CA2132132C - Process for the preparation of 3-arylbenzofuranones - Google Patents

Abstract

A process for the preparation of compounds of formula I

(See Formula I) wherein the general symbols are as defined in claim 1, which comprises reacting a com-pound of formula III

(See Formula III) wherein the general symbols are as defined in claim 1, with a compound of formula IV
[H]n-R (IV).

Description

Process for the preparation of 3-arylbenzofuranones The present invention relates to a novel process for the preparation of 3-arylbenzofura-nones that are suitable for stabilising organic materials against oxidative, thermal or light-induced degradation.
Individual benzofuran-2-ones are known in the literature, and have been mentioned, inter olio, in Beilstein 18, 17 and Beilstein E IIIIIV, 18, 154-166, or described by Th. Kappe et al., Monatshefte fur Chemie 99, 990 (1968); J. Morvan et al., Bull. Soc. Chim.
Fr. 1979, 583; L. F. Clarke et al., J. Org. Chem. 57, 362 (1992); M. Julia et al., Bull.
Soc. Chim. Fr.
1965, 2175, or by H. Sterk et al., Monatshefte fur Chemie 99, 2223 (1968). In no publica-tion are these compounds used as stabilisers for organic materials.
The use of some 3-phenyl-3H-benzofuran-2-ones as stabilisers for organic polymers is dis-closed, inter olio, in US-A-4 325 863; US-A-4 338 244 and US-A-5 175 312.
CH O
H3C \ ~ H3 OH H3C ~ C/ 3 O H
C HOOC /
H3C ~ ~ ~ CH - 2 H20 H3C
+ HO / I ---1 H3C-C-CH3 ~ H3C-C-CH3 I

(A) (B) (C) The hitherto preferred process for the preparation of 3-phenyl-3H-benzofuran-2-ones, for example the 5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one of formula C, comprises reacting the 2,4-di-tert-butylphenol of formula A with the mandelic acid of formula B, with elimination of water (q.v. US-A-4 325 863, Example l, column 8, lines 35-45).
For synthesising 3-phenyl-3H-benzofuran-2-ones which are substituted at the 3-phenyl ring or for preparing 3H-benzofuran-2-ones which are substituted in 3-position by a hete-rocycle, the drawback of the process is that it is necessary to use mandelic acids that are substituted at the phenyl ring or heterocyclic mandelic acids. However, not very many of these acids are known in the literature and the known syntheses for the preparation of these mandelic acids are quite troublesome.

Accordingly, the invention relates to a process for the preparation of compounds of for-mina I
O
O H

(I) R~

Ra n wherein, when n is l, Rl is an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system, when n is 2, Rl is unsubstituted or C1-C4alkyl- or hydroxy-substituted phenylene or naphthylene; or is -~-x-R~-R2, R3, R4 and RS are each independently of one another hydrogen, chloro, hydraxy, C1-C~alkyl, C~-C9-phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl, unsubsti-tuted or C1-C4alkyl-substituted CS-C8cycloalkyl; C1-ClBalkoxy, C1-Clgalkylthio, C1-C4-alkylamino, di-(C1-C4alkyl)amino, C1-C25alkanoyloxy, C1-C25alkanoylamino, C3-C~-alkenoyloxy, C3-C25alkanoyloxy which is interrupted by oxygen, sulfur or ,mss ;
C6-C9cycloalkylcarbonyloxy, benzoyloxy or C1-Cl2alkyl-substituted benzoyloxy;
or each pair of substituents RZ and R3 or R3 and R4 or R4 and R5, together with the linking carbon atoms, forms a benzene ring; R4 is additionally -(CH2)p CORg or -(CHZ)qOH, or, if R3 and RS are hydrogen, R4 is additionally a radical of formula II

H

~B) R1o - i - R11 wherein Rl is as defined above when n = 1, R6 and R~ are each independently of the other unsubstituted or C1-C4alkyl-substituted phe-nylene or naphthylene, R8 is hydrogen or Cl-C8alkyl, R9 is hydroxy, ~-Oe r M r + ~ , C1-Clgalkoxy or -N~~,.., , Rlo and Rll are each independently of the other hydrogen, CF3, Cl-Cl2a.lkyl or phenyl, or Rlo and Rll, together with the linking carbon atom, form a CS-Cgcycloalkylidene ring which is unsubstituted or substituted by 1 to 3 C1-C4alkyl groups, R14 is hydrogen or Cl-Clgalkyl, M is a metal canon of valency r, X is a direct bond, oxygen, sulfur or NR14, n is 1 or 2, p is 0, 1 or 2, q is l, 2, 3, 4, 5 or 6, and r is l, 2 or 3, which process comprises reacting a compound of formula III
O
H
R15 (III) wherein R15 is halogen or -OR' 1s, R'15 is hydrogen, C1-C25alkanoyl, C3-C~alkenoyl, C3-C25alkanoyl which is interrupted by oxygen, sulfur or j -Rs ; C6-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C1-Cl2alkyl-substituted benzoyl; naphthoyl or C1-Cl2alkyl-substituted naphthoyl; Cl-C2s alkanesulfonyl, fluoro-substituted C1-C~alkanesulfonyl; phenylsulfonyl or C1-Cl2alkyl-O O O
substituted phenylsulfonyl; - ~ _ R~6 C - R9 or - C - Ri~ R~$
R16 is a direct bond, C1-Ci8alkylene, C2-C1$alkylene which is interrupted by oxygen, sulfur or ~s ; CZ-Cigalkenylene, C2-C2oalkylidene, C~-C2ophenylalkylidene, CS-C8cycloalkylene, C~-C8bicycloalkylene, unsubstituted or Ci-C4alkyl-substituted phenylene, ~O' or ~S, , O
Rl~ is oxygen, -NH- or ~N - C - N H- R 1 $ , and Rlg is C1-Clsalkyl or phenyl, with a compound of formula IV
[H]ri Rl (IV).
Halogen substituents will conveniently be chloro, bromo or iodo. Chloro is preferred.
Alkanoyl of up to 25 carbon atoms inclusive is a branched or unbranched radical, typically including formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, eicosanoyl or docosanoyl. R' is defined as alkanoyl preferably contains 2 to 18, most preferably 2 to 12, e.g. 2 to 6, carbon atoms.
Acetyl is particularly preferred.
C2-C25Alkanoyl substituted by a di(C1-C6alkyl)phosphonate group will typically be (CH3CH20)2POCH2C0-, {CH30)2POCH2C0-, (CH3CH2CH2CH20)2POCH2C0-, (CH3CH20)2POCH2CH2C0-, {CH3O)2POCH2CH2C0-, {CH3CHZCHZCH20)2POCH2CH2C0-, {CH3CH2O)2PO(CH2)4CO-, (CH3CH20)2P0(CH2)gC0- or {CH3CH20)2P0(CH2)1~C0-.
Alkanoyloxy of up to 25 carbon atoms inclusive is an unbranched or branched radical and is typically formyloxy, acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyl-oxy, octadecanoyloxy, eicosanoyloxy or docosanoyloxy. Alkanoyloxy of 2 to 18, preferab-ly 2 to 12, e.g. 2 to 6, carbon atoms is preferred. Acetoxy is particularly preferred..
Alkenoyl of 3 to 25 carbon atoms is a branched or unbranched radical, typically including propenoyl, 2-butenoyl, 3-butenoyl, isobutenoyl, n-2,4-pentadienoyl, 3-methyl-2-butenoyl, n-2-octenoyl, n-2-dodecenayl, isododecenoyl, oleoyl, n-2-octadecenoyl or n-4-octadece-noyl. Alkenoyl of 3 to 18, preferably 3 to 12, e.g. 3 to b, most preferably 3 to 4, carbon atoms is preferred.
C3-C25Alkenoyl interrupted by oxygen, sulfur or j 1-Ra is typically CH30CH2CH2CH=CHCO- or CH30CH2CH20CH=CHCO-.
Alkenoyioxy of 3 to 25 carbon atoms is a branched or unbranched radical, typically inclu-ding propenoyloxy, 2-butenoyloxy, 3-butenoyloxy, isobutenoyloxy, n-2,4-pentadienoyl-oxy, 3-methyl-2-butenoyloxy, n-2-octenoyloxy, n-2-dodecenoyloxy, isododecenoyloxy, oleoyloxy, n-2-octadecenoyloxy or n-4-octadecenoyloxy. Alkenoyloxy of 3 to 18, prefe-rably 3 to 12, typically 3 to 6, most preferably 3 to 4, carbon atoms is preferred.
C3-CZSAlkenoyloxy interrupted by oxygen, sulfur or j 1-Rs will typically be CH30CH2CH2CH=CHCOO- or CH30CH2CH20CH=CHCOO-.
C3-C25-Alkanoyl interrupted by oxygen, sulfur or j -Ra will typically be CH3-O-CH2C0-, CH3-S-CH2C0-, CH3-NH-CH2C0-, CH3-N(CH3)-CHZCO-, CH3-O-CH2CH2-O-CH2C0-, CH3-(O-CH2CH2-)20-CH2C0-, CH3-(O-CHZCH2-)3O-CH2CO- Or CH3-(O-CH2CH2-)4O-CH2CO-.
C3-C25-Alkanoyloxy interrupoted by oxygen, sulfur or ,N-Rs will typically be CH3-O-CH2COO-, CH3-S-CH2C00-, CH3-NH-CH2C00-, CH3-N(CH3)-CH2C00-, CH3-O-CH2CH2-O-CH2C00-, CH3-(O-CH2CH2-)2O-CH2COO-, CH3-(O-CHZCHZ-)30-CH2C00- or CH3-(O-CHZCH2-)40-CH2C00-.

C6-C9Cycloalkylcarbonyl is typically cyclopentylcarbonyl, cyclohexylcarbonyl, cyclohep-tylcarbonyl or cyclooctylcarbonyl. Cyclohexylcarbonyl is preferred.
C6-C9Cycloalkylcarbonyloxy is typically cyclopentylcarbonyloxy, cyclohexylcarbonyl-oxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy. Cyclohexylcarbonyloxy is pre-ferred.
C1-Cl2Alky1-substituted benzoyl which preferably carries 1 to 3, most preferably 1 or 2 alkyl groups, is typically o-, m- or p-methylbenzoyl, 2,3-dimethylbenzoyl, 2,4-dimethyl-benzoyl, 2,5-dimethylbenzoyl, 2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl, 3,5-dimethyl-benzoyl, 2-methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl, 2-ethylbenzoyl, 2,4,6-trimethyl-benzoyl, 2,6-dimethyl-4-tert-butylbenzoyl or 3,5-di-tert-butylbenzoyl.
Preferred substitu-ents are Cl-Cgalkyl, most preferably C1-C4alkyl.
Ci-Cl2Alkyl-substituted benzoyloxy which preferably carries 1 to 3, most preferably 1 or 2 alkyl groups, is typically o-, m- or p-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2,4-di-methylbenzoyloxy, 2,5-dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-dimethyl-benzoyloxy, 3,5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy, 4-tert-butylbenzoyl-oxy, 2-ethylbenzoyloxy, 2,4,6-trimethylbenzoyloxy, 2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert-butylbenzoyloxy. Preferred substituents are C1-Cgalkyl, preferably C 1-C4alkyl.
C1-Cl2Alkyl-substituted naphthoyl, which is 1-naphthoyl or 2-naphthoyl and preferably contains 1 to 3, most preferably 1 or 2 alkyl groups, will typically be 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-methylnaphthoyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethylnaphthoyl, 4-tert-butylnaphthoyl or 6-tert-butylnaphthoyl. Particularly preferred substituents are C1-Cgalkyl, most preferab-ly C1-C4alkyl.
C1-C25Alkanesulfonyl is a branched or unbranched radical, typically methanesulfonyl, ethanesulfonyl, propanesulfonyl, butanesulfonyl, pentanesulfonyl, hexanesulfonyl, hep-tanesulfonyl, octanesulfonyl, nonanesulfonyl or docosanesulfonyl.
Alkanesulfonyl of 1 to 18, preferably 1 to 12, e.g. 2 to 6, carbon atoms is preferred.
Methanesulfonyl is particular-ly preferred.
Fluoro-substituted C1-C25alkanesulfonyl is typically trifluoromethanesulfonyl.

C1-Cl2Alkyl-substituted phenylsulfonyl which carries preferably 1 to 3, most preferably 1 or 2, alkyl groups is typically o-, m- or p-methylphenylsulfonyl, p-ethylphenylsulfonyl, p-propylphenylsulfonyl or p-butylphenylsulfonyl. Preferred substituents are C1-Cgalkyl, most preferably C1-C4alkyl. p-Methylphenylsulfonyl is particularly preferred.
Alkyl of up to 25 carbon atoms is a branched or unbranched radical and is typically methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepta-decyl, octadecyl, eicosyl or dacosyl. A preferred meaning of R2 and R4 is typically C1-Clgalkyl. A particularly preferred meaning of R4 is C1-C4alkyl.
Alkenyl of 3 to 25 carbon atoms is a branched or unbranched radical, typically including propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Alkenyl of 3 to 18, preferably 3 to 12, typically 3 to 6, most preferably 3 to 4, carbon atoms is pre-ferred.
Alkenyloxy of 3 to 25 carbon atoms is a branched or unbranched radical, typically inclu-ding propenyloxy, 2-butenyloxy, 3-butenyloxy, isobutenyloxy, n-2,4-pentadienyloxy, 3-methyl-2-butenyloxy, n-2-octenyloxy, n-2-dodecenyloxy, isododecenyloxy, oleyloxy, n-2-octadecenyloxy or n-4-octadecenyloxy. Alkenyloxy of 3 to 18, preferably 3 to 12, typically 3 to 6, most preferably 3 to 4, carbon atoms is preferred.
Alkynyl of 3 to 25 carbon atoms is a branched or unbranched radical, typically including propynyl ( -CH2-C=CH ), 2-butynyl, 3-butynyl, n-2-octynyl or n-2-dodecynyl.
Alky-nyl of 3 to 18, preferably 3 to 12, typically 3 to 6, most preferably 3 to 4, carbon atoms is preferred.
Alkynyloxy of 3 to 25 carbon atoms is a branched or unbranched radical, typically inclu-ding propynyloxy ( -OCH2-C=CH ), 2-butynyloxy, 3-butynyloxy, n-2-octynyloxy, or n-2-dodecynyloxy. Alkynyloxy of 3 to 18, preferably 3 to 12, typically 3 to 6, most prefe-rably 3 to 4, carbon atoms is preferred.

~~~2I3~
_g_ C2-C25-Alkyl interrupted by oxygen, sulfur or ,N-Rs will typically be CH3-O-CH2-, CH3-S-CH2-, CH3-NH-CH2-, CH3-N(CH3)-CHZ-, CH3-O-CH2CH2-O-CH2-, CH3-(O-CH2CH2-)2O-CH2-, CH3-(O-CH2CH2-)3O-CHZ- Or CH3-(O-CH2CH2-)40-CH2-.
C~-C9Phenylalkyl may typically be benzyl, a-methylbenzyl, a,a-dimethylbenzyl or 2-phe-nylethyl. Benzyl and a,a-dimethylbenzyl are preferred.
C7-C9-Phenylalkyl which is unsubstituted or substituted in the phenyl moiety by 1 to 3 C1-C4alkyl groups will typically be benzyl, a-methylbenzyl, a,a-dimethylbenzyl, 2-phe-nylethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dime-thylbenzyl or 4-tert-butylbenzyl. Benzyl is preferred.
C~-C25Phenylalkyl which is interrupted by oxygen, sulfur or N-R8 and is unsubstitu-ted or substituted in the phenyl moiety by 1 to 3 C1-C4alkyl groups is a branched or un-branched radical such as phenoxymethyl, 2-methylphenoxymethyl, 3-methylphenoxy-methyl, 4-methylphenoxymethyl, 2,4-dimethylphenoxymethyl, 2,3-dimethylphenoxy-methyl, phenylthiomethyl, N-methyl-N-phenyl-amino-methyl, N-ethyl-N-phenyl-amino-methyl, 4-tert-butylphenoxymethyl, 4-tert-butylphenoxyethoxymethyl, 2,4-di-tert-butyl-phenoxymethyl, 2,4-di-tert-butylphenoxyethoxyrnethyl, phenoxyethoxyethoxyethoxy-methyl, benzyloxymethyl, benzyloxyethoxymethyl, N-benzyl-N-ethyl-amino-methyl or N-benzyl-N-isopropyl-amino-methyl.
C~-C9Phenylalkoxy is typically benzyloxy, a-methylbenzyloxy, a,a-dimethylbenzyloxy or 2-phenylethoxy. Benzyloxy is preferred.
C1-C4Alky1-substituted phenyl that preferably contains 1 to 3, preferably 1 or 2, alkyl groups, will typically be o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethyl-phenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.
C1-C4Alky1-substituiertes phenoxy which preferably contains 1 to 3, most preferably 1 or 2, alkyl groups, is typically o-, m- or p-methylphenoxy, 2,3-dimethylphenoxy, 2,4-di-methylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or 2,6-_g_ diethylphenoxy.
Unsubstituted or Cl-C4alkyl-substituted CS-Cgcycloalkyl is typically cyclopentyl, methyl-cyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, tri-methylcyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Cyclohexyl and tert-butylcyclohexyl are preferred.
Unsubstituted or C1-C4alkyl-substituted CS-Cgcycloalkoxy is typically cyclopentoxy, methylcyclopentoxy, dimethylcyclopentoxy, cyclohexoxy, methylcyclohexoxy, dimethyl-cyclohexoxy, trimethylcyclohexoxy, tert-butylcyclohexoxy, cycloheptoxy or cyclooctoxy.
Cyclohexoxy and tent-butylcyclohexoxy are preferred.
Alkoxy of up to 25 carbon atoms is a branched or unbranched radical and is typically methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Alkoxy of 1 to 12, preferably 1 to 8, e.g. 1 to 6, carbon atoms is preferred.
C2-C25Alkoxy interrupted by oxygen, sulfur or j 1-R8 is typically CH3-O-CH2CH20-, CH3-S-CH2CH20-, CH3-NH-CH2CH20-, CH3-N(CH3)-CH2CH20-, CH3-O-CH2CH2-D-CH2CH20-, CH3-(O-CH2CH2-)20-CHZCH20-, CH3-(O-CH2CH2-)3(?-CH2CH2O- Or CH3-(O-CH2CH2-)4O-CH2CH2(?-.
Alkylthio of up to 25 carbon atoms is a branched or unbranched radical and is typically methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, pentylthio, iso-pentylthio, hexylthio, heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio or octadecylthio. Alkylthio of 1 to 12, preferably 1 to 8, e.g. 1 to 6, carbon atoms is preferred.
Alkylamino of up to 4 carbon atoms is a branched or unbranched radical and is typically methylamino, ethylamino, propylamino, isopropylamino, n-butylamino, isobutylamino or tert-butylamino.
Di(C1-C4)alkylamino also signifies that the two moieties, each independently of the other, are branched or unbranched, and is typically dimethylamino, methylethylamino, diethyl-amino, methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino, methylisobu-tylamino, ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl-tert-butyl-~~~~32 amino, diethylamino, diisopropylamino, isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino or diisobutylamino.
Alkanoylamino of up to 25 carbon atoms is an unbranched or branched radical and is typi-cally formylamino, acetylamino, propionylamino, butanoylamino, pentanoylamino, hexa-noylamino, heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undeca-noylamino, dodecanoylamino, tridecanoylamino, tetradecanoylamino, pentadecanoyl-amino, hexadecanoylamino, heptadecanoylamino, octadecanoylamino, eicosanoylamino oiler docosanoylamino. Alkanoylamino of 2 to 18, preferably 2 to 12, e.g. 2 to 6, carbon atoms is preferred.
Ci-ClgAlkylene is a branched or unbranched radical, typically methylene, ethylene, pro-pylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene. C1-Cl2Alkylene is preferred, and C1-C8alkylene is particularly preferred.
A C1-C4alkyl-substituted CS-Cl2cycloalkylene ring which preferably contains 1 to 3, pre-ferably 1 or 2 branched or unbranched alkyl groups will typically be cyclopentylene, methylcyclopentylene, dimethylcyclopentylene, cyclohexylene, methylcyclohexylene, di-methylcyclohexylene, trimethylcyclohexylene, tent-butylcyclohexylene, cycloheptylene, cyclooctylene or cyclodecylene. Cyclohexylene and tert-butylcyclohexylene.
C2-Cl8Alkylene which is interrupted by oxygen, sulfur or ,n1-Rs will typically be -CH2-O-CH2-, -CH2-S-CH2-, -CH2-NH-CH2-, -CH2-N(CH3}-CH2-, -CH2-O-CH2CH2-O-CH2-, -CH2-(O-CH2CH2-}20-CH2-, -CH2-(O-CH2CH2-}3O-CH2- , -CH2-(O-CH2CH2-)40-CH2- or -CH2CH2-S-CH2CH2-.
C2-ClgAlkenylene is typically vinylene, methylvinylene, octenylethylene or dodecenyl-ethylene. C2-CgAlkenylene is preferred.
Alkylidene of 2 to 20 carbon atoms may typically be ethylidene, propyliden, butylidene, pentylidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene, nonadecylidene, 1-methylethylidene, 1-ethylpropylidene or 1-ethylpentylidene. C2-CgAlkylidene is pre-ferred.

Phenylalkylidene of 7 to 20 carbon atoms may typically be benzylidene, 2-phenylethyli-dene or 1-phenyl-2-hexylidene. C~-C9Phenylalkylidene is preferred.
CS-CgCycloalkylene is a saturated hydrocarbon group having two free valences and at least one ring unit and is typically cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene. Cyclohexylene is preferred.
C~-CgBicycloalkylene may be bicycloheptylene or bicyclooctylene.
Unsubstituted or C1-C4alkyl-substituted phenylene or naphthylene is typically 1,2-, 1,3-, 1,4-phenylene, 1,2-, 1,3-, 1,4-, 1,6-, 1,7-, 2,6- or 2,7-naphthylene. 1,4-phenylene is pre-ferred.
A C1-C4alkyl-substituted CS-C8cycloalkylidene ring that preferably contains 1 to 3, most preferably 1 or 2, branched or unbranched alkyl groups, is typically cyclopentylidene, methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene, methylcyclohexyli-dene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene or cyclooctylidene. Cyclohexylidene and tert-butylcyclohexylidene are preferred.
A mono-, di- or trivalent metal cation is preferably an alkali metal cation, an alkaline earth metal cation or an aluminium cation, typically Na+, K+, Mg++, Ca++ or Al+++.
R1 (if n = 1) may be any aromatic, carbocyclic or heterocyclic ring system which is unsub-stituted or substituted.
Suitable carbocyclic ring systems are based on a benzene ring, or on a system of fused benzene rings, typically of 2 to 5, preferably 2 or 3, rings, one or more of which rings may be wholly or partially hydrogenated. It is essential that the linkage to the benzofuranone is through an aromatic ring. Heterocyclic rings, which may themselves be aromatic or non-aromatic, may also be fused to the benzene ring or the fused benzene rings, preferably those containing 5 or 6 ring members, typically 1 to 3 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur.
Suitable heterocyclic aromatic ring systems are preferably 5- or 6-membered heterocyclic rings having aromaticity, which contain 1 to 3, preferably 1 or 2; hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur. To these rings may be fused fur-ther carbocyclic or heterocyclic aromatic or non-aromatic rings, carbocyclic 6-membered, preferably aromatic, rings being preferred.
Possible substituents for the aromatic radical Rl (n = 1) typically include those defined in connection with the substituents Ri9 to R23. Such substituents are preferably chloro, amino, hydroxy, Cl-Clgalkyl, C1-Clgalkoxy, C1-Cl8alkylthio, C3-C4alkenyloxy, C3-C4a1-kynyloxy, C1-C4alkylamino, di(C1-C4alkyl)amino, phenyl, benzyl, benzoyl or benzoyloxy, preferably chloro, amino, hydroxy, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkyl-amino or di{Cl-C4alkyl)amino.
An interesting process is that for the preparation of compounds of formula I, wherein, if n is 1, Rl is an unsubstituted or substituted 5- or 6-membered aromatic ring to which further rings may be fused.
Also of interest is a process for the preparation of compounds of formula I, wherein, if n is 1, R1 is unsubstituted or substituted phenyl, naphthyl, phenanthryl, anthryl, 5,6,7,8-tetra-hydro-2-naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thiathrenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quino-xalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, (3-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazo-lyl, furazanyl, biphenyl, tetralinyl, fluorenyl or phenoxazinyl. Preferred substituents of the above heterocyclic ring systems are chloro, amino, hydroxy, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di{C1-C4alkyl)amino.
A particularly interesting process is that for the preparation of compounds of formula I, wherein , when n is 1, R1 is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C1-C4alkyl-substituted carbazo-lyl; or is fluorenyl, or Rl is a radical of formula V or VI

Ris Ris R
R2s R2o / R2a (V) \ ( R \ ~ O/ \CH3 (VI) R2g ~ 21 R23 wherein Ri9, R2o, R21, R22 ~d R23 ~'e each independently of one another hydrogen, halogen, hydroxy, C1-C25alkyl, C2-C~alkyl which is interrupted by oxygen, sulfur or Ct-C25alkoxy, C2-C25alkoxy which is interrupted by oxygen, sulfur or j -Ra ;

alkylthio, C3-C25alkenyl, C3-C25alkenyloxy, C3-C~alkynyl, C3-C25alkynyloxy, C~-C~-phenylalkyl, C~-C9phenylaikoxy, unsubstituted or C1-C4alkyl-substituted phenyl; unsub-stituted or Cl-C4alkyl-substituted phenoxy; unsubstituted or C1-Caalkyl-substituted CS-Cg-cycloalkyl; unsubstituted or C1-C4alkyl-substituted CS-Cgcycloalkoxy; C1-C4alkylamino, di(Cl-C4alkyl)amino, C1-C25alkanoyl, C3-C25alkanoyl which is interrupted by oxygen, sulfur or ,t~-Ra ; C1-C25-alkanoyloxy, C3-C25alkanoyloxy which is interrupted by oxygen, sulfur or j -Ra ; Cl-C25alkanoylamino, C3-C25alkenoyl, C3-C25alkenoyl which is interrupted by oxygen, sulfur or ~s ; C3-C25alkenoyloxy, C3-C~alkenoyl-oxy which is interrupted by oxygen, sulfur or ,N-R8 ; C6-C9cycloalkylcarbonyl, C6-C9cycloalkylcarbonyloxy, benzoyl or C1-Cl2alkyl-substituted benzoyl;
benzoyloxy or R27 ~ R29 R30 C 1-C l2alkyl-substituted benzoyloxy; - O - C - C - Rs , - O - C - C - O - R32 , or R2s H Rsi in formula V each pair of substituents R19 and R2o or R2o and R21, together with the linking carbon atoms, forms a benzene ring, R~ is hydrogen, Cl-C4alkyl, unsubstituted or C1-Caalkyl-substituted phenyl, R25 and R26 are hydrogen, C1-Caalkyl or phenyl, with the proviso that at least one of R2s and R26 is hydrogen, R27 and R2g are each independently of the other hydrogen, C1-Caalkyl or phenyl, R29 is hydrogen or C1-Caalkyl, R3o is hydrogen, unsubstituted or C1-C4alkyl-substituted phenyl; C1-C2salkyl, C2-C2salkyl which is interrupted by oxygen, sulfur or ,N-R8 ; C~_C9phenylalkyl which is unsubsti-tuted or substituted at the phenyl moiety by 1 to 3 C1-C4alkyl groups; C~-C2sphenylalkyl which is interrupted by oxygen, sulfur or N-R8 and is unsubstituted or substituted in the phenyl moiety by 1 to 3 Cl-C4alkyl groups; or R29 and R3o, together with the linking carbon atoms, form a Cs-Cl2cycloalkylene ring which is unsubstituted or substituted by 1 to 3 C1-C4alkyl groups, R31 is hydrogen or C1-C4alkyl, R32 is hydrogen, C1-CZSalkanoyl, C3-C2salkenoyl, C3-C2salkanoyl which is interrupted by oxygen, sulfur or ,N-Rs ; C2-C2salkanoyl which is substituted by a di(CI-C6alkyl)-phosphonate group; C6-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C1-Cl2alkyl H3C w CH3 C
O ~ CH3 substituted benzoyl; ~ -CsH2s / \ OH ' O H3C \ C CH3 H3C \ C CH3 NCH O ~CH3 C - CH2 S - CH2 ~ ~ OH ' - C - CH2 C ~ ~ OH
R33 CH3 \R33 O p O
-C-R34-C-R35 ~r -C-R3fi R37 ' R33 is hydrogen or C1-C8alkyl, R34 is a direct bond, C1-Clgalkylene, C2-Clgalkylene which is interrupted by oxygen, sulfur or ,N-R$ ; C2-Clgalkenylene, C2-C2oalkylidene, C~-CZophenylalkylidene, Cs-C8cycloalkylene, C~-C8bicycloalkylene, unsubstituted or C1-C4alkyl-substituted phenylene, X01 or ~S 1 , ~,~ ..-R35 is hydroxy, ~-Oe ~ M r+ ~ , Cl-Clgalkoxy or -N~ , O
Rs6 is oxygen, -NH- or ~N - C - N H- R3~ , R3~ is C1-Clgalkyl or phenyl, and s is 0, 1 or 2.
Also of particular interest is a process for the preparation of compounds of formula I, wherein, when n is 2, Rl is -R6-X-R~-, R6 and R~ are phenylene, X is oxygen or -NR14-, and R14 is Cl-C4alkyl.
A process of very particular interest is that for the preparation of compounds of formula I, wherein, when n is 1, R1 is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C1-C4alkyl-substituted carbazo-lyl; or is fluorenyl, or Rl is a radical of formula V or VI

R2o ~ R2a (v~ ~ ~ ~ ~ ~ (vI~
y R ~ '~ O CH3 wherein Ri9, R2o, Ran Raa and R23 are each independently of one another hydrogen, halogen, hydroxy, C1-Cl8alkyl, C2-Clgalkyl which is interrupted by oxygen, sulfur or C1-Clgalkoxy, C2-Cl8alkoxy which is interrupted by oxygen, sulfur or ,N-Ra ;
C1-Clg-alkylthio, C3-Clgalkenyl, C3-Cl8alkenyloxy, C3-Cl8alkynyl, C3-Cl8alkynyloxy, C~-C9-phenylalkyl, C~-C9phenylalkoxy, unsubstituted or C1-C4alkyl-substituted phenyl; unsub-stituted or Cl-C4alkyl-substituted phenoxy; unsubstituted or C1-C4alkyl-substituted CS-C8-cycloalkyl; unsubstituted or C1-C4alkyl-substituted CS-Cgcycloalkoxy; C1-C4alkylamino, di(C1-C4alkyl)amino, C1-Clga7kanoyl, C3-Cl8alkanoyl which is interrupted by oxygen, sulfur or ~a ; C1-C18-alkanoyloxy, C3-Clgalkanoyloxy which is interrupted by oxygen, sulfur or /N-Ra ; Ci-Cl8alkanoylamino, C3-Cigalkenoyl, C3-Clgalkenoyl which is interrupted by oxygen, sulfur or j -Ra ; C3-Clgalkenoyloxy, C3-Clgalkenoyl-oxy which is interrupted by oxygen, sulfur or ~a ; C6-C9cycloa.lkylcarbonyl, C6-C9cycloalkylcarbonyloxy, benzoyl or C1-Cl2alkyl-substituted benzoyl;
benzoyloxy or R27 O R~ R~
C 1-Cgalkyl-substituted benzoyloxy; - ~ - C - C - Rg ~ - O - C - C - O - R32 , or R2s H R3~
in formula V each pair of substituents R19 and RZO or R2o and R21, together with the linking carbon atoms, forms a benzene ring, R~ is hydrogen, C1-C4alkyl, unsubstituted or C1-C4alkyl-substituted phenyl, R~ and R26 are hydrogen, Cl-C4alkyl or phenyl, with the proviso that at least one of R2s and R26 is hydrogen, R2~ and R2$ are each independently of the other hydrogen, C1-C4alkyl or phenyl, R29 1S hydrogen or C1-C4alkyl, R3o is hydrogen, unsubstituted or Cl-C4alkyl-substituted phenyl; C1-Clgalkyl, C2-Clgalkyl which is interrupted by oxygen, sulfur or ,N-Rs ; C~-C9phenylalkyl which is unsubsti-tuted or substituted in the phenyl moiety by 1 to 3 C1-C4alkyl groups; C~-Clgphenylalkyl which is interrupted by oxygen, sulfur or ,N-R8 or is unsubstituted or substituted at the phenyl moiety by 1 to 3 Cl-C4alkyl groups; or R29 arid R3o, together with the linking carbon atoms, form a CS-C9cycloalkylene ring which is unsubstituted or substituted by 1 to 3 C1-C4alkyl groups, R31 is hydrogen or C1-C4alkyl, R32 is hydrogen, C1-Clgalkanoyl, C3-Clgalkenoyl, C3-Cigalkanoyl which is interrupted by oxygen, sulfur or ,N--Ra ; C2-Clgalkanoyl which is substituted by a di(C1-C6alkyl)-phosphonate group; C6-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C1-CBalkyl-sub-H3C \ ~ H3 C
O ~ CH3 stituted benzoyl; ~ -CSH2S
OH

O H3C \ C CH3 H3C 'C 'H3 II CH
~CH3 O 3 C - CH2- S - CH2 ~ ~ OH ~ - C - CH2- j ~ ~ OH

O O O
- C - R3a C - R3s or - C - R3s R3~ ' R33 is hydrogen or C1-Cgalkyl, R~ is a direct bond, C1-Cl8alkylene, C2-Cl2alkylene which is interrupted by oxygen, sulfur or ~a , C2-Cl2alkenylene, C2-Cl2alkylidene, C~-Cl2phenylalkylidene, CS-Cgcycloalkylene, C~-Cgbicycloalkylene, unsubstituted or C1-C4alkyl-substituted phenylene, ~O, or ~S' , ~R~a R35 is hydroxy, ~-Oe ~ M r + ~ , C 1-C i salkoxy or -N ~ , O
R36 is oxygen, -NH- or ~N - C - N H- R3~ , R3~ is C1-Clgalkyl or phenyl, and s is 0, 1 or 2.
A preferred process is a process for the preparation of compounds of formula I, wherein Ri9~ Rzo~ Ran Raa ~d RZS ~'e each independently of one another hydrogen, chloro, bromo, hydroxy, C1-Clgalkyl, C2-Cisalkyi which is interrupted by oxygen or sulfur;
C1-Clgalkoxy, CZ-Clgalkoxy which is interrupted by oxygen or sulfur; C1-Clgalkylthio, C3-Ct2alkenyloxy, C3-Cl2alkynyloxy, C~-C9phenylalkyl, C~-C9phenylalkoxy, unsubstitu-ted or C1-C4alkyl-substituted phenyl; phenoxy, cyclohexyl, CS-Cgcycloalkoxy;

alkylamino, di(Ci-C4alkyl)amino, C1-Cl2alkanoyl, C3-Cl2alkanoyl which is interrupted by oxygen or sulfur; C1-Cl2alkanoyloxy, C3-Cl2alkanoyloxy which is interrupted by oxygen or sulfur; C1-Cl2alkanoylamino, C3-Cl2alkenoyl, C3-Cl2alkenoyloxy, cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoyl or C1-C4alkyl-substituted benzoyl; benzoyloxy or C1-C4-R2~ 0 R2s R3o alkyl substituted benzoyloxy; - O - C - C - Rs , - O - C - C - O - R32 , or in R2s H R3i formula V each pair of substituents R19 and R2o or R2o and R21, together with the linking carbon atoms, forms a benzene ring, R~ is hydrogen or C1-C4alkyl, R~ and R26 are hydrogen or Cl-C4alkyl, with the proviso that at least one of R~ and R26 is hydrogen, R2~ and R2g are each independently of the other hydrogen or C1-C4alkyl, R29 is hydrogen, R3o is hydrogen, phenyl, C1-Cl8alkyl, C2-Clgalkyl which is interrupted by oxygen or sulfur] C~-C9phenylalkyl, C~-Clgphenylalkyl which is interrupted by oxygen or sulfur and unsubstituted or substituted in the phenyl moiety by 1 to 3 Cl-C4alkyl groups, and R29 and R3o, together with the linking carbon atoms, form a cyclohexylene ring which is unsubsti-tuted or substituted by 1 to 3 C1-C4alkyl groups, R31 is hydrogen or Cl-C4alkyl, R32 is hydrogen, C1-Clgalkanoyl, C3-Cl2alkenoyl, C3-Cl2alkanoyl which is interrupted by oxygen or sulfur; CZ-Cl2alkanoyl which is substituted by a di(C1-C6-alkyl)phosphonate H3C ~CH3 ~C
O ~ CH3 group; C6-C9cycloalkylcarbonyl, benzoyl, ~ -CSH2S
OH

O H3C 'C CH3 H3C ~ C \ H3 ~CH3 ~ CH3 CI - CH2 S - CH2 ~ ~ OH ~ - C - CH2 C ~ ~ OH

o o O
- C - R3a C - R3s or - C ' R3s R3~ ' R33 is hydrogen or C1-C4alkyl, R34 is C1-Cl2alkylene, C2-Cgalkenylene, C2-Cgalkylidene, C~-Cl2phenylalkylidene, CS-Cgcycloalkylene or phenylene, R35 is hydroxy, ~--0e r M r + ~ or C1-Clgalkoxy, R36 is oxygen or -NH-, R3~ is C 1-Cgalkyl or phenyl, and s is 1 or 2.
Also preferred is a process for the preparation of compounds of formula I, wherein Rl is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C1-C4alkyl-substituted carbazo-lyl; or fluorenyl, or Rl is a radical of formula V
R~9 R2o (v) R23 ~ ' R21 wherein R19, R2o, Ral, Rza and R23 are each independently of one another hydrogen, chloro, hydroxy, C1-Clgalkyl, C1-Clgalkoxy, C1-Cl8alkylthio, C3-C4alkenyloxy, C3-C4-alkynyl-oxy, phenyl, benzoyl, benzoyloxy or - O - C - C - O - R32 , H R3~
R29 is hydrogen, R3o is hydrogen, phenyl or C1-Cigalkyl, or R29 and R3o, together with the linking carbon atoms, form a cyclohexylene ring which is unsubstituted or substituted by 1 to alkyl groups, R31 is hydrogen or C1-C4alkyl, and R32 is hydrogen, C1-Cl2alkanoyl or benzoyl.
An especially preferred process is a process for the preparation of compounds of formu-la I, wherein ~ ~ 32 i 32 R19 is hydrogen or C1-C4alkyl, R2o is hydrogen or C1-C4alkyl, R21 is hydrogen, chloro, hydroxy, C1-Cl2alkyl, Cl-C4alkoxy, C1-C4alkylthio, phenyl or -~-CH2-CH2-0-R32~
R22 is hydrogen or C1-C4alkyl, R23 is hydrogen or C1-C~alkyl, and R32 is Cl-C4alkanoyl.
A very particularly preferred process is that for the preparation of compounds of formula I, wherein R2, R3, R4 and RS are each independently of one another hydrogen, chloro, hydroxy, C1-C25alkyl, C~-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl, unsubsti-tuted or C1-C4alkyl-substituted CS-Cgcycloalkyl; Cl-Cl2alkoxy, Cz-Cl2alkylthio, C1-C4-alkylamino, di(C1-C4alkyl)amino, C1-Clgalkanoyloxy, C1-Ci8alkanoylamino, C3-Cl8alke-noyloxy, C3-Cl8alkanoyloxy which is interrupted by oxygen, sulfur or ,N-Rg ;

cycloalkylcarbonyloxy, benzoyloxy or CI-C8alkyl-substituted benzoyloxy, or each pair of substituents R2 and R3 or R3 and R4 or R4 and R5, together with the linking carbon atoms, forms a benzene ring, R4 is additionally -(CH2)p COR9 or -(CH2)qOH, or, if R3 and RS are hydrogen, R4 is additionally a radical of formula II
O
(II) R10 - ~ - R11 Rg is hydrogen or C1-C6alkyl, ~R12 R9 is hydroxy, C ~ -C 1 galkoxy or -N ~ , Rlo and R11 are methyl groups or, together with the linking carbon atom, form a C5-Cg-cycloalkylidene ring which is unsubstituted or substituted by 1 to 3 C1-C4alkyl groups;
R12 and R13 are each independently of the other hydrogen or C1-Cgalkyl, and qis2,3,4,5or6.

2:~~2.~~~

A very particularly preferred process for the preparation of compounds of formula I is that wherein at least two of the substituents R2, R3, R4 and RS are hydrogen.
Also very particularly preferred is a process for the preparation of compounds of formu-la I, wherein R3 and RS are hydrogen.
A further very particularly preferred process for the preparation of compounds of formu-la I is that wherein R2, R3, R4 and RS are each independently of one another hydrogen, chloro, hydroxy, C1-Clgalkyl, C~-C9phenylalkyl, phenyl, CS-Cscycloalkyl, Cl-C6alkoxy, cyclohexylcarbo-nyloxy or benzoylaxy, or each pair of substituents R2 and R3 or R3 and R4 or R4 and R5, together with the linking carbon atoms, forms a benzene ring, R4 is additionally -(CH2)P CORg, or if R3 and RS are hydrogen, R4 is additionally a radical of formula II
R9 is hydroxy or C1-Clgalkoxy, and Rto and R11 are methyl groups or, together with the linking carbon atom, form a C5-Cg-cycloalkylidene ring.
A particularly interesting process for the preparation of compounds of formula I is that wherein R2 is Cl-Clgalkyl or cyclohexyl, R3 is hydrogen, R4 is C1-C4alkyl, cyclohexyl or a radical of formula II, RS is hydrogen, and Rlo and Rll together with the linking carbon atom, form a cyclohexylidene ring.
A further particularly interesting process for the preparation of compounds of formula I is that wherein R'l5 is hydrogen, C1-Cl8alkanoyl, C3-Clgalkenoyl, C3-Cl8alkanoyl which is interrupted by oxygen, sulfur or ,N-Ra ; C6-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C 1-Cg-alkyl-substituted benzoyl; naphthoyl or C1-Cgalkyl-substituted naphthoyl; C1-Clgalkane-sulfonyl, fluoro-substituted C1-Clgalkanesulfonyl; phenylsulfonyl or C1-Cgalkyl-substitu-O O O
ii ii ted phenylsulfonyl; - C _ R1 s C - R9 or - ~ - R» Ri$ >
R16 is a direct bond, Cl-Cl2alkylene, C2-Cl2alkylene which is interrupted by oxygen, ~1~~~3~~

sulfur or ~a ; CZ-Cl2alkenylene, C2-Cl2alkylidene, C~-Cl2phenylaikylidene, CS-CBCycloalkylene, C~-Cgbicycloalkylene or phenylene, R1~ is oxygen or -NH-, and Rlg is C1-Cl2alkyl or phenyl.
A process of very special interest is that for the preparation of compounds of formula I, wherein Rls is chloro, bromo or -OR' 1s, R'15 is hydrogen, Cl-Cl2alkanoyl, C3-Cl2alkanoyl which is interrupted by oxygen; cyclo-hexylcarbonyl, benzoyl, naphthoyl, Ci-Cl2alkanesulfonyl, fluoro-substituted C1-alkanesulfonyl; phenylsulfonyl or Cl-C4alkyl-substituted phenylsulfonyl; or O
-C-Ri~ Ris ' Rl~ is -NH-, and Rlg is C1-Cgalkyl or phenyl.
A process of very psecial interest is also that for the preparation of compounds of formu-la I, wherein Rls is -OR' 1s, O
R'15 is hydrogen, C1-C4alkanoyl or -~ _ R»_ R~s , R1~ is -NH-, and R1g is C1-C4alkyl.
Preferred reaction conditions of the inventive process are the following:
The reaction can be carried out at elevated temperature, preferably in the range from 70 to 200°C, in the melt or in a solvent and under normal pressure or slight vacuum.
It is particularly preferred to carry out the reaction in the boiling range of the compound of formula IV.
The preferred solvent is the compound of formula IV, which is simultaneously the reac-tant.

Suitable solvents are those which do not participate in the reaction, typically halogenated hydrocarbons, hydrocarbons, ethers or aromatic hydrocarbons.
Preferred halogenated hydrocarbons are dichloromethane, 1,2-dichloroethane, chloroform or carbon tetrachloride.
Preferred hydrocarbons are typically octane and the commercially available isomeric frac-tions such as the hexane faction, white spirit or ligroin.
Preferred ethers are typically dibutyl ether, methyl tert-butyl ether or diethylene glycol di-methyl ether.
Illustrative examples of deactivated aromatic hydrocarbons are nitrobenzene or pyridine.
When R' 15 is hydrogen in the compound of formula III (3-hydroxy-3H-benzofuran-2-one), the water of reation is conveniently removed continuously, preferably by adding an agent that absorbs water, for example a molecular sieve. Most preferably the water is removed continuously as an azeotrope by distillation via a water separator.
A process for the preparation of compounds of formula I, wherein the reaction ios carned out in the presence of a catalyst, is also of interest.
Suitable catalysts are protonic acids, Lewis acids, aluminium silicates, ion exchange resins, zeolites, naturally occurring sheet silicates or modified sheet silicates.
Illustrative examples of suitable protonic acids are acids of inorganic or organic salts, typi-cally hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesul-fonic acid, or carboxylic acids such as acetic acid. p-Toluenesulfonic acid is particularly preferred.
Illustrative examples of suitable Lewis acids are tin tetrachloride, aluminium chloride, zinc chloride or borotrifluoride etherate. Tin tetrachloride and aluminium chloride are es-pecially preferred.
Illustrative examples of suitable aluminium silicates are those that are widely used in the petrochemical industry and are also known as amorphous aluminium silicates.
These ~~.~~.~~2 compounds contain c. 10-30 % of silicon monoxide and 70-90 % of aluminium oxide. A
particularly preferred aluminium silicate is HA-HPV~ available from Ketjen (Akzo).
Illustrative examples of suitable ion exchange resins are styrene-divinylbenzene resins which additionally carry sulfonic acid groups, for example Amberlite 200~ and Amber-lyst~ available from Rohm and Haas, or Dowex 50~ available from Dow Chemicals;
per-fluorinated ion exchange resins such as Nafion H~ sold by DuPont; or other superacid ion exchange resins such as those as described by T. Yamaguchi, Applied Catalysis, 61, 1-25 (1990) or M. Hino et al., J. Chem. Soc. Chem. Commun. 1980, 851-852.
Suitable zeolites are typically those widely used in petrochemistry as cracking catalysts and known as crystalline silicon-aluminium oxides of different crystal structure. Particu-larly preferred zeolites are the Faujasites available from Union Carbide, for example Zeolith X~, Zeolith Y~ and ultrastable Zeolith Y~; Zeolith Beta~ and Zeolith ZSM-12~ available from Mobil Oil Co.; and Zeolith Mordenit~ available from Norton.
Suitable naturally occurring sheet silicates are termed "acid clays" and typically include bentonites or montmorillonites, which are degraded, ground, treated with mineral acids and calcined industrially. Particularly suitable naturally occurring sheet silicates are the Fulcat~ types available from Laporte Adsorbents Co., for example Fulcat 22A~, Fulcat 22B~, Fulcat 20~, Fulcat 30~ or Fulcat 40~; or the Fulmont~ types available from Laporte Adsobents Co., for example Fulmont XMP-3~ or Fulmont XMP-4~. A particu-larly preferred catalyst is Fulcat 22B~. The other Fulcat~ types and Fulmont~
types also belong to this preferred class, because there are only minor differences between the indi-vidual types, as for example in the number of acid centres.
Modified sheet silicates are also termed "pillared clays" and are derived from the above described naturally occurnng sheet silicates by additionally containing between the sili-cate layers oxides of e.g. zirconium, iron, zinc, nickel, chromium, cobalt or magnesium.
This type of catalyst is widely used, as described in the literature, inter alia by J. Clark et al., J. Chem. Soc. Chem. Commun. 1989, 1353-1354, but is available from only a very few firms. Particularly preferred modified sheet silicates typically include Enviro-cat EPZ-10~, Envirocat EPZG~ or Envirocat EPIC~ available from Contract Chemicals.
A particularly preferred process for the preparation of compounds of formula I
is also that wherein the reaction is carried out in the presence of a catalyst which is a naturally occur-ring sheet siliate or a modified sheet silicate.
Also especially preferred is a process for the preparation of compounds of formula I, wherein the reaction is carried out in the presence of a catalyst of the Fulcat~ type.
The catalyst is conveniently added in an amount of 1 to b0 % by weight and, if a particu-larly preferred catalyst of the Fulcat~ type is used, in an amount of 1 to 30 % by weight, with respect to the compound of formula III.
A particularly interesting process is that for the preparation of compounds of formula I, wherein, when n is 1, the molar ratio of the compound of formula III to the compound of formula IV is l: l to 1:20, and, when n is 2, the molar ratio of the compound of formula iII
to the compound of formula IV is 3:1 to 2:1.
In the process of this invention, compounds of formula IV, which also yield mixtures of isomers in other known electrophilic substitution reactions, likewise give compounds of formula I in the form of mixtures of isomers. The relative distribution of the isomers will depend on the commonly known basic rules of organic chemistry for electrophilic aroma-tic substitution reactions.

HsC\ / O H H3C\ / O-C C
HaC/ / ~ / ~ HaC/ /
\ \ CH2CH3 \

I I

(105) (105A) H3C\C p H CH2CH3 HaC/

I

(105B) 4 ~ 3213 As described in Example 4, reaction of e.g. 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2) with ethyl benzene, using Fulcat 22B as catalyst, gives 59.2 % of the para-isomer (compound (105). Table 1), 10.8 % of the meta-isomer (com-pound (105A) and 21.1 % of the ortho-isomer {compound (1058).
The isomers can be purified and separated by fractional crystallisation or chromatography on e.g. silica gel. It is preferred to use the mixtures of isomers as stabilisers for organic materials.
The compounds of formula IV are novel and some are commercially available or can be prepared by per se known methods.
Some of the compounds of formula III, wherein R' 15 is hydrogen, can be obtained in their tautomeric forms of formula IIIa or formula IIIb OH HO

(IIIa) {IIIb) Ra Ra as described by H. Sterk et al., Monatshefte fur Chemie 99, 2223 (1968).
Within the scope of this application, formula III is always to be understood as also embracing the two tautomeric formulae IIIa and IIIb.
The compounds of formula III can be prepared by methods analogous to literature methods described at the outset. Preferred, however, is a novel process that is the subject matter of a parallel patent application, which comprises reacting a) one equivalent of a phenol of formula VII

OH

(va}
Rs Rs Ra wherein the general symbols are as defined for formula I, with 0.8 to 2.0 equivalents, pre-ferably with 0.8 to 1.2 equivalents, of glyoxylic acid, to a compound of formula VIII
O
OH (VIII) Ra wherein the general symbols are as defined for formula I, and b} to prepare compounds of formula I, wherein R' is is not hydrogen, reacting the resultant compound of formula VIII with a hydrohalic acid, a halide of an oxysulfuric acid, a halide of phosphoric acid, a halide of phosphorous acid, with an acid of formula IX
R' ls-OH (IX}
an acid halide of formula X
R' is-y (X) an ester of formula XI
R~ is-O-Rss (XI) a symmetrical or unsymmetrical anhydride of formula XII
R' is-O-R' is (XB) or an isocyanate of formula XIII
R39_N-C-O (IX) wherein R' 15 is as defined above, with the proviso that R' is in the compounds of formu-lae IX, X, XI and XII is not hydrogen;
R38 is C1-Cgalkyl, R39 is Cl-Clsalkyl or phenyl, and Y is fluoro, chloro, bromo or iodo.
The glyoxylic acid can be used either in crystalline form or, conveniently, in the form of a commercial aqueous solution, usually a 40 to 60 % aqueous solution.
A particularly interesting process for the preparation of compounds of formula VIII there-fore comprises using the glyoxylic acid in the form of a 40 to 60 % aqueous solution, pre-ferably of 50 % aqueous glyoxylic acid.
The water present in the glyoxylic acid and the water of reaction is removed by distillation during the reaction, conveniently using a solvent that forms an azeotropic mixture with water.
Suitable solvents that form an azeotropic mixture with water do not participate in the reac-tion and typically include hydrocarbons such as cyclohexane or methyl cyclohexane; aro-matic hydrocarbons such as benzene or toluene; halogenated hydrocarbons such as 1,2-di-chloroethane; or ethers such as methyl tert-butyl ether.
When carrying out the reaction of the phenol of formula VII with glyoxylic acid without a solvent to give the compounds of formula VIII in the melt, the water of reaction is conve-niently distilled off under normal pressure, preferably under a slight vacuum.
It is preferred to carry out the reaction at elevated temperature, preferably in the range from 60 to 120°C. A particularly preferred temperature range is from 60 to 90°C.
The reaction can be catalysed by the addition of a minor amount of a protonic acid such as p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid or hydrochloric acid; or of a ~~3~a3?

Lewis acid such as borotrifluoride etherate or aluminium chloride.
The amount of catalyst is 0.01 to 5 mol %, preferably 0.1 to 1.0 mol %, based on the phenol of formula VII.
The reaction conditions for process step b) for the preparation of compounds of formu-la III, wherein R' 15 is not hydrogen, starting from compounds of formula VIII, are commonly known and can be chosen, inter alia, in analogy to esterification procedures described in Organikum 1986, pages 186-191, page 388 and pages 402-408.
Suitable hydrohalic acids are typically hydrochloric acid, hydrobromic acid or hydriodic acid. Hydrochloric acid is preferred.
Suitable halides of an oxysulfuric acid are typically thionyl chloride, sulfuryl chloride or thionyl bromide. Thionyl chloride is preferred.
Suitable halides of phosphoric acid and phosphorous acid typically include phosphorus tri-chloride, phosphorus tribromide, phosphorus triiodide, phosphorus pentachloride, phos-phoroxy chloride or phosphorus pentafluoride. Phosphoroxy chloride is particularly pre-ferred.
In process step b) it is preferred to use a halide of an oxysulfuric acid such as thionyl chloride; an acid halide of formula X; an ester of formula XI; or a symmetrical anhydride of formula XII.
When using a halide of an oxysulfuric acid such as thionyl chloride in process step b), it is preferred to carry out the reaction of a compound of formula VIII without a solvent and in the temperature range from 0 to 40°C, preferably at room temperature.
The thionyl chlo-ride is conveniently used in a 2- to 10-fold excess, preferably in a 2- to 6-fold excess, with respect to the compound of formula VIII. The reaction can also be carried out in the pre-sence of a catalyst such as dimethyl formamide.
When using an acid of formula IX (R' 15-OH) in process step b), the reaction is preferably carried out in the presence of an inert organic solvent such as dichloromethane, dioxane, diethyl ether or tetrahydrofuran, and in the presence of a reagent that binds water physical-ly or chemically, conveniently a molecular sieve or dicyclohexylcarbodiimide.

If an acid halide of formula X (R' 15-Y), wherein Y is preferably chloro or bromo, most preferably chloro, is used in process step b), it is preferred to carry out the reaction of the compound of formula VIII in the presence of a solvent and a base. The base can be used in varying amounts, from catalytic through stochiometric amounts to the multiple molar ex-cess with respect to the compound of formula VIII. The hydrogen chloride formed during the reaction may be converted by the base into the chloride, which can be removed by fil-tration and/or washing with a suitable aqueous or solid phase, in which case a second water-immiscible solvent can also be used. The product is conveniently purified by recry-stallising the residue of the organic phase, which is concentrated or evaporated to dryness.
Suitable solvents for carrying out the reaction include hydrocarbons (typically toluene, xy-lene, hexane, pentane or further petroleum ether fractions), halogenated hydrocarbons (ty-pically di- or trichloromethane, 1,2-dichloroethan, 1,1,1-trichloroethane), ethers (e.g. di-ethyl ether, dibutyl ether or tetrahydrofuran), and also acetonitrile, dimethyl formamide, dimethyl sulfoxide, N-methylpyrrolidane.
Suitable bases include tertiary amines, e.g. trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline; pyridines; hydrides (e.g. lithium, sodium or potassium hydride) or alcoholates (e.g. sodium methylate).
If an ester of formula XI (R'15-O-R3g), wherein R3g is preferably C1-C4alkyl, most prefe-rably methyl or ethyl, is used in process step b}, it is preferred to carry out the reaction of the compound of formula VIII in the presence of a solvent that forms an azeotropic mix-ture with alcohols. The alcohol (R38-OH) that forms during the reaction can be removed continuously by distillation.
Suitable solvents that form an azeotropic mixture with alcohols do not participate in the reaction and typically include hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene or toluene; halogenated hydrocarbons such as 1,2-dichloroethane; or ethers such as methyl tert-butyl ether.
The reaction can be catalysed with a minor amount of a protonic acid such as p-toluene-sulfonic acid, methanesulfonic acid, sulfuric acid or hydrochloric acid; as well as of a Lewis acid such as borotrifluoride etherate or aluminium chloride.

~1~213~

If a symmetrical anhydride of formula XII (R' 15-O-R' 15} wherein R' 15 is preferably C2-C6alkanoyl, preferably acetyl, is used in process step b), it is preferred to carry out the reaction with a compound of formula VIII without the addition of a further solvent and in the temperature range from 20 to 200°C, e.g. the boiling temperature of the anhydride of formula XII, preferably from 60 to 180°C.
If an isocyanate of formula XIII (R39-N=C=O) is used, it is preferred to carry out the reac-tion with a compound of formula VIII without the addition of a further solvent and in the temperature range from 20 to 200°C, e.g. the boiling temperature of the isocyanate of for-mula XIII, preferably from 60 to 180°C.
The reaction with an isocyanate is likewise preferably carried out in the presence of a ca-talyst. Preferred catalysts correspond to those referred to above previously in connection with the reaction of the compound of formula III with a compound of formula IV.
The phenols of formula VII are known or can be prepared by per se known processes.
Bisphenols of formula XIV

HO / ~ OH
I / (XIV) w can be prepared in accordance with Houben-Weyl, Methoden der organischen Chemie, Vol. 6/1c, 1030.
The compounds of formula I can also be prepared by a so-called one-pot process starting from the phenols of formula VII.
Accordingly, the invention also relates to a process for the preparation of compounds of formula I
...

~.~2~.32 O H

R~

I (I}

Rs Rs Ra n which comprises reacting one equivalent of the phenol of formula VII
OH
R2 ~ H
(Va}
Rs ~ , Rs Ra with 0.8 to 2.0 equivalents of glyoxylic acid to a compound of formula VIII
O
O H
OOH (VIII}
Rs ~f ~ Rs Ra and subsequently reacting said compound of formula VIII, without isolation, with a com-pound of formula IV
[H]n Rl (IV).
The definitions of the general symbols in connection with the inventive one-pot process are the same as for the inventive processes discussed previously.
The preferred reaction parameters for the one-pot process correspond to those previously discussed in detail in connection with the two single steps.

-33- 2 ~ 3~2 i 3~
Prior to the further reaction with a compound of formula IV, the 3-hydroxy-3H-benzo-furan-2-ones of formula VIII initially formed in the one-pot process can be subjected to an additional reaction step by substituting the hydroxyl group with halogen or activating it with a leaving group.
Accordingly, the invention also relates to a one-pot process for the preparation of com-pounds of formula I, which comprises reacting one equivalent of the phenol of formu-la VII with 0.8 to 2.0 equivalents of glyoxylic acid to the 3-hydroxy-3H-benzofuran-2-one of formula VIII which, without isolation before the further reaction with a compound of formula IV, is reacted in an additional reaction step with a hydrohalic acid, a halide of an oxysulfuric acid, a halide of phosphoric acid, a halide of a phosphorous acid, an acid of formula IX
R' 15-OH (IX) an acid halide of formula X, R' is-Y (X) an ester of formula XI
R' is-O-R3s (Xn a symmetrical or unsymmetrical anhydride of formula XII
R'is0-R'is (XII) or an isocyanate of formula XIII
R39-N=C=O (XIII) wherein R' 15 in formulae IX, X, XI and XII is not hydrogen;
R3g is C 1-Cgalkyl, R39 is C 1-C l galkyl or phenyl, and Y is fluoro, chloro, bromo or iodo, to a compound of formula III

..~k' H
R~5 (III) wherein, when Rls = -OR' 1s, R' is is not hydrogen.
The preferred reaction parameters for this additional reaction step correspond to those previously described in detail in connection with the preparation of the compounds of for-mula III starting from campounds of formula VIII.
A particularly preferred one-pot process for the preparation of compounds of formula I
comprises using a compound of formula VII that differs from the compound of formu-la IV .
The invention is illustrated in more detail by the following Examples, in which parts and percentages are by weight.
Example 1: Process for the preparation of 5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one (compound (101), Table 1) starting from 5,7-di-tert-butyl-3-hydroxy-3H-benzafuran-2-one (compound (201), Table 2) with p-xylene, as well as Fulcat 22B as catalyst.
a) Preparation of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201}, Table 2}.
A mixture of 212.5 g (1.00 mol) of 2,4-di-tert-butylphenol {97 %), 163.0 g (1.10 mol} of 50 %o aqueous glyoxylic acid and 0.5 g (2.6 mmol) of p-toluenesulfonic acid monohydrate in 300 ml of 1,2-dichloroethane is refluxed under nitrogen for 3.S hours on a water separa-tor. Afterwards the reaction mixture is concentrated on a vacuum rotary evaporator. The residue is taken up in 800 ml of hexane and washed three times with water. The aqueous phases are separated in the separating funnel and further extracted with 300 ml of hexane.
The organic phases are combined, dried over magnesium sulfate and concentrated on a va-cuum rotary evaporator. The residue yields 262.3 g 0100 %) of analytically pure 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one in the form of a thick yellowish resin (com-pound (201), Table 2).
In analogy to Example la, compounds (202), (203), (204), (205), (209), (210) and (211) are prepared from the corresponding phenols such as 2-tert-butyl-4-methylphenol, 4-tert-butyl-2-methylphenol, 2,4-dicyclohexylphenol, 2-(hexadec-2-yl)-4-methylphenol, 3-[3-tert-butyl-4-hydroxyphenyl]propionic acid, 2,4-bis(a,a-dimethylbenzyl)phenol and 4-methyl-2-{1,1,3,3-tetramethylbut-1-yl)phenol with glyoxylic acid. To prepare compound (207), 2 equivalents of glyoxylic acid are used starting from 1,1-bis(3-tert-butyl-4-hy-droxyphenyl)cyclohexane.
b) Preparation of 5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one (com-pound {101), Table 1) To a solution of 262.3 g (1.00 mol) of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201}, Table 2, Example la) in 500 ml (4.05 mol) of p-xylene are added 40 g of Fulcat 22B and the mixture is refluxed for 1.5 hours on a water separator.
The Ful-cat 22B catalyst is then removed by filtration and excess p-xylene is removed by distilla-tion on a vacuum rotary evaporator. Crystallisation of the residue from 400 ml of metha-nol yields 280.6 g {80 %) of 5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one, m.p. 93-97°C (compound (101), Table 1).
Example 2: Process for the preparation of 5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one (compound {106}, Table 1) starting from 3-acetoxy-5,7-di-tert-butyl-3H-benzofuran-2-one (compound (206), Table 2) with p-xylene, as well as Fulcat 22B as catalyst.
a) Preparation of 3-acetoxy-5,7-di-tert-butyl-3H-benzofuran-2-one {compound (206), Table 2).
A mixture of 21.2 g (0.10 mol) of 2,4-di-tert-butylphenol (97 %), 16.3 g (0.11 mol) of 50 % aqueous glyoxylic acid and 0.05 g {0.26 mmol) of p-toluenesulfonic acid monohy-drate in 30 ml of 1,2-dichloroethane is refluxed under nitrogen for 3.5 hours on a water se-parator. Afterwards the reaction mixture is concentrated on a vacuum ratary evaporator.
The residue is taken up in 9.9 ml (0.105 mol) of acetic anhydride and the solution is re-fluxed for 90 minutes. The reaction mixture is then cooled to room temperature, diluted _.~t.
a with 100 ml of tert-butyl methyl ether and washed in succession with water and dilute so-dium hydrogencarbonate solution. The aqueous phases are separated and extracted with 50 ml of tert-butyl methyl ether. The organic phases are combined, dried over magnesium sulfate and concentrated on a vacuum rotary evaporator. Chromatography of the residue on silica gel with the solvent system dichloromethane/hexane = 2:1 yields 28.0 g (92 %) of 3-acetoxy-5,7-di-tert-butyl-3H-benzofuran-2-one (compound (206), Table 2) as a thick reddish resin.
b) Preparation of 5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one (com-pound { 101 ), Table 1 ) To a solution of 15.3 g (50.0 mmol) of 3-acetoxy-5,7-di-tert-butyl-3H-benzofuran-2-one {compound (206), Table 2, Example 2a) in 25 ml (0.20 mol) of p-xylene is added 1.0 g of Fulcat 22B and the mixture is refluxed for 17 hours on a water separator. The Fulcat 22B
catalyst is then removed by filtration and excess p-xylene is removed by distillation on a vacuum rotary evaporator. Crystallisation of the residue from 20 ml of methanol yields 10.5 g (60 %) of 5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one, m.p. 93-97°C (compound (101), Table 1).
Example 3: Process for the preparation of 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-3H-benzofuran-2-one (compound (103), Table 1) starting from 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one {compound (201), Table 2) with o-xylene, as well as Fulcat 22B as catalyst.
To a solution of 262.3 g ( 1.00 mol) of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201 ), Table 2, Example 1 a) in 500 ml (4.05 mol) of o-xylene are added 40 g of Fulcat 22B and the mixture is refluxed for 1.5 hours on a water separator.
The Ful-cat 22B catalyst is then removed by filtration and excess p-xylene is removed by distilla-tion on a vacuum rotaray evaporator. Crystallisation of the residue from 500 ml of metha-nol yields 244 g (69 %) of 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl)-3H-benzofuran-2-one, m.p. 130-132°C (compound (103), Table 1), which additionally contains c. 1.3 % of the structural isomer [3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-3H-benzofuran-2-one, com-pound (103A)]. The mother liquor yields a further 42.4 g of product which, according to GC-MS analysis, consists of 12.3 % of the compound (103) and 87.7 % of the isomeric compound (103A).

Example 4: Process for the preparation of 5,7-di-tert-butyl-3-(4-ethylphenyl)-3H-benzo-furan-2-one {compound (105), Table 1) starting from 5,7-di-tert-butyl-3-hydroxy-3H-ben-zofuran-2-one (compound (201}, Table 2}, with ethyl benzene, as well as Fulcat 22B as catalyst.
To a solution of 262.3 g (1.00 mol} of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2, Example la) in 500 ml (4.08 mol) of ethyl benzene are added 40 g of Fulcat 22B and the mixture is refluxed for 1.5 hours on a water separator. The Fulcat 22B catalyst is then removed by filtration and excess ethyl benzene is removed by distillation on a vacuum rota.ray evaporator. GC-MS analysis shows the residue to consist of a mixture of 59.2 % of the para-isomer (compound (105), Table 1), 10.8 % of the meta-isomer (compound (105A) and 21.1 °1o of the ortho-isomer(compound (105B). Cry-stallisation of the residue from 400 ml of methanol yields 163.8 g (47 °1o) of 5,7-di-tert-butyl)-3-(4-ethylphenyl)-3H-benzofuran-2-one (compound (105), Table 1) (para-isomer), which additionally contains 5.6 % of the meta-isomer 5,7-di-tert-butyl-3-(3-ethylphenyl)-3H-benzofuran-2-one (compound (105A} and 1.3 % of the ortho-isomer 5,7-di-tert-butyl-3-(2-ethylphenyl)3H-benzofuran-2-one (compound (105B). Further crystallisation from methanol yields the almost pure para-isomer (compound (105),~Table 1), m.p.
127-132°C.
In accordance with the general procedure described in this Example, compounds ( 102), {106), (107), (116), {117}, (118), {120), (122), (123), (124), (125), {126) and {127) are pre-pared from 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2, Example la) and the corresponding aromatic hydrocarbons, typically including m-xylene, isopropylbenzene (cumene), tert-butylbenzene, 2,6-dimethylanisole, anisole, acetoxy-ethoxybenzene, chlorobenzene, biphenyl, thiophene, p-xylene, dibenzofuran, phenanthren and diphenyl ether. To prepare compound (127), 2 equivalents of 5,7-di-tert-butyl-3-hy-droxy-3H-benzofuran-2-one are used starting from diphenyl ether.
Example 5: Process for the preparation of 5,7-di-tert-butyl-3-(2,3,4,5,6-pentamethylphe-nyl)-3H-benzofuran-2-one (compound (111), Table 1) starting from 5,7-di-tert-butyl-3-hy-droxy-3H-benzofuran-2-one (compound (201), Table 2) with pentamethylbenzene, as well as tin tetrachloride as catalyst.
11.5 g (77.5 mmol) of pentamethylbenzene and 10 ml {85.0 mmol) of tin tetrachloride are added to a solution of 19.7 g (75.0 mmol} of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2, Example la} in 50 ml of 1,2-dichloroethane and the reaction mixture is refluxed for 1 hour. The reaction mixture is diluted with water and extracted 3 times with toluene. The organic phases are combined, washed with water, dried over sodium sulfate and concentrated on a vacuum rotary evaporator.
Crystallisation of the residue from ethanol yields 26.3 g (89 %) of 5,7-di-tert-butyl-3-{2,3,4,5,6-penta-methylphenyl)-3H-benzofuran-2-one, m.p. 185-190°C (compound (111), Table 1}.
In accordance with the general procedure of this Example, compounds (109) and (110) are prepared from 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2, Example la) and the corresponding aromatic hydrocarbons, for example n-dode-cylbenzene and 1,2,3-trimethylbenzene.
Example 6: Process for the preparation of 5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one (compound {108), Table 1) starting from 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2) with benzene, as well as aluminium trichloride as catalyst.
73.3 g (0.55 mol) of ground aluminium trichloride are added over 25 minutes to a solution of 131.2 g (0.50 mol) of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one {compound (201}, Table 2, Example la) in 250 ml (2.82 mol) of benzene and the reaction mixture is heated for 1.5 hours to reflux temperature and then refluxed for 1.5 hours.
The reaction mixture is cooled to room temperature and then, cautiously with cooling, 200 ml of water are added, followed by the addition of concentrated hydrochloric acid until a homoge-neous two-phase mixture forms. The organic phase is separated, washed with water, dried over sodium sulfate and concentrated on a vacuum rotary evaporator.
Crystallisation of the residue from ethanol yields 97.8 g (64 %) of 5,7-di-tert-butyl-3-phenyl-3H-benzofuran-2-one, m.p. 116-119°C (compound (108}, Table 1}.
In accordance with the procedure of this Example, compounds {113), (114} and (119) are prepared from the corresponding 3-hydroxy-3H-benzofuran-2-ones such as 7-[2-(hexa-dec-2-yl)]-3-hydroxy-5-methyl-3H-benzofuran-2-one (compound (205), Table 2), 5,7-di-cyclohexyl-3-hydroxy-3H-benzofuran-2-one (compound (204), Table 2) and 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound {201), Table 2) and the corresponding aromatic hydrocarbons such as benzene and thioanisole.
Example 7: Process for the preparation of 5,7-di-tert-butyl-3-(4-methylphenyl)-3H-benzo-furan-2-one (compound { 104}, Table 1 ) starting from 2,4-di-tert-butylphenol, without iso-lation of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2}, with glyoxylic acid and toluene, as well as Fulcat 22B as catalyst.
A mixture of 21.2 g (0.10 mol) of 2,4-di-tert-butylphenol (97 %), 16.3 g (0.11 mol} of 50 % aqueous glyoxylic acid, 2.0 g of Fulcat 22B and 50 ml of toluene is refluxed for 8 hours under nitrogen on a water separator. The Fulcat 22B catalyst is then removed by filtration and excess toluene is distilled off on a vacuum rotary evaporator.
Crystallisation of the residue from 40 ml of ethanol yields 14.2 g (42 %) of 5,7-di-tert-butyl-3-(4-methyl-phenyl}-3H-benzofuran-2-one, m.p. 130-133°C (compound (104), Table 1).
In accordance with the general procedure of this Example, compound ( 112) is prepared starting from 2-tert-butyl-4-methylphenol instead of from 2,4-di-tert-butylphenol.
Example 8: Process for the preparation of 4,4'-bis(5,7-di-tert-butyl-3H-benzofuran-2-on-3-yl)-N-methyl-diphenylamine (compound (121), Table 1) starting from 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one {compound (201), Table 2), with N-methyl-diphenyl-amine, as well as p-toluenesulfonic acid as catalyst 30.2 g (115.0 mmol) of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (com-pound (201), Table 2, Example la) are added over 2 hours to a boiling solution of 9.20 g (50.0 mural) of N-methyl-diphenylamine and 0.20 g of p-toluenesulfonic acid monohy-drate in 50 ml of ligroin {mixture of alkanes with a boiling range of 140-160°C). The reac-tion mixture is then refluxed for 4 hours on a water separator, then cooled and concentra-ted on a vacuum rotaxy evaporator. Crystallisation of the residue from isopropanol/water =
9:1 yields 18.9 g {56 %) of 4,4'-bis(5,7-di-tert-butyl-3H-benzofuran-2-on-3-yl)-N-methyl-diphenylamine, m.p. 135-145°C (compound (121), Table 1).
Example 9: Process for the preparation of 5,7-di-tert-butyl-3-(3,5-dimethyl-4-hydroxy-phenyl)-3H-benzofuran-2-one (compound (115), Table 1) starting from 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2) with 2,6-dimethylphenol, as well as p-taluenesulfonic acid as catalyst.
30.2 g (115.0 mmol) of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (com-pound (201), Table 2, Example la} are added over 2 hours to a boiling solution of 12.2 g ( 100.0 mmol} of 2,6-dimethylphenol and 0.20 g of p-toluenesulfonic acid monohydrate in 50 ml of acetic acid. The reaction mixture is then refluxed for 4 hours, cooled, and con-centrated on a vacuum rotary evaporator. Two crystallisations of the residue from isopro-~.~3~~~~

panol/water = 9:1 yield 28.5 g (78 %) of 5,7-di-tert-butyl-3-(3,5-dimethyl-4-hydroxyphe-nyl)-3H-benzofuran-2-one, m.p. 225-228°C (compound {115), Table 1).
Example 10: Process for the preparation of 7-tert-butyl-5-methyl-3-(9-methyl-9H-carba-zol-3-yl)-3H-benzofuran-2-one (compound (128), Table 1) starting from 7-tent-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (compound (202), Table 2) with N-methylcarba-zole and n-octane, as well as Fulcat 22B as catalyst.
A mixture of 2.2 g (10.0 mmol) of 7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (compound (202), Example la, Table 2), 1.8 g (10.0 mmol) of N-methylcarbazole and 0.2 g of Fulcat 22B and 20 ml of n-octane is refluxed for 5 hours under nitrogen. The Ful-cat 22B catalyst is subsequently removed by filtration and excess n-octane is distilled off on a vacuum rotary evaporator. Chromatography of the residue on silica gel with the sol-vent system dichloromethanelhexane = 1:2 to l: l and subsequent crystallisation of the pure fractions from methanol yields 0.70 g (10 %) of 7-tert-butyl-5-methyl-3-(9-methyl-9H-carbazol-3-yl)-3H-benzofuran-2-one, m.p. 84-90°C {compound (128), Table 1). The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the carbazole ring.
Example 11: Process for the preparation of 5,7-di-tert-butyl-3-(9H-fluoren-3-yl}-3H-ben-zofuran-2-one (compound ( 129}, Table 1 ) starting from 2,4-di-tert-butylphenol, without isolation of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2), with glyoxylic acid and fluorene, as well as p-toluenesulfonic acid and Fulcat 22B as cata-lyst.
A mixture of 15.9 g (75 mmol} of 2,4-di-tert-butylphenol (97 %}, 12.2 g (82 mmol) of 50 % aqueous glyoxylic acid, 40 mg (0.20 mmol) of p-toluenesulfonic acid monohydrate and 25 ml of 1,2-dichloroethane is refluxed for 3.5 hours under nitrogen on a water separa-tor. The reaction mixture is thereafter concentrated on a vacuum rotary evaporator. The re-sidue is dissolved in 30 ml of n-octane and 12.5 g {75 mmol) of fluorene and 3 g of Ful-cat 22B are added to the solution. This reaction mixture is refluxed for 3.5 hours under nitrogen on a water separator, then cooled and filtered. The filtrate is concentrated on a va-cuum rotary evaporator. Chromatography of the residue on silica gel with the solvent sy-stem dichloromethane/hexane = 2:1 and subsequent crystallisation of the pure fractions from methanol yields 5.28 g {17 %) of 5,7-di-tert-butyl-3-(9H-fluoren-3-yl)-3H-benzo-furan-2-one, m.p. 140-153°C (compound (129), Table 1). The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the fluorene ring.
Example 12: Process for the preparation of a c. 5.7:1 mixture of 3-(3,4-dimethylphenyl}-5,7-di-tert-butyl-3H-benzofuran-2-one (compound (103), Table 1) and 3-(2,3-dimethyl-phenyl)-5,7-di-tert-butyl-3H-benzofuran-2-one (compound (103A)) isomers starting from 2,4-di-tert-butylphenol with glyoxylic acid and o-xylene, as well as Fulcat or Fulmont as catalyst.
To a 1.51 double-walled reactor with water separator are charged 206.3 g {1.0 mol) of 2,4-di-tert-butylphenol, 485 g (5.5 mol} of o-xylene, 0.5 g {2.6 mmol) of p-toluenesulfonic acid monohydrate and 163 g ( 1.1 mol} of 50 % aqueous glyoxylic acid. With stirring, the mixture is heated to 85-90°C and the apparatus is simultaneously evacuated to c.450 mbar.
As soon as the temperature in the reactor is 85-90°C, a mixture of o-xylene/water begins to distill from the mixture, the o-xylene being refluxed and the water removed from the system. The vacuum is then raised continuously so that the temperature in the reactor can be kept at 85-90°C. Altogether c. 98-100 ml of water are distilled over 3 to 4 hours. The vacuum is then released with nitrogen and 40 g of catalyst {Fulcat 30 or 40, Ful-mont XMP-3 or XMP-4) are added to the clear yellow solution. The apparatus is evacu-ated to a pressure of 700 mbar and the suspension is stirred at a heating bath temperature of 165°C. The water of reaction begins to distill from the system as an azeotrope from a temperature of c. 128°C. The temperature in the apparatus rises towards the end to a maxi-mum of 140°C. A total amount of c. 20 ml of water distills from the system over 1 to 2 hours. The vacuum is then released with nitrogen. The reaction mixture is cooled to 90-100°C and filtered. The apparatus and the filter residue are rinsed with 100 g of o-xy-lene. The filtrate is transferred to a 1500 ml double-walled reactor and concentrated under vacuum and 360 g of o-xylene are recovered. The reddish-yellow residue is cooled to 70°C and 636 g of methanol are added cautiously from a dropping funnel, while keeping the temperature at 60-65°C. The solution is seeded and stirred for c.
30 minutes at 60-65°C to effect crystallisation. The crystalline slurry is then cooled over 2 hours to -5°C
and stirring is continued at this temperature for a further 1 hour. The crystals are collected by suction filtration and the residue is washed with 400 g of cold (-5°C) methanol in portions. The well dry-pressed product is dried in a vacuum drier at 50-60°C, yielding 266 g of a white solid. Analysis by gas chromatography shows this material to consist of c. 85 °70 of 3-(3,4-dimethylphenyl}-5,7-di-tert-butyl-3H-benzofuran-2-one (com-pound {103)> Table 1) as well as of c. 15 % of the 3-(2,3-dimethylphenyl)-5,7-di-tert-bu-tyl-3H-benzofuran-2-one isomer (compound {103A)).
Example 13: Preparation of 3-(N-methylcarbamoyloxy)-5-methyl-7-tert-butyl-3H-benzo-furan-2-one (compound (212), Table 2).
A mixture of 5.5 g (25.0 mmol) of 7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (compound (202), Example 1 a), 3 ml {50.0 mmol) of methyl isocyanate and 2 drops of methanesulfonic acid are refluxed for 3 1/4 hours. Then a further 3 ml (50.0 mmol) of methyl isocyanate and 2 drops of methanesulfonic acid are added. The reaction mixture is refluxed for another 16 hours, then cooled, diluted with dichloromethane and washed with water and a 5 % aqueous solution of sodium hydrogencarbonate. The organic phases are combined, dried over magnesium sulfate and concentrated on a vacuum rotary evaporator.
Crystallisation of the residue from toluene yields 4.45 g (65 %) of 3-(N-methylcarbamoyl-oxy)-5-methyl-7-tert-butyl-3H-benzofuran-2-one, m.p. 138-143°C
(compound (212}, Table 2).
Example 14: Preparation of 7-tert-butyl-3-chloro-5-methyl-3H-benzofuran-2-one {com-pound (208), Table 2).
To a suspension of 2.2 g (10.0 mmol} of 7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (compound (202), Example la, Table 2} in 2.4 ml (55.0 mmol) of thionyl chloride is added one drop of dimethyl formamide and the mixture is stirred for 2 hours at room tem-perature. Excess thionyl chloride is afterwards distilled off on a vacuum rotary evaporator.
Chromatography of the residue on silica gel with the solvent system dichloromethane/-hexane = 1:l and crystallisation of the pure fractions from methanol yields 0.30 g {13 %) of 7-tert-butyl-3-chloro-5-methyl-3H-benzofuran-2-one, m.p. 81-86°C
(compound (208), Table 2).

Table 1:
No. Compound m'p' C .(%), H (%) Yield {C) (calcd/found) (%) H3C~C O H CH3 ~ 82.24 8.63 101 i 93-97 80 H C
3 ~ ( ~ ~

82.10 8.66 I

CH
O

HsC~C O H CH3 H3C ~ I ~ I 82.24 86.3 102 ~ ~ CH3 92-96 52a) 82.19 8.78 I

HsC~C O H

~ CH3 82.24 8.63 C ~

.
H

I
I

103 ~ 130-132- 69a) ~
CH

H3C - C - CH3 82.36 8.62 I

CH
O

H3C \

H

C 82.10 8.39 104 HaC \ ~ \ ~ 130-133 42a) CH3 82.13 8.31 a) The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the phenyl ring in 3-position of the benzofuran-2-one.

~~.~~.~3~

Table l: {continuation) m~P~ C (%), H (%) Yield No. Compound (oC} (calcd/found) (%}

H3C~C O H

82.24 8.63 lOS H3C ~ ~ ~ ~ 127-132 47a) CH2CH3 82.39 8.6s I

H3C~C O H

H3~ .- ~ , ~ 82.37 8.8s ~

106 ~ 109-l 41a) CH CH3 is H3C-C-CH3 cH 82.24 8.91 ( 3 H3C~C O H

~ 82.49 9.0s H3c ~ cH
~
( ~ 3 107 ~ 110-lls 68a) ~
C

H3C - C - CH3 H C CH3 82.49 9.03 H3C~C O H * characterised by 108 H3c~ \ ~ ' ~ 116-1191 H-NMR (CDC13) 64 8(H*) = 4.84 ppm H3c - c - cH3 I

a) The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the phenyl ring in 3-position of the benzofuran-2-one.

Table 1: (continuation) m'p' C (%), H (%) Yield No. Compound (C) (calcd/found) {%) ~

H3C ~C O H characterised by 109 H3c w ~ w ~ Oel 1 H-NMR (CDCl3)66a) (CH2)i~CH3 H3C-C-CH3 8(H*) = 4.84 I ppm H3C~C O H CH3 CH
H3c~ \ ~ ~ 3 82.37 8.85 110 cH3 118-122 74a) H3C-C-CH3 82.31 8.84 I

H3C~ / O H CH3 ~ ~ i cH3 82.61 9.24 H c I
I

111 ~ 185-190 89 cH
H c ~

H3C-C-CH3 CH3 82.41 9.43 I

H3C~C O H 81.60 7.53 112 H3c~ \ I \ I 69-$0 70a) cH3 81.42 7.57 a} The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the phenyl ring in 3-position of the benzofuran-2-one.

Table l: (continuation) No. Compound m'p' C (%), H (%) Yield (~C) (calcd/found) (%) *

CH O H characterised by 113 ~-H29c'4 \ ~ \ ~ oil 1 H-NMR (CDC13)56 8(H*) = 4.85 ppm O

H o H*

i characterised by 114 ~ resin 1 H-NMR (CDCl3)57 ~ ~

8(H*) = 4.86 ppm H

H3C\C O H*

cH3 characterised by 115 H3c ~ ~ ~ ~ 225-2281 H-NMR (CDCIg)78a) off H3c- ~ -cH3 cH3 8(H*) = 4.70 ppm H3C~C O H * characterised by CH
116 H3C/ ~ ~ ~ ~ 3 133-1351 H-NMR (CDCIg)52a) b(H*} = 4.72 ppm H C-C-CH CH

a} The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the phenyl ring in 3-position of the benzofuran-2-one.

Table l: {continuation) m'p' C (%)~ H (%) Yield No. Compound (~C) (calcdlfound) (%) c o H*
H3c ~ characterised by 117 ~ ~ ~ I 102-1041 H-NMR (CDC13)65a>

ocH

H3C-C-CH3 8(H*) = 4.78 I ppm CHaO O H*
HaC.

C characterised HsC ~ I ' I by 118 H3C - C - CH3 H _~ 0 91-94 1 H-NMR (CDC13)23a~

CH *
H
C~

3 ${H
H ) = 4.78 ppm H y H3Cy O H*

characterised ~ by 119 H3C 12S-1311 H-NMR (CDCIg)18a~
~ ~ ~ ~

sCH

H3c- ~ -cH3 S{H*) = 4.79 ppm - H3C~C O H 74.04 7.06 i 120 H3c ~ ~ \ ~ 121-126 37a>

c1 74.02 7.11 I

a) The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the phenyl ring in 3-position of the benzofuran-2-one.

Table l: (continuation) m.p. C {%), H (%), N (%) Yield No. Compound (°C) (calcd/found) (%}
CH O O
HgC~C 3 O H H C
H O 3 ~ ,CH3 °' 80.44 7.95 2.08 121 H3° ~ ~ ~ N ~ ~ ~ cH3 135-145 56a) H3C-CH CH3 CH3 H3C- i -CH3 80.20 8.06 1.96 H3C~C O H
H3c~ \ ~ ~ 84.38 7.57 122 ~ I 168-170 25a>
H3C-C-CH3 w 84.23 7.66 I

CH O C (%), H (%), S {%) H3C~C 3 O H
H3ci i ~ 73.13 7.37 9.76 123 ~ ~ S ~ 86-93 11a>
H3C-C-CH3 73.10 7.38 9.69 I

°H3 °H3 82,.60 7.84 124 ° ° ~ , ~ , ° 0 220-228 40 H3C v v CH3 H H H ' ~ 82.58 7.85 a) The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the phenyl ring in 3-position of the benzofuran-2-one.

Table l: (continuation) m~P~ C (%), H (%) Yield No. Compound (°C) (calcd/found) {%) H3C~C O H
I ~ 81.52 6.84 125 W I w I p 142-154 33a) H3C-C-CH3 80.97 6.5 I

H3C~C O H
H3~~ i i w 85.27 7.16 I I
126 ~ ~ ~ I 186-189 17a) H3C-C-CH3 ~ 85.15 7.20 I

CH3 ° ° H C
HgC~C ° H * ' H ° 3 C,CH3 characterised by H3° ' I ' I ' 1 ' ( \CH3 127 ° ~ Harz 1 H-NMR (CDC13) 31a) H3C-;-CH3 H3C-C-CH3 CH3 CH3 8(H*) = 4.82 ppm H3C~ ~ O H
81.43 6,57 128 H3c a) 84-90 g 1.37 6,72 10 a) The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the aryl ring in 3-position of the benzofuran-2-one.

Table 1: (continuation) No. Compound m'p' C (%), H (%) Yield (C) (calcd/found) (%) H3C~C O H

~ ~ 84.84 7.37 ~

~ i H c ( 129 w 140-153 17a) w ~ cHY

H3C-C-CH3 84.b6 7.52 I

a) The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the fluorene ring in 3-position of the benzofuran-2-one.

Table 2:
m'p' C (%), H (%) Yield No. Compound (C) (calcd/found) (%) O
CH

HaC ~ / O H

C 73.25 8.45 ~ OH
H C

~

201 ~ resin 100 73.33 8.50 I

H3C~C O H

_ 70.89 7.32 202 ~ OH 152-160 g2 HsC

\ 70.40 7.40 O characterised by H3C O H * 1H-NMR (CDC13) ~OH g(H*) = 5.33 I ppm 203 w resin 45a) a) chromatographed on HgC - C - CH3 silica gel (CH2CIz/hexane =

CH3 4 : 1 ) O

H O H* characterised by i 204 ~ 'OH resin 1H-NMR (CDC13) 100 ~

8(H*) = 5.30 ppm H

Table 2: (continuation) No. Compound m'p' C (%), H (%) Yield (C) (calcd(found) (%}

NCH O H* characterised by 205 n H29C14 ~ I OOH resin 1 H-NMR (CDCi3}98 8(H*) = 5.31 ppm H3C~C O H
O

J

H 71.03 7.95 C
~O' C ~

' ~

206 resin 92 71.10 7.98 I

H3C-C-CH3 H3C-C-CH3 characterised by 207 0 0 \ ~ \ ( o o resin 1 H-NMR (CDCl3)100 H OH H OH H b(tert-butyl) = 1.34 ppm O

H3C ~ j characterised O H * by C
208 H3~ i I C~ 81-86 1 H-NMR (CDC13)13 8(H*} = 5.34 ppm Table 2: (continuation) No. Compound m'p' C {%), H {%) Yield (°C) {calcd/found) (%) H3C ~C O H * characterised by 209 H3C ~ ~ ~OH 1 resin H-NMR (CDC13) 100 (CH2)2 b(H*} = 5.29 ppm COOH
1 cH3 0 ~C O H*
H c~ ~ o ff characterised by 210 ~ I resin 1 H-NMR {CDC13) 38 H3c-c-cH3 g(1-1*) = 5.08 ppm I
H3C\ ~ Ha H3c~c~c ~~~ H3 o c H 73.88 8.75 211 H c/ i aH 100-103 61 73.73 8.75 H3C~C O H NH 64.97 6.91 212 H3C ~ ) ~O- \; 138-143 65 O 65.02 6.89

Claims (21)

1. A process for the preparation of a compound of formula I

wherein, when n is 1, R1 is unsubstituted or substituted phenyl, naphthyl, phenanthryl, anthryl, 5,6,7,8-tetra-hydro-2-naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thiathrenyl, furyl, benzofuryl, isobenzofuryl, 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, .beta.-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, tetralinyl, fluorenyl or phenoxazinyl, when n is 2, R1 is unsubstituted or C1-C4alkyl- or hydroxy-substituted phenylene or naphthylene; or is -R6-X-R7-, R2, R3, R4 and R5 are each independently of one another hydrogen, chloro, hydroxy, C1-C25alkyl, C7-C9-phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl, unsubsti-tuted or C1-C4alkyl-substituted C5-C8cycloalkyl; C1-C18alkoxy, C1-C18alkylthio, C1-C4-alkylamino, di-(C1-C4alkyl)amino, C1-C25alkanoyloxy, C1-C25alkanoylamino, C3-alkenoyloxy, C3-C25alkanoyloxy which is interrupted by oxygen, sulfur or ;
C6-C9cycloalkylcarbonyloxy, benzoyloxy or C1-C12alkyl-substituted benzoyloxy;
or each pair of substituents R2 and R3 or R3 and R4 or R4 and R5, together with the linking carbon atoms, forms a benzene ring; R4 is additionally -(CH2)p COR9 or -(CH2)qOH, or, if R3 and R5 are hydrogen, R4 is additionally a radical of formula II

wherein R1 is as defined above when n = l, R6 and R7 are each independently of the other unsubstituted or C1-C4alkyl-substituted phe-nylene or naphthylene, R8 is hydrogen or C1-C8alkyl, R9 is hydroxy, < 1 M G >
R10and R11 are each independently of the other hydrogen, CF3, C1-C12alkyl or phenyl, or R10and R11, together with the linking carbon atom, form a C5-C8cycloalkylidene ring which is unsubstituted or substituted by 1 to 3 C1-C4alkyl groups, R12 and R13 are each independently of the other hydrogen or C1-C18alkyl, R14 is hydrogen or C1-C18alkyl, M is a metal ration of valency r, X is a direct bond, oxygen, sulfur or -NR14-, n is 1 or 2, p is 0, 1 or 2, q is 1, 2, 3, 4, 5 or 6, and r is 1,2 or 3, which process comprises reacting a compound of formula III

wherein R15 is halogen or -OR'15, R'15 is hydrogen, C1-C25alkanoyl, C3-C25alkenoyl, C3-C25alkanoyl which is interrupted by oxygen, sulfur or < I M G > ; C6-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C1-C12alkyl-substituted benzoyl; naphthoyl or C1-C12alkyl-substituted naphthoyl; C1-C25-alkanesulfonyl, fluoro-substituted C1-C25alkanesulfonyl; phenylsulfonyl or C1-C12alkyl-substituted phenylsulfonyl; R16 is a directe bond, C1-C18alkylene, C2-C18alkylene which is interrupted by oxygen, sulfur or ; C2_C18alkenylene, C2-C20alkylidene, C7-C20phenylalkylidene, C5-C8cycloalkylene, C7-C8bicycloalkylene, unsubstituted or C1-C4alkyl-substituted phenylene, < I M G >

R17 is oxygen, -NH- or < I M G > , and R18 is C1C18alkyl or phenyl, with a compound of formula IV

[H]n-R1 (IV).

2. A process according to claim 1, wherein , when n is 1, R1 is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C1-C4alkyl-substituted carbazo-lyl; or is fluorenyl, or R1 is a radical of formula V or VI

wherein R19, R20, R21, R22 and R23 are each independently of one another hydrogen, halogen, hydroxy, C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen, sulfur or C1-C25alkoxy, C2-C25alkoxy which is interrupted by oxygen, sulfur or ; C1-alkylthio, C3-C25alkenyl, C3-C25alkenyloxy, C3-C25alkynyl, C3-C25alkynyloxy, phenylalkyl, C7-C9phenylalkoxy, unsubstituted or C1-C4alkyl-substituted phenyl; unsub-stituted or C1-C4alkyl-substituted phenoxy; unsubstituted or C1-C4alkyl-substituted C5-C8-cycloalkyl; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkoxy; C1-C4alkylamino, di(C1-C4alkyl)amino, C1-C25alkanoyl, C3-C25alkanoyl which is interrupted by oxygen, sulfur or ; C1-C25-alkanoyloxy, C3-C25alkanoyloxy which is interrupted by oxygen, sulfur or ; C1-C25alkanoylamino, C3-C25alkenoyl, C3-C25alkenoyl which is interrupted by oxygen, sulfur or ; C3-C25alkenoyloxy, C3-C25alke-noyloxy which is interrupted by oxygen, sulfur or ; C6-C9cycloalkylcarbonyl, C6-C9cycloalkylcarbonyloxy, benzoyl or C1-C12alkyl-substituted benzoyl;
benzoyloxy or C1-C12alkyl-substituted benzoyloxy; , or in formula V each pair of substituents R19 and R20 or R20 and R21, together with the linking carbon atoms, forms a benzene ring, R24 is hydrogen, C1-C4alkyl, unsubstituted or C1-C4alkyl-substituted phenyl, R25 and R26 are hydrogen, C1-C4alkyl or phenyl, with the proviso that at least one of R25 and R26 is hydrogen, R27 and R28 are each independently of the other hydrogen, C1-C4alkyl or phenyl, R29 is hydrogen or C1-C4alkyl, R30 is hydrogen, unsubstituted or C1-C4alkyl-substituted phenyl; C1-C25alkyl, C2-C25alkyl which is interrupted by oxygen, sulfur or ; C7-C9phenylalkyl which is unsubsti-tuted or substituted at the phenyl moiety by 1 to 3 C1-C4alkyl groups; C7-C25phenylalkyl which is interrupted by oxygen, sulfur or or is unsubstituted or substituted in the phenyl moiety by 1 to 3 C1-C4alkyl groups; or R29 and R30, together with the linking carbon atoms, form a C5-C12cycloalkylene ring which is unsubstituted or substituted by 1 to 3 C1-C4alkyl groups, R31 is hydrogen or C1-C4alkyl, R32 is hydrogen, C1-C25alkanoyl, C3-C25alkenoyl, C3-C25alkanoyl which is interrupted by oxygen, sulfur or ;C2-C25alkanoyl which is substituted by a di(C1-C6alkyl)-phosphonate group; C6-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C1-C12alkyl-substituted benzoyl; R33 is hydrogen or C1-C8alkyl, R34 is a direct bond, C1-C18alkylene, C2-C18alkylene which is interrupted by oxygen, sulfur or C2-C18alkenylene, C2-C20alkylidene, C7-C20phenylalkylidene, C5-C8cycloalkylene, C7-C8bicycloalkylene, unsubstituted or C1-C4alkyl-substituted phenylene, R35 is hydroxy, R36 is oxygen, -NH- or R37 is C1-C18alkyl or phenyl, and s is 0, 1 or 2.

3. A process according to claim 1, wherein, when n is 2, R1 is -R6-X-R7-, R6 and R7 are phenylene, X is oxygen or-NR14-, and R14 is C1-C4alkyl.

4. A process according to claim 2, wherein R19, R20, R21, R22 and R23 are each independently of one another hydrogen, chloro, bromo, hydroxy, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or sulfur;
C1-C18alkoxy, C2-C18alkoxy which is interrupted by oxygen or sulfur; C1-C18alkylthio, C3-C12alkenyloxy, C3-C12alkynyloxy, C7-C9phenylalkyl, C7-C9phenylalkoxy, unsubstitu-ted or C1-C4alkyl-substituted phenyl; phenoxy, cyclohexyl, C5-C8cycloalkoxy;

alkylamino, di(C1-C4alkyl)amino, C1-C12alkanoyl, C3-C12alkanoyl which is interrupted by oxygen or sulfur; C1-C12alkanoyloxy, C3-C12alkanoyloxy which is interrupted by oxygen or sulfur; C1-C12alkanoylamino, C3-C12alkenoyl, C3-C12alkenoyoxy, cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoyl or C1-C4alkyl-substituted benzoyl; benzoyloxy or C1-C4-alkyl substituted benzoyloxy; , or in formula V each pair of substituents R19 and R20 or R20 and R21, together with the linking carbon atoms, forms a benzene ring, R24 is hydrogen or C1-C4alkyl, R25 and R26 are hydrogen or C1-C4alkyl, with the proviso that at least one of R25 and R26 is hydrogen, R27 and R28 are each independently of the other hydrogen or C1-C4alkyl, R29 is hydrogen, R30 is hydrogen, phenyl, C1-C18alkyl, C2-C18alkyl which is interrupted by oxygen or sulfur; C7-C9phenylalkyl, C7-C18phenylalkyl which is interrupted by oxygen or sulfur and unsubstituted or substituted in the phenyl moiety by 1 to 3 C1-C4alkyl groups, and R29 and R30, together with the linking carbon atoms, form a cyclohexylene ring which is unsubsti-tuted or substituted by 1 to 3 C1-C4alkyl groups, R31 is hydrogen or C1-C4alkyl, R32 is hydrogen, C1-C18alkanoyl, C3-C12alkenoyl, C3-C12alkanoyl which is interrupted by oxygen or sulfur; C2-C12alkanoyl which is substituted by a di(C1-C6-alkyl)phosphonate group; C6-C9cycloalkylcarbonyl, benzoyl, < I M G >
R33 is hydrogen or C1-C4alkyl, R34 is C1-C12alkylene, C2-C8alkenylene, C2-C8alkylidene, C7-C12phenylalkylidene, C5-C8cycloalkylene or phenylene, R35 is hydroxy, or C1-C18alkoxy, R36 is oxygen or -NH-, R37 is C1-C8alkyl or phenyl, and s is 1 or 2.

5. A process according to claim 2, wherein R1 is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C1-C4alkyl-substituted carbazo-lyl; or fluorenyl, or R1 is a radical of formula V

wherein R19, R20, R21, R22 and R23 are each independently of one another hydrogen, chloro, hydroxy, C1-C18alkyl, C1-C18alkoxy, C1-C18alkylthio, C3-C4alkenyloxy, C3-C4-alkynyl-oxy, phenyl, benzoyl, benzoyloxy or R29 is hydrogen, R30 is hydrogen, phenyl or C1-C18alkyl, or R29 and R30, together with the linking carbon atoms, form a cyclohexylene ring which is unsubstituted or substituted by 1 to C1-C4alkyl groups, R31 is hydrogen or C1-C4alkyl, and R32 is hydrogen, C1-C12alkanoyl or benzoyl.

6. A process according to claim 5, wherein R19 is hydrogen or C1-C4alkyl, R20 is hydrogen or C1-C4alkyl, R21 is hydrogen, chloro, hydroxy, C1-C12alkyl, C1-C4alkoxy, C1-C4alkylthio, phenyl or -O-CH2-CH2-O-R32, R22 is hydrogen or C1-C-4alkyl, R23 is hydrogen or C1-C4alkyl, and R32 is C1-C4alkanoyl.

7. A process according to any one of claims 1 to 6, wherein R2, R3, R4 and R5 are each independently of one another hydrogen, chloro, hydroxy, C1-C25alkyl, C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl, unsubsti-tuted or C1-C4alkyl-substituted C5-C8cycloalkyl; C1-C12alkoxy, C1-C12alkylthio, C1-C4-alkylamino, di(C1-C4alkyl)amino, C1-C18alkanoyloxy, C1-C18alkanoylamino, C3-C18alke-noyloxy, C3-C18alkanoyloxy which is interrupted by oxygen, sulfur or ;

cycloalkylcarbonyloxy, benzoyloxy or C1-C8alky)-substituted benzoyloxy, or each pair of substituents R2 and R3 or R3 and R4 or R4 and R5, together with the linking carbon atoms, forms a benzene ring, R4 is additionally -(CH2)p COR9 or -(CH2)q OH, or, if R3 and R5 are hydrogen, R4 is additionally a radical of formula II

R8 is hydrogen or C1-C6alkyl, R9 is hydroxy, C1-C18alkoxy or R10 and R11 are methyl groups or, together with the linking carbon atom, form a C5-C8-cycloalkylidene ring which is unsubstituted or substituted by 1 to 3 C1-C4alkyl groups;
R12 and R13 are each independently of the other hydrogen or C1-C8alkyl, and q is 2, 3, 4,5 or 6.

8. A process according to any one of claims 1 to 7, wherein at least two of the substituents R2, R3, R4 and R5 are hydrogen.

9. A process according to any one of claims 1 to 7, wherein R3 and R5 are hydrogen.

10. A process according to any one of claims 1 to 6, wherein R2, R3, R4 and R5 are each independently of one another hydrogen, chloro, hydroxy, C1-C18alkyl, C7-C9phenylalkyl, phenyl, C5-C8cycloalkyl, C1-C6alkoxy, cyclohexylcarbo-nyloxy or benzoyloxy, or each pair of substituents R2 and R3 or R3 and R4 or R4 and R5, together with the linking carbon atoms, forms a benzene ring, R4 is additionally -(CH2)p-COR9, or if R3 and R5 are hydrogen, R4 is additionally a radical of formula II
R9 is hydroxy or C1-C18alkoxy, and R10 and R11 are methyl groups or, together with the linking carbon atom, form a C5-C8-cycloalkylidene ring.

11. A process according to any one of claims 1 to 6, wherein R2 is C1-C18alkyl or cyclohexyl, R3 is hydrogen, R4 is C1-C4alkyl, cyclohexyl or a radical of formula II, R5 is hydrogen, and R10 and R11 together with the linking carbon atom, form a cyclohexylidene ring.

12. A process according to any one of claims 1 to 11, wherein R'15 is hydrogen, C1-C18alkanoyl, C3-C18alkenoyl, C3-C18alkanoyl which is interrupted by oxygen, sulfur or ; C6-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or alkyl substituted benzoyl; naphthoyl or C1-C8alkyl-substituted naphthoyl; C1-C18alkane-sulfonyl, fluoro-substituted C1-C18alkanesulfonyl; phenylsulfonyl or C1-C8alkyl-substitu-ted phenylsulfonyl; R16 is a direct bond, C1-C12alkylene, C2-C12alkylene which is interrupted by oxygen, sulfur or ;C2-C12alkenylene,C2-C12alkylidene,C7-C12phenylalkylidene, C5-C8cycloalkylene, C7-C8bicycloalkylene or phenylene, R17 is oxygen or -NH-, and R18 is C1-C12alkyl or phenyl.

13. A process according to any one of claims 1 to 11, wherein R15 is chloro, bromo or-OR'15, R'15 is hydrogen, C1-C12alkanoyl, C1-C12alkanoyl which is interrupted by oxygen; cyclo-hexylcarbonyl, benzoyl, naphthoyl, C1-C12alkanesulfonyl, fluoro-substituted C1-alkanesulfonyl; phenylsulfonyl or C1-C4alkyl-substituted phenylsulfonyl; or R17 is -NH-, and R18 is C1-C8alkyl or phenyl.

14. A process according to any one of claims 1 to 11, wherein R15 is -OR'15, R'15 is hydrogen, C1-C4alkanoyl or R17 is -NH-, and R18 is C1-C4alkyl.

15. A process according to any one of claims 1 to 14, wherein the reaction is carried out in the presence of a catalyst.

16. A process according to claim 15, wherein the catalyst is selected from the group con-sisting of a protonic acid, a Lewis acid, an aluminium silicate, an ion exchange resin, a zeolite, a naturally occurring sheet silicate and a modified sheet silicate.

17. A process according to claim 15, wherein the catalyst is a naturally occurring sheet silicate or a modified sheet silicate.

18. A process according to claim 17, wherein the naturally occurring sheet silicate is a Fulcat* or Fulmont* type.

19. A process according to claim 1, wherein, when n is 1, the molar ratio of the compound of formula III to the compound of formula IV is 1:1 to 1:20 and, when n is 2, the molar ratio of the compound of formula III to the compound of formula IV is 3:1 to 2:1

20. A process for the preparation of a compound of formula I

wherein R1, R2, R3, R4 and R5 are as defined in claim 1, which comprises reacting one equi-valent of the phenol of formula VII

wherein R2, R3, R4 and R5 are as defined in claim 1, with 0.8 to 2.0 equivalents of glyoxylic acid to a compound of formula VIII

*Trade-mark Wherein R2, R3, R4 and R5 are as defined in claim 1, and subsequently reacting said compound of formula V111, without isolation, with a compound of formula 1V

[H]nR1 (1V).

wherein R1 and n as as defined in claim 1.

21. A process according to claim 20, which comprises reacting the compound of formu-la VIII, without isolation before the further reaction with a compound of formula IV, in an additional reaction step with a hydrohalic acid, a halide of an oxysulfuric acid, a halide of phosphoric acid, a halide of a phosphorous acid, an acid of formula IX

R'15-OH (IX) an acid halide of formula X, R'15Y (X) an ester of formula XI

R'15-0-R38 (XI) a symmetrical or unsymmetrical anhydride of formula XII
R'15-O-R'15 (XII) or an isocyanate of formula XIII

R39-N=C=O (XIII) wherein R'15 in formulae IX, X, XI and XII is as defined in claim 1, with the proviso that R'15 is not hydrogen;
R38 is C1-C8alkyl, R39 is C1-C18alkyl or phenyl, and Y is fluoro, chloro, bromo or iodo, to a compound of formula III

wherein the substituents R2, R3, R4, R5 and R15 are as defined in claim 1, with the proviso that, when R15 = -OR'15, R'15 is not hydrogen.