49.22 / 49.48; % H4 38 / 4.40; N 20.28 / 20.12

Example 16 of

2- (N, N-dimethylthiocarbamosulfenylmethyl) -5-chloroacetoxy-4-pyrone]

To 0.03 µl of 2- (N, N-dimethylthiocarbamosulfenylmethyl) -5-hydroxy-4-pyrone and 0.033 mol of triethylamine in 80 ml of toluene was added with stirring 0.33 mol of chloroacetyl chloride over 20 min at 20-30 ° C. C. Stirring was continued for 2 h at 60 ° C, after cooling, the reaction mixture was washed with 3x50 mL of water, the toluene layer was dried and the toluene was distilled off under reduced pressure. 6.8 g of a yellowish solid with m.p. t. 182.8 C.

Analysis for ^C n ^II I 2 ^C '' - ^NO 4 ^S 2 (M = 321.76)

Off. / rep:% Cl 11.0 / 11.2; % N 4.35 / 4.6; % S 19.90 / 20.12

Example 17

2 / N, N-dimetyltiokarbamosulfenylmetyl / 5-hydroxy-6-bromo-4-pyrone

From 0.05 mole of 2-chloromethyl-5-hydroxy-6-bromo-4-pyrone and 0.06 mole of N, N-dimethyldithiocarbamic acid sodium salt in 60 ml of methyl ethyl ketone, 11.8 g of white crystalline solid was prepared as in Example 4. substances with t. t. Mp 169 ° C.

Analysis for C 8 H ₁ gBrNOgS2 (M = 324.20)

PDF. found:% N 4.32 / 4.13; % Br 24.65 / 24.71; % S 19.78 / 19.92

Claims (2)

7 264978 OBJECT OF THE INVENTION 1. 2,5,6-Trisubstituted 4-pyrones of Formula I R. θ CH2-R1 wherein R is hydrogen, chloro, bromo, R is a radical of formula (IIR3) R4 (II), in which R and R are the same or radical alkyl of 1 to 4 carbon atoms, optionally forming a six-membered heterocyclic ring with a nitrogen atom; wherein the additional heteroatom may be oxygen, the group of Formula III SP II x in which R is ethyl or -XR, where X is oxygen or sulfur and R is alkyl of 1 to 8 carbon atoms or phenyl, is alkyl of 1 to 4 carbon atoms and isophenyl, X1 is oxygen or sulfur, a group of formula (IV) -Sco-R7 (S) (IV), wherein R is alkyl of 1 to 4 carbon atoms, allyl or - (O) = N (V), R 2 is hydrogen, methyl or chloroacetyl. 2. A process for the preparation of the compounds according to claim 1, characterized in that the 2-chloromethyl-5,6-disubstituted 4-pyrone of the formula VI is reacted with the compound of the general formula VIR2 ch2-ci (VI), of formula VII, VIII, IX or X MS-CN II with 4 MSP (vin), MS-C-OR IIs N == mn '(VII), IIi "- 6 X 1 O R b 7 (X), (IX), Wherein R @ 1, R @ 4, R @ 5, R @ 2 and R @ 6 are as defined above and M is sodium, NH @ +, in an organic diluent at 20 DEG to 120 DEG C., potassium or Severografia, n, p., MOST. 2,40 Kčs