A novel process for producing mercaptophenols by the hydrogenolysis of polythiobisphenols in the presence of a nickel catalyst is disclosed. Raney nickel catalyst which is in advance poisoned with an organosulfur compound in which the sulfur atom has unshared electron pairs is especially effective as a catalyst.

A process for producing polythiobisphenols which comprises: reacting a phenol having the general formula wherein each R independently represents a hydrogen, a halogen or an alkyl, with sulfur monochloride in a polar organic solvent in the presence of a nitrogen-containing organic compound as a catalyst which is selected from the group consisting of tertiary amines, quaternary ammoniums, alkylated acid amides and heteroaromatic compounds, in amounts of about 1-30 % by weight based on the amount of the phenol used. As a catalyst, bromine or an alkali metal halide is also usable.

A novel process for producing mercaptophenols by the hydrogenolysis of polythiobisphenols in the presence of a nickel catalyst is disclosed. Raney nickel catalyst which is in advance poisoned with an organosulfur compound in which the sulfur atom has unshared electron pairs is especially effective as a catalyst.

A process for producing polythiobisphenols which comprises: reacting a phenol having the general formula wherein each R independently represents a hydrogen, a halogen or an alkyl, with sulfur monochloride in a polar organic solvent in the presence of a nitrogen-containing organic compound as a catalyst which is selected from the group consisting of tertiary amines, quaternary ammoniums, alkylated acid amides and heteroaromatic compounds, in amounts of about 1-30 % by weight based on the amount of the phenol used. As a catalyst, bromine or an alkali metal halide is also usable.

Ester von 3-tert.Butyl-bzw. 3-tert.Butyl-5-alkyi-4-hydroxy-phenyl-(alkan-)carbonsäuren der Formel I mit Oxethylaten von Polythiolaromaten der allgemeinen Formeln II und III, vorzugsweise der Formel II, mit 2 bis 6 Thiolgruppen sowie mit Oxethylaten von Dithiolcycloalkanen der allgemeinen Formel IV, die maximal 6 Alkylenoxideinheiten enthalten,

• mit X ₌ (CH₂)_mSH
• X' = (CH₂)_rSH
• X" = (CH₂)_sSH, wobei m,r,s = 0 oder 1 sein können,
• R,R',R" = H, Alkyl,Halogen, Hydroxyl,
• R_{3 =} H,C₁-bis C₄-Alkyl,
• R₄,R₅ = Cz-bis C₄-Alkylen,
• q = 0 bis 7, vorzugweise 1,
• n = 2 bis 6 für z bzw. z' = 0
• n = 1 bis 5 für z bzw. z' ≠0
• o + p = n und wobei
• 0 ≤ a,z ≤ a + z ≤ 6-n (in Formel II) bzw.
• 0 ≤ b,c,z' ≤ 4 ≤ 8-n (in Formel III) sein können.

Zur Herstellung dieser Ester werden die 3-tert.Butyl-bzw. 3-tert.-Butyl-5_-alkyl-4-hydroxyphenyl-(alkan)-carbonsäuren bzw. deren Derivate mit Oxethylaten von Polythiolaromaten und Dithiolcycloalkanen in Gegenwart von an sich bekannten Katalysatoren verestert oder umgeestert.

Die erfindungsgemäßen Ester verwendet man zur Stabilisierung von Polymeren.

The invention provides compounds of the general formula (I) and physiologically acceptable salts and solvates thereof, wherein

Ar represents the group where Q¹ represents a straight or branched C₁₋₃alkylene group, where Q² represents a group R³CO-, R³NHCO-, R³R⁴NSO₂- or R⁵SO₂-, where R³ and R⁴ each represent a hydrogen atom or a C₁₋₃alkyl group, and R⁵ represents a C₁₋₃alkyl group, R represents a hydrogen atom or a C₁₋₃alkyl group;

R¹ and R² each independently represent a hydrogen atom or a methyl or ethyl group; and

k represents an integer from 1 to 8;

m represents zero or an integer from 2 to 7, and;

n represents an integer from 1 to 7 with the proviso that the sum total of k, m and n is 4 to 12;

X represents an oxygen or sulphur atom, and;

Y and Z each represent a bond, or an oxygen or sulphur atom with the proviso that when Y is a bond m is zero, or when Y represents an oxygen or sulphur atom m is an integer from 2 to 7, or when Y and Z each independently represent an oxygen or sulphur atom then n is an integer from 2 to 7;

Q represents a naphthalenyl group which may optionally be substituted by one or two groups selected from C₁₋₄alkyl, C₁₋₄alkoxy, hydroxy and halogen.

The compounds have a stimulant action at β₂-­adrenoreceptors and may be used in the treatment of diseases associated with reversible airways obstruction such as asthma and chronic bronchitis.

A new diphenyl-methane derivative is useful to inhibit agglomeration of blood and is defined by the formula, including a diphenylethylene derivative and a benzophenone oxime ether derivative. in which R1 and R2 each are hydrogen, hydroxyl or a lower alkoxy,

W is -CH2-CO-CH2-COOR13, R13 being hydrogen or a lower alkyl, -CH2-C(=NOR14)-CH2-COOR15, R15 being hydrogen or a lower alkyl, R14 being a lower alkyl, -CH(CN)-(CH2)q-COOR16, R16 being hydrogen or a lower alkyl, q being an integer of 1 to 3, or -(CH2)p-Z, Z being -SH, -SCN or a monovalent group derived from a five- or six-membered ring which may be substituted by a ring having one or more sulfur atoms in the ring, p being 1 or 2.

A pharmaceutical composition containing compounds of formula (I) or their pharmaceutically acceptable salts as active ingredients, and the use of compounds of for­mula (I) or their pharmaceutically acceptable salts in the preparation of a medicament for treatment of diseases caused by blood stream disorders are also disclosed.

The invention provides compounds of the general formula (I) and physiologically acceptable salts and solvates thereof, wherein

Ar represents the group where Q¹ represents a straight or branched C₁₋₃alkylene group, where Q² represents a group R³CO-, R³NHCO-, R³R⁴NSO₂- or R⁵SO₂-, where R³ and R⁴ each represent a hydrogen atom or a C₁₋₃alkyl group, and R⁵ represents a C₁₋₃alkyl group, R represents a hydrogen atom or a C₁₋₃alkyl group;

R¹ and R² each independently represent a hydrogen atom or a methyl or ethyl group; and

k represents an integer from 1 to 8;

m represents zero or an integer from 2 to 7, and;

n represents an integer from 1 to 7 with the proviso that the sum total of k, m and n is 4 to 12;

X represents an oxygen or sulphur atom, and;

Y and Z each represent a bond, or an oxygen or sulphur atom with the proviso that when Y is a bond m is zero, or when Y represents an oxygen or sulphur atom m is an integer from 2 to 7, or when Y and Z each independently represent an oxygen or sulphur atom then n is an integer from 2 to 7;

Q represents a naphthalenyl group which may optionally be substituted by one or two groups selected from C₁₋₄alkyl, C₁₋₄alkoxy, hydroxy and halogen.

The compounds have a stimulant action at β₂-­adrenoreceptors and may be used in the treatment of diseases associated with reversible airways obstruction such as asthma and chronic bronchitis.

Verbindungen der Formel I worin R¹, R², R³, R⁴, R⁵, R⁶ und X die angegebenen Bedeutungen haben, Verfahren zur Herstellung dieser Verbindungen, ihre Anwendung als Arzneimittel und pharmazeutische Präparate auf Basis dieser Verbindungen werden beschrieben. Außerdem werden Vorprodukte für die Herstellung von Verbindungen der Formel I beschrieben.

A process for preparing a fluorine-substituted alicyclic diol comprising hydrogenating in the presence of a catalyst a fluorine-substituted aromatic diol represented by formula (I): wherein Ph represents a divalent organic group containing at least one aromatic group, to obtain the fluorine-­substituted alicyclic diol represented by formula (II): wherein Ph(H) represents a divalent organic group containing at least one perhydroaromatic group.

A method for preparing a water soluble lubricating additive having the generic structural formula: wherein R₁ is an alkyl, cycloalkyl, aryl, alkaryl or aralkyl group having from 1 to 34 carbon atoms; R₂, R₃ and R₄ are independent alkylene groups having from 2 to 30 carbon atoms; x is either 1 or 2; y is either 0 or 1 when x = 1 and is 0 when x = 2; m is either 0 or 1 and n = 2 to 30 is disclosed, wherein a sulfur-containing alcohol is initially reacted with an organic carboxylic acid to produce an alkylmercapto ester which is then further reacted with an alkylene oxide to produce the lubricating additive. The water-soluble lubricating additives produced in this manner are useful as lubricating additives for water-based fluids used in metalworking operations.

Verfahren zur Herstellung von Verbindungen der Formel (1) worin R ein Chlor- oder Bromatom, X ein Wasserstoff-, Chlor- oder Bromatom oder eine Alkyl-C₁-C₆-gruppe und n die Zahl 0, 1 oder 2 bedeuten, indem man Halogenbenzole der Formel (2) worin R und X die genannten Bedeutungen haben und Y ein Chlor- oder Bromatom darstellt, mit Mercaptoethanol in einem dipolar-aprotischen Lösungsmittel in Gegenwart eines Alkalimetalloxids, -hydroxids oder -carbonats bei 80 bis 140°C umsetzt zu den Halogenphenyl-oxethylsulfiden der Formel (3) worin R und X die genannten Bedeutungen haben und diese direkt in der angefallenen Reaktionsmischung oder nach Abtrennung der flüchtigen und festen Bestandteile, vorzugs­weise in Gegenwart von Wasser, bei einem pH-Wert von 1 bis 7 bei 20 bis 120°C mit 1 Mol Oxidationsmittel (pro Mol Halogenphenyloxethylsulfid) umsetzt zu den Verbindungen der Formel (1) mit n=1, oder mit mindestens 2 Mol Oxydations­mittel (pro Mol Halogenphenyl-oxethylsulfid) umsetzt zu den Verbindungen der Formel (1) mit n = 2.