Antioxidant for fats,oils and food

A composition of matter normally subject to oxidative deterioration comprising an edible organic substance normally subject to oxidative deterioration and a minor amount effective as an antioxidant of one or more compounds selected from the group consisting of (i) 3-arylbenzofuranones in the present invention are compounds of the formula I

• in which, if n is 1,
• R1 is unsubstituted or C1-C4alkyl-, C1-C4alkoxy-, C1-C4alkylthio-, hydroxyl-, halo-, amino-, C1-C4alkylamino-, phenylamino- or di(C1-C4alkyl)amino-substituted naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, or R1 is a radical of the formula II
• and
• if n is 2,
• R1 is unsubstituted or C1-C4alkyl- or hydroxy-substituted phenylene or naphthylene;
• or is —R12—X—R13—,
• R2, R3, R4 and R5 independently of one another are hydrogen, chlorine, hydroxyl, C1-C25alkyl, C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl;
• unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl;
• C1-C18alkoxy, C1-C18alkylthio, C1-C4alkylamino, di(C1-C4alkyl)amino, C1-C25alkanoyloxy, C1-C25alkanoylamino, C3-C25alkenoyloxy, C3-C25alkanoyloxy which is interrupted by oxygen, sulfur or
• C8-C9cycloalkyl-carbonyloxy, benzoyloxy or C1-C12alkyl-substituted benzoyloxy;
• or else the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and R5, together with the carbon atoms to which they are attached, form a benzo ring, R4 is additionally —(CH2)p—COR15 or —(CH2)qOH or, if R3, R5 and R6 are hydrogen, R4 is additionally a radical of the formula III
• in which R1 is defined as indicated above for n=1,
• R6 is hydrogen or a radical of the formula IV
• where R4 is not a radical of the formula III and R1 is defined as indicated above for n=1,
• R7, R8, R9, R10 and R11 independently of one another are hydrogen, halogen, hydroxyl, C1-C25alkyl, C2-C25alkyl interrupted by oxygen, sulfur or
• C1-C25alkoxy, C2-C25alkoxy interrupted by oxygen, sulfur or
• C1-C25alkylthio, C3-C25alkenyl, C3-C25alkenyloxy, C3-C25alkynyl, C3-C25alkynyloxy, C7-C9phenylalkyl, C7-C9phenylalkoxy, unsubstituted or C1-C4alkyl-substituted phenyl;
• unsubstituted or C1-C4alkyl-substituted phenoxy;
• unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl;
• unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkoxy;
• C1-C4alkylamino, di(C1-C4alkyl)amino, C1-C25alkanoyl, C3-C25alkanoyl interrupted by oxygen, sulfur or
• C1-C25alkanoyloxy, C3-C25alkanoyloxy interrupted by oxygen, sulfur or
• C1-C25alkanoylamino, C3-C25alkenoyl, C3-C25alkenoyl interrupted by oxygen, sulfur or
• C3-C25alkenoyloxy, C3-C25alkenoyloxy interrupted by oxygen, sulfur or
• C6-C9cycloalkylcarbonyl, C6-C9cycloalkylcarbonyloxy, benzoyl or C1-C12alkyl-substituted benzoyl;
• benzoyloxy or C1-C12alkyl-substituted benzoyloxy;
• or else, in formula II, the radicals R7 and R8 or the radicals R8 and R11, together with the carbon atoms to which they are attached, form a benzo ring,
• R12 and R13 independently of one another are unsubstituted or C1-C4alkyl-substituted phenylene or naphthylene,
• R14 is hydrogen or C1-C8alkyl,
• R15 is hydroxyl,
• C1-C18alkoxy or
• R16 and R17 independently of one another are hydrogen, CF3, C1-C12alkyl or phenyl, or R16 and R17, together with the C atom to which they are attached, form a C5-C8cycloalkylidene ring which is unsubstituted or substituted from 1 to 3 times by C1-C4alkyl;
• R18 and R19 independently of one another are hydrogen, C1-C4alkyl or phenyl,
• R20 is hydrogen or C1-C4alkyl,
• R21 is hydrogen, unsubstituted or C1-C4alkyl-substituted phenyl;
• C1-C25alkyl, C2-C25alkyl interrupted by oxygen, sulfur or
• C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl radical from 1 to 3 times by C1-C4alkyl;
• C7-C25phenylalkyl which is unsubstituted or substituted on the phenyl radical from 1 to 3 times by C1-C4alkyl and interrupted by oxygen, sulfur or
• or else the radicals R20 and R21, together with the carbon atoms to which they are attached, form a C5-C12cycloalkylene ring which is unsubstituted or substituted from 1 to 3 times by C1-C4alkyl;
• R22 is hydrogen or C1-C4alkyl,
• R23 is hydrogen, C1-C25alkanoyl, C3-C25alkenoyl, C3-C25alkanoyl interrupted by oxygen, sulfur or
• C2-C25alkanoyl substituted by a di(C1-C8alkyl)phosphonate group;
• C8-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C1-C12alkyl-substituted benzoyl;
• R24 and R25 independently of one another are hydrogen or C1-C18alkyl,
• R26 is hydrogen or C1-C8alkyl,
• R27 is a direct bond, C1-C18alkylene, C2-C18alkylene interrupted by oxygen, sulfur or
• C2-C18alkenylene, C2-C20alkylidene, C7-C20phenylalkylidene, C5-C8cycloalkylene, C7-C8bicydoalkylene, unsubstituted or C1-C4alkyl-substituted phenylene, or
• R28 is hydroxyl,
• C1-C18alkoxy or
• R29 is oxygen, —NH— or
• R30 is C1-C18alkyl or phenyl,
• R31 is hydrogen or C1-C18alkyl,
• M is an r-valent metal cation,
• X is a direct bond, oxygen, sulfur or —NR31—,
• n is 1 or 2,
• p is 0, 1 or 2,
• q is 1, 2, 3, 4, 5 or 6,
• r is 1, 2 or 3, and
• s is 0, 1 or 2;
• (ii) a long chain N,N-dialkylhydroxylamine of formula (VI)
• wherein T1 and T2 are independently straight or branched chain alkyl of 6 to 36 carbon atoms;
• (III) substituted hydroxylamines may be for example of the formula (VIII) or (IX)
• wherein
• T1 is straight or branched chain alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms, or said aralkyl substituted by one or two alkyl of 1 to 12 carbon atoms or by one or two halogen atoms;
• T2 is hydrogen, or independently has the same meaning as T1;
• and
• T3 is allyl, straight or branched chain alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 18 carbon atoms, cycloalkenyl of 5 to 18 carbon atoms or a straight or branched chain alkyl of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl groups of 1 to 4 carbon atoms or by 1 or 2 halogen atoms;
• (iv) nitrones of the formula (X)
• wherein
• L1 is straight or branched chain alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms, or said aralkyl substituted by one or two alkyl of 1 to 12 carbon atoms or by one or two halogen atoms;
• L2 and L3 are independently hydrogen, straight or branched chain alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms, or said aralkyl substituted by one or two alkyl of 1 to 12 carbon atoms or by one or two halogen atoms;
• or L1 and L2 together form a five- or six-membered ring including the nitrogen atom;
• and
• (v) amine oxides are for example saturated tertiary amine oxides as represented by general formula (XI):
• wherein
• G1 and G2 are independently a straight or branched chain alkyl of 6 to 36 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 36 carbon atoms, alkaryl of 7 to 36 carbon atoms, cycloalkyl of 5 to 36 carbon atoms, alkcycloalkyl of 6 to 36 carbon atoms or cycloalkylalkyl of 6 to 36 carbon atoms;
• G3 is a straight or branched chain alkyl of 1 to 36 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 36 carbon atoms, alkaryl of 7 to 36 carbon atoms, cycloalkyl of 5 to 36 carbon atoms, alkcycloalkyl of 6 to 36 carbon atoms or cycloalkylalkyl of 6 to 36 carbon atoms;
• with the proviso that at least one of G1, G2 and G3 contains a b carbon-hydrogen bond;
• and
• wherein said aryl groups may be substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;
• and
• wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups may be interrupted by one to sixteen —O—, —S—, —SO—, —SO2—, —COO—, —OCO—, —CO—, —NG4—, —CONG4— and —NG4CO— groups, or wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups may be substituted by one to sixteen groups selected from —OG4, —SG4, —COOG4, —OCOG4, —COG4, —N(G4)2, —CON(G4)2, —NG4COG4 and 5- and 6-membered rings containing the —C(CH3)(CH2Rx)NL(CH2Rx)(CH3)C— group or wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups are both interrupted and substituted by the groups mentioned above;
• and
• wherein
• G4 is independently hydrogen or alkyl of 1 to 8 carbon atoms;
• Rx is hydrogen or methyl;
• L is hydrogen, hydroxy, C1-30 straight or branched chain alkyl moiety, a —C(O)R moiety where R is a C1-30 straight or branched chain alkyl group, or a —ORy moiety;
• and
• Ry is C1-30 straight or branched chain alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C5-C12 cycloalkyl, C6-C10 bicycloalkyl, C5-C8 cycloalkenyl, C6-C10 aryl, C7-C9aralkyl, C7-C9 aralkyl substituted by alkyl or aryl, or —CO(D), where D is C1-C18 alkyl, C1-C18 alkoxy, phenyl, phenyl substituted by hydroxy, alkyl or alkoxy, or amino or amino mono- or di-substituted by alkyl or phenyl.