DE2041479A1 - Chemical process - Google Patents

Description

Folder 22347 - Dr.V / hr
Gases MD = 22140/22574

BÜSCHRBIBÜNG to the patent application of

IMPERIAL CHEMICAL INDUSTRIBS LIHITED, London Sf 1, Örosabritannien,

concerning
"Chemical process"

Priorities : August 20, 1969 and March 4, 1970 Gr o 8 ebr it an ni en

The present invention is directed to that. Production of bipyridylium salts and in particular on a. Terfatasn for the production of l _t l ^e ~ disubstituted 4 ₉ 4 ⁰ - "Bipy3ridjliwö _! - ealzen» which represent useful herbioids »ο

That part of the subject matter of the present invention goes for the production of Ι, Ι'-diiubstltaiert «! 4 _f 4 ^% '- pyridyliufflesaleeiiy in which the substitution "nti" n to itu contain 10 carbon atoms, consists in the fact that the corresponding M-substituted pyridinium alloys. under Tbaeitchen conditions with anions of the structure JWP-O ""odtr> P-3 ° "

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is converted, whereupon the resulting intermediate product is oxidized »

The anions can, for example, have the formula

P-O

or

P-S

where R ₁ and R _{a can be the} same or different and each denote an alkyl (e.g. up to 22 carbon atoms), aryl (e.g. phenyl), alkaryl or aralkyl group or a group of the formula R ¹ O-, R ¹ S -, R ' ₈ N or R' _S P, in which R * is a hydrocarbon radical, for example an alkyl, aryl, alkaryl or aralkyl group and in addition R "can be a hydrogen atom in the group R ^g _t H ~ and in which each of R ₁ and R _{1 is} a group of the formula R ¹ O-, R ¹ S-, R * _t N or R * »P, in which case the R ⁹ groups taken together can form an oyolic structure o R * preferably a phenyl group or an alkyl group containing 1 to 8 carbon atoms containing ₉ for example, a 'Äthylgruppeο

According to a particular imple mentation of the invention is the N-substituted pyridinium salt umgeeetet basisohen under conditions with a phosphonate _o Preferably, the phosphonate is one which au a phosphonate anion of the formula

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R ⁰ O

P-O R «0

leads, in which R ⁹ and R ″, which can be the same or different, are alkyl groups, aryl groups or aralkyl groups or groups which form part of a cyclic system

A large variety of cations can be combined with the anions, whereby the cations can conveniently be alkali metal ic ations phosphinites the Anionan may be added as described above in association with cations or they may, if desired seizures be formed in situ, "Sun, for example, phosphorus compounds are used, which lead under the prevailing reaction conditions to the desired anions _o under appropriate conditions can be applied phosphor itself are, for example in the presence of an alkali metal hydroxide "Examples of anions which can be used are dialkyl or diarylphosphinites and" thiophosphinites and üialkyl- or diarylphoaphonates and thiophosphonates and these can be made in situ from the corresponding n dialkyl or diaryl phosphines, phosphine oxide or phosphite are formed »The nomenclature used in the present description with regard to the phosphorus compounds is based on the" Handbook for Chemical Society Authors "1961, special edition 14, second edition«

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The reaction can be carried out in a simple manner by mixing the reactants and, if necessary, with heating, but ea is preweighed, the reaction is carried out in a solvent for the N-substituted pyridinium salt by supplying _u In general, aprotic solvents, especially polar aprotic solvents, are preferred although in certain cases, especially when working with a phosphine, protic solvents such as water and alcohol can be used, for example mixtures of water and ethanol. Examples of organic solvents which can be used are ethers and thioethers , for example tetrahydrofuran, 1,2-dimethoxyethane, bis (2 ~ ethoxyethyl) ether, 1,4-dioxane and thiophene; Ketones, for example acetone; Hydrocarbons such as benzene, toluene, xylene and hexane; organic bases, for example pyridine; halogenated hydrocarbons and in particular chlorinated hydrocarbons, for example chlorobenzene, chloroform, carbon tetrachloride and methylene dichloride; Amides, in particular tertiary alkylamides, for example dimethylformemic; Sulfoxides, for example dimethyl sulfoxide; Sulfones, for example suIfolan; Nitriles, for example acetonitrile; Nitro compounds, for example nitro propane; and alkyl carbonates and sulfates, for example propylene carbonate and dimethyl sulfate

Dipolar aprotisohe solvent, for example dimethylformamide, dimethylsulfoxide and acetonitrile are particularly suitable solvents, as high yields in their use are obtained at BipyridyliumsalBen _c If desired, can also be used Löeungaaittelmlsohungen.

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Me temperature j at which the reaction is carried out "not iat critical, although it is advantageous in pointed cases Reaktionsmiechung to warm" In general, the reaction may be at a temperature of 25 fei® 120 ⁰ O, preferably from 40 to 9O ⁰ G , be performed. Temperatures above 150 ⁰ C should generally be avoided »The reaction is usually carried out under an inert atmosphere,

The reaction takes place under basic conditions and preferably, but not necessarily, in the presence of an added base. Ee can also be used with organic bases, for example with Diazabicvclö-octane, 1 _f 5-Biazabicyelo (5,4, O) undec "5'-en, 1,5-Diazabicyelo (4,3,0) -non" 5 ~ ene, triethylamine and piperidine,

The amount of phosphorus compound used to deliver the anions is ... not critical and the optimal amount depends on the particular reaction conditions used, including whether the reaction is carried out in the presence of an organic substance or * in deffi case, - where the reaction a β organic amine is carried out in the absence, it will bvorgezogen, MoI iee a phosphorus containing anion aindeettnn · per haul P / ridinlution aaettiwa- ■ * the Anderereeite where in the PaIIe ₉ dio. leolction ia .presence of an organic amine takes place, the inio »regenerates, so there is catalytic amounts of the same .sufficient binding , '' . ....

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Any N-substituted pyridinium salt can be converted into a bipyridylium salt by the process which is the subject of the invention which contains an N-substituent which has up to 10 carbon atoms o Particularly suitable salts are those which have an alkyl or carbamidoalkyl substituent and in particular a methyl - or carbamidonethyl substituents, and »was on the nitrogen atom of the pvridine nucleus. The Oarbamidoalkylaubstituent has the formula -R ₄ -CJO-NR ₈ Rg, wherein R _{4 is} a hydrocarbon radical, for example alkylene (In particular the methylene radical) and R, and Rg are hydrocarbon or substituted hydrocarbon radicals, for example alkyl, where R ₁ and Rg together with the bonded nitrogen atom can form a heterocyclic ring, for example an optionally substituted piperidine or horpholine group a halide and, in particular, an chloride ideal, although the nature of the anion is not critical and, if desired, other salts can also be used. The pyridine nucleus can be substituted, for example by alkyl groups or aryl or functional groups, ie carboxyl, nitrile or carboxyaldehyde groups in the 2 ·, 3, 5 ™ and 6-S divisions, whereby the 4-position is preferred » wise should not be substituted leg. In the case of an N-alkyl or N-carbamide alkyl pyridinium salt, the Alkyl group preferably contain from 1 to 4 carbon atoms ο

The reaction product, namely a 1'-disubstituted 1,1'-dihydro-4,4'-pyridyl derived from the pyridinium salt and the phosphorus compound, can easily become the corresponding Ι, Ι'-disubstituted 4,4 * -bipyridylium salB

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are oxidized by treatment with an oxidizing agent, which is an electron acceptor and has a redox potential in water which is more positive than = 0.50 volts, compared with the saturated GaLomel "electrode" Examples of suitable Oxidizing agent and Ger sulfate (in dilute sulfuric acid) '■; .Metal salts, especially the halides! inorganic oxyacid anhydrides, especially sulfur dioxide! Chlorine § Air, preferably in combination with water and / or carbon dioxide and / or an acid, for example acetic acid or sulfur start; iiowle organic oxidants, for example quinones, such as benzoquinone, chlorenil and anthraquinone. The oxidation is preferably performed under acidic conditions durchgeführt® wherein the pH value of preferably below 7, and Reaktionemisoaung zweckmäseig 4-6 is · The Zuaats the oxidizing agent in an acidic medium is gewunnliolL sufficient to xu to this result, gel say ₀ Gewilnscli ™ case scenario, the dihydrobipyridyl interstitial product can be isolated before oxidation «,

If the reaction is carried out in the presence of a polar aprotic solvent, the resulting dihydrobipyridyl can be isolated, _for example, by adding water, an organic acid or a base to the reaction mixture; acetic acid is the preferred organic one Acids and organic bases are "the preferred bases. The base can be anhydrous" or it can be used in the form of its aqueous solution. The addition of these substances forms a sludge in which the dihydrobipyridyl can be separated out by extraction or filtration. The temperature of the treatment can be between O and 100 ⁰ O vorsjugsweiee and between 20 to 50 ⁰ C _c lieg®n

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In the case where the intermediate product is a sludge, the Feetatoff can be filtered off or, preferably, isolated by solvent extraction. Suitable solvents for the extraction are hydrocarbons, especially aromatic hydrocarbons and especially toluenes. The temperature can be between 0 and 10O ⁰ C. After the pesticide has been removed, part of the intermediate product remains in the liquid phase oxidized to the bipyridylium salt, this sale being isolated in the manner described or by reduction, whereby a further amount of the solid is obtained, which can be isolated in the manner indicated before it is oxidized an alkali metal amalgamβ or a dithionite Sn

The product obtained as a result of this treatment is easily oxidized with a greater variety of oxidizing agents than is the case with respect to the solution The case before the treatment is »The solid which is obtained by adding a barrel or a base to the solution of the intermediate product is a!, l'-substituted one 1,1'-dihydro-4,4'-bipyridyls

l, l '~ disubstituted 4 _t 4 ^l -pyridylium cations can be separated in two ways from the ions of the phosphorus compound in the reaction mixture by treating the mixture with 4,4'-diaminoethylbene-2.2 ^t -dieulfonic acid, which is also known as Amsonic acid is called "The bipyridylium cation is precipitated from the mixture in the form of the amsonate salt, while the ions of the phosphorus compound remain in the mixture." The precipitate can then be separated off by filtration, washed and

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conventional manner are dried and dia AmBonsäure can be regenerated and recovered for reuse, by acidifying the Amsonaalisee, Tonragswüie® by applying an aqueous Säurelijiung "which is used for recovering the Amsonsäur® This Säur® ,, _$ can be selected in such a way that · da · desired anion of the resulting bipyridylium is supplied and it may consist of beispielsweiae Salzeäurt _v · Hioaphoraiur or acetic acid.

The amino acid is only iiohwaoii lttalioh in water and is therefore usually in the form of an aqueous solution in the form of an aqueous solution in water, preferably in the form of an alkali metal salt or de Treatment of the reaction chemistry with Ameontäuro loum “can be carried out at a pH value within the range from 7 to 12 and at a temperature of over 10O ⁰ C”,

The l ₉ l'-dieubrtftuierten 4 _f 4 ⁹ -BipjridyliiiBike, tioiifii klBameia also be separated from the Aaionea of the Phoephorverbiadung ta 4er Recktionifflieoh.miig, thee · Mieohuag with eiaeai the suitable cation is brought here Urn! IiaÄorcb and remaining ia the mieehung, mo da ·· ei · το a Ami BipyridylluBkatioa are tronated · The bipyridylium cation kfyan sweokmäeeig do de lonenaustaueohhors freiftHÄOlit become ·· elite, and swar 4ureh BnhaÄd BIpyrIdylluaisals received, at dom due Anion da · duroh the acid · delivered · let _o Beiapiei · ναa JUiionta, iraloh · on the ·· lei ·· im di · Mivehuiag βΐΐιβ · -

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ίο ->

are chloride, sulfate and acetate ions.

The temperature at which the mixture with the ion exchange resin into contact made is not critical, and can lie between O and 10O ⁰ C, "Examples of suitable Kationaüstauaohharzen are the Zeocarb-Kationenaustauechharze, for example Zeooarb 225 (SRC-8), wl "Amberlite ion exchangers Kat ze _y example, Amber lite Resin C6-120 and Deaclditüarze _r

The invention is explained in more detail in the following examples, without being restricted thereto

example 1

This example explains the use of Diphenylphos * phinite anions, which have been produced in situ from diphenylphosphine oxide, which itself is a complex in situ was produced by diphenylphosphine oxide and acetone «,

A complex of diphenylphosphine oxide and acetone (10.4 g) was ^{heated to 150 ° C.} under vacuum (0.1 mm Hg) until the acetone had been removed. The residue was cooled and it was then poured into dimethylformamide (60 ml) was, after which sodium metal (0.9 g) were wurdOc then, 1.2 g of N-Methylpyridiniumohlorid zugesetztο the Ruhr treatment was continued for a further 3 hours at 6O ⁰ C, whereupon the mixture was cooled to room temperature and poured into an aqueous solution of sulfur dioxide ο Hi ine apektrophotometriaohe analysis of the resulting solution indicated the presence of 6.45 g 1,1 "-Dimethyl-4 | 4 ^J -bipyridylium-dication, which is a reaction * - *

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yield of $ 53, based on the approach of the methylpyridinium salt, corresponded.

Example 2

This example illustrates the use of sodium diphenyl pho sphonat ο

0.9 g of sodium metal were added to a stirred solution; added of 10.36 g of diphenyl phosphite in 10 ml dioxane at a temperature of 40 ⁰ G and di © RiShr treatment.-was continued until .to calibration das..Natrium gelbst had For _o a solution of 1.27 g N-Methylbipyridyniumohloriä in 30 *. ml of dimethyl sulfoxide eye set and the mixture was made

Stirred for 3 hours at 65 ⁰ C and cooled after the lapse of this time and in an aqueous solution of sulfur dioxide gegosBen ₀ A spectrophotometric analysis of the imaging he mixture showed the presence WAO ₉ Ig l l _f ^Q ^ dimethyl-4.4 ° "bipyridyllum -dication * an ,. which corresponds to a reaction yield of 14 % with reference to the N-methylpyridinium salt used ο

Example 3

Kine dispersion of 1.44 g.ITätriumhydroxyd, in-O'l a solution of 4.14 g (0.03 mole) of diethyl phosphite in 40 ml of anhydrous dimethylformamide was added to form the _β Natriumdiäthylphosphonat Then, 1.264 g. N-methylpyridinium chloride was added and the mixture was added

Stirred for 4 hours at 75 ^° C. and then cooled. Di © resulting solution contained 1.1 _{°.-Dimethyl-9} I I "-dihydro-4,4 bipyridyl ^a ~ (determined by a peak at 400 mu in the ultraviolet spectrum and a shoulder at 374 mu)"

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An aqueous solution of 100 ml of sulfur dioxide was added to the cooled reaction mixture. The resulting solution was analyzed by polarographic and spectrophotometric analysis and it was found that it contained 62.8 mg of ^{1,1'-dimethyl-4,4 0} -bipyridylation, which a reaction yield of 6.9 ^ nit BeBug on the N-methylpyridinium chloride used corresponded ο

Example 4

The procedure of Example 3 was repeated with the modification that the Reaktionsmisohung during the 4 hour reaction period in portions 1.44 g of sodium hydride was added to _e The reaction yield was 12 i 'with respect to the N-methylpyridinium chloride _o

Example 5

1.44 g of sodium hydride as a 50 ^ dispersion in oil were added to a solution of 7.02 g (0.03 mol) of diphenyl phosphite in 40 ml of dimethylformamide and the mixture was stirred under heating at 7O ⁰ C _o

Then 1.356 g of N-methylpyridinium chloride was added, whereby a dark brown discoloration developed. The heating to 70 ⁰ O was carried out for 4 hours, after which the mixture was then cooled and an aqueous solution of sulfur dioxide was added to it. The resulting solution contained 404 mg l, l ^c -dimethyl ~ 4,4 ' ^! ~ bipyridyliuinkation what a Reaktionsauebeute of 41 i 'with respect to the N-methylpyridinium correspond

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Example 6

0.618 M sulfur was added to a solution of 3 »59 g diphenylphosphine in 10 ml benzene to give a solution of diphenylphosphine sulfide. This solution was added with 30 ml of dimethylformamide and 0.925 g of sodium hydride in 50 ^ pore of a dispersion in oil and the resulting mixture was heated under Rühren.auf 70 ⁰ C. Then a solution of 1.08 g N-methylpyridinium chloride in 10 ml Dimethylformamide was added and heating was continued for an additional 3 hours, after which the mixture was cooled. An aqueous solution of sulfur dioxide was then added to give a solution containing 177 mg of ^{1,1 o} -dimethyl-4,4 * -bipyridylium " cation contained, waa a reaction yield of 23 pounds with respect to the N-methylpyridinium chloride used.

Example 7

A solution of 1.6 g (0.03 mol) of sodium hydroxide in 5 liters of water was added dropwise over 30 minutes to a stirred slurry of 3 g of yellow phosphorus and 1.3 g of N-methylpyridinium chloride in 30 ml of dimethyl sulfoxide at 60 ° C The resulting mixture was heated for an additional two and a half hours, then cooled and added to an aqueous solution of carbohydrate dioxide. The product consisted of the l, l ^u -dimethyl-4,4 ° -bipyridylium cation and the reaction yield was 3 # with respect to the methylpyridiniunorido used

Example β

1.27 λ (0.01 mol) of N-methylpyridinium chloride was added to a stirred solution of 4.68 g (0.02 mol) of diphenylphosphite

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and 3.7 * g (0.03 mol) I ₁ 5-diazabicyclo- (4,3, O) ~ non ~ 5-ene in 40 ml of dimethylformamide at 65 ⁰ C added o The color of the solution went from orange to dark green / brown over _{c The} ultraviolet spectrum of this solution showed strong absorptions at 400 m and 374 m _t which indicate the presence of

indicates tec

After 4 hours the mixture was cooled and poured into an aqueous solution of Schwef'eldioxyd _c Through polarographic analysis and spectroscopy ^ was found DAEs _t the resulting solution I, l ^3-dimethyl ~ 4,4 '~ bipyridyliumkation in an amount of 0.183 g contained, representing a reaction yield of 20 f> Bezu "to the N-methylpyridinium chloride corresponded _β

Example 9

Bine solution -from 0.02 mol methylpyridinium chloride in 30 ml of dimethylformamide was added in 20 ml dioxane dropwise with stirring a solution of 0.02 mol Oiäthylphosphonat r The mixture turned immediately to yellow to "After like einstund i heating the mixture to 90 ⁰ O this was cooled and chilled liquid sulfur dioxide was added

The excess sulfur dioxide was removed from the mixture by blowing nitrogen through it. The mixture contained 1,1'-dimethyl-4,4 ^ bIPyIIdJIiUiIiOn ₁ .

Example 10

with a stirred solution of sodium diphenylphoaphonate (made from 7.26 g diphenyl phosphite and 0.72 g sodium hydride) in 35 ml of dimethylformamide were 1.29 g of N-dieethyl

BATHROOM 0RK3HNAL 109810/2273

15 - ■ - '

aminoacetylpyridinium chloride added. The mixture was added Heated for 3 hours to 60 ° 0 and 'it turned red-brown with the separation of a red-brown solid so Di Mixture was then cooled, treated with an aqueous solution of sulfur dioxide and extracted with "ether * The aqueous phase separated and it showed up. by spectrophotometric determination of the blue residue, the with the addition of. Sodium dithionite to a sample of the

a pH of 9.2 buffered aqueous phase was obtained that this contained 0.94 g of N ^ -Pi-Cdimethylaininoacetyl) - *!, * » ¹ -bipyridylium chloride» which corresponded to a efficiency of T0% based on the pyridiniuras salt used.

The aqueous phase was evaporated to a volume of 20 ml and a saturated solution of ammonium amsonate was added, resulting in a deep purple precipitate of the amsonate salt. The amsonate salt was suspended in water and treated with dilute hydrochloric acid to separate out the amsonate acid was removed and the aqueous solution was evaporated to dryness and gave a pale brown Peststoffα By recrystallization of this Peststoffes from "ethanol 0 * 75 g of N, N ⁰ -di (dimethylaminoacetyl) -4.4 ⁰ ° bipyridylium.-dichloride in the form obtained from white crystals, which turned blue when exposed to sunlight-

r ■ ■

Example 11

1.09 g N-methylpyridinium chloride a solution of Natriumdiphenylphosphonat (prepared from 7.26 g of diphenyl phosphite and 0.72 g of sodium hydride) in 40 ml of dimethylformamide, added at 90 ⁰ O After 2 1/2 hours, the reaction 'mixture was cooled and filtered through Addition of aqueous sulfur

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dioxide The oxidized aqueous phase contained, as determined by epektrophotometrische Analyee, 0.35 g of 1,1-dimethyl ° 4.4 ° -bipyridyliumkat ions ο The reaction »» yield was 44 based i> to the N-Ii eingesetgte ethylpyridinium .

Example 12

If09 g of methylpyridinium chloride were added under nitrogen to a stirred solution of sodium diphenylphosphonate (made from 7 * 26 g of diphenylphosphite and 0.72 g of sodium hydride) in 40 ml of dimethylformamide at 150 ^° C. After 2 1/2 hours, the reaction mixture was cooled and The yield of bipyridylium ion in the aqueous phase was determined apectrophotometrically and the reaction yield was 40%, based on the N-methylpyridinium chloride used

Example 13

This example and examples 14 to 16 explain the use of protic solvents,

A slurry of 0.01 mol of diphenylphosphine oxide and 0.6 g of lithium hydroxide in 15 ml of water was a solution of. 1.35 g of N-methyl pyridinium chloride in IC ml of water were added. The mixture was stirred under nitrogen for 3 hours, cooled and oxidized by the addition of aqueous sulfur dioxide. The l _f l ^t -dimethyl'-4 ₉ 4 ^q -bipyrldyliumkatlon was obtained with a yield of 3.3 ^ based on the pyridinium salt used.

1 0 9 8 1 0/7? 7 3

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Example 14

2.6 g of the complex compound Diphsnylphosphinoxyd ^ acetone were heated under vacuum (1.0 mm Hg) for one hour at 15O ⁰ C. The cooled down. Residue of Diphenylphosphinoxyd was a .Lesung of 1.35 g N-Methylpyridiniumchlorld in 10 ml water and a solution of 0.81 g in 10 ml water Lithiumhydroxydmonohydrat zügesetBt ₀ The stirred mixture was then heated to 9O ⁰ C for 3 hours, cooled and treated with aqueous sulfur dioxide

The solution was analyzed spektrophotometrisoh and it was found that these ° -dim ethyl 1 to 4.4 ^u ~ bipyridyliumkation contained _v what entsprach- 0.03 g 1,1 a Reaktionsausbeut «3.5 ^

Example 15

0.02 mol of diphenylphosphine oxide was added to a solution of 0.02 mol of sodium ethoxide in 30 ml of absolute ethanol. Diethylene mixture was heated under nitrogen to 75 to 80 ⁰ C and treated with 1.22 g N ~ Methylpyrldiniumohlorld treated After 3 hours the mixture was cooled and oxidized to l, l ^J ~ dieubetituierhftß 4,4'-Bipyridyliumion with a reaction yield from 33 '/ » to surrender-,

Example 16 e

A solution of 0.02 mol of the Diphenylphoephinoxyd-Aoetonkomplexes in absolute ethanol was a solution of 0.02 mol of sodium ethoxide in 10 ml of ethanol sugeseteto the mixture was heated under gentle reflux and 1.22 g of Ν-methylpyridinium chloride were replaced Stirred for hours at 70 to ÖO ^Ü C, cooled and done

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Addition of aqueous sulfur dioxide oxidized

By analyzing the solution, it was found that the 1,1 * -dimethylpyridinium ion was obtained in an amount corresponding to a yield of 33 * 0 f>

Pattntanaprtlohti

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Claims (1)

Patent claims e ι Process for the preparation of!, L'-disubstituted ', 4 ⁹ ~ bipyridylium salts _f with each of the substituents containing up to 10 carbon atoms, characterized in that the corresponding N-substituted pyridinium salt is reacted under basic conditions with anions which have the structure> P ~ 0 "or> PS ~, whereupon the resulting intermediate is oxidized o ? .o Method according to claim 1, characterized in that that the anions of the formula P-O or P-S where R ₁ and R _{t can be} identical or different and each of them is an alkyl, aryl, alkaryl or aralkyl group or a group of the formula R'0 ~, R ⁰ S = -, R ° ₂ N or R ° _{a is} P, where R ^{v is} a hydrocarbon radical and additionally R ^{0 can be} a hydrogen atom in the group R '»N ~ and where, if each of the radicals Rt and R _{8 is} a group R« Ό-, R'S · = ·, R ', N or R ^tt _t P, then the · R' groups taken together can form an cyclic structure ^ 3ο method according to claim 2, characterized in that that H _x UHdE _{1 are} groups of the formula R ¹ O, R ⁰ S, RV ₈ N or R ' ₈ P, where R ^{D is} a phenyl group or an alkyl group containing 1 to 8 carbon atoms. 109810/2273 204H79 4ϊ method according to one of the preceding claims, characterized in that the converted pyridinium alkali an alkylpyridinium salt or an N-carbamidoalkylpyridinium salt Ibto 5. The method according to any one of the preceding claims, characterized in that the reaction of the N-substituted pyridinium salt with the anion is carried out at a temperature of 25 to 12O ⁰ C Sc method according to any of the preceding claims, characterized in that the reaction of N-substituted pyridinium salt is carried out with the anion in a polar aprotic solvent> 7- Method according to one of the preceding claims, characterized in that the intermediate product is isolated before it is oxidized ₀ 8- method according to one of the preceding claims, characterized in that the oxidation occurs at a pH performed by less than 7 r 9- Method according to one of the preceding claims, characterized in that the oxidation using sulfur dioxide as an oxidant performed wirdo 10. The method according to any one of the preceding claims, characterized in that the N-substituted pyridinium salt is reacted with elnoia phosphonate under basic conditions, patent attorney IUO. H. HtKKI. DIPt-WA H. ^ g s 109810/2273