5530-30-3

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An iridium-catalyzed hydrogen-borrowing process has been developed whereby 2,6-di-tert-butylphenol can be alkylated at the C4-position by using a range of primary alcohols (11 examples, 40-93% yield). Following this, a selection of the products obtained underwent retro-Friedel-Crafts reactions to provide para-substituted phenols, which could potentially undergo further synthetic manipulations.

Investigation of the catalyzed reaction of 2,6-di-tert-butylphenol with ethanol, ethylene glycol, oligomeric glycols, and paraldehyde in a strongly basic medium permitted to develop a technologically suitable procedure for manufacture of 2,6-di-tert-4-ethyl-butylphenol, used in the synthesis of Antioxidant-425.

The present invention relates to 4-formylamino-N-methylpiperidine derivatives of the formula (I) where the variables are as defined in the Description, to a process for preparing these piperidine derivatives, to the use of these piperidine derivatives of the invention, or prepared according to the invention, for stabilizing organic material, in particular for stabilizing plastics or coating materials, and also to the use of these piperidine derivatives of the invention, or prepared according to the invention, as light stabilizers or stabilizers for wood surfaces. The present invention further relates to stabilized organic material which comprises these piperidine derivatives of the invention or prepared according to the invention.

2-Hydroxybenzophenone derivatives substituted in the 4′-position by a thioether moiety exhibit enhanced absorption in the UV at longer wavelength. Compositions comprising organic material subject to actinic degradation are beneficially stabilized with such derivatives.

A composition comprising a) a lubricant or a hydraulic fluid and b) at least one compound of the general formula I STR1 in which x=1 or 2 and, if x=1, R is as defined for R1 or R3 --O-- or, if x=2, R is as defined for R8, and R1 and R3 are, for example, alkyl, cycloalkyl, alkenyl, phenyl, naphthyl, aralkyl or alkaryl, or alkyl, cycloalkyl, alkenyl, phenyl, naphthyl, aralkyl or alkaryl, which are monosubstituted or polysubstituted by groups from the series comprising halogen, cyano, nitro, e.g. --OCH3 or e.g. --COOCH3, or alkyl, cycloalkyl, alkenyl, aralkyl or alkaryl which are interrupted by one or more groups from the series comprising --O--, --S--, --NH--, STR2 or alkyl, cycloalkyl, alkenyl, aralkyl or alkaryl which are monosubstituted or polysubstituted by groups from the series comprising halogen, cyano, nitro, e.g. --OCH3 or e.g. --COOCH3 and interrupted by one or more groups from the series comprising --O--, --S--, --NH--, STR3 and R2 is NR4 R5, --OR6 or --SR7, and R4 and R5 are identical or different and are, for example, --H, alkyl, phenyl, naphthyl, aralkyl or alkaryl, or R4 and R5, together with the N atom linking them, form, for example, a piperidine or morpholine radical, and R6 and R7 can be alkyl which may be interrupted by one or more groups from the series comprising --O--, --S--, --NH--, STR4 or are, for example, phenyl, naphthyl, alkaryl or aralkyl, and R8 can be alkylene which may be interrupted by at least one --O-- group or alkylidene which may be interrupted by at least one --O-- group. Some of the compounds of the formula I are novel. The compositions show an improved stability towards oxidative degradation, confer protection under extreme pressures and reduce frictional wear.

Perfluoroalkyl substituted neopentyl alcohols can be reacted with substituted hydroxphenylalkanoic esters to form perfluoroalkyl containing hydroxyphenylalkanoic ester antioxidants. The perfluoroalkyl substituted hindered hydroxyphenyl alkanoates are stablizers which confer superior processing stability to polymers processed at elevated temperatures such as polypropylene, as well as protecting said polymers from thermal and oxidative degradation.

Carbohydrate substituted phosphites of Formula I STR1 where A is a carbohydrate residue are effective stabilizers for polymers processed at elevated temperatures and subject to thermal or oxidative degradation.

The beta crystalline modification of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite] is obtained by crystallizing said compound from the melt at elevated temperatures. The beta crystalline form is an effective process stabilizer for polyolefins, particularly polypropylene.

Carbohydrate substituted dibenzo[d,f][1,3,2]dioxaphosphepin compounds of formula I STR1 where A is a carbohydrate residue are effective stabilizers for polymers processed at elevated temperatures and subject to thermal or oxidative degradation.

N,N,N',N'-Tetrasubstituted 1,4-diamino-2-butenes where the substituents are alkyl, cycloalkyl, aralkyl, aryl or mixtures thereof provide effective antioxidant protection to lubricants and/or synthetic polymers.

2-(2-Hydroxy-3-perfluoroalkylthiomethyl-5-alkylphenyl)-2H-benzotriazoles are prepared by reacting the Mannich base hydrohalide or quaternary salt of a 2-(2-hydroxy-5-alkylphenyl)-2H-benzotriazole with a perfluoroalkyl mercaptan. The products exhibit outstanding efficacy in protecting organic substrates from light induced deterioration as well as good resistance to loss by volatilization or exudation during the processing of stabilized compositions at elevated temperatures.

1-Hydrocarbyloxy-2,2,6,6-tetramethylpiperidine derivatives of s-triazines having functional groups such as hydroxy, amino, carboxy, epoxy, isocyanate or the like present are capable of chemically bonding with polymer substrates having anhydride, epoxide, alkoxymethylmelamine or isocyanate moieties present. This chemical bonding prevents migration or loss of the stabilizer during subsequent processing or end-use application of the stabilized polymer.

1-Hydroxy-2,6-diaryl-4-piperidone ketal derivatives, such as the compound of formula I STR1 wherein Ar1 and Ar2 are each phenyl, R1 to R6 are all hydrogen, X1 and X2 are each --O-- and T is a direct bond, are novel compounds and are effective process stabilizers, such as polypropylene, for polymers processed at elevated tempertures providing both good melt flow stabilization and good resistance against discoloration during said processing.

Compositions are described which comprise (a) a lubricant, subject to oxidative or thermal degradation, and (b) at least one compound of formula I wherein, R5, R6, R7 and R8 are independently hydrogen, alkenyl of 3 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 15 carbon atoms, -CN, -NO6, halogen, -ORψ, -NR?R?, -SR?, -COOR and -CONR54R55 where Rψ, R?, R?, R?, R , R54 and R55 are independently hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, aryl of 6 to 10 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or aralkyl of 7 to 15 carbon atoms. Some of the compounds of formula one are novel.

Substituted 1-aminonaphthalenes of formula I STR1 wherein n is 1-3, Ar is arylene, R1 and R2 are independently hydrogen, alkyl or phenyl, R3 is hydrogen, alkyl or substituted alkyl, and R4 and R5 have independently the same definitions as R3 or are independently aryl, substituted aryl or cycloalkyl, are effective stabilizers for lubricating oil or polymer compositions. The instant compounds are particularly effective in lubricating oil compositions when used with a diarylamine antioxidant.

N-Allyl and N-methylene-thio substituted 2,3-dihydroperimidine compounds are very effective antioxidant stabilizers for organic material subject to oxidative or thermal degradation, particularly for lubricant compositions.

New triazole compounds, useful as metal deactivators and/or antioxidants in organic material, having the formula I: wherein X is the triazole residue of formula II: or the benzotriazole residue of formula III or IIIA: in which R is hydrogen or methyl.

Composition comprising a functional fluid or fuel susceptible to degradation by a metal; and b) a metal deactivator having the formula I: in which X is a group having the formula II or III: in which R is hydrogen or C1-C4 alkyl. The compounds of formula I are new.

New composition comprises a functional fluid in contact with ferrous metal and a corrosion inhibiting amount of at least one compound of formula (I) STR1 or a derivative thereof in which R1, R2 and R3 are, independently, hydrogen, a C1 -C15 straight or branched chain alkyl residue, a C5 -C12 cycloalkyl residue, a C6 -C15 aryl residue or C7 -C12 alkaryl residue, and R4 and R5 are, independently, hydrogen, 2-hydroxyethyl or 2-hydroxypropyl with the provisos that (a) R4 and R5 are not simultaneously hydrogen, (b) when R4 and R5 are each --CH2 --CH2 --OH, R1 and R2 are not simultaneously hydrogen and R3 is not a pentyl residue and (c) that polyalkylene and phenol or polycarboxylic ester co-additives are absent; as well as salts thereof. Some of the compounds of formula I are new.

A composition, in contact with a corrodable metal surface, which composition comprises: (a) an aqueous-based or oil-based system; and (b) as inhibitor for protecting the metal surface against corrosion, at least one compound having the formula I: STR1 as well as salts or partial esters thereof wherein: n is 0 or an integer ranging from 1 to 20, R is a straight or branched chain C4 -C30 alkyl group, optionally interrupted by one, two or three oxygen atoms or substituted by one, two or three hydroxy groups, a C5 -C12 cycloalkyl group, a C6 -C10 aryl group optionally substituted by one, two or three C1 -C12 alkyl groups, or a C7 -C13 aralkyl group which is optionally substituted by a hydroxyl group; R1 is H or a straight- or branched chain C1 -C4 alkyl group; R2 is H, a straight or branched chain C1 -C4 alkyl group or CO2 H; R3 is H, a straight or branched chain C1 -C4 alkyl group, --CH2 CO2 H or --CH2 CH2 CO2 H; R4 is H, a straight or branched chain C1 -C4 alkyl group or CO2 H; R5 is H, a straight or branched chain C1 -C4 alkyl group, CH2 CO2 H or CH2 CH2 CO2 H; provided that at least one group R4 must be CO2 H, with the provisio, that compositions comprising an oil-based system and a compound having the formula STR2 wherein R, R1 and R2 are hydrogen or alkyl radicals, having a total from 10 to 38 C-atoms, are excluded.

Compounds useful as additives for lubricants, hydraulic oils and metal-working fluids include those of formula IV STR1 where R1 and R2 are independently alkyl or substituted aryl, R3 and R13 are independently hydrogen or methyl, R6 is alkyl, alkenyl, aralkyl or substituted benzyl, and R15 and R16 are independently hydrogen, alkyl, aryl or aralkyl.

Compounds of the formula STR1 and of the formula STR2 in which X and X' are, for example, --S--CHR1, --NR2 R3, --S--R3, --NR2 R3 or --OR3, R1 is, for example, --H, alkyl, cycloalkyl or phenyl, R2 and R3 are, for example, --H, alkyl, cycloalkyl or phenyl, or R2 and R3 together form a 3- to 7-membered heterocyclic ring, and R is alkylene, and compositions containing at least one compound of the formulae I and/or II and at least one lubricant, one hydraulic fluid or one metal working fluid, the compounds of the formula I and/or II being used as extreme pressure and wear-reducing additives.

The present invention provides a lubricant composition comprising a lubricating oil and, as multifunctional additive, at least one compound having the formula I: or amine salts thereof; wherein R1 and R2, independently, are hydrogen or methyl; n and m, independently, are 0 or 1; and X is SR3 or NR4R3 wherein R3 is C12-C20 linear or branched alkyl R4 and R5 are independently, C8-C20 linear or branched aikyl provided that those compounds of formula I are excluded in which m and n are each 0, X is S-C8-C20 linear or branched alkyl and R1 and R2 are as defined.

The present invention provides a composition in contact with a corrodable metal surface, comprising a functional fluid and, as corrosion inhibitor, a compound having the formula I: as well as salts or esters thereof, wherein, R1 is C4-C20 linear or branched alkyl, phenyl or C7-C20 alkylphenyl;, R2 is C1-C12 linear or branched alkyl, phenyl or C7-C20 alkylphenyl, or arylalkyl containing 7-20 carbon atoms;, X is CH2, O or S;, Y is O or S; and, Z is -(CH2)n- in which n is 1, 2, 3, 4 or 5, or Z is -CH2-CH(CH3)-. Some of the compounds of formula I are new.

Novel salts of methylphosphonic acid with primary amines are described. These compounds are preferably used as extreme pressure additives in lubricant compositions.

Compounds of the formula (I) STR1 in which the Rs independently of one another are H, phenyl, naphthyl or C7 -C30 alkaryl and R1 is H, C1 -C8 alkyl, C7 -C9 aralkyl, C5 -C12 cycloalkyl, phenyl, naphthyl, C7 -C30 alkaryl or a group of the formula (II) R2 is C7 -C30 alkaryl, phenyl, naphthyl or phenyl containing, in the para-position, an HO or C1 -C18 alkoxy group or a group of the formulae STR2 or R1 and R2, together with the nitrogen atom to which they are attached, are a radical of the formula (III) STR3 R3 is a radical of the formulae --(CH2)b --COOR6 or --(CH2)2 OCOR7, a is the number 1, 2 or 3 and b is the number 1 or 2, and R4 is phenyl or a group of the formula (II), the two R5 s independently of one another are H, C1 -C24 alkyl, C5 -C12 cycloalkyl or C7 -C9 aralkyl, and R6 is H, C1 -C18 alkyl or benzyl, R7 is C1 -C14 alkyl, phenyl or a group of the formula in which Y is --O-- or --S--, a is the number 1, 2 or 3 and m is the number 1 or 2, B is a direct bond, --S--, --S--S-- or a C1 -C12 alkylene radical, X in the formula (III) is a direct bond, --S-- or a group of the formulae STR4 form a phenothiazine, phenazine, acridine or carbazole radical.

The compounds of the formula STR1 in which R is C1 -C24 alkyl, C3 -C20 alkenyl, C5 -C6 cycloalkyl, unsubstituted or C1 -C4 alkyl-substituted phenyl or phenyl-C1 -C4 alkyl, n is 1 or 2, and X is S or O, are highly suitable as additives, in particular as antiwear and high-pressure additives, and as corrosion inhibitors in functional fluids, for example in lubricants, fuels, hydraulic fluids, metal-working fluids and drilling fluids.

A composition, in contact with a corrodable metal surface, comprising: a) an aqueous-based or oil-based system; and b) as an inhibitor for protecting the metal surface against corrosion, at least one compound having the formula I or II: in which, R is C4-C20alkyl, C4-C20alkyl interrupted by one or more oxygen atoms, C4-C20alkenyl, C6-C10aryl, C7-C15alkaryl, C7-C15aralkyl or C5-C12cyclo-alkyl;, R1, R2 and R3 are the same or different and each is methyl or, preferably, hydrogen;, M is hydrogen, a metal ion, ammonium or substituted ammonium ion;, a is 0 or 1;, b is 0 or an integer from 1 to 6, preferably 0, 1, 2 or 3 especially 0 or 1; and, c is an integer from 1 to 6; and/or at least one compound having the formula II: in which R, R3 and a are as defined above.

New reaction products, useful as additives for functional fluids, are obtained by reacting, at elevated temperature, (A) a triazole having the formula IA or IB: STR1 wherein R7 is hydrogen or a C1 -C20 alkyl residue; R8 and R9 are the same or different and each is C1 -C20 alkyl, C3 -C20 alkenyl, C5 -C12 cycloalkyl, C7 -C13 aralkyl, C6 -C10 aryl or R8 and R9, together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic residue or R8 and R9 is each a residue of formula: wherein X is O, S or N(R12), R12 is hydrogen or C1 -C20 alkyl, "alkylene" is a C1 -C12 alkylene residue and n is 0 or an integer from 1 to 6; R10 is hydrogen, C1 -C20 alkyl or C6 -C10 aryl or C7 -C18 alkyl phenyl; and R11 is hydrogen, C1 -C20 alkyl or a residue --CH2 NR8 R9 wherein R8 and R9 have their previous significance; with (B) an organodithiophosphate having the formula: STR2 in which R13 is a C1 -C20 alkyl or C7 -C18 alkyl phenyl or C7 -C13 aralkyl group, M is a metal ion of Group IA, IB, IIA, IIB, VB, VIB, VIIB or VIII of the Periodic System of Elements, and y is the valency of M.