CS248918B1 - Substituted 3,4-dichlorine-5-propenyl-oxy-2(5)-furanones and method of their preparation - Google Patents

Description

The invention relates to 3,4-dichloro-5-propenoyloxy 2 (5H) furanones and a process for their preparation. A suitable method for their preparation is the reaction of chlorides or mixed anhydride-3-substituted propenoic acids with mucochloric acid.

5-acyloxy-3,5-disubstituted 2 / 5H / furanones have good fungicidal properties suitable, in particular, for controlling the growth of phytopathogenic fungi such as Fusarium nievale, Tilletia tritioi, Sclerotinia fructiocola, Botrysis cineres / Czech. pat. 166 140 (1976) //.

Said compounds / J. Amer. Chem. Soc. 72, 2535 (1950); US Pat. 2786798/1957 // may serve as seed dressing, in particular to protect caliber against fusariosis and wheat against the greasy antifungal.

Ss. patent / čsl. No. 148,592 (1973) is a protected process for the preparation of acetylenic pseudoesters of 3,4-dihalogen-2 (5H) furanones and their fungicidal activity, in particular against phytopathogenic fungi.

As set forth in other patents, no. Patents: 138,821 (1970), 149,048 (1973)

No. 170,448 (1977), other pseudoesters of mucohoric acid are also intended to combat phyto pathogenic fungi.

A literature study has shown that the substituted 3,4-dichloro-5-propenoyloxy-2 (5H) furanones have not been prepared yet.

The present invention provides substituted 3,4-dichloro-5-propenoyloxy-2 (5H) furanones of formula (1),

Cl

R-CH = CH-COO

wherein R is phenyl, 3-chlorophenyl, 3,4-dichlorophenyl, 3-methoxyphenyl, 4-methylphenyl, 2-furyl, 5-nitro-2-furyl

The essence of the process for the preparation of substituted 3,4-dichloro-5-propenoyloxy-2 (5H) furanones is to substitute the chloride-substituted propenoic acid of formula II

R-CH · CH-COCl (11) or a mixed anhydride of formula II

R-CH * CHCOOCCF ₃ (III) wherein R is as defined above for acting on mucoicuric acid in an organic diluent, preferably benzene or toluene, at temperatures of 60-80 ° C.

Advantages of the process for the preparation of the compounds according to the invention are, inter alia, that the reaction of chlorides or mixed anhydrides of substituted propenoic acids with mucochloric acid is carried out in one step under undemanding conditions with good yield to give compounds I.

The following examples illustrate but do not limit the novel compounds and the process for their preparation.

Example 1

3,4-dichloro-5- (3-phenylpropenoyloxy) -2 (5H) furanone (1a)

3,4-Dichloro-5-hydroxy-2-furanone (2.1 g) in benzene (15 ml) and 3-phenyl-propenoic acid chloride (2.7 g) are heated at boiling point (until the HCl gas escapes). After completion of the reaction, 10 ml of benzene are distilled off, the residue is cooled and the crystallized product is recrystallized from benzene.

Example 2

3,4-dichloro-5- [3-73,4-dichlorophenyl] propenoyloxy] -2- (5H) furanone (1b)

3,4-dichloro-5-hydroxy-2-furanone / acid. mucochloric acid (2.1 g) in toluene and mixed trifluoroacetic anhydride and 5- (3-methoxyphenyl) propenoic anhydride were stirred at room temperature for 2 hours. After completion of the reaction, the solvent was distilled off in vacuo and the reaction product was recrystallized from methanol or benzene.

Similarly synthesized compounds: 3,4-dichloro-5- [3- (3-chlorophenyl) propenoyloxy] -2- (5H) furanone (IC); 3,4-dichloro-3- (4-methylphenyl) propenoyloxy] -2 (5H) furanone (1d); 3,4-dichloro-5- [3- (3-methoxyphenyl) propenoyloxy] -2 (5H) furanone (1e); 3,4-dichloro-5- [3-2-phenyl-propenoyloxy] -2 (5H) furanone (if); 3,4-dichloro-5- [3- (5-nitro-2-furyl) propenoyloxy] -2 (5H) furanone

1 H NMR spectra were recorded on an 80 MHz MS 487C Tesla spectrophotometer in hexadeuteroate using tetramethylsilane as an internal standard. Chemical shifts are given in ppm.

Table 1

Substituted 3,4-dichloro-5-propenoyloxy-2 (5H) furanones

Cl

Cl

R-CH = CH- to _Q > = - 0

Compound number summary formula / MH / Calcd / found % C% H% Cl % N MP: ° c (yield) la C H Cl 0 55,15 2.84 25,04 93 to 94 1 J O z. 0 / 283.1 / 55,10 2.72 25.20 / 75 / lb ^C 13 ^H 6 ^C 14 ° 3 44.35 1.72 40.28 145 to 148 / 352.0 / 44.32 1.70 40.26 / 70 / ic ^C 13 ^H 7 ^Cl 3 ° 4 49,17 2.22 33.49 92 to 95 / 317,6 / 49.07 2.08 33.39 / 65 / Id ^C 14 ^H 10 ^Cl 2 ° 3 56.59 3.39 23.86 85 to 86 / 297,1 / 56.49 3.29 23.76 / 65 / le ^C 14 ^H 10 ^Cl 2 ° 4 53.70 3.22 22.64 85 to 87 / 313.1 / 53.80 3.20 22.60 / 68 / If ^C 11 ^H 6 ^Cl 2 ° 4 48.38 2.21 25.96 100 to 101.5 / 273.1 / 48.40 2.28 25.92 / 60 / - Ig ^C 11 ^H 5 ^Cl 2 ^NO 6 41.54 1.58 22.29 4.40 135 to 138 / 218.1 / 41,38 1.70 22,09 4.32 / 60 /

TABLE 2 ¹ H NMR data of substituted 3,4-dichloro-5-propenoyloxy-2 (5H) furanones (Ia-Ie)

compound X ^h a H B ^J AB ^H c H Carom other ia H 7.92 6.63 16.0 7.24 7.37 to 8.87 ib _3,4-Cl2 7.90 6.67 16.0 7.24 7.62 to 8.12 ic 3-C1 7.92 6.75 16.0 7.27 7.37 to 7.87 Id 4- _C H ₃ 7.87 6.57 16.0 7.23 7.26 to 7.62 2.37 (CH ₃ ) Ie 3-OCH ₃ 7.90 6.66 16.0 7.26 6.93 to 7.50 3.85 (OCH ₃ )

Table 3

If

H

H "

A B

7.90 6.65 ^H AB

16.0

B

^H C

7.23 ^H 3

7.64 ^H 4 ^J 3.4

7.30 3.8

Table 1

The fungicidal activity of the compounds Ia to g

compound

Tilletia caries

Tusarium avenaceum

Botrytis cinerea

Alternaria

alternata

Phytophora infestans

Ia 3

Ib 3

Ic 0

Id 0 le 3

If 3 ig 3

Vitavax št. 4

Captan Šť.

Ditiane M-4567

The methodology for determining the efficacy is described in U.S. Pat. AO 248215.

Claims (2)

Substituted 3,4-dichloro-5-propenoyloxy-2 (5H) furanones of formula I Cl Cl / 1 / R-CH 2 CH-COO- < _O > = O where R is phenyl, 3-chlorophenyl, 3,4-dichlorophenyl, 3-methoxyphenyl, 4-methylphenyl, 2-furyl, 3-nitro-2-furyl 2. A process for the preparation of substituted 3,4-dichloro-5-propeonyloxy-2 (5H) furanones according to claim 1, characterized in that it is treated with a chloride substituted propenoic acid of the formula: R CHtsCH-COCl / 11 / or a mixed anhydride of formula IX R-CH _{'chloro-coooc-CF3} / 111 / wherein R is as defined above to the acid mukochiórovú in an organic diluent preferably benzene aiebo of toluene at 60 DEG-80 DEG C. .