FR2765579A1 - NOVEL 4-HYDROXY-2H-1- (THIO) PYRAN-2-ONES DERIVATIVES, THEIR PREPARATIONS AND THEIR USES AS RODONTICIDES - Google Patents

Abstract

The invention concerns novel 4-hydroxy-2H-1-(Thio)pyran-2-ones corresponding to formula (I) in which: R1 represents a halogen, a C1-C6 alkoxy radical, a C1-C7 alkyl radical, a trifluoromethyl radical, a cyano radical; R2 represents hydrogen, a C1-C7 alkyl radical, an aralkyl radical, a (hetero)aryl radical, a cyclohexyl radical; R3 and R4 represent hydrogen, a C1-C7 alkyl radical, or together can for a benzene ring, a heterocycle or a -(CH2)n group with n = 3.5; X represents O or S. The compounds are useful as rat poison.

Description

The present invention relates to 4-hydroxy-2H-1- (thio) pyran-2-ones, their

preparation

  and their use as rodenticides.

  The use of 4-hydroxy-2H-1- (thio) pyran-2-ones derivatives in the fight against

  rodents has been described in US Patents 3,764,693, US 3,957,824, EP 161,163.

  The subject of the present invention is new derivatives of 4-hydroxy-2H-1 (thio) pyran- 2-ones represented by formula I. R3

R4 / "X"

  Ri in which: X represents O or S, R1 represents hydrogen, a halogen, a CO-C6 alkoxy radical, a C1-C7 alkyl radical, a trifluoromethyl radical, a cyano radical, R2 represents hydrogen, a C1-C7 alkyl radical, an aralkyl radical, a (hetero) aryl radical, a cyclohexyl radical, R3 and R4 represent hydrogen, a C1-C7 alkyl radical or can form a ring

  benzene, a heterocycle or a group - (CH2) n- with n = 3-5.

  The term C1-C7 alkyl means that the radical can be linear or branched and that it can comprise from 1 to 7 carbon atoms such as methyl, ethyl, propyl, isopropyl,

  butyl, tert-butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, heptyle.

  The term "aralkyl" represents a group of formula:

RS, (CH2) -

R5

  with R5 = H, C1-C7 alkyl, halogen, C1-C6 alkoxy and n = 1-3.

  The term "(hetero) aryl" represents an aromatic ring such as phenyl, naphthyl,

  or an aromatic heterocycle such as thienyl, furyl, pyridyl, quinolinyl.

  The term "heterocycle" designates a ring with an aromatic or non-aromatic character comprising 3 to 11 atoms including 1 to 4 identical or different heteroatoms chosen from oxygen, sulfur and nitrogen, such as, for example, furyl, tetrahydrofuryl, thienyl, imidazolyl , quinolinyl. The compounds of the invention may contain chiral centers. Derivatives such as

  optical isomers, racemates, enantiomers are part of the invention.

  The Applicant has found that the compounds of general formula I have shown a

  real activity as rodonticides, their essential property being an anticoagulant effect.

  The rodonticidal activity of this compound has been shown in tests carried out on

  wild rodents (Rattus Norvegicus, Mus-Musculus).

  For this, a bait dosed at 25 ppm of substance to be examined is prepared by impregnation of wheat EPPO method. This bait is then given for 3 days to wild male or female rodents. The activity is examined by determining the

I0 mortality.

  By way of example, the compound of Example 1 at the dose of 25 ppm administered to rats

  wild (Rattus Norvegicus), resulted in 100% mortality.

  Among the preferred compounds of formula I, there may be mentioned for example: 3 (4- (4-bromophenyl) -benzyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1- (4'bromobiphenyl- 4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzopyran-2 -one 3- (1 - (4'bromobiphenyl-4-yl) -1 -cyclohexyl-methyl) -4-hydroxy-2H-1 -benzopyran-2one 3- (1 - (4'-bromobiphenyl-4-yl) -2-methyl-propyl) -4-hydroxy-2H-1 benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 benzothiopyran-2- one 3 - ((1- (4'-bromobiphenyl-4-yl) -2-phenyl) -ethyl) -4hydroxy-2H-1 -benzopyran-2-one 3 - ((1 I- (4'-bromobiphenyl- 4-yl) -3-methyl) butyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -33-dimethyl-butyl) -4- hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'fluorobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1- (4 ' trifluoromethylbiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 - benzothiopyran-2- one 3- ( 1- (4'-methylbiphenyl-4-yl) -ethyl) -4-hydroxy-1 -benzopyran-2-one 3- (1 - (4'-isopropylbiphenyl-4-yl) -ethyl) -4-hydroxy- 1 -benzopyran-2-one 3- (1 - (4'cyanobiphenyl-4-yl) -ethyl) -4-hydroxy-1 -benzopyran-2-one 3 - (- 1 (4'-bromobiphenyl-4-yl ) -3-methyl-butyl) -4-hydroxy-2H-1 -benzothiopyran-2one 3 - (- 1- (4'-bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H-1 -benzopyran2- one 3 - (- 1 - (4'-bromobiphenyl-4-yl) -methyl-pentyl) -4-hydroxy-2H-1 benzopyran-2-one 3- (1- (4'-bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H-1 benzothiopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -butyl) -4-hydroxy-2H-1 -benzothiopyran-2-one 3- (1 - (4'-bromodiphenyl-4-yl) -butyl) -4-hydroxy-2H- 1 -benzopyran-2-one 3 The invention also relates to a process for the preparation of the compounds of formula I. This is summarized in Figure 1 TO Figure 1

Stage I1-

R / \ CI- R2 R2

  R - R IV Stage 2: RR IV V Stage 3: OH R

I * R, R

R4 O OH

VI V

  OH Rz R3 (11R In stage 1, a biphenyl derivative (II) is reacted with an acid chloride (111), in particular in a solvent such as carbon sulphide or methylene chloride and

  in the presence of aluminum chloride.

  In stage 2, the ketone group is reduced to alcohol, in particular using sodium borohydride, in a solvent such as ethanol, methanol.

  In stage 3, the alcoholic derivative is condensed with a 4-hydroxy-2H-1 (thio) pyran-

  2-one, in particular in a solvent such as acetic acid, in the presence of sulfuric acid and at a temperature between 20 C and 150 C. The compounds of the invention have excellent rodonticidal properties such as

  this has been shown in tests with wild rodents.

  The compounds of the invention and in particular the compound of Example 1 constitute anticoagulant active substances of rodonticidal composition in combination with a

  support consumable by rodents.

  Examples are given below which illustrate the invention without limitation: ls Example I: 3- (1-4'-Bromobiphenyl-4-yl) -3-methylbutyl) -4-hydroxy-2H-1- benzopyran-2-one C26H23BrO3 PM = 463.38 Br a) 559.2 g (2.4 moles) of 4-bromobiphenyl are dissolved in 3.6 liters of methylene chloride. Then added in 15 minutes 304.8 ml (2.4 moles) of isovaleryl chloride. The mixture is cooled to 10 ° C. and 352.8 g (2.6 moles) of aluminum chloride are added over 1 hour. The temperature is brought to 21 ° C. and the mixture is brought to stirring for 3 hours at this temperature. Pour into 15 liters of water containing 0.5 liters of concentrated hydrochloric acid. Decanted, extracted with 2 x 1.5 liters of methylene chloride, washed with 5 liters of 10% sodium hydroxide and then with 5 liters of water. After

  decantation and drying are concentrated under vacuum. We obtain 661 g of 1- (4'-

  bromobiphenyl-4-yl) -3-methyl-1-oxo-butane which is recrystallized from ethanol.

Weight obtained: 518 g (Yield: 68%)

PFK = 100 C

  lRPc = o0: 1680 cm-1 b) 158.5 g (0.5 mole) of 1- (4'-bromobiphenyl4-yl) -3-methyl-1-oxo-butane are placed in 2 liters of ethanol. The mixture is brought to reflux with stirring to dissolve. 150 g of Kataboran (alkaline sodium borohydride solution) are then added and the reflux is maintained for 2 hours. A white precipitate forms. The mixture is left stirring for 1 hour at room temperature. We pour in 15 liters of water. After extraction with 2 x 3 liters of methylene chloride, washing with 10 liters of water and drying, the organic phase is concentrated under vacuum at 40 C. 153 g of

  1- (4'-bromobiphenyl-4-yl) -1-hydroxy-3-methyl-butane.

YId: 95.8%

PFK = 95 C

IRyOH: 3350 cm- '

  c) 166 g (0.52 mole) of 1- (4'-bromobiphenyl-4-yl) -1hydroxy-3-methyl- are dissolved.

  butane and 100.7 g (0.61 mole) of 4-hydroxycoumarin in 1.4 liters of acetic acid. The mixture is brought to reflux and 14.2 ml of concentrated sulfuric acid are added over 30 minutes. The reflux is maintained for 2 hours. It is cooled and then poured into 17 liters of water. Extraction is carried out with 10 l of ethyl ether. After decantation, the organic phase is taken up in 6 liters of 10% sodium hydroxide. An oily layer forms between the ethereal phase and the aqueous phase. This oil is isolated and dissolved in 5 liters of ethyl acetate. Then treated with 2.5 liters of 1/2 hydrochloric acid, decanted, washed the organic phase with water, dried and concentrated in vacuo, 142 g of the product of Example 1 are obtained. After recrystallization from 1 'acetic acid,

  119.5 g of a white solid are obtained.

YId: 49.6%

PFG = 172-175 C

  IRóc = o: 1668 cm "1 IRYoH: 3256 cm-1 1H NMR (CDCI3) ô in ppm: 1.04 (dd, 2CH3); 1.63-1.67 (m, CH); 2.15-19 , 4 (m, CH2); 4.72 (m, CH); 6.3 (s, OH); 7.24-7.7 (m, 12 AR) Weight analysis: C% H% Br% / 0 0% Calculated 67.39 5.00 17.24 10.36 Found 67.13 5.07 16.99

Example 2:

  3- (4- (4-Bromophenyl) -benzyl) -4-hydroxy-2H-1 -benzopyran-2-one C22H15BrO3 PM = 407.27 OH Br

PFG = 275-279 C

  IRyc = o 1670 cm1 IRyOH: 3250 cm '1H NMR (DMSO) 6 in ppm 4.07 (s, CH2); 7.47-8.15 (m, 12 AR) Weight analysis: C% H% Br% / Calculated 64.88 3.71 19.62 Found 64.64 3.79 19.29

Example 3:

  3- (1 - (4'-Bromobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one C23H17BrO3 PM = 421.29 OH Br

PFG = 204-212 C

  IRmo: 1680 cm 'IRYoH: 3250 cm1 1H NMR (CDCI3) 5 in ppm: 1.51 (d, CH3); 4.58 (q, CH); 5.87 (s, OH); 7.05-7.5 (m, 12 AR) Weight analysis: C% H% Br% Calculated 65.57 4.07 18.97 Found 65.81 3.88 19.17

Example 4:

  3- (1- (4'-Bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzopyran-2-one C26H23BrO3 PM = 463.38 OHX Br o PFG = 146-150 CI R4. = o: 1680 cm 'IRoH: 3250 cm1 1H NMR (CDCI3) 5 in ppm 0.97 (t, CH3); 1.5 (m, 2CH2); 2.24 (m, CH2) 4.69 (t, CH); 6.65 (s, OH); 7.31-7.81 (m, 12 AR) Dondérale Analysis: C% H% Br% / o Calculated 67.39 5.00 17.25 Found 67.19 4.80 16.94

Example 5:

  3- (1 - (4'-Bromobiphenyl-4-yl) -1 -cyclohexyl-methyl) -4-hydroxy-2H-1 benzopyran-2-

one C28H25BrO3 PM = 489.41 OHX Br

PFG = 205-209 C

  IR.yc, = o: 1660 cm- 'IROH: 3250 cm-' 1H NMR (DMSO) 6 in ppm: 1-1.85 (m, 5CH2); 2.9-3 (m, CH); 4.35 (m, CH); 7.52-8.23 (m, 12 AR) Weight analysis: C% H% BrI / o Calculated 68.71 5.15 16.33 l0 Found 68.41 5.24 16.33

Example 6:

  3- (1 - (4'-Bromobiphenyl-4-yl) -2-methyl-propyl) -4-hydroxy-2H-1 benzopyran-2-one C25H21BrO3 PM = 449.35 OH Br

PFG = 163-168 C

  I Ryc = o: 1670 cm1 IRrOH: 3250 cm "1H NMR (CDCI3) 6 in ppm: 1.28 (d, 2CH3); 3.23 (m, CH); 4.4 (m, CH); 7, 31-8.02 (m,

12 AR)

  Weight analysis: C% H% Br% Calculated 66.82 4.71 17.79 Found 67.07 4.82 17.69

Example 7:

  3- (1 - (4'-Bromobiphenyl-4-yl) -ethyl-4-hydroxy-2H-1 -benzothiopyran-2-one C23H17BrO2S PM = 437.36 OH g 'OBr

PFG = 138-140 C

  IRP, .o: 1580 cm'1 IRyOH: 3330 cm1 1H NMR (CDCI3) ô in ppm: 1.67 (d, 2CH3); 5.14 (q, CH); 6.16 (s, OH); 7.27-8.01 (m,

12 AR)

  0o Weight analysis: C% H% Br% S% Calculated 63.16 3.92 18.27 7.33 Found 63.02 3.89 17.83 7.25

Example 8:

  1i 5 3- (1 - (4'-Bromobiphenyl-4-yl) -2-phenyl-ethyl) -4-hydroxy-2H-1 benzopyran-2-one C29H21BrO3 PM = 497.39 OH Br

PFG = 221-226 C

IRyc = o: 1665 cm'1 IRFOH: 3150 cm '

  1H NMR (DMSO) ô in ppm: 3.17-3.23 (m, CH); 3.42-3.5 (m, CH); 4.66 (m, CH); 6.85-

  7.7 (m, 17 AR) Weight analysis: C% H% Br% Calculated 70.03 4.26 16.07 Found 69.99 4.26 15.93

Example 9:

  3 - (- 1 - (4'-Bromobiphenyl-4-yl) -3-3-dimethyl-butyl) -4-hydroxy-2H-1 benzopyran-2-

one C27H25BrO3 PM = 477.40

OH /

Br

PFG = 233-235 C

  I1R C = o: 1675 cm-1 IRPOH: 3180 cm 'H NMR (DMSO) 6 in ppm 0.67 (s, 3CH3); 1.78-1.84 (dd, CH); 2.18-2.26 (dd, CH) 4.38 (m, CH); 7.1-7.83 (m, 12 AR) Weight analysis: C% H% Br / o Calculated 67, 93 5.28 16.74 Found 67.97 5.30 16.59

Example 10:

  3- (1 - (4'-Fluorobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1-benzopyran-2-one

C23H17FO3 PM = 360.39

OH 1l

PFG = 168-170 C

  IRyc = o: 1670 cm 'IRoH: 3250 cm' 1H NMR (CDCI3) 5 in ppm: 1.75 (d, 3CH3) 4.82 (q, CH); 6.38 (s, OH); 7.15-7.77 (m,

12 AR)

  Weight analysis: C% H% Br% Calculated 76, 65 4.76 5.27 Found 76.41 4.98 5.28

Example 11:

  3- (1 - (4'-Trifluoromethylbiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 benzopyran-2-one

C24H17F303 PM = 410.40

OH

15 .... CF3

PFG = 207-209 C

  IRrc = o: 1675 cm- 'IRyOH: 3230 cm' 1H NMR (CDCI3) 5 in ppm: 1.58 (d, CH3); 4.65 (q, CH); 5.92 (s, OH); 7.1-7.56 (m, 12 AR) Weight analysis:

C% H% F%

  Calculated 70.24 4.18 13.89 Found 69.95 4.10 13.96

Example 12:

  3- (1 - (4'-Bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzothiopyran-2one C26H23BrO2S PM = 479.44 OH Br

PFG = 136-137 C

  IRYc = o: 1590 cm "IRyOH: 3250 cm-1 'H NMR (CDCI3) 6 in ppm: 0.93 (t, CH3); 1.44 (m, 2CH2); 2-2.27 (m, CH2 ); 5.5 (t, CH); 6.24 (s, OH); 7.28-8.03 (m, 12 AR) Weight analysis: C% H% Br% / S% Calculated 65.13 4 , 84 16.67 6.69 Found 64.86 5.01 16.67 6.86

Example 13:

  3-1 - (4'-Methylbiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one

C24H2003 PM = 356.43

OH

PFG = 227-231 0 C

  IRyc = o: 1670 cm 'IRyoH: 3230 cm1 H NMR (DMSO) 6 in ppm: 1.57 (d, CH3); 2.24 (s, CH3); 4.55 (m, CH); 7.15-7.95 (m,

12 AR)

Weight analysis:

C% H%

  Calculated 80.88 5.66 Found 80.64 5.80

Example 14:

  3- (1 - (4'-Isopropylbiphenyl-4-yl) -ethyl) -4-hydroxy-2H-benzopyran-2-one

C26H2403 PM = 384.48

OH

PFG = 210-220 C

  IRyc = o: 1675 cm1 IRyOH: 3230 cm- '1H NMR (CDCI3) 5 in ppm: 1.31 (d, 2CH3); 1.66 (d, CH3); 2.98 (m, CH); 4.78 (m, CH); 6.08 (s, OH); 7.22-7.70 (m, 12 AR) Weight analysis:

C% H%

  Calculated 81.22 6.29 Found 81.28 6.34

Example 15:

  3- (1 - (4'-Cyanobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one

C24H17NO3 PM = 367.41

OH N

PFG = 227-230 C

  IRyc.0: 1665 cm 'IRyOH: 3180 cm "1H NMR (CDCI3) 5 in ppm: 1.75 (d, CH3); 4.80 (q, CH); 5.95 (s, OH); 7, 26-7.78 (m, 12 AR) Weight analysis

C% H% N%

  Calculated 78.46 4.66 3.81 Found 78, 37 4.63 3.75

Example 16:

  3 - (- 1 - (4'-Bromobiphenyl-4-yl) -3-methyl-butyl) -4-hydroxy-2H-1 benzothiopyran-2-

one C26H23BrO2S PM = 479.44 OH y

PFG = 105-106 C

  IRyc = o: 1590 cm-1 1H NMR (CDCI3) b in ppm: 1.04 (d, d, 2CH3); 1.63 (m, CH); 1.93-2.11 (m, CH2); 5.16 (m, CH); 6.25 (s, OH); 7.2-8.02 (m, 12 AR) Weight analysis: C% H% Br% S% Calculated 65.13 4.84 16.67 6.69 Found 65.27 4.95 16.54 6.91

Example 17:

  33-1 - (4'-Bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H-1 -benzopyran-2-one C24H19BrO3 PM = 435.3 OH / CSA00

PFG = 194-195 C

  IR.c = o: 1670 cm 'IRroH: 3270 cm'1 1H NMR (DMSO) 6 in ppm: 0.81 (t, CH3); 2.01-2.4 (m, CH2) 4.31 (m, CH) 7.09-7.95 (m, 12 AR) Weight analysis: C% H% Br / o Calculated 66.22 4.40 18.36! O Found 66.34 4.22 18.08

Example 18:

  3 - (- 1 -4'-Bromobiphenyl-4-yl) -4-methyl-pentyl) -4-hydroxy-2H-1 benzopyran-2-one C27H25BrO3 PM = 477.40 OH Br

PFG = 203-206 C

  IRc.o: 1680 cm 'IRoH: 3200 cm "1H NMR (CDCI3) 6 in ppm: 1.15 (d, d, 2CH3); 1.58 (m, CH2) 1.86 (m, CH) 2, 36 (m, CH2); 4.83 (t, CH); 6.62 (s, OH); 7.49-7.96 (m, 12 AR) Dondérale Analysis: C% H% Br / o Calculated 67 .93 5.28 16.74 Found 68.33 5.21 16.90

Example 19:

  3- (1 -4'-Bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H-1 -benzothiopyran-2- one C24H19BrO2S PM = 451.39 OH Br

PFG = 177-181 C

  IRc = o: 1590 cm-1 IRyOH: 3230 cm-1 1H NMR (CDC13) 8 in ppm: 1.25 (t, CH3); 2.18-2.56 (m, CH2); 5.15 (m, CH); 6.4 (s, OH); 7.37-8.19 (m, 12 AR) Weight analysis: C% H% Br / o S% Calculated 63.86 4.24 17.71 7.10 1o Found 63.93 4.14 17.41 7 . 06

Example 20:

  3- (1 - (4'-Bromobiphenyl-4-yl) -butyl) -4-hydroxy-2H-1 -benzothiopyran-2- one C25J21BrO2S PM = 462.41 OHJ v - Br

PFG = 134-136 C

  IRYc = o: 1590 cm- 'IRyOH: 3425 cm1 H NMR (CDCI3) 5 in ppm: 0.92 (t, CH3); 1.41 (m, CH2); 1.96 (m, CH2); 4.98 (m, CH); 6.17 (s, OH); 7.26-7.93 (m, 12 AR) Weight analysis: C% H% Br / o S% Calculated 64.52 4.55 17.17 6.89 Found 64.52 4.52 17.04 6, 55

Example 21:

  3- (1 - (4'-Bromobiphenyl-4-yl) -butyl) -4-hydroxy-2H-1 -benzopyran-2-one C25H21BrO3 PM = 449.35 OH) Br

PFG = 161-163 C

  IRyc = o: 1670 cm- 'IRyoH: 3300 cm' 1H NMR (CDCI3) ô in ppm: 1.5 (t, CH3); 1.65 (m, CH2); 2.28 (m, CH2); 4.79 (m, CH); 6.54 (s, OH); 7.39-7.87 (m, 12 AR) Weight analysis: C% H% Br0 / o Calculated 66.82 4.71 17.79 Found 66.69 4, 79 17.64

Claims (4)

  1) 4-Hydroxy-2H-1 - (thio) pyran-2-ones of formula I: OH R   R3R in which: X represents O or S, R1 represents hydrogen, a halogen, a C1-C6 alkoxy radical, a C1-C7 alkyl radical, a trifluoromethyl radical, a cyano radical, R2 represents hydrogen, a C1-C7 alkyl radical, an aralkyl radical, a (hetero) aryl radical, a cyclohexyl radical, R3 and R4 represent hydrogen, a C1-C7 alkyl radical, or can form   together a benzene ring, a heterocycle or a group - (CH2) n- with n = 3-5.   2) Compounds according to claim 1 characterized in that X is oxygen.   3) Compounds according to claim 1 characterized in that X is a sulfur.   Is 4) Compounds according to claim 1, chosen from the following compounds: 3- (4- (4-bromophenyl) -benzyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1- (4 ' bromobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 (4'-bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzopyran -2-one 3- (1 (4-bromobiphenyl-4-yl) -I -cyclohexyl-methyl) -4-hydroxy-2H-1 -benzopyran2-one 3- (1- (4'-bromobiphenyl-4-yl ) -2-methyl-propyl) -4-hydroxy-2H-1 benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 benzothiopyran-2 -one 3- (1 - (4'-bromobiphenyl-4-yl) -2-phenyl-ethyl) -4hydroxy-2H-1 -benzopyran-2-one 3 - ((1 - (4'-bromobiphenyl-4- yl) -3-methyl) butyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -33-dimethyl-butyl) -4-hydroxy- 2H-1 -benzopyran-2-one 3- (1- (4'fluorobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'trifluoromethylbiphenyl- 4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3 (1 - (4'-bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzothiopyran-2 -one 3- (1 - (4'-methylbiphenyl-4-yl) -ethyl) -4-hydroxy-1 -benzopyran-2-one 3- (1 (4'-isopropylbiphenyl-4-yl) -ethyl) -4-hydroxy-1 - benzopyran-2-one 3- (1 (4'cyanobiphenyl-4-yl) -ethyl) -4-hydroxy- 1 -benzopyran-2-one 3 - (- 1 - (4'bromobiphenyl-4-yi) -3 -methyl-butyl) -4-hydroxy-2H- 1 -benzothiopyran-2- one 3 - (- 1 - (4'-bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H- 1 -benzopyran-2 - one 3 - (- 1 - (4'-bromobiphenyl-4-yl) -methyl) -pentyl) -4-hydroxy-2H- 1 benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4- yl) -propyl) -4-hydroxy-2H- 1 -benzothiopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -butyl) -4-hydroxy- 2H-1 -benzoth iopyran-2 -one 3- (1 - (4'-bromobiphenyl-4-yl) -butyl) -4hydroxy-2H- 1 -benzopyra n-2-one) Process for the preparation of the compounds of formula I according to claim 1, which consists: - reacting a biphenyl derivative of formula II Ri in which R1 has the meaning given to claim 1, with an acid chloride of formula III: ci R2 III in which R2 has the meaning given to claim 1, to obtain a compound of formula IV: R1 R2   - to reduce the ketone compound of formula IV to alcohol of formula V: OH - to condense the compound of formula V with a 4-hydroxy-2H-2 (thio) pyran-2-one of formula VI: OH Vt R: I R4 o in which R3 and R4 have the meaning given to claim 1, to obtain a compound of formula I. 6) Rodonticidal composition characterized in that it contains as active substance a compound according to claim 1 in association with a consumable carrier by rodents.   7) Rodonticidal composition according to claim 6, characterized in that it contains   as active substance 3 - ((- 1- (4'-bromobiphenyl-4-yl) -3-methyl) butyl) -4-hydroxy- 2H-1 -benzopyran-2-one.