Chemistry of hydrocarbon compounds – Alicyclic compound synthesis – Polycyclic product
Reexamination Certificate
2000-06-09
2002-04-30
Lambkin, Deborah C. (Department: 1626)
Chemistry of hydrocarbon compounds
Alicyclic compound synthesis
Polycyclic product
Reexamination Certificate
active
06380447
ABSTRACT:
FIELD OF THE INVENTION
The present invention concerns Diels-Alder reactions of epoxybutene and derivatives thereof, and compounds produced from such reactions.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 2,616,899 to Ladd reports the Diels-Alder reaction of hexachlorocyclopentadiene with epoxybutene (EpB). The Diels-Alder product was found to be a flame retardant and a stabilizer for polyvinyl chloride (PVC).
In 1989, a Kodak Research Laboratories technical report described the screening of various dienes in Diels-Alder reactions with EpB. Most reactions, including that with cyclopentadiene, produced none of the desired cycloaddition adduct. Only EpB reacted with diphenylisobenzofuran to produce a Diels-Alder cycloadduct, at 38% yield.
Cyclic compounds are useful for a variety of purposes, including the production of polymers and copolymers as described in U.S. Pat. No. 3,277,036 to Whitworth and Zutty and U.S. Pat. No. and 3,494,897 to Reding et al. Accordingly, there is a need for new ways to carry out, the Diels-Alder reaction, and a need for products thereof.
SUMMARY OF THE INVENTION
The Diels Alder reaction of certain dienes with certain dienophiles, when carried out under pressure, can be utilized to produce cyclic and bicyclic compounds described herein.
Accordingly, a first aspect of the present invention is a method of making a bicyclic compound selected from the group consisting of compounds of Formula X and compounds of Formula XI:
wherein:
R, R
1
, R
2
, R
3
, and R
4
are each independently selected from the group consisting of H, and C1-C4 lower alkyl; and
R
11
, and R
12
each independently represent —H, —OH, —OCOCH
3
, —OCH
2
C
6
H
5
, or —OR
13
wherein R
13
represents C1-C4 lower alkyl, or
R
11
, and R
12
together represent —O—, —O—C(O)—O— or —O—C(CH
3
)
2
—O—; comprising reacting a diene according to Formula I:
wherein R, R
1
, R
2
, R
3
, and R
4
are as given above with a dieneophile according to Formula VI:
wherein R
11
and R
12
are as given above in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound selected from the group consisting of compounds of Formula X and compounds of Formula XI.
A second aspect of the invention is a method of making a bicyclic compound selected from the group consisting of compounds of Formula XII and Formula XIII:
wherein:
R, R
1
, R
2
, R
3
, R
4
and R
5
are each independently selected from the group consisting of H, and C1-C4 lower alkyl; and
R
11
and R
12
each independently represent —H, —OH, —OCOCH
3
, —OCH
2
C
6
H
5
, or —OR
13
wherein R
13
represents C1-C4 lower alkyl, or
R
11
and R
12
together represent —O—, —O—C(O)—O— or —O—C(CH
3
)
2
—O—; comprising reacting a diene according to Formula II:
wherein R, R
1
, R
2
, R
3
, R
4
and R
5
are as given above with a dieneophile according to Formula VI:
wherein R
11
and R
12
are as given above in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound selected from the group consisting of compounds of Formula XII and compounds of Formula XIII.
A third aspect of the present invention is a method of making a compound selected from the group consisting of compounds of Formula XIV and Formula XV:
wherein:
R
6
is —H;
R
7
is —H or —CH
3
; and R
11
and R
12
each independently represent —H, —OH, -OCOCH
3
, —OCH
2
C
6
H
5
, or —OR
13
wherein R
13
represents C1-C4 lower alkyl, or
R
11
and R
12
together represent —O—, —O—C(O)—O— or —O—C(CH
3
)
2
—O—;
comprising reacting a diene of Formula III or Formula IV:
with a dieneophile according to Formula VI:
wherein R
11
and R
12
are as given above in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound selected from the group consisting of compounds of Formula XII and compounds of Formula XIII.
A further aspect of the present invention is a method of making a bicyclic compound selected from the group consisting of compounds of Formula XVI and compounds of Formula XVII:
wherein R, R
1
, R
2
, R
3
, R
4
, R
13
, R
14
, R
15
and R
16
are each independently selected from the group consisting of H, and C1-C4 lower alkyl; comprising
reacting a diene according to Formula I:
wherein R, R
1
, R
2
, R
3
, and R
4
are as given above with a dieneophile according to Formula VII:
wherein R
13
, R
14
, R
15
and R
16
are as given above in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound selected from the group consisting of compounds of Formula XVI and compounds of Formula XVII.
A still further aspect of the present invention is a method of making a bicyclic compound selected from the group consisting of compounds of Formula XVII and compounds of Formula XIX:
wherein R, R
1
, R
2
, R
3
, R
4
, R
5
, R
13
, R
14
, R
15
and R
16
are each independently selected from the group consisting of H, and C1-C4 lower alkyl; comprising reacting a diene according to Formula II:
wherein R, R
1
, R
2
, R
3
, R
4
and R
5
are as given above with a dieneophile according to Formula VII:
wherein R
13
, R
14
, R
15
and R
16
are as given above in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound selected from the group consisting of compounds of Formula XVIII and compounds of Formula XIX.
A still further aspect of the invention is a method of making a compound according to Formula XX
wherein R
6
is —H, R
7
is —H or —CH
3
, and R
13
, R
14
, R
15
and R
16
are each independently selected from the group consisting of H and C1-C4 alkyl;
comprising reacting a diene of Formula III or Formula IV:
with a dieneophile according to Formula VI:
wherein R
13
, R
14
, R
15
and R
16
are as given above in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound of Formula XX.
The present invention also provides compounds, particularly novel compounds, produced by the methods described above.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention concerns the reaction of certain dienes as described below with epoxybutene or epoxybutene derivatives as a dienophile, as also described below, to form cyclic product compounds as described below.
A. Dienes. Dienes that may be used to carry out the present invention include isoprene, butadiene, cyclohexadiene, cyclopentadiene, and derivatives thereof.
Cyclopentadiene, cyclohexadiene and derivatives thereof that may be used to carry out the present invention are illustrated by Formulas I and II below:
R, R
1
, R
2
, R
3
, R
4
and R
5
are each independently selected from the group consisting of H, and C1-C4 lower alkyl.
Isoprene and butadiene, which may also be used as dienes to carry out the present invention, are illustrated by Formulas III and IV below:
B. Dienophiles. The present invention may be carried out with epoxybutene (EpB) as the dienophile, which has the structure according to Formula V below, or EpB and derivatives thereof which are generally represented by Formula VI below:
R
11
and R
12
in Formula VI, may together represent —O—, in which case Formula VI represents epoxybutene as shown in Formula V. R
11
and R
12
may also represent —O—C(O)—O— or —O—C(CH
3
)
2
—O—, each of which forms a five member ring system. Such compounds are epoxybutene derivatives.
In addition, R
11
and R
12
may each independently represent —H, —OH, —OAc(—OCOCH
3
), —OBz (—OCH
2
C
6
H
5
), or —OR
13
wherein R
13
represents C1-C4 lower alkyl, preferably methyl. In particular preferred embodiments of formula VI above,
R
11
is —H and R
12
is —OH;
R
11
is —OAc and R
12
is —OAc;
R
11
is —OR
13
R
12
is —OAc;
R
11
is —OBz and R
12
is —OH; and
R
11
is —OH and R
12
is —OH.
Still further dienophiles that may be used to carry out the present invention are compounds of Formula VII:
In which R
13
, R
14
, R
15
and R
16
are each independently selected from the group consisting of H and C1-C4 lower alkyl.
C. Reaction conditions. The Diels-Alder reaction may be carried out in any suitable solvent, typically an organic solvent and typically an in
Franks Marion A.
Welker Mark E.
Lambkin Deborah C.
Myers Bigel & Sibley & Sajovec
Wake Forest University
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