AU2004288759B2 - Ortho-substituted pentafluoride sulfanyl-benzenes, method for the production thereof and the use thereof in the form of valuable synthesis intermediate stages - Google Patents

Description

1 Ortho-substituted pentafluoride sulfanyl-benzenes, method for the production thereof and the use thereof in the form of valuable synthesis intermediate stages 5 The chemistry of pentafluorosulfanyl derivatives has gained importance in the last few years, especially since novel preparation processes have been found (Tetrahedron 56 (2000) 3399; Organic Letters 4(17) (2002) 3013). However, to date only very few compounds are known which bear substituents other than hydrogen and fluorine on a phenyl ring in the ortho 10 position to the pentafluorosulfanyl group. The only known synthetic route (Journal of Fluorine Chemistry 112 (2001) 287) uses expensive reagents such as AgF2 and is afflicted with poor yields. The authors account for this by the large bulk of the pentafluorosulfanyl group which generally makes ortho-substitution very difficult. This opinion is also shared by other authors 15 (J. Am. Chem. Soc. 84 (1962) 3064). It is therefore surprising that it is possible to electrophilically substitute in the ortho-position to the pentafluorosulfanyl group. In this way, novel ortho-substituted pentafluorosulfanylbenzenes are obtained which constitute valuable intermediates, for example for preparing medicaments, diagnostic aids, 20 liquid crystals, polymers, pesticides, herbicides, fungicides, nematicides, parasiticides, insecticides, acaricides and arthropodicides. The invention relates to pentafluorosulfanylbenzenes of the formula I R4 R5 R3 F F Sl' R2 F F R1 25 where R1 is Cl, Br, I, -S02R6 or N02; R6 is OH, F, Cl, Br, I or alkyl having 1, 2, 3 or 4 carbon atoms; R2 and R4 are each independently hydrogen F, Cl, Br, I, -CN, 30 NR9R1 0, -OR11, -SR1 2, -COR1 3, -(SOr)s-(CH2)t-(CF2)u-CF3, alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms, cycloalkyl having 3, 4, 5, 6, 7 or 8 carbon atoms, in which 1, 2, 3 or 4 hydrogen atoms may be replaced by fluorine 2 atoms; R9 and R10 are each independently alkyl having 1, 2, 3 or 4 carbon atoms, -(CH2)v-(CF2)w-CF3, alkylcarbonyl having 1, 2, 3 or 4 carbon 5 atoms, alkylsulfonyl having 1, 2, 3 or 4 carbon atoms; or R9 and R10, together with the nitrogen atom bearing them, form a heterocycle of the formula Ilia: 0 N | O Ilia 10 R11 and R12 are each independently hydrogen, alkyl having 1, 2, 3 or 4 carbon atoms, -(CH2)v-(CF2)w-CF3, alkylcarbonyl having 1, 2, 3 or 4 carbon atoms, alkylsulfonyl having 1, 2, 3 or 4 carbon atoms; R13 is OH, alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms or alkoxy having 1, 2, 3, 4, 5 or 6 carbon atoms; 15 s is zero; t and u are each independently zero or 1; v and w are each independently zero or 1; where at least one of the R2 and R4 radicals is not hydrogen, CI, CN, 20 COR1 3 or -(SOr)s-(CH2)t-(CF2)u-CF3; R3 is hydrogen, F, CI, Br, I, -CN, -N02, -COR14, -SO 2

CH

3 , alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms, alkoxy having 1, 2, 3 or 4 carbon atoms, -Ox-(CH2)y-CF3, 25 R14 is OH, alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms, alkoxy having 1, 2, 3, 4, 5 or 6 carbon atoms or -Oaa-(CH2)bb-CF3; x is zero or 1; y is zero, 1, 2 or 3; 30 aa is zero or 1; bb is zero, 1, 2 or 3; R5 is hydrogen or F; 3 and salts thereof; excluding compounds of the formula I in which R2 and R4 are each Cl and R3 is F or CI, 5 excluding compounds of the formula I in which one of the R2 and R4 substituents is CI and the other of the R2 and R4 substituents is CN and R3 is CI and excluding compounds of the formula I in which R1 is N02 and the other substituents are each hydrogen. 10 In a further embodiment, preference is given to compounds of the formula I in which R5 is described by hydrogen or F; particular preference is given to compounds of the formula I in which R5 is described by hydrogen. 15 Radicals which occur more than once may be the same or different and each independently have the definitions specified. When the substituents R1 to R5 contain one or more centers of asymmetry, they may each independently have either the S or the R configuration. The 20 compounds may be in the form of optical isomers, of diastereomers, of racemates or of mixtures thereof in all ratios.

5 10 15 Pages 4-12 have been left blank intentionally. 20 25 30 35 13 The present invention encompasses all tautomeric forms of the compounds of the formula 1. Alkyl radicals may be straight-chain or branched. This also applies if they 5 bear substituents or occur as substituents of other radicals, for example in fluoroalkyl radicals or alkoxy radicals. Examples of alkyl radicals are methyl, ethyl, n-propyl, isopropyl (= 1 -methylethyl), n-butyl, isobutyl (= 2-methylpropyl), sec-butyl (= 1 -methylpropyl), tert-butyl (= 1,1-dimethylethyl), n-pentyl, isopentyl, tert-pentyl, neopentyl and hexyl. 10 Preferred alkyl radicals are methyl, ethyl, n-propyl and isopropyl. One or more, for example 1, 2, 3, 4 or 5, hydrogen atoms in alkyl radicals may be replaced by fluorine atoms. Examples of such fluoroalkyl radicals are trifluoromethyl, 2,2,2-trifluoroethyl and pentafluoroethyl. Substituted alkyl radicals may be substituted in any positions. 15 Examples of cycloalkyl radicals are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. In cycloalkyl radicals, one or more, for example 1, 2, 3 or 4, hydrogen atoms may be replaced by fluorine atoms. Substituted cycloalkyl radicals may be substituted in any positions.

14 Phenyl radicals may be unsubstituted or be mono- or polysubstituted, for example mono-, di- or trisubstituted, by identical or different radicals. When a phenyl radical is substituted, it preferably has one or two identical or different substituents. This likewise applies to substituted phenyl radicals in 5 groups such as, for example, phenylalkyl or phenyloxy. In monosubstituted phenyl radicals, the substituent may be in the 2-position, 3-position or 4-position. Disubstituted phenyl may be substituted in the 2,3-position, 2,4-position, 2,5-position, 2,6-position, 3,4-position or 3,5-position. The substituents in trisubstituted phenyl radicals may be in the 2,3,4-position, 10 2,3,5-position, 2,4,5-position, 2,4,6-position, 2,3,6-position or 3,4,5-position. Heteroaryl radicals are aromatic ring compounds in which one or more ring atoms are oxygen atoms, sulfur atoms or nitrogen atoms, for example 1, 2 or 3 nitrogen atoms, 1 or 2 oxygen atoms, 1 or 2 sulfur atoms or a 15 combination of different heteroatoms. The heteroaryl radicals may be attached via all positions, for example via the 1-position, 2-position, 3-position, 4-position, 5-position, 6-position, 7-position or 8-position. Heteroaryl radicals may be unsubstituted or be mono- or polysubstituted, for example mono-, di- or trisubstituted, by identical or different radicals. 20 This applies likewise to heteroaryl radicals, for example in the heteroarylalkyl radical. Examples of heteroaryl are furanyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, indazolyl, quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, quinazolinyl and cinnolinyl. 25 Heteroaryl radicals are in particular 2- or 3-thienyl, 2- or 3-furyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 1-, 3-, 4- or 5-pyrazolyl, 1,2,3-triazol 1-, -4- or -5-yl, 1,2,4-triazol-1-, -3- or -5-yl, 1- or 5-tetrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 1,2,3-oxadiazol-4- or -5-yl, 1,2,4-oxadiazol-3- or -5-yl, 1,3,4-oxadiazol-2-yl or -5-yl, 2-, 4- or 5-thiazolyl, 30 3-, 4- or 5-isothiazolyl, 1,3,4-thiadiazol-2- or -5-yl, 1,2,4-thiadiazol-3 or -5-yl, 1,2,3-thiadiazol-4- or -5-yl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, 3- or 4-pyridazinyl, 2- or 3-pyrazinyl, 1-, 2-, 3-, 4-, 5-, 6- or 7 indolyl, 1-, 2-, 4- or 5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-indazolyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolyl, 1-, 3-, 4-, 5-, 6-, 7- or 8-isoquinolyl, 2-, 4-, 5-, 6-, 35 7- or 8-quinazolinyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-, 3-, 5-, 6-, 7- or 8-quinoxalinyl, 1-, 4-, 5-, 6-, 7- or 8-phthalazinyl. Also included are the corresponding N-oxides of these compounds, for example 1-oxy-2-, -3 or -4-pyridyl.

15 Particularly preferred heteroaromatic radicals are 2- or 3-thienyl, 2- or 3-furyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolyl, 1-, 3-, 4- or 5-pyrazolyl, 2-, 3- or 4-pyridyl, 2- or 3-pyrazinyl, 2-, 5 4-, 5- or 6-pyrimidinyl and 3- or 4-pyridazinyl. The invention further relates to a process for preparing the compounds of the formula I or the salts thereof, which comprises converting compounds of the formula il by electrophilic aromatic substitution to compounds of the 10 formula I R4 R4 R5 R3 R5 R3 F | F I F--\ F1!5/ R2 Fs R2FF F \S F F F R1 where R1 to R5 are each as defined above. In the preparation of the compounds of the formula 1, the procedure is to 15 carry out an electrophilic aromatic substitution, preferably a halogenation, chlorosulfonation or nitration. In one embodiment, halogenation (R1 = Cl, Br or 1) is affected as described in R.C. Larock, Comprehensive Organic Transformations: A Guide to Functional Group Preparations, VCH Publishers, New York, Weinheim, 20 1999, pages 619-628 and in the literature cited therein. The chlorination is effected, for example, with NCIS in an inert solvent, for example isopropanol, CHC 3 , CH 2 Cl 2 or EA at a temperature between -30*C and 100*C, preferably between 40 0 C and the boiling point of the solvent. In another embodiment, sulfonation or chlorosulfonation (R1 = S0 2 R6 25 where R6 is OH or CI) is effected as described in March's Advanced Organic Chemistry 5th edition 2001, pages 702-703 and in the literature cited therein. In another embodiment, nitration (R1 = N02) is effected as described, for example, in Houben-Weyl, Methoden der organischen Chemie, 4th edition, 30 Organo-Stickstoff-Verbindungen IV, part 1, Georg Thieme Verlag Stuttgart 1992, pages 262-341 and in the literature cited therein. Compounds of the formula 11 where R3 = COOH are nitrated, for example, with a mixture of 16 90% HNO 3 and 96% H 2

SO

4 at a temperature between -40*C and 80 0 C, preferably between 0*C and 40 0 C. From the compounds of the formula I where R1 = N02, it is possible to 5 prepare the corresponding anilines (R1 = NH 2 ) as described in R.C. Larock, Comprehensive Organic Transformations: A Guide to Functional Group Preparations, VCH Publishers, New York, Weinheim, 1999, 821-828 and the literature cited therein. From these anilines, it is possible to synthesize, via the diazonium salts by methods known to those 10 skilled in the art, as described, for example, in Houben-Weyl, Methoden der organischen Chemie, 4th edition, Organo-Stickstoff-Verbindungen I, part 2, Georg Thieme Verlag Stuttgart 1990, pages 1060-1136 and in the references cited therein, the compounds of the formula I with further definitions of R1. 15 The starting compounds of the formulae 11 are commercially available or can be prepared by processes similar to those described in the literature and/or known to those skilled in the art. 20 In the starting compounds, functional groups may also be present in protected form or in the form of precursors, and then be converted to the desired groups in the compounds of the formula I prepared by the process described above. Appropriate protecting group techniques are known to those skilled in the art. 25 The workup and, if desired, the purification of the products and/or intermediates is effected by conventional methods such as extraction, chromatography or crystallization and conventional dryings. 30 Also claimed are the compounds of the formula I and/or the salts thereof for use as a synthetic intermediate, in particular for use as a synthetic intermediate for preparing medicaments, diagnostic aids, liquid crystals, polymers, pesticides, herbicides, fungicides, nematicides, parasiticides, insecticides, acaricides and arthropodicides. 35 Examples of the various possible uses of pentafluorosulfanyl derivatives are described in the following publications: WO 9421606, WO 03093228 (insectides, acaricides); DE 19711953, GB 2276379 (herbicides); 17 DE 10124480, DE 10353658, Angew. Chem. 1999, 111, 2174, Angew. Chem. 2000, 112, 4384 (liquid crystals); WO 03097591, DE 10353202 (medicaments, diagnostic aids); US 5220070, US 5302692 (polymers); WO 03093228, WO 9625401 (pesticides); GB 2276381, GB 2276380 5 (fungicides), US 5637607 (nematicides), WO 9947139 (parasiticides), US 6531501, WO 9516676 (arthropodicides). The compounds of the formula I can be isolated in the form of their salts. These are obtained by the conventional methods by reaction with acids or 10 bases. Useful acid addition salts are, for example, halides, especially hydrochlorides, hydrobromides, lactates, sulfates, citrates, tartrates, acetates, phosphates, methylsulfonates, benzenesulfonates, p-toluenesulfonates, adipates, fumarates, gluconates, glutamates, glycerolphosphates, maleates, benzoates, oxalates and pamoates and 15 trifluoroacetates, and in the case of the preparation of active ingredients preferably pharmaceutically acceptable salts. If the compounds contain an acidic group, they can form salts with bases, for example alkali metal salts, preferably sodium or potassium salts, or ammonium salts, for example as salts with ammonia or organic amines or amino acids. They may also be in 20 the form of a zwitterion. List of abbreviations: DBU 1,8-diazabicyclo[5.4.0]undec-7-ene N DIP diisopropyl ether 25 DIPEA diisopropylethylamine DME 1,2-dimethoxyethane DMF N,N-dimethylformamide EA ethyl acetate (EtOAc) eq. equivalent 30 HEP n-heptane HOAc acetic acid MeOH methanol mp melting point MTB tert-butyl methyl ether 35 NCIS N-chlorosuccinimide 18 dppf 1 ,1'bis(diphenylphosphino)ferrocene RT room temperature THF tetrahydrofuran 5 Example 1 2-Methyl-5-nitro-4-pentafluorosulfuranylbenzoic acid F F,\ ,F F'S .F-/ oN' II 0 OH a) 4-Aminophenylsulfur pentafluoride FS S

NH

2 A solution of tin(II) chloride (1465 g, 7.73 mol) in concentrated (32 percent) 10 aqueous HCI solution was heated with stirring to 800C and then, with ice cooling, 4-nitrophenylsulfur pentafluoride (584 g, 2.344 mol) was introduced in 8 portions within 1 h. The internal temperature was kept below 100*C. Subsequently, the mixture was stirred at an internal temperature of 85*C for 1.5 h and then allowed to cool to 450C within a further hour. A mixture of 15 ice (12 kg), NaOH (2 kg) and dichloromethane (1.5 1) was prepared and added to the reaction mixture with vigorous stirring. The phases were separated, the aqueous phase was extracted 3 times with 1 I each time of dichloromethane, and the combined organic phases were dried over Na2SO4 and concentrated under reduced pressure. 510 g of 20 4-aminophenylsulfur pentafluoride were obtained as a bright yellow crystalline powder, m.p. 63-650C (lit.: 57-59*C) b) 4-Amino-3-bromophenylsulfur pentafluoride

F'

5 S -- Br

NH

2 25 4-Aminophenylsulfur pentafluoride (510 g, 2.327 mol) was dissolved in dichloromethane (7 I), the solution was cooled to 50C and, while stirring, 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione (326 g, 1.14 mol) was 19 introduced in several portions with ice cooling such that the internal temperature was kept at 3-8'C (about 1 h). Subsequently, the mixture was stirred without external cooling for 1 h and allowed to warm to room temperature. The mixture was filtered through a bed of silica gel (volume 5 about 1 1) and washed with dichloromethane (5.5 I), and the filtrate was concentrated under reduced pressure. About 700 g of a red-brown crystalline mass were obtained and were dissolved in n-heptane (600 ml) at 60 0 C and then crystallized in a refrigerator at 4 0 C. Filtration with suction gave 590 g (85%) of 4-amino-3-bromophenylsulfur pentafluoride as 10 brownish crystals, m.p. 59-59.5 0 C. c) 4-Amino-3-methylphenylsulfur pentafluoride FS ~CH 3

NH

2 A mixture of Cs2CO3 (794 g, 2.7 mol), dimethoxyethane (2 I), water 15 (300 ml) and trimethylboroxine (50 percent solution in THF, 225 g, 0.9 mol) was heated to 70*C, PdCl 2 (dppf) - CH 2

CI

2 (37 g, 45 mmol) was added, and a solution of 4-amino-3-bromophenylsulfur pentafluoride (270 g, 0.9 mol) in dimethoxyethane (400 ml) was added dropwise within 2 h while the reaction mixture was heated to reflux. It was subsequently heated to 20 reflux for a further 3 h and then cooled to room temperature, diluted with MTB (500 ml), filtered through a silica gel column (14 x 7 cm, 70-200 pm) and washed with MTB (2500 ml). The filtrate was concentrated under reduced pressure. 490 g of a black, semicrystalline mass were obtained and were subjected to a steam distillation. A total of 5.5 I of condensate 25 was collected, from which the crystals of the product separated out. The condensate was extracted 3 times with MTB, and the combined organic phases were dried over Na2SO4 and concentrated under reduced pressure. 4-Amino-3-methylphenylsulfur pentafluoride (181 g, 76%) was obtained as colorless crystals, m.p. 65-66 0 C. 30 d) 4-Bromo-3-methylphenylsulfur pentafluoride

F

5 S ,a

CH

3 Br A mixture of tert-butyl nitrite (90 percent, 37 ml, 280 mmol) and CuBr2 20 (35.8 g, 160 mmol) in acetonitrile (260 ml) was cooled to 5*C and, while stirring and cooling with ice, a solution of 4-amino-3-methylphenylsulfur pentafluoride (30.9 g, 132.5 mmol) in MTB (140 ml) was added dropwise at 5-8*C within 1 h. Evolution of nitrogen started after about 2 min. The 5 mixture was then allowed to warm with stirring to room temperature within 1 h, a mixture of ice (250 g), 26 percent aqueous NH 3 solution (50 ml) and MTB (250 ml) was added, and the mixture was stirred for 10 min. The phases were separated, the aqueous phase was extracted 3 times with MTB (150 ml each time), and the combined organic phases were shaken 10 once with 400 ml of water. Drying with Na2SO4 and evaporation of the organic phase gave 39 g of 4-bromo-3-methylphenylsulfur pentafluoride as a red-brown oil which was contaminated with 8 mol% 4,5-dibromo 3-methylphenylsulfur pentafluoride, but was used further without further purification. Yield 89% based on a purity of 90%. 15 e) 4-Cyano-3-methylphenylsulfur pentafluoride

F

5 S

CH

3 CN A mixture of 4-bromo-3-methylphenylsulfur pentafluoride (136.4 g, purity 80%, 0.367 mol), Zn(CN) 2 (72.8 g, 0.62 mol) and Zn dust (7.2 g, 0.11 mol) 20 in dimethylacetamide (900 ml) and water (40 ml) was initially charged with nitrogen sparging, heated to 125'C with stirring, and PdCl 2 (dppf) - CH 2 Cl2 (32.7 g, 40 mmol) was added. After stirring at 125*C for one hour, PdCl2(dppf) - CH2CI2 (16.3 g, 20 mmol) and Zn dust (3.6 g, 55 mmol) was again added, and stirring was continued at 125*C for 2 h. Subsequently, 25 the mixture was cooled to room temperature, diluted with n-heptane (400 ml) and stirred vigorously with addition of 5 N aqueous NH 4 CI solution (250 ml) and water (450 ml) for 15 min. The mixture was filtered with suction through a layer of kieselguhr, the phases were separated, and the aqueous phase was extracted twice with n-heptane (200 ml). The 30 combined organic phases were shaken with water (450 ml), dried over MgSO4 and concentrated under reduced pressure. The resulting black residue was dissolved in 200 ml of n-heptane, filtered and again concentrated under reduced pressure. 78 g of a dark brown liquid were obtained and were purified by chromatography on a silica gel column 35 (7 x 55 cm, 60-200 ptm, 4:1 to 3:2 n-heptane/dichloromethane). The first 21 fraction obtained was 6.5 g of 4-bromo-3-methylphenylsulfur pentafluoride (reactant) as yellowish liquid, and then 71.1 g (80%) of 4-cyano 3-methylphenylsulfur pentafluoride as a pale yellow oil. 5 f) 2-Methyl-4-pentafluorosulfuranylbenzoic acid F S 3C H 3

CO

2 H A mixture of 4-cyano-3-methylphenylsulfur pentafluoride (41.2 g, 169.4 g), NaOH (20.4 g, 510 mmol) and water (60 ml) in ethylene glycol (160 ml) was heated to 130*C and stirred at this temperature for 4 h. It was then 10 cooled to room temperature and diluted with MTB (150 ml) and water (250 ml), and the mixture was filtered with suction. The phases of the filtrate were separated, and the aqueous phase was acidified with concentrated aqueous HCI solution, and the precipitated solid was filtered off with suction. 41.1 g (93%) of 2-methyl-4-pentafluorosulfuranylbenzoic 15 acid were obtained as colorless crystals, m.p. 138-139*C. g) 2-Methyl-5-nitro-4-pentafluorosulfuranylbenzoic acid 6.0 g of 2-methyl-4-pentafluorosulfuranylbenzoic acid were dissolved in 60 ml of a 90% aqueous HNO 3 solution and, at RT, 6 ml of a 96% H 2 SO4 20 were added dropwise. The mixture was left to stand at RT for 28 h, then poured onto 300 g of ice, 300 ml of water were added, the mixture was stirred for 1 h and then the product was filtered off. The pale yellow solid was dried in air to give 6.5 g, m.p. 218-220'C. Rf (DIP/2%HOAc) = 0.27 MS (ES-): 306 25 Example 2: Methyl 3-amino-4-chloro-5-pentafluorosulfanylbenzoate F O -S F'/ O F Ci

NH

2 22 and methyl 5-amino-2-chloro-3-pentafluorosulfanylbenzoate F Cl 0 F,\ -S F O

NH

2 a) 3-Pentafluorosulfanylbenzoic acid F OH F,\ /F -S F / F 5 13.00 g of (3-iodophenyl)sulfur pentafluoride (Tetrahedron 56, (2000) 3399) and 6.15 g of methyl iodide were dissolved in 200 ml of diethyl ether (anhydrous) and the solution was added dropwise to 2.87 g of magnesium/20 ml of diethyl ether. The reaction mixture was stirred at reflux for one hour, then cooled to -10*C and sparged under atmospheric 10 pressure with C02. The mixture was stirred at RT for 16 hours, then the reaction mixture was adjusted to pH 3-4 using dilute aqueous HCI solution and extracted 3 times with 200 ml each time of EA. Drying was effected over MgSO4 and the solvent was removed under reduced pressure. 7.20 g of a colorless, amorphous powder were obtained. 15 Rf (DIP)/2%HOAc) = 0.51 MS (DCI): 249 b) 3-Nitro-5-pentafluorosulfanylbenzoic acid F OH -S F |

NO

2 4.0 g of 3-pentafluorosulfanylbenzoic acid were dissolved at RT in 50 ml of 20 100% HNO3 and 10 ml of H2SO 4 were added with ice cooling. The mixture was stirred at RT for 6 days, then poured onto 200 g of ice and stirred for a further hour, and finally the product was filtered off with suction. 4.4 g of bright yellow crystals were obtained, m.p. 140*C. MS (ES-): 292 23 c) Methyl 3-nitro-5-pentafluorosulfanylbenzoate F 0 FO -S F |

NO

2 4.4 g of 3-nitro-5-pentafluorosulfanylbenzoic acid were dissolved in 100 ml 5 of MeOH and 5.4 ml of SOC12 were added dropwise at RT. The mixture was boiled to reflux for 5 h, the volatile constituents were removed under reduced pressure and the residue was coevaporated once with 100 ml of toluene. The residue was chromatographed on silica gel using 1:8 EA/HEP and 4.2 g of a colorless oil were obtained. 10 Rf (EA/HEP 1:8) = 0.18 MS (DCI): 308 d) Methyl 3-amino-5-pentafluorosulfanylbenzoate F O F'/O o F

NH

2 3.0 g of methyl 3-nitro-5-pentafluorosulfanylbenzoate were dissolved in 15 50 ml of MeOH and 5 ml of HOAc and 200 mg of Pd/C (10%) were added. The mixture was hydrogenated under a standard pressure of hydrogen atmosphere for 20 h, then hydrogenation was effected under 6 bar of hydrogen for a further 2 days. The catalyst was filtered off and the solvent removed under reduced pressure to obtain 2.5 g of an amorphous solid. 20 Rf (DIP) = 0.48 MS (DCI): 278 e) Methyl 3-amino-4-chloro-5-pentafluorosulfanylbenzoate and methyl 5-amino-2-chloro-3-pentafluorosulfanylbenzoate 25 2.2 g of methyl 3-amino-5-pentafluorosulfanylbenzoate were dissolved in 20 ml of isopropanol and 1.1 g of NCIS were added at 60*C. The solution was boiled to reflux for 2 h, then allowed to cool to RT. 10 ml of a saturated aqueous Na2SO3 solution and 100 ml of a saturated aqueous Na2CO3 24 solution were then added and extraction was effected 3 times with 150 ml each time of EA. Drying was effected over MgSO4, the solvent was removed under reduced pressure and the residue was chromatographed on silica gel using 1:6 EAHEP. 508 mg of methyl 3-amino-4-chloro 5 5-pentafluorosulfanylbenzoate and 94 mg of methyl 5-amino-2-chloro 3-pentafluorosulfanylbenzoate as well as 1.39 g of methyl 3-amino 2-chloro-5-pentafluorosulfanylbenzoate were obtained; each as colorless oils. Rf (EAHEP 1:6) = 0.26: methyl 3-amino-2-chloro-5-pentafluorosulfanyl 10 benzoate Rf (EA/HEP 1:6) = 0.15: methyl 3-amino-4-chloro-5-pentafluorosulfanyl benzoate Rf (EAHEP 1:6) = 0.26: methyl 5-amino-2-chloro-5-pentafluorosulfanyl benzoate 15 MS (ES+): each 352 (M+CH3C=N) Example 3: 2-Chloro-3-pentafluorosulfanylaniline and 4-chloro-3-penta fluorosulfanylaniline F Cl F F F, \/F F, \ / F

NH

2 FS NH2 F | F | CI 20 8.00 g of 3-pentafluorosulfanylaniline (Tetrahedron 56, (2000) 3399) were dissolved in 200 ml of isopropanol and 4.87 g of NCIS were added in portions at 60*C (within 30 minutes). The mixture was stirred at 600C for a further 20 minutes, then boiled under reflux for 2 h. The reaction mixture was allowed to cool to RT and half of the solvent was removed under 25 reduced pressure. 300 ml of a semisaturated aqueous NaHCO3 solution and 50 ml of a saturated aqueous Na2SO3 solution were then added and extraction was effected 3 times with 100 ml each time of CH2CI2. Drying was effected over MgSO4, the solvent was removed under reduced pressure and the residue was chromatographed on silica gel using 1:4 30 EAHEP. 2.02 g of 2-chloro-3-pentafluorosulfanylaniline and 1.10 g of 4-chloro-3-pentafluorosulfanylaniline as well as 2.73 g of 2-chloro 5-pentafluorosulfanylaniline were obtained. Rf (EAHEP 1:4) = 0.31: 2-chloro-5-pentafluorosulfanylaniline Rf (EAHEP 1:4) = 0.18: 2-chloro-3-pentafluorosulfanylaniline 35 Rf (ENHEP 1:4) = 0.11: 4-chloro-3-pentafluorosulfanylaniline 25 MS (DCI): each 253 Example 4: 2-(4-Nitro-3-pentafluorosulfanylphenyl)isoindole-1,3-dione and 2-(2-nitro-5-pentafluorosulfanylphenyl)isoindole-1,3-dione 0 /

N

+

0 / NN N. 0 --F S F F / \F F F 5 FF F F a) 2-(3-Pentafluorosulfanylphenyl)isoindole-1,3-dione: 0 N

.

" 0 -F F /\ F F F 15 g (68.44 mmol) of 3-pentafluorosulfanylphenylamine was suspended with 10.14 g (68.44 mmol) of phthalic anhydride in 40 ml of a acetic acid 10 and boiled under reflux for 2 h. The cool reaction mixture was admixed with 400 ml of water, heated in an ultrasound bath for 30 min and filtered. The residue was washed with water and subsequently with a little ethanol and dried under reduced pressure. 2-(3-Pentafluorosulfanylphenyl)isoindole 1,3-dione was obtained with a melting point of 188-190'C. 15 b) 2-(4-Nitro-3-pentafluorosulfanylphenyl)isoindole-1,3-dione and 2-(2-nitro 5-pentafluorosulfanylphenyl)isoindole-1,3-dione 1 g (2.863 mmol) of 2-(3-pentafluorosulfanylphenyl)isoindole-1,3-dione was 20 dissolved at 0*C in 3.29 ml of concentrated nitric acid, and the mixture was stirred at 00C for 2 h. Afterward, the mixture was left to stand at room temperature overnight. The reaction solution was added to 50 g of ice water and the mixture was stirred for 1 h; then the precipitate was filtered off with suction, washed with water, dried and purified chromatographically 26 on silica gel using toluene as the eluent. 2-(4-Nitro-3-pentafluorosulfanyl phenyl)isoindole-1,3-dione having a melting point of 200-203*C and 2-(2-nitro-5-pentafluorosulfanylphenyl)isoindole-1,3-dione having a melting point of 175-177*C were obtained in a ratio of 1:2. 5 Example 5: 2-(4-Amino-3-pentafluorosulfanylphenyl)isoindole-1,3-dione 0 N 0

H

2N F'/ F F F 1.94 g (4.92 mmol) of 2-(4-nitro-3-pentafluorosulfanylphenyl)isoindole 1,3-dione (prepared in example 4) were dissolved in 20 ml of methanol, 10 admixed with 53mg of 10% palladium on activated carbon and hydrogenated at room temperature at a hydrogen pressure of 5 bar. On completion of reaction, the catalyst was filtered off and the filtrate concentrated. The residue was stirred in a mixture of dichloromethane and n-heptane, filtered with suction and dried under reduced pressure. 15 2-(4-amino-3-pentafluorosulfanylphenyl)isoindole-1,3-dione having a melting point of 176-178 0 C was obtained. When the above-described reaction was terminated prematurely, 2-(4-hydroxyamino-3-pentafluorosulfanylphenyl)isoindole-1,3-dione 0 N HO, 0 N Hi? H -F F F 20 FF having a melting point (with decomposition) of 171-173 0 C was obtained.

27 Example 6: 4-(1,3-Dioxo-1,3-dihydroisoindole-2-yl)-2-pentafluorosulfanyl benzonitrile: 0 N 0 N "F F /" F FF 0.46 ml (8.24 mmol) of semiconcentrated sulfuric acid was slowly added 5 dropwise at 00C to a solution of 1 g (2.74 mmol) of 2-(4-amino 3-pentafluorosulfanylphenyl)isoindole-1,3-dione (prepared in example 5) in acetic acid. The mixture was stirred at 00C for 10 min; then a solution of 189.4 mg of sodium nitrite in 2 ml of water was slowly added dropwise with stirring, and the resulting solution was stirred at 0*C for 30 min. This 10 solution was finally added dropwise to a solution, cooled to 0*C, of 246 mg (2.74 mmol) of copper(l) cyanide and 536 mg (8.23 mmol) of potassium cyanide in 5 ml of water. The reaction mixture was stirred at 0 C for 30 min and afterward at room temperature for another 3 h. After the end of the reaction, the mixture was added to water and the aqueous phase extracted 15 twice with ethyl acetate. The organic phase was dried over magnesium sulfate and filtered, the filtrate was concentrated and the residue purified chromatographically on silica gel first with toluene and then with 20/1 toluene/ethyl acetate. 4-(1,3-Dioxo-1,3-dihydroisoindol-2-yl)-2-pentafluoro sulfanylbenzonitrile was obtained. H NMR (500 MHz; d 6 -dmso: 6 [ppm] = 20 8.4 (m, 2H); 8.1-7.95 (m, 5H). Example 7: 4-Amino-2-pentafluorosulfanylbenzonitrile and ethyl N-(4-cyano 3-pentafluorosulfanylphenyl)phthalamate 0 0 N NH 2 NH F / F IF /I F FF FF 28 610mg (1.63 mmol) of 4-(1,3-dioxo-1,3-dihydroisoindol-2-yl)-2-penta fluorosulfanylbenzonitrile (prepared in example 7) were dissolved in 30 ml of ethanol and admixed with 100 mg (1.956 mmol) of hydrazine hydrate (100%). The mixture was stirred at room temperature overnight. Afterward, 5 the reaction mixture was concentrated under reduced pressure and the residue was purified by chromatography (preparative HPLC; Purospher STAR RP-18e (10 pm); eluent: 5/95 --+ 95/5 [45 min.] acetonitrile/water (0.5% trifluoroacetic acid)). 4-Amino-2-pentafluorosulfanylbenzonitrile ( H NMR (500 MHz; d 6 -dmso) 6 [ppm] = 7.65 (s, 1H); 7.2 (s, 1H; 6.8 (m, 10 3H)) and N-(4-cyano-3-pentafluorosulfanylphenyl)phthalamate ( H NMR (500 MHz; d 6 -dmso) 6 [ppm] = 11.3 (s, 1H); 8.6 (s, 1H); 8.2 (d, 1H); 8.1 (d, 1H); 7.95 (d, 1H); 7.75 (m, 1H); 7.7 (m, 2H); 4.2 (q, 2H); 1.15 (t, 3H)) were obtained. 15 Example 8: N-(4-Nitro-3-pentafluorosulfanylphenyl)acetamide and N-(2,4 dinitro-5-pentafluorosulfanylphenyl)acetamide F -F , F F S NHSNH F |-F| O'N N N.-.0 II II I _ 0 0 0 1.0 g of N-(3-pentafluorosulfanylphenyl)acetamide (preparation as in Tetrahedron 56, (2000) 3399) was dissolved in portions at 0-3*C in 10 ml of 20 90% HNO 3 . The mixture was stirred at 0*C for 15 minutes, then poured onto 100 g of ice and extracted 3 times with 100 ml each time of EA. Drying was effected over MgSO4, the solvent was removed under reduced pressure and the residue was chromatographed on silica gel using DIP. 195 mg of N-(4-nitro-3-pentafluorosulfanylphenyl)acetamide and 280 mg of 25 N-(2,4-dinitro-5-pentafluorosulfanylphenyl)acetamide as well as 645 mg of N-(2-nitro-5-pentafluorosulfanylphenyl)acetamide were obtained. Rf (DIP) = 0.41: N-(2-nitro-5-pentafluorosulfanylphenyl)acetamide MS (El): 306 Rf (DIP) = 0.18: N-(2,4-dinitro-5-pentafluorosulfanylphenyl)acetamide 30 MS (El): 351 Rf (DIP) = 0.11: N-(4-nitro-3-pentafluorosulfanylphenyl)acetamide MS (El): 306 29 Example 9: N-(4-Nitro-3-pentafluorosulfanylphenyl)acetamide F | O'NNH O. 0,N 11 0 20.00 g of N-(3-pentafluorosulfanylphenyl)acetamide (preparation as in Tetrahedron 56, (2000) 3399) were dissolved in portions at from -35 0 C 5 to -40*C in 100 ml of 90% HNO 3 . The mixture was stirred at -40 0 C for 15 minutes, then poured onto 1 kg of ice and stirred at RT for 1 h. The product was then filtered, washed with water and dried under reduced pressure. Chromatography on silica gel using DIP afforded 3.61 g of N-(4-nitro-3-pentafluorosulfanylphenyl)acetamide as well as 17.00 g of 10 N-(2-nitro-5-pentafluorosulfanylphenyl)acetamide. Rf (DIP) = 0.41: N-(2-nitro-5-pentafluorosulfanylphenyl)acetamide MS (El): 306 Rf (DIP) = 0.11: N-(4-nitro-3-pentafluorosulfanylphenyl)acetamide MS (El): 306 15 Example 10: 1,3-Dibromo-2-methoxy-4-nitro-5-pentafluorosulfanylbenzene O ..o F N F'/ Br F 0 Br a) 4-Pentafluorosulfanylphenol F F' F |a O OH 20 40.00 g of 4-pentafluorosulfanylaniline were suspended in 500 ml of a 35% aqueous H 2 SO4 solution and a solution of 13.85 g of NaNO 2 in 30 ml of water was added dropwise at 0C over a period of 10 minutes. Subsequently, the mixture was stirred at 0*C for 35 minutes, then a solution, at 0*C, of 171.10 g of Cu(N0 3

)

2 in 200 ml of water was poured in 30 and, directly thereafter, 26.11 g of Cu20 were added in portions. The mixture is stirred at RT for a further 2 hours, then extraction is effected 3 times with 200 ml each time of CH 2

CI

2 . Drying was effected over MgSO 4 and the solvent was removed under reduced pressure. 38.00 g of a pale 5 yellow oil were obtained which was used further without purification. b) 4-Methoxypentafluorosulfanylbenzene F F'/ Fj 0 5.00 g of 4-pentafluorosulfanylphenol were dissolved in 50.00 g of dimethyl 10 carbonate and 3.46 g of DBU were added. The mixture was boiled under reflux for 10 hours, then allowed to cool and diluted with 200 ml of EA. Subsequently, the mixture was washed twice with 100 ml each time of a 5% aqueous HCI solution, then with 100 ml of a 5% aqueous NaOH solution. Drying was effected over MgSO4 and the solvent was removed 15 under reduced pressure. Chromatography on silica gel using 1:1 DIP/HEP afforded 2.2g of a colorless oil. Rf (DIP/HEP 1:1)= 0.52 c) 2,6-Dibromo-4-pentafluorosulfanylphenol F F.' /F F' IS Br F | OH 20 Br 3.34 g of 4-methoxypentafluorosulfanylbenze were dissolved in 200 ml of CHC1 3 and 0.46 g of FeBr2 were added. At RT, 6.84 g of bromine were then added dropwise and the mixture was stirred at RT for 4 days. Subsequently, a further 400 mg of FeBr2 were added and the mixture was 25 stirred at RT for a further 23 hours. The reaction mixture was then poured cautiously onto 100 ml of a saturated aqueous Na2SO 3 solution and extracted 3 times with 50 ml each time of CH 2

CI

2 . Drying was effected over MgSO 4 and the solvent was removed under reduced pressure. Chromatography on silica gel using DIP afforded 3.00 g of an amorphous 31 solid. Rf (DIP) = 0.22 d) 1,3-Dibromo-2-methoxy-5-pentafluorosulfanylbenzene 5 F F.,\ ,F F''/JS Br F I 1? 0 Br 450 mg of 2,6-dibromo-4-pentafluorosulfanylphenol, 329 mg of K2CO3 and 186 mg of CH31 were stirred at RT in 5 ml of anhydrous DMF for 24 hours. Subsequently, the reaction mixture was poured onto 100 ml of EA and 10 extracted 3 times with 30 ml each time of water. Drying was effected over MgSO4 and the solvent was removed under reduced pressure to obtain 500 mg of a colorless oil. Rf (DIP/HEP 1:1) = 0.51 MS (El): 392 15 e) 1,3-Dibromo-2-methoxy-4-nitro-5-pentafluorosulfanylbenzene 630 mg of 1,3-d ibromo-2-methoxy-5-pentafluorosulfany benzene were stirred in 2 ml of a 90% aqueous HNO 3 solution at 00C for 1 hour. Subsequently, the mixture was stirred at RT for 20 minutes and then poured onto 50 g of ice. An aqueous Na2CO3 solution was used to adjust 20 to pH = 6 and extraction was effected three times with 50 ml each of EA. Drying was effected over Na2SO4 and the solvent was removed under reduced pressure. Chromatography on silica gel using 1:3 DIP/HEP afforded 260 mg of a pale yellow oil. Rf (DIP/HEP 1:3) = 0.40 25 Example 11: 1 -Bromo-3-chloro-2-methoxy-4-nitro-5-pentafluorosulfanyl benzene and 3-bromo-1-chloro-2-methoxy-4-nitro-5-pentafluorosulfanyl benzene F ON. F 0N. .O F /F F' Br F | F | Br Cl 32 a) 2-Chloro-4-pentafluorosulfanylphenol 5.00 g of 4-pentafluorosulfanylphenol (prepared in example 11a) were dissolved in 100 ml of acetic acid and a chlorine gas stream was passed through at OC for 10 minutes. This warmed the solution to 30*C which was 5 subsequently stirred at RT for a further 90 minutes. Argon was used to drive the chlorine out of the solution and the solvent was subsequently removed under reduced pressure. 5.50 g of a pale yellow oil were obtained. Rf (DIP) = 0.23 10 b) 2-Chloro-1-methoxy-4-pentafluorosulfanylbenzene F F'IS Cl F 0 5.50 g of 2-chloro-4-pentafluorosulfanylphenol, 7.89 g of K 2

CO

3 and 4.05 g of CH 3 1 were stirred at RT in 30 ml of anhydrous DMF for 2 hours and left to stand at RT for 2 days. The mixture was then diluted with 300 ml of EA 15 and washed 3 times with 100 ml each time of water. Drying was effected with Na2SO4 and the solvent was removed under reduced pressure to obtain 5.40 g of a pale yellow oil. Rf (DIP) = 0.68 20 c) 2-Bromo-6-chloro-4-pentafluorosulfanylphenol F F,\1 S Cl F | F OH Br 5.30 g of 2-chloro-1-methoxy-4-pentafluorosulfanylbenzene were dissolved in 150 ml of CHC13 and admixed with 4.73 g of bromine and 638 mg of FeBr2. The mixture was stirred at RT for 18 hours, then admixed with a 25 further 200 mg of FeBr2, stirred at RT for 6 hours and then admixed with a further 300 mg of FeBr2, stirred at RT for 2 hours and left to stand at RT for 18 hours. The reaction mixture was then poured onto 300 ml of a saturated aqueous Na2SO3 solution and extracted with 300 ml of CH 2

CI

2 . The organic phase was then washed with 100 ml of water and dried over 30 Na2SO4, and the solvent was removed under reduced pressure. 4.20 g of 33 a colorless oil were obtained which was reacted further without purification. d) 1-Bromo-3-chloro-2-methoxy-5-pentafluorosulfanylbenzene F FS -Cl F IF I 0 Br 5 4.20 g of 2-bromo-6-chloro-4-pentafluorosulfanylphenol were stirred together with 3.48 g of K 2

CO

3 and 2.68 g of CH 3 1 in 50 ml of anhydrous DMF at RT for 24 hours. The solvent was then removed under reduced pressure and subsequently taken up with 100 ml each of water and EA. The phases were left to separate and extraction was then effected twice 10 more with 100 ml each time of EA. Drying was effected over Na2SO4 and the solvent was removed under reduced pressure. Chromatography on silica gel using 1:1 DIP/HEP afforded 3.44 g of a colorless viscous liquid. Rf (DIP/HEP 1:1) = 0.53 MS (El): 346 15 e) 1-Bromo-3-chloro-2-methoxy-4-nitro-5-pentafluorosulfanylbenzene and 3-bromo-1 -chloro-2-methoxy-4-nitro-5-pentafluorosulfanylbenzene 3.40 g of 1-bromo-3-chloro-2-methoxy-5-pentafluorosulfanylbenzene were added dropwise at from 00C to 5 0 C to 40 ml of a 90% aqueous HNO3 20 solution. The mixture was stirred at 0*C for 60 minutes, then stirred at RT for 90 minutes. Subsequently, the reaction mixture was poured onto 200 g of ice and extracted 3 times with 200 ml each time of EA. Drying was effected over Na2SO4 and the solvent was removed under reduced pressure. Chromatography on silica gel using 1:3 DIP/HEP afforded 2.00 g 25 of a pale yellow oil. MS (El): 391 Example 12: 2-Chloro-4-nitro-5-pentafluorosulfanylaniline F F NH 2 N CI II 0 34 a) 2.60 g of 2-chloro-5-pentafluorosulfanylaniline (example 3) were added dropwise at 0"C to 30 ml of 100% HNO 3 . The mixture was stirred at O*C for 1 hour, then poured onto 100 g of ice and adjusted to pH = 7 using saturated aqueous NaHCO 3 solution. Extraction was then effected 3 times 5 using 100 ml each time of EA, then drying was effected over MgSO4. The solvent was removed under reduced pressure to obtain 2.50 g of a pale yellow oil. Rf (EA) = 0.13 10 Comprises/comprising and grammatical variations thereof when used in this specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof. 15

Claims (5)

1. A compound of the formula I R4 R5 R3 F Ft O F R2 F F R1 5 where R1 is Cl, Br, I, -S0 2 R6 or NO2; R6 is OH, F, Cl, Br, I or alkyl having 1, 2, 3 or 4 carbon atoms; 10 R2 and R4 are each independently hydrogen F, Cl, Br, I, -CN, NR9R1 0, -OR1 1, -SRi 2, -CORI 3, -(SOr)s-(CH2)t-(CF2)u-CF3, alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms, cycloalkyl having 3, 4, 5, 6, 7 or 8 carbon atoms, in which 1, 2, 3 or 4 hydrogen atoms may be replaced by fluorine 15 atoms; R9 and R10 are each independently alkyl having 1, 2, 3 or 4 carbon atoms, -(CH2)v-(CF2)w-CF3, alkylcarbonyl having 1, 2, 3 or 4 carbon atoms, alkylsulfonyl having 1, 2, 3 or 4 carbon atoms; 20 or R9 and R10, together with the nitrogen atom bearing them, form a heterocycle of the formula Ilia: 0 N |; SIlila R11 and R12 are each independently hydrogen, alkyl having 1, 2, 3 25 or 4 carbon atoms, -(CH2)v-(CF2)w-CF3, alkylcarbonyl having 1, 2, 3 or 4 carbon atoms, alkylsulfonyl having 1, 2, 3 or 4 carbon atoms; 36 R13 is OH, alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms or alkoxy having 1, 2, 3, 4, 5 or 6 carbon atoms; s is zero; t and u are each independently zero or 1; 5 v and w are each independently zero or 1; where at least one of the R2 and R4 radicals is not hydrogen, Cl, CN, CORI 3 or -(SOr)s-(CH2)t-(CF2)u-CF3; R3 is hydrogen, F, Cl, Br, 1, -CN, -N02, -COR14, -S02CH 3 , alkyl having 1, 10 2, 3, 4, 5 or 6 carbon atoms, alkoxy having 1, 2, 3 or 4 carbon atoms, -Ox-(CH2)y-CF3, R14 is OH, alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms, alkoxy having 1, 2, 3, 4, 5 or 6 carbon atoms or 15 -Oaa-(CH2)bb-CF3; x is zero or 1; y is zero, 1, 2 or 3; aa is zero or 1; bb is zero, 1, 2 or 3; 20 R5 is hydrogen or F; and salts thereof; excluding compounds of the formula I in which R2 and R4 are each Cl and 25 R3 is F or Cl, excluding compounds of the formula I in which one of the R2 and R4 substituents is Cl and the other of the R2 and R4 substituents is CN and R3 is Cl and excluding compounds of the formula I in which R1 is N02 and the other 30 substituents are each hydrogen.

2. A process for preparing compounds of the formula I as claimed in claim 1 or salts thereof, which process comprises converting compounds of the formula 11 by electrophilic aromatic substitution to compounds of the 35 formula I 37 R4 R4 R5 R3 R5 R3 F IM. F | F--\ /FG R2 F R2FS FrI\ R21" FF F F RI II where R1 to R5 are each as defined in claim 1.

3. A compound of the formula I as claimed in claim 1 and/or salts 5 thereof for use as a synthetic intermediate.

4. A compound of the formula I as claimed in claim 1 and/or salts thereof for use as a synthetic intermediate for the preparation of products selected from the group consisting of medicaments, diagnostic aids, liquid 10 crystals, polymers, pesticides, herbicides, fungicides, nematicides, parasiticides, insecticides, acaricides and arthropodicides.

5. A compound of the formula I as claimed in claim 1 and which is substantially as hereinbefore described with reference to any one of the 15 examples. SANOFI-AVENTIS DEUTSCHLAND GMBH WATERMARK PATENT AND TRADE MARKS ATTORNEYS 20 P26954AU00