DD298667A5 - ELECTROCHEMICAL METHOD FOR THE PREPARATION OF C-FLUORIZED AMIDOSULFONSAEUREDERIVATE - Google Patents

Abstract

The invention relates to the preparation of new C-fluorinated Amidosulfonsaeurederivate. The new amidosulfonic acid derivatives of the general formula ## STR4 ## in which R.sup.F and R.sup.F are either alkyl or cycloalkyl radicals having in each case one to seven C atoms, where R.sup.5 can also be R'F, which together with the nitrogen atom is a 5- to 7-membered form saturated or unseasoned cycle, which also contain other heteroatoms such as oxygen and / or nitrogen and which can carry up to two alkyl substituents each having up to four carbon atoms, in each case the hydrogen atoms of the RF and R 'F wholly or partially replaced by fluorine atoms are prepared by electrofluorination of the corresponding hydrogen-containing, saturated, unsaturated or aromatic compounds. The new compounds can be used as biologically active substances in agriculture or food industry or in medicine and serve as starting material for syntheses of such compounds. {C-F compounds; Amidosulfonic acid derivatives, fluorinated; electrofluorination; Means, biocides; herbicides; Insecticides; Preservatives; bactericidal}

Description

R '

N - SO ₂ X

in which R and R 'are either an alkyl or cycloalkyl radical or an aromatic compound having in each case up to seven C atoms, where R can also be R', or together with the nitrogen atom form a cycle which is saturated, unsaturated or aromatic may be and contain other heteroatoms such as oxygen and / or nitrogen and tragan up to two alkyl substituents each having up to four carbon atoms, X is halogen, hydroxyl, methyl, ethyl or propyl or acid anhydride, electrochemically in Anhydrous liquid hydrogen fluoride are fluorinated to nickel anodes.

2. The method according to claim 1, characterized in that R _F and R _F alike or each preferably for itself equal to trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, 1,1,1,2-tetrafluoroethyl, 1,1,2,2-tetrafluoroethyl, 1 , 1,1-trifluoroethyl, 1,1,2-trifluoroethyl, 1,2,2-trifluoroethyl or heptafluoropropyl.

3. The method according to claim 1, characterized in that R _F and R _F together with the nitrogen atom form a ring system preferably from the group Polyfluorpiperidino, -pyrrolidino, -morpholino or -piperazino.

4. Mixture C-fluorinated amidosulfonic acid derivatives, characterized in that it consists essentially of

N-N-bis (trifluoromethyl) amidosulfonylfluorid

N-difluoromethyl-N-trifluormethylamidosulfonylfluoridund

N-N-bis (difluoromethyl) amidosulfonylfluorid

consists.

Field of application of the invention

The invention relates to a process for the preparation of novel C-fluorinated, N-substituted amidosulfonic acid derivatives. The C-fluorinated Amidosulfonsäurederivate produced according to the invention can be used as biologically active compounds in the agricultural or food industry or in the Mediz ^! n find and serve as starting materials for Synlhesen such compounds.

Known state of the art

For the fluorination of amines, the method of electrochemical fluorination in liquid, anhydrous hydrogen fluoride, the so-called Simons process, has long been proven (see, for example, S. Nagase, Electrochemical Fluorination, Fluorine Chem. Rev. 1 (1), 77-106) (1967) The aim of this method is to exchange all hydrogen atoms for fluorine atoms to give the corresponding fluorine compounds, and to generate varying amounts of products containing both F and Η atoms as well as fragmentation products is also used to convert sulfonic acids to the corresponding perfluorosulfonic acids (see, for example, AJ Rudge, Electrochemical Flurination, ATKuhn, (rirsgb.) Industrial Electrochemical Processes, p.71-88, Amsterdam-London-New York, 1971 However, all these compounds differ from those which can be prepared according to the invention in that they contain no N-SO! X bond.

Object of the invention

It is the object of the invention to produce new C-fluorinated amidosulphonic acid derivatives.

Oarlegu ig the essence of the invention

The invention has for its object to develop processes for the preparation of new C-fluorinated Amidosulfonsäurederivate. C-fluorinated amidosulfonic acid derivatives of general formula I are prepared according to the invention

N - SO ₂ FI

* f

wherein R _F and Rf are either alkyl or cycloalkyl radicals each having one to seven C atoms, wherein R _{f may} also be Rf, or together with the nitrogen atom form a 5- to 7g! Low, saturated or unsaturated cycle, the also contain other heteroatoms such as oxygen and / or nitrogen and can carry up to four carbon atoms, in each case the hydrogen atoms of Rr and Rf are wholly or partially replaced by fluorine atoms.

Preferred compounds are those in which Rp and Rf are alike or each individually trifluoromethyl, difluoromethyl,

Fiuormethyl, pentafluoroethyl, 1,1,1,2-tetrafluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,1, vifluoroethyl, 1,1,2-trifluoroethyl, 1,2,2-trifluoroethyl, or those where Rf and Rf together with the nitrogen atom form the ring systems Perf'uorpiperidino, -pyrrolidino, -morpholine or -piperazino.

Most preferably, the compound is bis (trifluoromethyl) amidosulfonyl fluoride.

Further preferred compounds according to the invention are:

Bis (pentafluoroethyl) amidosulfonylfluorid

Trifluormethylpentafluorethylamidosulfonylfluorid

Perfluormorpholino-N-sulfonyl fluoride

Porfluorpiperidino-N-sulfonyl fluoride

Perfluorpyrrollidino-N-sulfonyl fluoride

Bis (difluoromethyl) amidosulfonylfluorid

The new compounds can be prepared by electrochemical fluorination in anhydrous liquid hydrogen fluoride from Amidosuifonsäurederivaten the general formula II

- SO ₂ X

in which R and R 'are either an alkyl or cycloalkyl radical or an aromatic radical having in each case up to seven carbon atoms, where R can also be R', or together with the nitrogen atom form a cycle which is saturated, unsaturated or may be aromatic and contain further heteroatoms such as oxygen and / or nitrogen and may carry up to two alkyl substituents each having up to four C atoms, X is halogen, hydroxyl, methyl, ethyl or propyl or acid anhydride.

The new C-fluorinated amidosulfonyl fluorides are biologically active compounds which can find use in the agricultural or food industry or in medicine or which can serve as starting materials for syntheses of such compounds.

Electrochemical fluorination is conducted in a Simons cell on nickel anodes in anhydrous liquid hydrogen fluoride at 4.5V to 9V, preferably at 5V to 8V, with densities of 0.05A / dm ² to 8A / dm ² , preferably at 0.1 A / dm ² to 3 A / dm ² , and at -20 ° C to + 40 ⁰ C, preferably at 0 ° C to 19 ⁰ C performed. The starting compounds are in liquid

Hydrogen fluoride with the formation of electrically conductive solutions readily soluble. The fluorination products formed are expelled from the hydrogen fluoride by an inert gas stream or separated off as a specific heavier soil phase. The crude fluorination product obtained is freed from hydrogen fluoride, e.g. B. by sodium or potassium fluoride, and if necessary separated by distillation. The identification of the obtained and optionally by preparative GC highly purified C-fluorinated Aminosulfonsäurederivate can be done by ^'9 F-NMR, MS and elemental analysis. It was surprising for the person skilled in the art that compounds with a nitrogen-sulfur bond can be prepared by means of electrofluorination. There were no publications so far.

The compounds of the invention may be used in medicine as bactericidal agents. Because of their excellent biocidal properties they are also useful in agriculture as fungicidal and insecticidal agents, in particular for controlling fungi and insects in cereals, preferably in grain deposits or during transport. In the food industry, use as a preservative is possible. Further details are contained in the simultaneously filed patent application, which is incorporated herein by reference.

embodiments

The invention will be explained in more detail by examples.

Unprecedented 3

104g (0.82 moles) of N-dimethylamidosulfonyl fluoride (A) are added portionwise into an electrofluorination cell filled with 500 ml of liquid anhydrous hydrogen fluoride and at a voltage of between 5 and 5 for a period ranging from 3 to 9A for currents of about 250A , 5V and current densities between 1 and

3 A dm ' ² electrolyzed. The portionwise addition of (A) was carried out in such a way that at OAh 39.2 g at 107.5Ah 20.4g, at 157 Ah 27.6g and at 218.4 Ah the last 16.8 g were added into the cell. The electrolysis was done with a

4 Ni anodes and 5 Ni cathodes existing electrode package performed. The distance between anode and death was 4.5 mm and the effective anodone area was 3 dm ² . The hydrogen fluoride losses were registered by means of a level indicator tube and constantly supplemented in such a way that the electrolyte level in the cell oscillated between 480 and 500 ml. The temperature of the Elektrofluorierungszelle was about 1O ⁰ C and the reflux -20 "C. Behind the reflux condenser there were three copper heat traps at -2O ⁰ C, -50 ⁰ C and -78 ⁰ C were cooled.

After completion of the electrolysis, the 3 cold traps were heated to 0 ° C, opened and the condensation contents combined. There were obtained 85 g of a biphasic condensate, which, after separation of the hydrogen fluoride, is converted into a one-phase crude product mixture which can be separated by distillation as follows:

(1) 70% Kp .: 29-35 ⁰ C.

(2) 5% bp .: 35-45 ⁰ C /

(3) 15% Kp .: 45-5O ⁰ C

(4) 4% Kp .: 50-75 ⁰ C.

(5) 5% Kp .: 75-100 ⁰ C.

By elemental analysis and NMR ( ¹⁹ F and 'HI investigations, the components of the individual fractions could be identified.

(1) as N, N-bis (trifluoromethyl) amidosulfonyl fluoride (I) (GC purity 85-90%)

(2) as I (GC 32%) and II (GC 53%)

(3) as N-trifluoromethyl-N-difluoromethylamidesulfonylfluoride (GC purity 85%) and about 10% III

(4) as Il (40%) and III (50%)

(5) as N, N-bis (difluoromethyl) amidesulfonyl fluoride (III) (GC purity 75%)

By fractional distillation, the compounds I bb III can be separated in a purity higher than 95%.

The analysis yielded the following results:

N N-bis (trifluoromethyl) amidosulfonylfiuorid (l),

. Bp = 32-33 ⁰ C; C ₂ F ₇ NSO ₂

The structure of the individual compound was proved by elemental analysis and ¹⁹ F NMR spectroscopy.

The "F-NMR spectrum was recorded in d" _{6 "} acetone as solvent over trifluoromethane as reference substance with a" BRUKER-WP-200 "device.

Elemental Analysis: Gef. Theo /.

F (%) 56.33; 56.45 56.57 N (%) 5.28; 5.48 5.96

¹⁹ F: -53.23 ppm, d, ⁴ Jp ρ = 5.9 Hz, 6F (CF ₃ ) 62.05 ppm, m, ⁴ J _F , F = 5.9 Hz, 1 F (SO ₂ ) N-difluoromethyl-N trifluoromethylamidosulphonyl fluoride (II)

. Bp = 52-53 ⁰ C; C ₂ HFeNSO ₂

Dio structure of the individual compound was detected by ' ⁹ F-NMR and' H-NMU spectroscopy. The ¹⁹ F-NMR Ή-NMR spectra were recorded in d _e -acetone as solvent over trichlorofluoromethane or hexamethyldisiloxane as reference substances with a "BRUKER-WP-200" device.

¹⁹ F: 61.12ppm, m, ⁴ Jf ₁ F = 6.0Hz, 1F (SO ₂ F) -53.5ppm, m, 3 F (CF ₃ )

-97.1 ppm, dm, ⁴ J _F F = 6.0 Hz, ^a J _H F = 54.5 Hz 2 F (CHF ₂ ) ¹ H: 7.68 ppm, tm, ² J _- F = 54.6 Hz ₁ IH (CuFj) N, N-bis (difluoromethyl) amidosulfonyl fluoride (III)

. Bp = 86-88 ⁰ C; C ₂ H ₂ F ₆ NSO ₂

The structure of the individual compound was confirmed by elemental analysis and ¹⁹ F and Ή NMR spectroscopy. The ¹⁹ F and Ή-NMR spectra were recorded in dyAcetone as solvent against trichlorofluoromethane and hexamethyldisiloxane as reference substances with a "BRUKER-WP-200" device.

Elemental Analysis: Gef. Theor.

C (%) 12.61; 12,63 12.07

H (%) 0.97; 1.03 1,00

F (%) 41.27, 41.13 42.71

¹⁹ F: -97.04 ppm, ie, ² J _n F = 56.7 Hz, ⁴ J ", f = 6.6 Hz 4 F (CHF ₂ )

61.05 ppm, t, ⁴ Jh.f = 6.6 Hz, 1F (SO ₂ F) ¹ H: 7,5ppm, tt, ² J = 56,7Hz _Hl F, ⁴ J = 6.6Hz _HIF, 2H (CHF ₂ )

Claims (1)

1. A process for the preparation of C-fluorinated Amidosulfonsäurederivaten aer general formula I ^R F N - SO _n F ι ^Rt F in which Rf and Rp are either alkyl or cycloalkyl radicals each having one to seven C atoms, wherein Rf may also be Rpsein, or together with the nitrogen atom form a 5- to 7-membered, saturated or unsaturated cycle, which also contains further heteroatoms such as Contain oxygen and / or nitrogen and carry up to two alkyl substituents each having up to four carbon atoms, ν 'ei in any case, the hydrogen atoms of Rf and R _{F are} wholly or partially replaced by fluorine atoms, characterized in that Amidosulfonsäurederivate the general formula II