Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
2000-12-22
2002-07-09
Solola, T. A. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
C544S257000, C546S102000, C546S108000, C546S152000, C546S278400, C548S265800, C548S463000, C548S525000, C549S060000, C549S223000, C549S299000, C549S304000
Reexamination Certificate
active
06417358
ABSTRACT:
The present invention relates to a novel process for the preparation of 3-aryl-benzofuran-ones, which are suitable for stabilising organic materials against oxidative, thermal or light-induced degradation.
The best processes hitherto for the preparation of 3-aryl-benzofuranones are described, for example, in U.S. Pat. No. 4,325,863 and U.S. Pat. No. 5,607,624.
The process disclosed in U.S. Pat. No. 4,325,863 (Example 1, column 8, lines 35-45) for the preparation of 3-phenyl-3H-benzofuran-2-ones, for example 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 removal of water.
A disadvantage of that process is that it requires the use of mandelic acids substituted on the phenyl ring or heterocyclic mandelic acids. Not very many of those mandelic acids are known from the literature, however, and the known synthesis procedures for the preparation thereof are relatively complicated.
The process disclosed in U.S. Pat. No. 5,607,624 (Example 1, column 24) for the preparation of 3-phenyl-3H-benzofuran-2-ones substituted on the 3-phenyl ring, for example 5,7-di-tert-butyl-3-(2,5-dimethyl-phenyl)-3H-benzofuran-2-one of formula F, comprises reacting the 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one of formula D with p-xylene of formula E, with removal of water.
A disadvantage of that process is that, for the preparation of unsubstituted 3phenyl-benzo-furanone derivatives, it requires the use of benzene, which is carcinogenic, instead of p-xylene.
R. F. Heldeweg, H. Hogeveen,
J. Amer. Chem. Soc
. 98 (19), 6040-6042 (1976) disclose novel rhodium-catalyzed additions of carbon monoxide to reactive dienes and enones with formation of five-membered rings.
There is therefore still a need to find an efficient process for the preparation of 3aryl-benzofuranones that does not have the disadvantages mentioned above.
The present invention therefore relates to a process for the preparation of compounds of formula I
wherein, when n is 1,
R
1
is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, &bgr;-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, each of which is unsubstituted or substituted by fluorine, hydroxy, C
1
-C
18
alkyl, C
1
-C
18
alkoxy, C
1
-C
18
alkylthio, di-(C
1
-C
4
alkyl)amino, phenyl, benzyl, benzoyl or by benzoyloxy or R
1
is a radical of formula II or III
when n is 2,
R
1
is phenylene or naphthylene each unsubstituted or substituted by C
1
-C
4
alkyl or by fluorine; or is —R
6
—X—R
7
—,
R
2
, R
3
, R
4
and R
5
are each independently of the others hydrogen, fluorine, hydroxy, C
1
-C
25
-alkyl, C
7
-C
9
phenylalkyl, unsubstituted or C
1
-C
4
alkyl-substituted phenyl, unsubstituted or C
1
-C
4
alkyl-substituted C
5
-C
8
cycloalkyl; C
1
-C
18
alkoxy, C
1
-C
18
alkylthio, C
1
-C
4
alkylamino, di-(C
1
-C
4
alkyl)amino, C
1
-C
25
alkanoyloxy, C
1
-C
25
alkanoylamino; C
3
-C
25
alkanoyloxy interrupted by oxygen, sulfur or by
C
6
-C
9
cycloalkylcarbonyloxy, benzoyloxy or C
1
-C
12
alkyl-substituted benzoyloxy, or furthermore the radicals R
2
and R
3
or the radicals R
3
and R
4
or the radicals R
4
and R
5
, together with the carbon atoms to which they are bonded, form a benzo ring, R
4
is additionally —(CH
2
)
p
—COR
9
or —(CH
2
)
q
OH or, when R
3
and R
5
are hydrogen, R
4
is additionally a radical of formula IV
wherein R
1
is as defined above for the case where n=1,
R
6
and R
7
are each independently of the other phenylene or naphthylene each unsubstituted or substituted by C
1
-C
4
alkyl,
R
8
is C
1
-C
8
alkyl,
R
9
is hydroxy,
[
—O
-
1
r
M
r
+
]
,
C
1
-C
18
alkoxy or
R
10
and R
11
are each independently of the other hydrogen, CF
3
, C
1
-C
12
alkyl or phenyl, or R
10
and R
11
, together with the carbon atom to which they are bonded, form a C
5
-C
8
cycloalkylidene ring unsubstituted or substituted by from 1 to 3 C
1
-C
4
alkyl groups;
R
12
and R
13
are each independently of the other hydrogen or C
1
-C
18
alkyl,
R
14
is hydrogen or C
1
-C
18
alkyl,
R
19
, R
20
, R
21
, R
22
and R
23
are each independently of the others hydrogen, fluorine, hydroxy, C
1
-C
25
alkyl; C
2
-C
25
alkyl interrupted by oxygen, sulfur or by
C
1
-C
25
alkoxy; C
2
-C
25
alkoxy interrupted by oxygen, sulfur or by
C
1
-C
25
alkylthio, C
7
-C
9
phenylalkyl, C
7
-C
9
phenylalkoxy, unsubstituted or C
1
-C
4
alkyl-substituted phenyl; unsubstituted or C
1
-C
4
alkyl-substituted phenoxy; unsubstituted or C
1
-C
4
alkyl-substituted C
5
-C
8
cycloalkyl; unsubstituted or C
1
-C
4
alkyl-substituted C
5
-C
8
cycloalkoxy; di(C
1
-C
4
alkyl)amino, C
1
-C
25
-alkanoyl; C
3
-C
25
alkanoyl interrupted by oxygen, sulfur or by
C
1
-C
25
alkanoyloxy; C
3
-C
25
alkanoyloxy interrupted by oxygen, sulfur or by
C
1
-C
25
alkanoylamino, C
6
-C
9
cycloalkylcarbonyl, C
6
-C
9
cycloalkylcarbonyloxy, benzoyl or C
1
-C
12
alkyl-substituted benzoyl; benzoyloxy or C
1
-C
12
alkyl-substituted benzoyloxy;
R
24
is hydrogen, C
1
-C
4
alkyl, or unsubstituted or C
1
-C
4
alkyl-substituted phenyl,
R
25
and R
26
are hydrogen, C
1
-C
4
alkyl or phenyl, with the proviso that at least one of the radicals R
25
and R
26
is hydrogen,
R
27
and R
28
are each independently of the other hydrogen, C
1
-C
4
alkyl or phenyl,
R
29
is hydrogen or C
1
-C
4
alkyl,
R
30
is hydrogen, unsubstituted or C
1
-C
4
alkyl-substituted phenyl; C
1
-C
25
alkyl; C
2
-C
25
alkyl interrupted by oxygen, sulfur or by
C
7
-C
9
phenylalkyl unsubstituted or substituted on the phenyl radical by from 1 to 3 C
1
-C
4
alkyl groups; or C
7
-C
25
phenylalkyl interrupted by oxygen, sulfur or by
and unsubstituted or substituted on the phenyl radical by from 1 to 3 C
1
-C
4
alkyl groups,
R
31
is hydrogen or C
1
-C
4
alkyl,
R
32
is hydrogen, C
1
-C
25
alkanoyl; C
3
-C
25
alkanoyl interrupted by oxygen, sulfur or by
C
2
-C
25
alkanoyl substituted by a di(C
1
-C
6
alkyl) phosphonate group; C
6
-C
9
cyclo-alkylcarbonyl, thenoyl, furoyl, benzoyl or C
1
-C
12
alkyl-substituted benzoyl;
R
33
is hydrogen or C
1
-C
8
alkyl,
R
34
is a direct bond, C
1
-C
18
alkylene; C
2
-C
18
alkylene interrupted by oxygen, sulfur or by
C
2
-C
20
alkylidene, C
7
-C
20
phenylalkylidene, C
5
-C
8
cycloalkylene, C
7
-C
8
bicyclo-alkylene, unsubstituted or C
1
-C
4
alkyl-substituted phenylene,
R
35
is hydroxy,
[
—O
-
1
r
M
r
+
]
,
C
1
-C
18
alkoxy or
R
36
is oxygen, —NH— or
R
37
is C
1
-C
18
alkyl or phenyl,
M is an r-valent metal cation,
X is a direct bond, oxygen, sulfur or —NR
14
—,
n is 1 or 2,
p is 0, 1 or 2,
q is 1, 2, 3, 4, 5 or 6,
r is 1, 2 or 3, and
s is 0, 1 or 2,
which process comprises reacting a compound of formula V
wherein
R
1
and n are as defined above,
R
2
, R
3
, R′
4
and R
5
are each independently of the others hydrogen, fluorine, hydroxy, C
1
-C
25
alkyl, C
7
-C
9
phenylalkyl, unsubstituted or C
1
-C
4
alkyl-substituted phenyl, unsubstituted or C
1
-C
4
alkyl-substituted C
5
-C
8
-cycloalkyl; C
1
-C
18
alkoxy, C
1
-C
18
alkylthio, C
1
-C
4
alkylamino, di(C
1
-C
4
alkyl)amino, C
1
-C
25
alkanoyloxy, C
1
-C
25
alkanoylamino; C
3
-C
25
alkanoyloxy interrupted by oxygen, sulfur or by
C
6
-C
9
cycloalkylcarbonyloxy, benzoyloxy or C
1
-C
12
alkyl-substituted benzoyloxy, or furthermore the radicals R
2
and R
3
or the radicals R
3
and R′
4
or the radicals R′
4
and R
5
, together with the carbon atoms to which they are bonded, form a benzo ring, R&pr
Evans Samuel
Nesvadba Peter
Tinkl Michael
Ciba Specialty Chemicals Corporation
Solola T. A.
Stevenson Tyler A.
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