Pentafluorosulfanylpyridine

[0001]The present invention relates to pentafluorosulfanyl pyridine and its manufacturing method. Background technique

[0002]Pentafluorosulfanyl group (hereinafter SF 5 group) is an electron-withdrawing and lipophilic substituents used in the design of functional organic molecules. Thus, SF 5 group-containing compounds are important in the development of liquid crystal molecules and low molecular medicine and agrochemicals molecule, it has been developed for the synthesis method in recent years (Non-Patent Document 1). Especially SF to the pyridine ring which is frequently used in the physiologically active substances such as pharmaceutical and agricultural chemicals 5 is the introduction of groups is important, because trifluoride loss Alpha sulfonyl pyridine and halo-tetrafluoro sulfanyl pyridine intermediates is unstable, its synthesis is difficult. SF to the pyridine ring 5 as a method for introducing a group, SF the 2-position of the pyridine ring halogen exchange reaction of disulfide compounds according silver fluoride followed oxidation with chlorine gas as a starting material 5 is a method for synthesizing a compound having a group It has been proposed (non-Patent Document 2). However, SF in the 3- or 4-position of the pyridine ring 5 practical ways of introducing the group has not yet been developed. AgF 2 Fluorination of pyridyl disulfide with SF at the 3-position of the pyridine ring 5 although there is a report that can be introduced group (Patent Document 1), compound data of the NMR or the like to the relevant literature merely called line described and examples are not shown. SF at the 3-position of this addition to the pyridine ring 5Although groups are reports of biologically active compounds which are introduced (Patent Documents 2-5), the compound data and examples merely Similarly line described is not shown.

[0003] SF in the 4-position of the pyridine ring 5 compounds having groups, and the 3- or 4-position of pyridine ring chlorotetrafluoroethane alkylsulfanyl group (hereinafter SF 4 compounds with Cl group) has not yet been reported. CITATION Patent Document

[0004] Patent Document 1: International Publication 1994/022817 Patent Document 2: U.S. Patent No. 5,739,326 Pat Patent Document 3: U.S. Patent No. 6,531,501 Pat Patent Document 4: International Publication 2011/105506 Patent Document 5: International Publication 2014/119674 Non-Patent Document

[0005] Non-Patent Document 1:. Chem Rev. 2015, 115 , 1130. Non-Patent Document 2:.. Angew Chem Int Ed 2015, 54, 280... Summary of the Invention Problems that the Invention is to Solve

[0006] SF 5 Synthesis of containing pyridine is very difficult because the intermediate is unstable, the example that was actually synthesized so far have been reported SF the 2-position of the pyridine ring 5 compound having a group only it is. On the other hand, SF 5 SF is group and its precursor 4 if synthesizing the compounds Cl group is bonded to a site other than the 2-position of the pyridine ring, bring significant benefits to the design of the next generation Life science molecule. In view of such circumstances, the present invention provides 3-position and 4-position SF of the pyridine ring 5 group or SF 4 and to provide a pyridine and a manufacturing method thereof having a Cl group. Means for Solving the Problems

[0007] By the pyridyl disulfide having a specific substituent as a starting material, found to solve the above problems, and completed the present invention. That is, the serial object is achieved by the following present invention. (1) SF represented by the formula (d), which will be described later 5 pentafluorosulfanyl pyridine group is substituted in the 3 or 4 position of the pyridine ring. In (2), wherein R 1 and R 4 at least one is a fluorine atom, pentafluorosulfanyl pyridine according to (1). (3) 2-fluoro-3-pentafluorosulfanyl pyridine, 2,6-difluoro-3-pentafluorosulfanyl pyridine, or 6-fluoro-3-pentafluorosulfanyl pyridine, pentafluorosulfanyl according to (1) pyridine. (4) SF represented by the below general formula (c ') 4 3-position or chlorotetrafluoroethane sulfanyl pyridine substituted at the 4-position of the Cl groups pyridine ring. (5) wherein R 1 and R 4 at least one is a fluorine atom, chloro tetra sulfanyl pyridine according to (4). (6) 2-fluoro-3-chloro-tetrafluoro sulfanyl pyridine, 2,6-difluoro-3-chloro-tetrafluoro sulfanyl pyridine or 6-fluoro-3-chloro-tetrafluoro sulfanyl pyridine, according to (4) chlorotetrafluoroethane sulfanyl pyridine. (7) The method of producing a pentafluorosulfanyl pyridine according to (1), is selected the pyridyl disulfide represented by the formula (a) described later chlorine, bromine, from the group consisting of iodine and halogen compounds halogens, and reacted with fluoro salt represented by the general formula (b) described below, to form a halo-tetrafluoro sulfanyl pyridine represented by the general formula (c) to be described later, a halo-tetrafluoro sulfanyl pyridine obtained It is reacted with a fluoride source comprises a pentafluorosulfanyl pyridine obtained step method. (8) halogen is reacted with pyridyl disulfide compound chlorine (Cl 2 is) The production method according to (7). (9) fluoro salt represented by the general formula (b) is an alkali metal fluoride, the production method according to (7). (10) wherein the fluoride source is hydrogen fluoride, the method according to any one of (7) to (9). Effect of the invention

[0008] The present invention, SF 5 3-position or 4-position substituted manufacture of pentafluorosulfanyl pyridine is a pyridine ring group, and can provide a manufacturing method of the compound. DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail. "X ~ Y" in the present invention includes a value or X and Y both ends.

[0010] 1. Pentafluorosulfanyl pyridine pentafluorosulfanyl pyridine of the present invention represented by the general formula (d).

[0011]

Formula 1

wherein, SF 5 group is attached to the 3- or 4-position of the pyridine ring. R 2 is of the 3 and 4 positions, SF 5 is bonded to either position unbound groups.

[0012] R 1 , R 2 , R 3 , R 4 is a substituent on the pyridine ring, independently, a hydrogen atom, a halogen atom, from 1 to 18 substituted or unsubstituted alkyl group having carbon atoms 6-30 number of substituted or unsubstituted aryl group having a carbon atom, a nitro group, a cyano group, from 1 to 18 substituted or unsubstituted alkanesulfonyl group having carbon atoms, a substituted or unsubstituted having from 6 to 30 carbons of arene sulfonyl group, from 1 to 18 substituted or unsubstituted alkoxy group having carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, acyloxy having 1 to 18 carbon atoms group, from 1 to 18 substituted or unsubstituted alkanesulfonyloxy group having carbon atoms, a substituted or unsubstituted arene sulfonyl having 6 to 30 carbon atoms Oki Shi group 2 to 18 substituted or unsubstituted alkoxycarbonyl group having carbon atoms from 7 to 30 substituted or unsubstituted aryloxycarbonyl group having carbon atoms, substituted carbamoyl of 2 to 18 carbon atoms group, 1 to 18 substituents amino group having a carbon atom, an amino group, azide group, 7 to 30 substituted or unsubstituted aralkyl group having carbon atoms, 7 to substituted or having 30 carbon atoms unsubstituted aralkyl sulfide group, or SF 5 is group. Halogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. 7 ~ The 30 substituted or unsubstituted aralkyl group having carbon atoms, a benzyloxy group (Ph-CH 2-O-) and substituted benzyloxy group. The substituted or unsubstituted aralkyl sulfide group having 7 to 30 carbon atoms, benzyl sulfide group (Ph-CH 2 include -S-) or substituted benzyl sulfide group. The substituted amino group having 1 to 18 carbon atoms, benzyl amino group or a substituted benzylamino group.

[0013] From easy availability of the compound halo-tetrafluoro sulfanyl compound is a precursor of (d), R 1 and R 2 are preferably sterically hindered are fewer hydrogen atom or a fluorine atom.

[0014] From the viewpoint of stability compound precursor is a halo-tetrafluoro sulfanyl compound of (d), R 1 and R 4 are preferably at least one of a halogen atom.

[0015] Further, R 1 and R 4 at least one is 1 to 18 substituted amino group having carbon atoms, an amino group, azide group, 7-30 amino substituted or unsubstituted aralkyl group having carbon atoms or, 7 ~ is preferably 30 substituted or unsubstituted aralkyl sulfide group having carbon atoms.

[0016] 2. Chlorotetrafluoroethane sulfanyl pyridine chlorotetrafluoroethane sulfanyl pyridine of the present invention represented by the general formula (c ').

[0017]

Formula 2

wherein, SF 4 Cl group, SF in the compound (d) 5 is a group that gives group. R 1 , R 2 , R 3 , and R 4 are defined as for compound (d).

[0018] 3. Method for producing a pentafluorosulfanyl pyridine pentafluorosulfanyl pyridine is preferably prepared by the following scheme.

[0019]

Formula 3

[0020] (1) halo tetrafluoro sulfanyl pyridine (c) Synthesis of chlorine pyridyl disulfide pyridine represented by formula (a), bromine, iodine, and halogens selected from the group of interhalogen compounds, and in formula (b) It is reacted with a fluoro salt represented by the production of halo tetrafluoro sulfanyl pyridine compound represented by the formula (c).

[0021] More specifically, first, obtain pyridyl disulfide compound (Compound (a)) and, in the presence halogens, is reacted with fluoro salt halo tetrafluoro sulfanyl pyridine (Compound (c)) the. The amount of the halogens may be any excess over pyridyl disulfide compound, but is preferably 12 to 16 equivalents. The amount of fluoro salt may be used in an excessive relative pyridyl disulfide, 14-18 equivalents is preferred. The solvent is not limited to, aprotic polar solvents such as acetonitrile to avoid reaction with the solubility and halogens fluoro salts. The reaction temperature may be appropriately adjusted, and is preferably -20 ~ 50 ° C.. The reaction time is not limited, several hours to several days, preferably, from 2-3 days. Further, the reaction vessel fluoropolymer containers such as polytetrafluoroethylene for inhibition of side reactions is preferred. Furthermore, the instability of the reaction intermediate, the reaction is preferably carried out in deoxygenated atmosphere and dry conditions.

[0022] R in the compound (d) 1 , R 2 , R 3 , and R 4 are, R of the compound which is the starting material (a) 1 , R 2 , R 3 , and R 4 may be different from. Accordingly, some aspects of the present invention R 1 , R 2 , R 3 , and R 4 different R 1 , R 2 , R 3 , and R 4 comprises converting the. This conversion can be carried out in a reaction to convert the reaction or compounds converted compound (a) to the compound (c) (c) is a compound (d).

[0023] Exemplary halogens which can be used in the present invention, chlorine (Cl 2 ), bromine (Br 2 ), iodine (I 2 ), as well as ClF, BrF, ClBr, ClI, Cl 3 I, among halogens such as BrI compounds. Chlorine (Cl from cost 2 ) is preferred.

[0024] Fluoro salt represented by the formula (b) are readily available, examples include metal fluorides, ammonium fluoride, and phosphonium halides and the like. Examples of suitable metal fluoride, lithium fluoride, sodium fluoride, (including potassium spray-dried fluoride) potassium fluoride, alkali metal fluorides, such as rubidium fluoride, and cesium fluoride. Examples of suitable ammonium fluorides, tetramethylammonium fluoride, tetrabutylammonium fluoride, benzyltrimethylammonium fluoride, and the like benzyltriethylammonium fluoride. Examples of suitable phosphonium compound is tetramethyl phosphonium fluoride, tetraethyl phosphonium fluoride, tetrapropylammonium phosphonium fluoride, tetrabutylphosphonium fluoride, tetraphenylphosphonium fluoride, and the like tetra-tolyl phosphonium fluoride. Alkali metal fluorides are preferred, such as easy availability and potassium fluoride in terms of ability to provide high yield and cesium fluoride, and most preferably consideration of potassium fluoride cost.

[0025] As fluoro salt represented by the formula (b), a mixture of metal fluoride and ammonium fluoride or phosphonium fluoride, a mixture of ammonium fluoride and phosphonium halides, and metal fluoride and an ammonium fluoride and phosphonium halides it is also possible to use mixtures of.

[0026] (2) Synthesis of pentafluorosulfanyl pyridine (d) halo-tetrafluoro sulfanyl pyridine of the formula (c) is reacted with a fluoride source to obtain a pentafluorosulfanyl of formula (d).

[0027] Specifically halo tetrafluoro sulfanyl pyridine (Compound (c)) to give reacted with a fluoride source pentafluorosulfanyl pyridine by halogen exchange reaction (Compound (d)) a. The amount of fluoride source may be in excess with respect to pyridyl disulfide, but is preferably 12 to 16 equivalents. The amount of fluoride source may be in excess with respect to halo-tetrafluoro sulfanyl pyridine but 1-3 equivalents is preferred. Preferably solventless reaction from the viewpoint of high reaction efficiency and low cost, but halocarbons in order to adjust the reactivity, ethers, nitriles (acetonitrile, etc.), can also be used nitro compound as the solvent. The reaction temperature may be appropriately adjusted, and is preferably -100 ~ 0.99 ° C.. The reaction time is not limited, several hours to several days, preferably, from 2-3 days. Further, the reaction vessel fluoropolymer containers such as polytetrafluoroethylene for inhibition of side reactions is preferred. Furthermore, the instability of the reaction intermediate, the reaction is preferably carried out in deoxygenated atmosphere and dry conditions.

[0028] Fluoride sources used are anhydrous compounds that exhibit activity fluorinating halo tetrafluoro sulfanyl pyridine of formula (c). Fluoride sources can be selected fluorides of typical elements of the Periodic Table, fluorides of transition elements in the Periodic Table, and mixtures or compounds of these fluorides of typical elements or transition elements. Fluoride source, hydrogen fluoride, or a mixture of one or more organic molecules do not limit the reaction of the present invention may be a salt or complex. As the fluoride source, fluoride source and SbCl 5 , AlCl 3 , PCl 5 , BCl 3 also include mixtures or compounds of fluoride source-activating compounds such as. Particularly high reactivity of the halogen exchange, transition metal fluorides are a Group 11 elements (Cu, Ag, Au) and Group 12 elements (Zn, Cd, Hg) fluoride is preferred.

[0029] The method is divided into stages the following reactions. 1) formation of the silver and 3-position of the pyridine ring by fluoro salt or 4-position bound oxidation of the sulfur atom, and a halo-tetrafluoro sulfanyl compound by a halogen exchange. 2) generation of pentafluorosulfanyl pyridine compounds by a halogen exchange.

[0030]

Chemical Formula 4

[0031] At the stage of the 1), SF represented by the intermediate expression (a ') 3 via a compound containing group. The compound is a tetravalent sulfur compounds, 19 can be confirmed its presence by F-NMR. SF 3 group or SF 4 pyridine compound having a Cl group is easily decomposed undergo nucleophilic attack by water and anionic species in the system. Therefore R 1 or R 4 when the halogen atom, can be chemical stability of pyridyl disulfides proceed to the reaction increased more efficiently.

[0032] R 1 or R 4 pentafluorosulfanyl pyridine is a halogen atom (d) is by reacting with a nucleophile, R 1 or R 4 can be substituted with yet another group of. An example of schemes and thus synthesized pentafluorosulfanyl pyridine of the reaction (d) are shown below.

[0033]

Formula 5

Example

[0034] [Example 1] performs the following reaction, it was synthesized pentafluorosulfanyl pyridine compound.

[0035]

Formula 6

[0036] In 30mL polytetrafluoroethylene container, potassium fluoride under nitrogen was charged (spray-dried product, 2.32 g, 40 mmol, Wako Pure Chemical Industries, Ltd.) and acetonitrile (15 mL). The stirred mixture was cooled in a water bath containing the ice at the outlet pressure 0.005MPa with polytetrafluoroethylene tube (inner diameter 1 mm), the chlorine on the mixture (Cl 2 ; about 2.5 g ~ 2 .8g, it was bubbled about 35 ~ 40mmol) for 10 minutes. Subsequently pyridyl disulfide synthesized by the inventor (a1) (641mg, 2.5mmol) was added under a nitrogen stream, the vessel was sealed and stirred for 36 hours at room temperature. After completion of the reaction, insoluble substances were removed using a glass filter under a nitrogen atmosphere. During polytetrafluoroethylene container the filtrate, evaporated in vacuo, the resulting residue (2-fluoro-3-chloro-tetrafluoro sulfanyl pyridine (c1)) leave the crude was used in the subsequent reaction.

[0037] To 2-fluoro-3-chloro-tetrafluoro sulfanyl-pyridine in 30mL polytetrafluoroethylene container obtained in the previous step (c1), silver fluoride and (I) (634mg, 5.0mmol) was added and the mixture under a nitrogen atmosphere at 100 ℃ was stirred for 24 hours. After cooling to room temperature, the mixture was stirred for 1 hour added water (5 mL) in dichloromethane (5 mL), the product was extracted with dichloromethane, the organic phase was dried over sodium sulfate. Then the solvent was distilled off under reduced pressure, silica gel column chromatography (pentane / dichloromethane = 5/1 → 2/1, Rf value 0.56) product was purified by (d1) (151 mg, 27%) It was obtained as a colorless oil.

[0038] Moreover, subjected to the same synthesized using the following compounds. It is summarized as analysis by mass spectrometry and NMR as follows. In the present invention, mass spectrometry is performed using a Model LCMS-2020, manufactured by Shimadzu Corporation, 1 H-NMR and 19 F-NMR was measured using a Mercury 300, Varian Corporation.

[0039]

Table 1

[0040]

Chemical Formula 7

[0041] Example 2 performs the following reaction, was synthesized pentafluorosulfanyl pyridine compound.

[0042]

Formula 8

[0043] In 60mL polytetrafluoroethylene container, potassium fluoride under nitrogen was charged (spray-dried product, 6.03 g, 104 mmol, Wako Pure Chemical Industries, Ltd.) and acetonitrile (39 mL). The stirred mixture was cooled in a water bath containing the ice at the outlet pressure 0.005MPa with polytetrafluoroethylene tube (inner diameter 1 mm), the chlorine on the mixture (Cl 2 ; about 6.5 g ~ 7 .4g, it was bubbled about 91 ~ 104mmol) for 10 minutes. Subsequently pyridyl disulfide synthesized by the inventor (a4) (1.90g, 6.5mmol) was added under a nitrogen stream, the vessel was sealed and stirred at room temperature for 48 hours. After completion of the reaction, insoluble substances were removed using a glass filter under a nitrogen atmosphere. The filtrate vessel made of polytetrafluoroethylene, evaporated in vacuo and the resulting residue (2,6-difluoro-4-chloro-tetrafluoro sulfanyl pyridine (c4), 3.01 g, 90% yield) unpurified while it used in the next reaction.

[0044] To previous step resulting 30mL polytetrafluoroethylene vessel of 2,6-difluoro-4-chloro-tetrafluoro sulfanyl pyridine (c4) (2.58g, 10mmol), silver fluoride (I) (2. 54 g, 20 mmol) was added and the mixture was stirred for 48 hours at 120 ° C. under a nitrogen atmosphere. After cooling to room temperature, the mixture was stirred for 1 hour added water (10 mL) in dichloromethane (10 mL), the product was extracted with dichloromethane, the organic phase was dried over sodium sulfate. Then the solvent was distilled off under reduced pressure, silica gel column chromatography (pentane / dichloromethane = 20/1, Rf value 0.34) product was purified by (d4) (844 mg, 35% yield) as a colorless oil It was obtained as a thing.

[0045] Furthermore, the same synthesis, gave the product (d5). It summarizes the results of analysis by mass spectrometry and NMR as follows.

[0046]

Table 2

[0047]

Formula 9

[0048] [Example 3] were carried out nucleophilic substitution reactions to pentafluorosulfanyl pyridine synthesized as above (d1). Nucleophile Table 3, the reaction conditions, and shows the products, and the like.

[0049]

table 3

[0050] [Example 4] were nucleophilic substitution reactions to pentafluorosulfanyl pyridine synthesized as above (d3). Nucleophile Table 4, the reaction conditions, and shows the products, and the like.

[0051]

Table 4

[0052] [Example 5] was carried out nucleophilic substitution reactions to pentafluorosulfanyl pyridine synthesized as above (d2). Nucleophile Table 5, the reaction conditions, and shows the products, and the like.

[0053]

table 5

[0054] [Example 6] were nucleophilic substitution reactions to pentafluorosulfanyl pyridine synthesized as above (d4). Nucleophile Table 6, reaction conditions, and shows the products, and the like.

[0055]

Table 6

[0056] The present invention, it is clear that pyridine compounds having a pentafluorosulfanyl group at the 3-position or 4-position can be obtained. In the present invention, although it is pyridine compound having simultaneously a halogen atom and pentafluorosulfanylphenyl group, by performing the modification of a coupling reaction using a halogen atom, are useful in the synthesis of physiological substances, such as pharmaceuticals is there.

claims

[Requested item 1]Formula (d):

Chemical formula 1

(In the formula, SF 5 group is attached to either the 3 or 4 position of the pyridine ring, and R 2 is coupled to the other, R 1 , R 2 , R 3 , R 4Independently, a hydrogen atom, a halogen atom, from 1 to 18 substituted or unsubstituted alkyl group having carbon atoms of 6 to 30 substituted or unsubstituted aryl group having a carbon atom, a nitro group, a cyano group, from 1 to 18 substituted or unsubstituted alkanesulfonyl group having carbon atoms of 6 to 30 substituted or unsubstituted arenesulfonyl group having carbon, from 1 to 18 substituted or unsubstituted alkoxy having a carbon atom group, 6-30 substituted or unsubstituted aryloxy group having carbon atoms 1 to 18 acyloxy group having a carbon atom, a substituted or unsubstituted alkanesulfonyloxy group having 1 to 18 carbon atoms , substituted or unsubstituted arenesulfonyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl having 2-18 carbon atoms Job aryloxycarbonyl group, 7-30 carbon substituted or unsubstituted aryloxycarbonyl group having carbon atoms 2 to 18 substituted carbamoyl group having a carbon atom, a substituted amino group having 1 to 18 carbon atoms, an amino group , azide group, 7-30 amino substituted or unsubstituted aralkyl group having carbon atoms from 7 to 30 substituted or unsubstituted aralkyl sulfide group having carbon atoms, or SF 5 is a group) is represented by pentafluorosulfanyl pyridine that.

Requested item 2

Wherein R 1 and R 4 at least one is a fluorine atom, pentafluorosulfanyl pyridine according to claim 1.

Requested item 3

2-fluoro-3-pentafluorosulfanyl pyridine, 2,6-difluoro-3-pentafluorosulfanyl pyridine, or 6-fluoro-3-pentafluorosulfanyl pyridine, pentafluorosulfanyl pyridine according to claim 1.

Requested item 4

Formula (c '): [Chemical Formula 2] (wherein,

SF 4 Cl group is attached to either the 3 or 4 position of the pyridine ring, and R 2 is coupled to the other, R 1 , R 2 , R 3 , R 4

Independently, a hydrogen atom, a halogen atom, from 1 to 18 substituted or unsubstituted alkyl group having carbon atoms of 6 to 30 substituted or unsubstituted aryl group having a carbon atom, a nitro group, a cyano group, from 1 to 18 substituted or unsubstituted alkanesulfonyl group having carbon atoms of 6 to 30 substituted or unsubstituted arenesulfonyl group having carbon, from 1 to 18 substituted or unsubstituted alkoxy having a carbon atom group, 6-30 substituted or unsubstituted aryloxy group having carbon atoms 1 to 18 acyloxy group having a carbon atom, a substituted or unsubstituted alkanesulfonyloxy group having 1 to 18 carbon atoms , substituted or unsubstituted arenesulfonyl group having 6 to 30 carbon atoms, a substituted or unsubstituted a having 2 to 18 carbon atoms Job aryloxycarbonyl group, 7-30 carbon substituted or unsubstituted aryloxycarbonyl group having carbon atoms 2 to 18 substituted carbamoyl group having a carbon atom, a substituted amino group having 1 to 18 carbon atoms, an amino group , azide group, 7-30 amino substituted or unsubstituted aralkyl group having carbon atoms from 7 to 30 substituted or unsubstituted aralkyl sulfide group having carbon atoms, or SF 5 is a group) is represented by chlorotetrafluoroethane sulfanyl pyridine that.

Requested item 5

Wherein R 1 and R 4 at least one is a fluorine atom, chloro tetra sulfanyl pyridine according to claim 4.

Requested item 6

2-fluoro-3-chloro-tetrafluoro sulfanyl pyridine, 2,6-difluoro-3-chloro-tetrafluoro sulfanyl pyridine, or 6-fluoro-3-chloro-tetrafluoro sulfanyl pyridine, according to claim 4 chlorotetrafluoroethane sulfanyl pyridine.

Requested item 7

A method of manufacturing a pentafluorosulfanyl pyridine according to claim 1, the general formula (a):

of 3

(R 1 , R 2 , R 3 , and R 4 are defined as above) Table with chlorine pyridyl disulfide compounds, bromine, halogens selected from the group consisting of iodine and halogen compounds, and fluoro salt represented by the general formula (b): M + F - (b) (M is a metal atom , an ammonium group or a phosphonium group), and reacted, the general formula (c)

of 4

(R 1 , R 2 , R 3 , and R 4Are defined as above, X is a chlorine atom, a bromine atom or form a halo-tetrafluoro sulfanyl pyridine represented by a is) iodine atom, and the halo-tetrafluoro sulfanyl pyridine is reacted with a fluoride source penta comprising the step of forming a fluoro sulfanyl pyridine, production method.

Requested item 8

Halogen is reacted with pyridyl disulfide chlorine (Cl 2 is) The method of claim 7.

Requested item 9

Fluoro salt represented by the general formula (b) is an alkali metal fluoride, The method of claim 7.

Requested item 10

Wherein the fluoride source is hydrogen fluoride, the method according to any one of claims 7-9.