DE1951803A1 - Process for the preparation of dihydroxyarylsulfonium salts - Google Patents

Description

Dr. F. Zumsteln ten. - Dr. E. Assmann 6F-2914 *

Dr. R. Koenigsberger - Dipl. Phys. R. Holzbauer

Dr. F. Zumstein jun.
P α t β η r α η w a I te. 8 Mönchen 2, Bräuhausstraße 4 / III 1951803

Process for the preparation of dihydroxyarylsulfonium salts

The present invention relates to a new method for Production of dihydroxyarylsulfonium salts and those obtained therewith new connections.

For the synthesis of aromatic sulfonium salts are different Processes known which generally use sulfoxides as starting materials in addition to the aromatic compound. It however, until now there was no generally applicable method to isolate dihydroxy-S arylsulfonium salts of various kinds to produce.

A method has now been found which allows these connections obtainable in a simple manner in high yields. It is characterized in that one has 1,4-quinones with a free m-position to a quinoid oxygen or to 1,2-quinones with free p-position to one of the two quinoid oxygen atoms organic sulfides accumulate in a strongly acidic medium.

Particularly compounds of the general formula I are used as quinones

(D

0
or compounds of the general formula II

(H)

used.

In these formulas mean

X, · Y and Z independently of one another are hydrogen, an alkyl group with 1 to 18 carbon atoms, a hydroxyl group, a lower alkoxycarbonyl group, a halogen atom, a un-

009617/1871

substituted or substituted phenyl group or an -SR or -OR group, in which R is an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms or an unsubstituted or substituted phenyl group or
X and Y together form a fused ring, preferably an unsub-

substituted or substituted bensor residue.

With the term "lower alkyl group", "lower alkoxy group" or "lower alkoxycarbony! group" is an alkyl, alkoxy or Alkoxycarbonyl group with 1 to 4 carbon atoms in the alkyl radical.

^, X, Y or Z is an alkyl group having up to 18 carbon atoms Φ, it is a straight or branched hydrocarbon chain, such as the methyl, ethyl, propyl, isopropyl, butyl, pentyl , Isopentyl, heptyl, octyl, decyl, dodecyl, hexadecyl or octadecyl group.

If X, Y or Z represents a halogen atom, it is e.g. around fluorine, chlorine or bromine, · X, Y or Z means a substi- ■ If a phenyl group is used, there are nonionic substituents, e.g. Halogens such as fluorine, chlorine and bromine, nitro groups or lower alkyl groups in question. Is X, Y or Z an -SR or -OR group in which R represents a substituted phenyl group, so can this the usual nonionic ring substituents, such as

with hydroxyl groups, halogen atoms, e.g. fluorine, chlorine or bromine, nitro-

m ■ ■■■ '■■' ■ ■ "· ■""'

groups, lower alkoxy groups, but especially lower alkyl groups contain; if R represents a substituted lower alkyl group, so Substituents that may be mentioned are, for example, carboxyl groups, carboxylic acid ester groups, cyano groups or lower alkoxy groups.

If X and Y together form a fused ring, then e.g. homo- or heterocyclic saturated or unsaturated fused Rings that are unsubstituted, substituted and, if aromatic, with further aromatic rings can be condensed into consideration. Preferably, X and Y together form an unsubstituted or substituted benzo radical. These fused rings can contain the same nonionic ring substituents as described above

009017/1071

for R given as meaning a substituted phenyl group are.

Are particularly suitable for the "process according to the invention" Quinones of the general formula I in which X, Y and Z independently of one another are hydrogen, a lower alkyl group or a halogen atom represent.

Examples of quinones which can be used as starting materials are: 1,2-benzoquinone, 1,4-benzoquinone, 5-methyl-1,2-benzoquinone, 2-methyl-1,4-benzoquinone, 2-butyl-1,4-benzoquinone , 2-dodecyl-1,4-benzoquinone, 5-hexadecyl-1,2-benzoquinone, 2-octadecyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, 3,5-di-tert .butyl-1,4-benzoquinone, 2-isopropyl ~ 5-methyl-1,4-benzoquinone, 3-chloro-1,2-benzoquinone, 2- "chloro-1,4-benzoquinone, 2, S-dichloro- l ^ -benzochinon, 2,6-dibromo-l, 4-benzoquinori, 2-chloro-3-m.ethy 1-1,4-benzoquinone, 2-erom-6-methyl ~ l, 4-benzochinbn, 2-pheny1-1,4-benzoquinone, 2,5-diphenyl-1,4-behzoquinane, 2- (4'-bromo) -pheny1-1,4-benzoquinone, 2- (2 ¹ -chloro) -pheny 1 -1,4-benzoquinone , 2- (4 ^l -methyl) -phenyl-1,4-benzoquinone, 2- (3'- or 4 ^t -nitro) -phenyl-1,4-benzoquinone, 2,5- Dimethylthio-, 2,5-diethyithio- or 2,5-dibutylthio-1,4-benzoquinone, 2-octylthio-1,4-benzoquinone, "2-dodecylthio-1,4-benzoquinone, 2-octadecylthio-1,4 -benzoquinone, 2-butoxy-1,4-benzoquinone, 2,5-dirnethoxy-1,4-benzoquinone, 3- or he 5-hydroxy-l, 2-benzoquinone, 3-Hydroχy-5-ethoxycarbonyl-1,2-benzoquinone, 2-carboxymethylthio-l, 4-benzoquinone, 2-cyclohexyloxycarbonylmethylthio-1,4-benzoquinone, 2-butoxycarbbnylmethy1-thio -l. ^ - benzoquinone, 2-octadecyloxycarbonylmethylthio-1,4-benzoquinone, 2-cyanoethylthio-1,4-benzoquinone, 2,5-diethoxyethio-1,4-benzoquinone, 2,5-diphenoxy-1,4-benzoquinone , 2-phenylthio-1,4-benzoquinone, 2,6-diphenylthio-1,4-benzoquinone, 2,5-diphenylthio-1,4-benzoquinone, 2,5-di- (4 ¹ -chlor) -phenylthio- 1,4-benzoquinone, 2- (2'-nitro) -phenylthio-1,4-benzoquinone, 2- (4 ^1- methoxy) -phenylthio-1,4-benzoquinone, 2- (4'-butyl) -phenylthio -1,4-benzoquinone, 2- (4'-chloro) -phenylthio-1,4-benzoquinone, 2,5-di- (4'-bromo> -phenoxy-1,4-benzoquinone, 2- (2 ' Methoxy) phenoxy-1,4-benzoquinone, 2- (4 ¹ -butoxy) -phenoxy-1,4-benzoquinone, 2,5-di- (4'-methyl) -phenoxy-1,4-benzoquinone; also 1,2-naphthoquinone, 1,4-naphthoquinone, 2-phenyl-1,4-naphthp-

00S817 / 1871

_ 4. 1851803

chtnon, 3-methyl-1,2-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, S-hydroxy-ljZ-naphthoquinone, 2-chloro-l <, 4-naphthoquinone, 2-methy I-1,4 naphthoquinone, 2-ethyl-l, 4-naphthoquinone _i ö-hydroxy-l ^ naphthoquinone, 6-hydroxy-l, 4-naphthoquinone _s 5,8-dihydroxy-l, 4-naphthoquinone, 5- or 6-chloro -l, 4-naphthoquinone, 3,6-dibromo-l, 4-naphthoquinone, 3, o-dibromo-l ^ -naphthoquinone, 8-nitro-1,4-naphthoquinone, 2,5-dimethyl-1,4 naphthoquinone, 2-methyl 1-5-hydroxy-1,4-naphtho'-chlnone, quinolinequinone-5,8 or 1,4-anthraquinone.

The organic sulfides used in the process according to the invention preferably those of the general formula III

. R ₁ - S -R ₂ (III).

used in. the

R, an unsubstituted or substituted, saturated or unsaturated acyclic or cyclic hydrocarbon radical, preferably an unsubstituted or substituted one Alkyl group with up to 12 carbon atoms in the main chain, a propeny group or an unsubstituted or substituted phenyl group and "

R _{2 is} an unsubstituted or substituted, saturated or unsaturated aliphatic or eyeloaliphatic hydrocarbon radical, preferably an unsubstituted or substituted alkyl group with up to 12 carbon atoms in the main chain, or
R, and R _{2 are} methylene groups, optionally including

of another hetero atom, especially of sulfur or acid * substance, are connected to one another via 2 to 4 methylene groups, where the methylene groups can be substituted by lower alkyl groups, represent.

If R ₁ and R _{2 are} unsubstituted alkyl groups with up to 12 carbon atoms, there are, for example, methyl, ethyl, propyl, iso, propyl, butyl, pentyl, isopentyl, heptyl, octyl, decyl or γ dodecyl groups in question. Examples of substituents in such alkyl groups include: phenyl groups, halogens such as chlorine or bromine, hydroxyl groups, alkoxy groups with 1 to 12 carbon

009817/1071 '

ORKSINÄL I ^ SFEGTED

., atoms, phenoxy groups, the phenyl radical of which is replaced by chlorine or bromine may be substituted, lower hydroxyalkoxy or alkoxyalkoxy groups, as well as lower alkylthio groups, which are represented by at least 3 Carbon atoms separated from the sulfur atom in the general formula III are.· ·

If R 1 is a substituted phenyl group, then the _a usual nonionic ring substituents, such as the halogens fluorine, chlorine or bromine, but especially lower alkyl groups or alkoxy groups come into consideration} but the phenyl radical is advantageously unsubstituted.

Organic sulfides of the general formula III in which _{at least one of R 1 and R 2 is} a lower alkyl group or in which R ₁ and R 2 are methylene groups that are connected to one another via 2 to 4 further methylene groups are particularly favorable for the process according to the invention .

Examples of such usable as starting materials in organic sulfides include dimethyl sulfide, Diäthylsulfid, dipropyl sulfide, diisopropyl sulfide, dibutyl sulfide, Diisobutylsulfid, dipentyl sulfide, Diisopentylsulfid, Diheptylsulfid, dioctyl sulfide, Didecylsulfid, Didodecylsulfid, Methylisobutylsulfid, Methylpentylsulfid, Methylhexylsulfid, Aethyloctylsulfid, Methyldecylsulfid, Methyldodecylsulfid, dibenzyl sulfide, Methylbenzylsulfid, (3'-Methyl) ben2yl- (4'-methoxy) benzyl sulfide, ethylphenethyl sulfide, 3,3'-dichlorodipropyl sulfide, di-ca-hydroxyethyl sulfide, di-co-hydroxybutyl sulfide, di-.> Hydroxyhexyl sulfide, methyl cu-hydroxyethyl sulfide , methyl-uj-hydroxybutylsulfid, dimethoxy or Dibutoxymethylsulfid, dimethoxy-, Diäthoxy-, Dipropoxy-, Diisopropoxy-, Dibutoxy- or Didodecyloxyäthylsulf id, 3-Chlorpropylmethylsxilf id, Dimethoxybutylsulf id, methyl-6J -me thoxy äthylsulf id, methyl tu -lethoxybuty isulf Id, didodecyloxypropyl sulfide, diphenoxyethyl sulfide, di-4-bromophenoxyethyl sulfide, methyl (4-methylthio) butyl sulfide, methyl (6-methylthio) hexyl sulfide, ethyl (6-ethylthio) hexyl sulfide, butyl (6-butylthio) hexyl sulfide, methyl allyl sulfide, methylprop-1-enesulfide and methylhex-1-enesulfide, also phenyl methyl sulfide, phenyl ethyl sulfide, phenyl butyl sulfide, phenyl isobutyl sulfide, phenyl pentyl sulfide, (2-, 3- or 4-methyl-

^; ; . OP8017 / 1871

phenyl-1) methyl or ethyl sulfide, (4-ethoxyphenyl-1) methyl sulfide, (2-chlorophenyl-1) methyl sulfide, (2- or 4-bromophenyl-1) -. methyl sulfide and (2-chlorophenyl-1) ethyl sulfide and tetrahydrothiophene, 2-methyl », 3-methyl- or 3-ethyltetrahydrothiphen, 3,4-dimethyltetrahydrothiophene, 2,3-dimethyltetrahydrothiophene, Tetrahydrothiapyran, hexahydrothiepin, 1,4-dithiane, 1,4-oxathiane, Methylcyclopropylsulfid, Methylcyclopentylsulfid, Methy! Cyclohexylsulfid, Methylcyclooctyl sulfide and dicyclohexyl sulfide.

The compounds which can be used as starting materials according to the invention are known or can be prepared by known methods will.

The reaction of the starting materials in a strongly acidic medium is conveniently carried out at temperatures of about -40 ° to 50 ^c C, W up to 25 ° C, can be used as acids Brtfnsted-Lowry acids or Lewis acids, preferably at -15 °.

As Br ^ nsted-Lowry acids, which donate a proton to a base can and therefore act as proton donors, can in the invention Processes used for example: sulfuric acid, pyrosulfuric acid, phosphoric acid, polyphosphoric acid, hydrofluoric acid, Tetrafluoroboric acid, formic acid, acetic acid, Trifluoroacetic acid, oxalic acid, or p-toluenesulfonic acid.

As Lewis acids that can accept an electron pair and ' therefore act as electron acceptors, can in the invention Processes used for example: aluminum chloride, ^ aluminum bromide, boron fluoride, phosphorus trichloride, phosphorus oxychloride, Antimony pentachloride or pentafluoride, iron trichloride or tin tetrachloride.

- The strongly acidic medium used is preferably an aqueous or aqueous-organic solution with a pH value below 1.0 or an inorganic or organic acid whose pK value in water is less than 4.8, or below Organic solvent that is inert to the reaction conditions, for example acetic acid, propionic acid, acetic anhydride, sulfolane, nitromethane, nitrobenzene or nitrotoluene, or a mixture of such solvents that contain a Brtfnsted-Lowry acid whose pK value in water is less than 4.8, or a

008817/1871

Contains Lewis acid. Examples of solvent mixtures used in Combination with an appropriate Br ^ nsted-Lowry acid for the Preparing a strongly acidic aqueous-organic solution with a pH value below 1 are possible: Mixtures of water with Acetic acid, propionic acid, suIfolane, methanol, ethanol, acetone or Methyl ethyl ketone.

A particularly preferred strongly acidic medium is aqueous Sulfuric acid, especially 60 to 85% aqueous sulfuric acid, furthermore, aqueous phosphoric acid or aqueous hydrofluoric acid can be used as well as polyphosphoric acid can often be used to advantage.

Equivalent amounts of the starting materials are used for the reaction or a 5 to 10% excess of organic matter Sulfide. Organic sulfides that have a second thio function, these two thio functions through at least 3 carbon atoms Must be separated from each other, can with both sulfur atoms react on a quinone, i. e. 1 mole of such a bisthio compound reacts with 2 moles of a corresponding quinone.

The acid must also be present in at least an equimolar amount However, it is preferable to work with an excess of acid, especially when the reaction is carried out in the presence of water or water-based solvents.

The practical implementation of the reaction can be carried out in such a way that that you mix the quinone with the organic sulfide and add it to the acidic medium enters; the quinone can also be used in acidic . Submit the medium and add the organic sulfide afterwards, or Finally, the organic sulfide can be placed in an acidic medium and then add the quinone.

For the isolation of the end products, depending on the reaction medium and solubility properties of the compounds, various methods be used. For example, the dihydroxyarylsulfonium salts directly from the acidic aqueous solution by adding anions »with which they form sparingly soluble salts, such as Pure cornerates, thiocyanates or picrates, are precipitated. In the Implementation in aqueous sulfuric acid or phosphoric acid can do that Reaction medium after dilution with ice water with calcium hydroxide

-ΟΟΟ8Ϊ7 / 1071

After separating the calcium sulfate or calcium phosphate, the solution is acidified with a volatile acid, for example hydrochloric acid or hydrobromic acid, whereupon the sulfonium compound is obtained as the corresponding salt, e.g. as chloride or bromide, after the solvent has been distilled off. If the reaction is carried out in an acidic, water-immiscible solvents which can be brought ^J sulfonium compound formed by the addition of water in the aq * engined phase and these are appropriately processed. Often the dihydroxysulfonium salts also precipitate directly as sulfates or phosphates when the sulfuric or phosphoric acid solution is diluted with ice water. When working in aqueous acid, preference is given to this with an alkali hydroxide, for example sodium or. Potassium hydroxide, neutralized and then acidified again with an excess of a hydrohalic acid, such as hydrochloric acid or hydrobromic acid, the corresponding halide precipitating. ■; ■■ "■

The process in which an equimolar amount of sulfide is added to a suspension of the quinone in 8 times the amount by weight of 60-70% strength aqueous sulfuric acid at ^{0 ° C.} to 5 ° C. has proven to be particularly suitable for the preparation of the dihydroxyarylsulfonium salts. The reaction time is generally about 15 minutes to 6 hours, depending on the reactivity of the components.

Another feature of the present invention is that, with the process according to the invention, new compounds of the * / _ formula

OH

Yj Z
OH

in the '

X, Y and Z independently of one another are hydrogen, an alkyl group with 1 to 18 carbon atoms, a hydroxyl group, a - / \ halogen atom, an unsubstituted or substituted phenyl group or an -SR or -OR group, in which R is an unsubstituted or »->

009817/1871 · ■ 'V

PfjTBB

t ibt

substituted alkyl group having 1 to 18 carbon atoms or a unsubstituted or substituted phenyl group is * represent, where, if 2 of the system substituents X, Y and Z are different from Are hydrogen, those substituents other than hydrogen are identical and, if 2 of the substituents X, Y and Z are hydrogen these are represented by X and Zj or

X and Y together represent a fused ring}

R, (i) an unsubstituted or substituted unsaturated one acyclic hydrocarbon radical or

(ii) a substituted saturated acyclic hydrocarbon radical or _ _ _f (iii) a phenyl radical which is substituted by lower alkoxy groups or

(iv) a cycloaliphatic hydrocarbon radical and

Ry represent an unsubstituted or substituted, saturated or unsaturated aliphatic or cycloaliphatic hydrocarbon radical,

or

if R, an unsubstituted or a halogen atom or phenyl radical substituted by lower alkyl groups, R2 an unsubstituted, saturated alkyl group having at least 2 carbon atoms is j

or ⁱ Ä

if R _{1 and R 2 are} unsubstituted alkyl radicals having 1 to 4 carbon atoms, these radicals are not identical; or

if at least one of the substituents X, Y and Z is not hydrogen, R, and R ^ are an alkyl radical having 1 to 4 carbon atoms, or R, an unsubstituted or substituted phenyl radical and R "denotes a methyl group,

or .

R 1 and R _{2 represent} methylene groups which, optionally with the inclusion of a further hetero atom, are connected to one another via 2 to 4 methylene groups, the methylene groups through

. 00981771871

lower alkyl groups can be substituted,

C)
and M represents a monovalent anion; or compounds of the formula

OH ~ GÖ

M ©

in the

X, Y and Z independently of one another are hydrogen, an alkyl group from 1 to 18 carbon atoms, a hydroxyl group, a lower alkoxy or alkoxycarbonyl group or a halogen atom represent V

or .

X and Y together mean a fused ring,

R, an unsubstituted or substituted, saturated one or unsaturated acyclic or cyclic hydrocarbon radical and

R _{2 represent} an unsubstituted or substituted, saturated or unsaturated aliphatic or cycloaliphatic radical,

or

R, and R _{2 represent} methylene groups which, optionally including a further hetero atom, are connected to one another via 2 to 4 methylene groups, it being possible for the methylene groups to be substituted by lower alkyl groups, M denotes a monovalent anion,

and in the,

if Y is hydrogen, the group -SR ₁₂ 4 or 5 of the o-quinone nucleus is bonded and,

if Y is different from hydrogen, the group -SR, is bonded to position 4 of the o-quinone nucleus, or compounds of the formula

at position

00981771871

OH H (CH ₂ > n R.
ι 3 OH χ '■' - x> YX - S - -S ν, ίΎ { ^ z Z OH OH

2Μ

in the

X, Y and Z independently of one another are hydrogen, a lower one Represent an alkyl group or a halogen atom, if 2 of the Substituents X, Y and Z are different from hydrogen, these substituents different from hydrogen are identical and, if 2 of the substituents X, Y and Z are hydrogen, these through X and Z are reproduced {

or

X and Y together represent a fused ring ^ Ry a lower alkyl group, *

η is an integer from 3 to 6, and "

- & """■'■" ■■

M ^ mean a monovalent anion,

can be produced. '

A preferred class of compounds, which by the invention Procedure becomes easily accessible corresponds to the formula

(CH ₂ ) _n

in the '

X, Y and Z are hydrogen or

X and Y together denote a benzoannellant and Z denote hydrogen, Ui

η is an integer from 4 to 6 and;

M ^ represent a monovalent anion. _;

The sulfonium salts produced by the new process are, Corresponding to their salt character, solid substances, however, in many cases they cannot be made to crystallize. At increased Temperatures, they usually melt in an indistinct manner with decomposition.

0 0 9817/1871

If possible, they are advantageously characterized as halides Thiocyanate, perchlorate, picrate or pure sugar. Most sulfonium salts, especially e.g. halides or sulfates, are easily soluble in water} but often they also dissolve in ethanol, Acetone or chloroform. As reactive compounds, dihydroxyarylsulfonium salts are valuable intermediates, for example in the dye industry, · They also show fungicidal or bactericidal effects in individual cases.

The advantages of the new process for the production of dihydroxyarylsulphonium salts lie in its wide range of applications, which is why compounds that were previously difficult or impossible to access can be synthesized in a simple manner. Here, W is surprising is that despite the highly acidic conditions virtually no byproducts are formed, and the yields therefore · usually very high.

The following examples illustrate the invention. the Temperatures are given in degrees Celsius.

9817/1871

i I

•Example 1

- 13 -

10.8 g of finely powdered 1,4-benzoquinone are at -5 ° to

more watery
O ⁰ suspended in 40 ml of 70% strength / sulfuric acid, part of which is in

The solution is then added to 9.4 g of diethyl sulphide with thorough stirring. The reaction is allowed to continue while stirring at 0 ° until the solution, which was initially dark in color, has lightened and a sample _# dissolves in water, colorless and clear. 100 ml of water are then added dropwise to the reaction mixture, the temperature still being kept at 0 °. The solution is then neutralized with 307c aqueous sodium hydroxide solution while cooling, 100 ml of concentrated hydrochloric acid are added and the mixture is kept at 0 ° for a few hours while stirring. The crystalline precipitated product is then filtered off and dried in vacuo. 22.0 g * (93% of theory) of an almost colorless sulfonium salt of the formula are obtained

CH ₂ CH ₃

)H

Cl

After two recirculations, it shows reveals at 60 ° from 27oiger aqueous or alcoholic hydrochloric acid has a melting point of 143 ° (decomposition).

The corresponding bromide can be obtained in an analogous manner if, in the above example, the hydrochloric acid is replaced by an equivalent amount

Replaced hydrobromic acid. .

more watery

If, instead of 40 ml of 70% IgA / sulfuric acid equal volumes 857oiger phosphoric acid, 85% formic acid, 707 _o perchloric acid or 667oiger hydrofluoric acid and the procedure is otherwise as shown in the above example, the result is the same sulfonium compound as the corresponding salt in similar yield .

If, instead of the starting materials described in Example 1, equivalent amounts of the in Table 1, column 2, indicated quinones, and the sulfides indicated in column 3, is obtained at reaction temperatures lying between -15 and +20 ^ ^c

; '* ■ -. '00 9-17 / 1871

can, according to the procedure described in the example, the in Column 4 listed dihydroxysulfonium salts »their melting points, if determinable, are indicated in column 5.

If the resulting from the reaction in sulfuric acid Sulphates are sparingly soluble, they can be removed after diluting the reaction solution can be filtered off directly with ice water.

008817/1971

t *

T A fi [L L Γ 1

² ^ "UJ- S (CH (CH J

ι 'J

0 098Ί7 / 1871

Table 1 continued

Example ! Quinone
\ r. j

009817/1871

ORiOiNAL! WSFEDTED

t- I

B t

- 17 -

Forts tzunq d: r Tab'Tle 1

ßeisptel

Chi non

sulfide

Dih) croxysul forrtu-.ssl ζ

Ji J-CH CH C !, ¹ ! / CH ²² is

S (CHCH ₂ OCH ₂ CH ₃ )

^CII 3 " ^S " W

Cl

Θ *

OH

Cl

3-S-

Cl

OH

Ct

Br

Θ 119 °

105 "

009817/1871

Continuation of I

Example Kr.

20th

Chi-

. I.

CH.

sulfide

.CIL

Br ¹

OH
OH

QU ₁ OL

Cl

OH

egg ⁰ !

OH

Cl

CIf

CH,

'-Cri,

.CH.

Br ⁽

- " ³

HlL-CH.CH.

CL

he

..L.J

009817/1871

de "

Example Sr.

Chi non

SuI fid

! 33

Cl

^I,, ! - € '- tH 3

O O

ίι

0 O

CH ₃ -S

CH-S- '

f ₂

US (CH ₃ )

₃ ) ₂

OH OH

OH

Cl OH

ι.

ClO

G)

OH

CH

OH

(7)

■ OH

Cl

JOH V 17 V ^

DH

T, ' ^tri 3

• DH

Ϊ.0,

-CH,

¹ CH

C.

0 0 9817/1871

Continuation of the table

at- ι

game j Chiron

Sulfide dihydroxysulfoniuti salt

CH ₃ -S -LJ

0 0

O J

JiJi

Br

J> J

27 3 ; l

1 Λ ί C

OCH.

i. '

3

Br OH, CH. S.

HSO,

- G)

-Br

CIO,

tv

134 "

T2S ^Ö

Ϊ16 "

HSO,

-S (CH ₀ L

Br '

0t811 / 1871 ÖRK31NAL INSPECTED -

Forts et ζ „.τα of the table

Example Kr.

Quinone

Sulphide Dihyiroxysuifoniujsalz

s-p.

Br

S (CH CHOCH ₃ )

W ~

CH, c

^{S (} W ₂

, CH

CH (M η: Θ

- w

Cl

Cl

OH CH
S.

OH

_

ClO,

-OH

Br ^v

HSO.

i HSO

[Cr (KHJjSCN), j® J i ⁷ . ■

155 °

124 "

I 150 ° j.

000817/1871

eel-, j
game j
¹ Jr.!

Chi non

sulfide

2 moles

Ii 0

2 »oil

2 sol 0

2 moles of 0

2 moles of 0

Ii ii

'b

CH,

r

.0

CH-S- (CH ₀ JS-CH,

CH-S- (CHJ-S-CH,

- Τ »

OH

... CH, OH

CH, Ot I 3.

' P

C, HC, H pH (4 9 (S 9!

?> ί! .η J

_ ₂ 0

s},

OK

^0H

2Er '"

C "H, C_H" r.j

12 ο 12 5 ^

S- (CH) .- 3 -r * ^

^2t ν

UH I) H ^CH 3

ι

! ir: ⁰

2Cl

CH, CH, OH I ³ I ^J OH

2HSO ₁

OH

SCf,

008017V ORKSiNAL INSfECTED ^:

ic the T'tel

sulfide

Dihydrcr.su] fan m \

^ «VniiCjy,

CK

■ 'V ±>

CH

T'i

Cl

OH

he-

ΟΟ9§1 7> 1871

ORiGiNAL SNSPECTED

19518Q3;

Example 63 . . '·

21.6 g of powdered 1,4-benzoquinone are suspended at -5 ° in 60 ml of 70% strength aqueous sulfuric acid, some of which goes into the solution. 12.8 g of dimethylsulfM are then added dropwise over a period of 30 minutes. The initially yellow-brown reaction mass shows after two hours of stirring at 0 "a light color and is slowly mixed with 200 ml of water while cooling. This solution is adjusted to a pH of approx After adding 40 g of NaCl, the mixture is left to crystallize for a few hours with cooling and stirring, the product is filtered off and dried in vacuo, giving 38 g (92% of theory) of a sulfonium salt of the formula

Cl ^Θ

with a melting point of 137-138 ° (decomposition),

The melting point of environmentally little from 37 _o hydrochloric acid at 6O °, the crystallized product is 142-143 ^C (decomposition),

Example 64 ■

15.8 g of finely powdered 1,4-naphthoquinone are ^{suspended at 0 °} to 5 ^{° C.} in 40 ml of 80% strength aqueous sulfuric acid, some of which go into solution; then 14.6 g of dibutyl sulfide are added with thorough stirring. The reaction is allowed to continue for a further 5 hours at 0 ° to 5 ° ^{C., while stirring.} 100 ml of water * are then added dropwise to the reaction mixture, the temperature still being kept between 0 ^c and 5 ". The solution is then neutralized with 30% aqueous sodium hydroxide solution while cooling, and 100 ml of concentrated hydrochloric acid are added. The mixture is then kept stirring during V to 0 "for about 12 hours, the precipitated product is filtered off, '. _X dissolves it in 120 ral methanol / water (4: 1), adds 50 ml of 47% aqueous hydrochloric acid to this warm, filtered solution and lets it crystallize / cool. The sulfonium salt is filtered off and

009817/1871 "■

dry it in a vacuum. The end product is a compound the formula

-•OH

CH ₂ CH ₂ CH ₂ GH ₃

Cl

melting point 132 ° (decomposition). If, in the process described, the neutralized reaction solution is not acidified again with hydrochloric acid, but diluted with water to double its volume and treated with a saturated aqueous solution of Reinecke's salt (NH ₄ (Cr (NH ₃ ) ₂ (SCN) ₄ ]), 50.8 g (89% of theory) of the pure sugar of the above sulfonium compound (melting point 77-80 ^c ) are obtained in this way.

The corresponding bromide is obtained in an analogous manner if the above example is repeated, except that the equivalent amount of hydrobromic acid is used instead of hydrochloric acid.

If, instead of the starting materials given in Example 64, equivalent amounts of the quinones given in Table 2, column 2 and the sulfides given in column 3 are used, the procedure described in the example and at reaction ^temperatures between -5 C and + are obtained 25 ^c , the dihydroxysulfonium salts listed in column 4, the melting points of which are given in column 5, if they can be determined.

If the resulting from the reaction in sulfuric acid " Sulphates are sparingly soluble, they can be filtered off directly after diluting the reaction solution with ice water.

9 * 17/1071

TABLE 2

00 981? / 1871

INSPECTED

t the ϊκ? Πβ

0098 17/1871

ORJQtNAL INSPECTED

fortcetzuna the Ta partly

example

Ct) iron

sulfide

Dihydroxysulfoniursaiζ

Sap.

NS,).

OH

.CH-CH, SfCH ₀ L

HSO

Br

SCN

106 "

108 "

.ORIGINAL IMSFSCTED

009817/1871

Example 82

To a suspension of 6 g of AlClo in 50 ml of dry methylene chloride add one drop by drop at -15 # while stirring well Solution of 4. * 2 g of 3-methoxy-o-benzoquinone and 3.5 ml of diethyl sulfide in 100 ml of dry methylene chloride. It is kept at room temperature for 30 minutes and the reaction mixture is poured onto 200 ml of ice water. After evaporation of the aqueous solution, the sulfonium compound can be isolated as Reineckat by adding a saturated aqueous solution of Reineckesalz. 11.5 g are obtained (69% of theory) of a sulfonium salt of the formula

[Cr (NH ₃ I ₂ (SCN) ₄ ]

which after two recrystallization in 30% aqueous Ethanol melts at 163 - 165 °.

Is used in the above example instead of Reineckesalz an aqueous trinitrophenol solution, the corresponding one is obtained Picrat that melts at 169-170 °.

If, instead of 6 g of AlCl, equimolar amounts of AlBr ^, BFo or FeCIo and works the approach as in the example described on, the corresponding sulfonium salts are obtained in good yields.

Instead of methylene chloride, the same solvent can be used Amounts of diethyl ether, nitrobenzene, benzene or carbon tetrachloride be used.

Used instead of the starting materials given in Example 82 Equivalent amounts of the quinones given in Table 3, column 2 and the sulfides given in column 3 are obtained according to the method of operation described in the example, the corresponding,, in column 4 listed dihydroxysulfonium salts.

009817/1871

TABLE 3

Example ί

ir.

Chiron

sulfide

83

86 87> 88 69

i ^ o

: ₂ H ₅ 00C OH

NS

3'2

NS,

OH © '

■ GH

Cl

CH

S (CHJ ₁

ο Z -1

OH

Cl

^C 16 ^H 33

ClO

OH

HSO.

OH

Cl

OH

Br ^v

3'2

OH

(CH J, C Γ C (CHJ, ³

Cl

Gtf 4, / OH

CJ

ClO.

oo-Aii7 / ie? i

ORKSiNAL INSPSGTED.

Claims (23)

Claims 1. A process for the preparation of Dihydroxyarylsulfoniumsalzen, characterized in that L, 4-quinones with a free m-position to a quinoid oxygen or to 1,2-quinones with free p-position to one of the two quinoid oxygen atoms organic sulfides accumulate in a strongly acidic medium. 2. The method according to claim 1, characterized in that one as quinones a compound of the general formula 1 used in the X, Y and Z independently of one another are hydrogen, an alkyl group having 1 to 18 carbon atoms, one hydroxyl group, one lower alkoxycarbonyl group, a halogen atom, an unsubstituted one or substituted phenyl group or an -SR or -OR group, in which R is an unsubstituted or substituted alkyl group with 1 to 1 carbon atoms or an unsubstituted or substituted phenyl group means, or X and Y together form a fused ring represent. 3. The method according to claim 2, characterized in that one a compound of the general formula I is used in which X and Y together represent an unsubstituted or substituted benzo radical. 4. The method according to claim 1, characterized in that one as quinones a compound of the general formula II 09: 8 177 1871 XX ^(ΙΙ) used in the '. "- ■ .'.'._''- X, Y and Z independently of one another are hydrogen, an alkyl group with 1 to 18 carbon atoms, a hydroxyl group, a lower alkoxycarbonyl group, a halogen atom, an unsubstituted one or substituted phenyl group or an -SR or -OR group, in which R is a lower unsubstituted one or substituted alkyl group with 1 to 18 carbon ** atoms or an unsubstituted or substituted one Phenyl group means . or X and Y together represent a fused ring. 5. The method according to claim 4, characterized in that one a compound of the general formula II is used in which X and Y together represent an unsubstituted or substituted benzo radical. 6. The method according to claim 1, characterized in that one as organic sulfides a compound of the general formula III ', ".. ^R l" ^S " ^R 2 ^ ¹¹ ^ used in the R, an unsubstituted or substituted saturated or unsaturated acyclic or cyclic hydrocarbon, rest and Rrt an unsubstituted or substituted saturated or unsaturated aliphatic or cycloaliphatic hydrocarbon radical or R | and R “methylene group”, optionally including inclusion of another hetero atom, with one another via 2 to 4 methylene "groups are connected, with the methylene groups through 0098 17/1871 ■ · ' ■■ '.' ■■ ORDINAL INSPECTED ti « lower alkyl groups may be substituted. 7. The method according to claim 6, characterized in that a compound of the general formula III is used in which R, an unsubstituted or substituted alkyl group with to * to 12 carbon atoms in the main chain, a propenyl group or an unsubstituted or substituted phenyl group and
Rft is an unsubstituted or substituted alkyl group with up to to represent 12 carbon atoms in the main chain. 8. The method according to claim 1, characterized in that an aqueous or aqueous-organic medium is used as the strongly acidic medium Solution with a pH below 1.0 used. 9. The method according to claim 1, characterized in that one an inorganic or organic acid is used as the strongly acidic medium, the pK value of which in water is less than 4.8. 10. The method according to claim 1, characterized in that one as a strongly acidic medium, one which is inert under the reaction conditions organic solvent used, which is a Br <zinsted-Lowry acid, whose pK value in water is less than 4.8, or a Lewis acid contains. 11. Compounds of the formula in the X, Y and Z independently of one another are hydrogen, an alkyl group having 1 to 18 carbon atoms, a hydroxyl group 0098 17/1871 Halogen atom, an unsubstituted or substituted phenyl group or a -SR or -OR group, in which R is an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms or a is unsubstituted or substituted phenyl group, where, if 2 of the substituents X, Y and Z are different from hydrogen, these substituents different from hydrogen are identical and, if 2 of the substituents X, Y and Z Are hydrogen ', represented by X and Zj or X and Y together represent a fused ring; R. (i) an unsubstituted or substituted unsaturated one acyclic hydrocarbon radical or (ii) a substituted saturated acyclic hydrocarbon residue or. (iii) one substituted by lower alkoxy groups Phenyl radical or (iv) a cycloaliphatic hydrocarbon radical and Ry an unsubstituted or substituted saturated or unsaturated aliphatic or cycloaliphatic hydrocarbon radical,.
or if Rj is unsubstituted or by halogen atoms or phenyl radical substituted by lower alkyl groups, R2 is an unsubstituted alkyl group having at least 2 carbon atoms or if R, and R "unsubstituted alkyl radicals having 1 to 4 carbon atoms mean that these residues are not identical j or if there is one of the substituents X, Y and Z is at least not hydrogen, R ₁ and R ₂ atoms an alkyl group having 1 to 4 carbon ^l, or R, is an unsubstituted or substituted phenyl radical and R ₂ represent a methyl group or R. and R _{2 represent} methylene groups which, optionally including a further hetero atom, with one another via 2 to 4 009817/1871 Methylene groups are connected * being the methylene groups through lower alkyl groups can be substituted, and M means a monovalent anion. 12. Compounds of the formula - θ in the X, Y and Z independently of one another are hydrogen, an alkyl group from 1 to 18 carbon atoms, one hydroxyl group, one represent lower alkoxy or alkoxycarbonyl group or a halogen atom, or X and Y together mean a fused ring, Usually an unsubstituted or substituted, saturated one or unsaturated acyclic or cyclic hydrocarbon radical and R «is an unsubstituted or substituted, saturated one or unsaturated aliphatic or cycloaliphatic radical, ν or R, and R _{2 represent} methylene groups, which, optionally including a further hetero atom, are connected to one another via 2 to 4 methylene groups, it being possible for the methylene groups to be substituted by lower alkyl groups, M ^ - denotes a monovalent anion and in which if Y is hydrogen, the group; , -SR ₁ R ₂ is bonded to position 4 or 5 of the o-quinone nucleus and if Y is different from hydrogen, the group —SR, R “is bonded to position 4 of the o-nucleus. , _; 13. Compounds of the formula ρ OH S, - (CH ₂ ) _n - S 2M OH OH in the ~ X, Y and Z independently of one another are hydrogen, a lower one Represent an alkyl group or a halogen atom, if 2 of the substituents X, Y and Z are different from hydrogen, these substituents other than hydrogen are identical and, if 2 of the substituents X, Y and Z are hydrogen, these through X and Z are reproduced? or . X and Y together represent a fused ring, Ro is a lower alkyl group, η is an integer from 3 to 6 and mean a monovalent anion. 14. Compounds of the formula ■ 2'n in the X, Y and Z are hydrogen or X and Y together denote a benzoannellant and Z denote hydrogen, η is an integer from 4 to 6 and 0-4 represent a monovalent anion. 23.9.69
St / sh 0098 17/1871