U.S. patent application number 10/849559 was filed with the patent office on 2005-11-24 for process for producing indenol esters or ethers.
Invention is credited to Mosimann, Herve, Snowden, Roger Lesile, Womack, Gary Bernard.
Application Number | 20050261513 10/849559 |
Document ID | / |
Family ID | 34978593 |
Filed Date | 2005-11-24 |
United States Patent
Application |
20050261513 |
Kind Code |
A1 |
Womack, Gary Bernard ; et
al. |
November 24, 2005 |
Process for producing indenol esters or ethers
Abstract
The present invention relates to a process for making indenol
esters or ether from an .alpha.-substituted cinnamic aldehyde
derivative such as an acetal or an acylal. This reaction is
promoted by the use of strong mineral acids, sulphonic acids,
acidic zeolites or Lewis acids.
Inventors: |
Womack, Gary Bernard;
(Hopewell, NJ) ; Snowden, Roger Lesile; (Viry,
FR) ; Mosimann, Herve; (Carouge, CH) |
Correspondence
Address: |
WINSTON & STRAWN LLP
1700 K STREET, N.W.
WASHINGTON
DC
20006
US
|
Family ID: |
34978593 |
Appl. No.: |
10/849559 |
Filed: |
May 18, 2004 |
Current U.S.
Class: |
560/129 |
Current CPC
Class: |
C07C 41/28 20130101;
C07C 41/28 20130101; C07C 67/297 20130101; C07C 2602/08 20170501;
C07C 67/297 20130101; C07C 69/013 20130101; C07C 43/188 20130101;
C07C 67/297 20130101; C07C 2602/10 20170501; C07C 69/157
20130101 |
Class at
Publication: |
560/129 |
International
Class: |
C07C 069/00 |
Claims
What is claimed is:
1. A process for making a compound of formula 6wherein m is 0, 1 or
2; R.sup.1 represents a formyl group, a --COCOOH group or a group
of formula --(CO).sub.n--R-T, in which n is 0 or 1, R is a
C.sub.6H.sub.4 group, C.sub.1-5 alkanediyl or alkenediyl group and
T is OH, COOH or a hydrogen atom; R.sup.2 represents a C.sub.1-6
alkyl or alkenyl group; at least one R.sup.3 represents a hydrogen
atom and the other R.sup.3 represent each a hydrogen atom or a
C.sub.1-5 alkyl, alkenyl or alkoxy group; and R.sup.4 represents a
hydrogen atom, a phenyl group or a R.sup.2 group; comprising the
cyclization, at a temperature above 10.degree. C., of the
corresponding compound of formula 7wherein each R.sup.5, taken
separately, represents a formyl group or a --(CO).sub.n--R--H
group, or the R.sup.5, taken together, represent a
--(CO).sub.n--R--(CO).sub.n-- group or a --COCO-- group; the wavy
line indicates that the configuration of the carbon-carbon double
bond is E or Z or a mixture thereof; and m, n, R, R.sup.2, R.sup.3
and R.sup.4 have the meaning as indicated above; in the presence of
a catalyst selected from the group consisting of strong mineral
protic acids, sulphonic acids, acidic zeolites and Lewis acids.
2. A process according to claim 1, wherein m is 0 or 1.
3. A process according to claim 1, wherein the compounds of formula
(I) are of formula 8and are obtained by cyclization of the
corresponding compounds of formula 9wherein R.sup.1, R.sup.2,
R.sup.3 and R.sup.5 have the same meaning as in claim 1.
4. A process according to claim 1, wherein the catalyst is selected
from the group consisting of H.sub.2SO.sub.4, p-toluenesulphonic
acid, NaHSO.sub.4, KHSO.sub.4, H.sub.3PO.sub.4, HCl, HNO.sub.3, and
BF.sub.3, and its adducts with C.sub.2-6 ethers or with C.sub.2-6
carboxylic acids, poly(styrene sulphonic acid) based resins, K-10
Clay, SnX.sub.4, FeX.sub.3 and ZnX.sub.2, X representing a halogen
atom, a C.sub.1-6 carboxylate, or a C.sub.1-7 sulphonate.
5. A process according to claim 4, wherein the catalyst is
H.sub.3PO.sub.4, FeX.sub.3 or ZnX.sub.2, X having the same meaning
as in claim 4.
6. A process according to claim 1, characterized in that it further
comprises the step of generating in situ the compound of formula
(II) starting from the corresponding enal of formula 10wherein
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the same meaning as
indicated in claim 1.
7. A process according to claim 6, wherein the compound of formula
(II) is an acetal or an acylal.
8. A compound of formula 11wherein one R.sup.3 is a hydrogen atom
and the other R.sup.3 is a C.sub.1-5 alkyl group, which n is 0 or
1, R is a C.sub.6H.sub.4 group, C.sub.1-5 alkanediyl or alkenediyl
group and T is OH, COOH or a hydrogen atom; and R.sup.2 represents
a C.sub.1-6 alkyl or alkenyl group.
9. A compound according to claim 8, wherein the compound is the
2-methyl, the 2,5-dimethyl or the 2,6-dimethyl derivative of
compound of formula I.
Description
TECHNICAL FIELD
[0001] The present invention relates to the field of organic
synthesis. More particularly it provides a process for making an
indenol ester or ether from an .alpha.-substituted cinnamic
aldehyde derivative such as an acetal or an acylal. This reaction
is promoted by the use of strong mineral acids, sulphonic acids,
acidic zeolites or Lewis acids.
BACKGROUND
[0002] The organic compounds of formula (I), as defined below, can
be useful as perfuming ingredients or as starting material for the
synthesis of compounds having a more complex skeleton. The methods
of preparation of such compounds as reported in the prior art are
in general quite long and/or expensive. Thus, there is a need for
improved processes for preparing such compounds.
[0003] It would be highly desirable to access such compounds by
means of a simple and efficient isomerization process wherein the
starting material is an easily accessible material. To the best of
our knowledge, there is no report in the prior art of an
isomerization process giving a direct access to compounds of
formula (I) from the compound of formula (II).
SUMMARY OF THE INVENTION
[0004] In order to solve the problems aforementioned, a first
embodiment of the present invention provides a process for making a
compound of formula 1
[0005] wherein m is 0, 1 or 2;
[0006] R.sup.1 represents a formyl group, a --COCOOH group or a
group of formula --(CO).sub.n--R-T, in which n is 0 or 1, R is a
C.sub.6H.sub.4 group, C.sub.1-5 alkanediyl or alkenediyl group and
T is OH, COOH or a hydrogen atom;
[0007] R.sup.2 represents a C.sub.1-6 alkyl or alkenyl group;
[0008] at least one R.sup.3 represents a hydrogen atom and the
other R.sup.3 represent each a hydrogen atom or a C.sub.1-5 alkyl,
alkenyl or alkoxy group; and
[0009] R.sup.4 represents a hydrogen atom, a phenyl group or a
R.sup.2 group;
[0010] comprising the cyclization, at a temperature above
10.degree. C. of the corresponding compound of formula 2
[0011] wherein each R.sup.5, taken separately, represents a formyl
group or a --(CO).sub.n--R--H group, or the R.sup.5, taken
together, represent a --(CO).sub.n--R--(CO).sub.n-- group or a
--COCO-- group;
[0012] the wavy line indicates that the configuration of the
carbon-carbon double bond is E or Z or a mixture thereof; and
[0013] m, n, R, R.sup.2, R.sup.3 and R.sup.4 have the meaning as
indicated above;
[0014] in the presence of a catalyst selected from the group
consisting of strong mineral protic acids, sulphonic acids, acidic
zeolites and Lewis acids.
[0015] For the invention purpose, it is important that R.sup.2 is
not a hydrogen atom, indeed if R.sup.2 is H then the reaction does
not take place.
[0016] According to an embodiment of the present invention, m is
preferably 0 or 1, or even more preferably 0.
[0017] Furthermore, according to one of the above-described
embodiments, R.sup.1 may also represent a group of formula
--(CO).sub.n--R-T, in which n is 0 or 1, R is a C.sub.6H.sub.4
group or a C.sub.1-C.sub.(5-n) alkanediyl or alkenediyl group and T
is OH, COOH or a hydrogen atom. Alternatively R.sup.1 may also
represent a group of formula --(CO).sub.n--R-T, in which n is 0 or
1, R is a C.sub.1-C.sub.(3-n) alkanediyl group and T is OH, COOH or
a hydrogen atom.
[0018] According to these embodiments R.sup.2 may represent a
C.sub.1-6 alkyl group.
[0019] Moreover, in such embodiments, at least two R.sup.3 may
represent a hydrogen atom and the other R.sup.3 may represent each
a hydrogen atom or a C.sub.1-5 alkyl or alkoxy group.
[0020] Furthermore, R.sup.4 may represent a hydrogen atom or a
C.sub.1-6 alkyl group, and preferably is a hydrogen atom.
[0021] The invention also relates to certain compounds that are
made by these processes.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] According to a particular embodiment of the invention the
compounds of formula (1) are of formula 3
[0023] and are obtained by cyclization of the corresponding
compounds of formula 4
[0024] wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.5 have the same
meaning as indicated above.
[0025] The compounds of formula (I') wherein one R.sup.3 is a
hydrogen atom and the other R.sup.3 is a C.sub.1-5 alkyl group are
new compounds and can be used as starting compounds for the
synthesis of indenols. Amongst these compounds can be cited the
2-methyl, the 2,5-dimethyl or the 2,6-dimethyl derivatives of
formula (I').
[0026] The catalyst, which can be used in the invention's process,
is a strong mineral protic acid, a suphonic acid, an acidic zeolite
or a Lewis acid. By "mineral" we mean here an acid having an anion
which does not contain a carbon atom. By "strong" we mean here a
protic acid having a pK.sub.AB<3, preferably below 2.
[0027] The catalyst can be in the anhydrous form or also in the
hydrate form, except for those acids which are unstable in the
presence of water.
[0028] According to another particular embodiment of the invention,
the catalyst is selected from the group consisting of
H.sub.2SO.sub.4, p-toluenesulphonic acid, NaHSO.sub.4, KHSO.sub.4,
H.sub.3PO.sub.4, HCl, HNO.sub.3, BF.sub.3 and its adducts with
C.sub.2-6 ethers or with C.sub.2-6 carboxylic acids, poly(styrene
sulphonic acid) based resins, K-10 Clay, SnX.sub.4, FeX.sub.3 and
ZnX.sub.2, X representing a halogen atom, such as Cl or Br, or a
C.sub.1-6 carboxylate, such as acetate or trifluoroacetate, or a
C.sub.1-7 sulphonate, such as a triflate or tosylate.
[0029] Preferably, the catalyst is H.sub.3PO.sub.4, FeX.sub.3 or
ZnX.sub.2.
[0030] The catalyst can be added to the reaction medium in a large
range of concentrations. As non-limiting examples, one can cite
catalyst concentrations ranging from 0.001 to 0.30 molar
equivalents, relative to the molar amount of the starting compound
(II). Preferably, the catalyst concentrations will be comprised
between 0.005 and 0.15 molar equivalents. It goes without saying
that the optimum concentration of catalyst will depend on the
nature of the catalyst and on the desired reaction time.
[0031] Another parameter of the invention's process is the
temperature. In order to allow the cyclization to occur, it is
useful to carry out the invention's process at a temperature of at
least 10.degree. C. Below this temperature the speed of the
reaction decreases quite rapidly. The upper limit of temperature
range is fixed by the reflux temperature of the reaction mixture
that, as skilled persons know, depends on the exact nature of the
starting and final product and optionally, as explained below, of
the solvent. However, as non-limiting example, one can cite a
preferred temperature ranging between 60.degree. C. and 180.degree.
C. Of course, a person skilled in the art is also able to select
the preferred temperature as a function of the melting and boiling
point of the starting and final products as well as of the
solvent.
[0032] The process of the invention can be carried out in the
presence or in the absence of solvent. As a person skilled in the
art can anticipate, the presence of a solvent is mandatory only in
the case in which the starting compound is a solid compound under
the reaction conditions.
[0033] According to a preferred embodiment of the invention, and
independently of the physical state of the starting compound, the
process is advantageously carried out in the presence of a solvent.
Preferably, the solvent is anhydrous or does not contain more than
5% w/w water.
[0034] Non-limiting examples of such a solvent are C.sub.4-C.sub.8
ethers, C.sub.3-C.sub.6 esters, C.sub.3-C.sub.6 amides,
C.sub.6-C.sub.9 aromatic solvents, C.sub.5-C.sub.7 linear or
branched or cyclic hydrocarbons, C.sub.1-C.sub.2 chlorinated
solvents and mixtures thereof.
[0035] Furthermore, the reaction can also be carried out in the
presence of a solvent belonging to the family of carboxylic
anhydride of formula R.sup.2C(O)O(O)CR.sup.2, R.sup.2 being defined
as above, optionally containing the corresponding carboxylic acid
R.sup.2COOH.
[0036] The compound of formula (II) can be made and isolated
according to any prior art method. Alternatively, compound (II) can
be also generated in situ, i.e. in the reaction medium just before
its use, according to any know prior art method. In particular,
preferably the compound of formula (II) is made or generated by a
method using the corresponding enal as starting material. Indeed,
the enal can be easily obtained by an aldolic condensation, as a
person skilled in the art knows well.
[0037] Therefore, another object of the present invention is an
invention's process, as defined above, further comprising the step
of generating in situ the compound of formula (II) starting from
the corresponding enal of formula 5
[0038] wherein R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the same
meaning indicated above.
[0039] A process comprising the in situ generation of the compound
of formula (II) is particularly useful when the compound (II) is an
acetal or an acylal, the latter being a geminal dicarboxylate.
[0040] Now, when the compound of formula (II) is an acylal, we have
also noticed that the catalysts that are able to promote the
cyclization of the acylal are also useful to promote the conversion
of the enal into the corresponding acylal.
[0041] Therefore, another object of the present invention, and in
fact a particular embodiment of the above-mentioned process, is a
process for making an ester of formula (I), as defined above,
comprising the step of reacting, in the presence of a catalyst as
defined for the cyclization step, an enal of formula (III), as
defined above, with a carboxylic anhydride of formula
R.sup.7C(O)O(O)CR.sup.7, wherein R.sup.7, taken separately,
represents a R.sup.2 group as defined above or the R.sup.7, taken
together, represent a R group as defined above.
EXAMPLES
[0042] The invention will now be described in further detail by way
of the following examples, wherein the abbreviations have the usual
meaning in the art, the temperatures are indicated in degrees
centigrade (.degree. C.). The NMR spectral data were recorded in
CDCl.sub.3 at 400 MHz or 100 MHz for .sup.1H or .sup.13C,
respectively, the chemical displacements 8 are indicated in ppm
with respect to TMS as standard, and the coupling constants J are
expressed in Hz. All the abbreviations have the usual meaning in
the art.
Example 1
Cyclization of 2-alkylcinnamic aldehyde via the acylal
derivative
a) Preparation of 2-pentyl-1H-inden-1-yl acetate
[0043] 4.13 ml of a 0.25 M solution of FeCl.sub.3, 6H.sub.2O in
Ac.sub.2O (1.03 mmol) where diluted into Ac.sub.2O (30.2 g) and the
resulting solution was added dropwise during 1 hour to a stirred
solution of 2-pentylcinnamaldehyde (20 g, 99 mmol) in AcOH (18.5 g)
at reflux. After a further 2 hours at reflux the cooled mixture was
poured into a mixture of H.sub.2O and Et.sub.2O. Then, solid
Na.sub.2CO.sub.3 (44.7 g) was added portionwise to the stirred
mixture. After one hour stirring the aqueous phase was saturated
with NaCl and extracted with Et.sub.2O. The organic layers were
dried over anhydrous Na.sub.2SO.sub.4, and the solvent evaporated
to afford a crude product, which was further purified by
distillation in vacuum to give the desired compound
(yield=87%).
[0044] B.p. 86-93.degree./0.05 mbar
[0045] .sup.1H-NMR: 0.90 (br.t, J=7, 3H); 1.35 (4H); 1.58 (m, 2H);
2.17 (s, 3H); 2.29 (m, 2H); 6.21 (s, 1H); 6.43 (s, 1H); 7.09 (dd,
J=7, J=7, 1H); 7.13 (d, J=7, 1H); 7.23 (m, 1H); 7.37 (d, J=7,
1H)
[0046] .sup.13C-NMR: 171.4(s); 149.2(s); 143.7(s); 142.0(s);
128.9(d); 128.2(d); 125.1(d); 124.2(d); 120.4(d); 77.5(d); 31.6(t);
28.2(t); 27.7(t); 22.5(t); 21.1(q); 14.0(q)
b) Preparation of 2-hexyl-1H-inden-1-yl acetate
[0047] Using the same experimental procedure as under a),
2-hexylcinnamaldehyde (20 g, 92.6 mmol), FeCl.sub.3, 6H.sub.2O
(3.85 ml of a 0.25 M solution in Ac.sub.2O, 0.96 mmol), Ac.sub.2O
(28.3 g, 0.28 mol) in AcOH (17.4 g) were reacted together. After a
further 3 hours at reflux the cooled mixture was treated to the
same workup as before to provide the title compound (yield=83%)
[0048] B.p. 89-101.degree./0.035 mbar
[0049] .sup.1H-NMR: 0.89 (t, J=7, 3H); 1.25-1.40 (6H); 1.58(m, 2H);
2.17 (s, 3H); 2.29 (m, 2H); 6.21 (s, 1H); 6.43 (s, 1H); 7.09 (dd,
J=7, J=7, 1H); 7.13 (d, J=7, 1H); 7.22 (m, 1H); 7.36 (d, J=7,
1H)
[0050] .sup.13C-NMR: 171.4(s); 149.3(s); 143.7(s); 142.0(s);
128.9(d); 128.2(d); 125.1(d); 124.2(d); 120.4(d); 77.5(d); 31.7(t);
29.1(t); 28.3(t); 28.0(t); 22.6(t); 21.1(q); 14.1(q)
c) Preparation of 2-methyl-1H-inden-1-yl acetate
[0051] Using the same experimental procedure as under a),
2-methylcinnamaldehyde (21 g, 0.14 mol) in AcOH (27 g),
FeCl.sub.3-6H.sub.2O (6 ml of a 0.25 M solution in Ac.sub.2O, 1.5
mmol) in Ac.sub.2O (53 g) were reacted together. After a further 2
hours at reflux the cooled mixture was treated to the same workup
and purification as before to provide the title compound
(yield=70%)
[0052] B.p. 70-95.degree./0.04 mbar.
[0053] .sup.1H-NMR: 1.98 (s, 3H); 2.18 (s, 3H); 6.15 (s, 1H); 6.41
(s, 1H); 7.09 (dd, J=7, 7, 1H); 7.12 (d, J=7, 1H); 7.23 (m, 1H);
7.37 (d, J=7, 1H)
[0054] .sup.13C-NMR: 171.5(s); 144.4(s); 143.7(s); 142.1(s);
129.3(d); 128.9(d); 125.1(d); 124.2(d); 120.3(d); 78.4(d); 21.1
(q); 14.0(q)
Example 2
a) Preparation of 1-methoxy-2-methyl-1H-indene via cyclization of
the acetal
[0055] A solution of FeCl.sub.3 anhydrous (42 mg, 0.25 mmol) in
BuOAc (4 ml) was added dropwise during 10 minutes to a stirred
solution of the 3,3-dimethoxy-2-methyl-1-phenyl-1-propene (5 g,
24.7 mmol) in BuOAc (13 ml) at 123.degree. C. After 3 hours the
cooled mixture was diluted with Et.sub.2O (50 ml) and washed with
saturated aqueous NaHCO.sub.3 and brine. Extraction, drying over
anhydrous Na.sub.2SO.sub.4, concentration and fractional
distillation in vacuum gave a crude product that was further
purified by chromatography (SiO.sub.2, cyclohexane/AcOEt 95:5 then
AcOEt/Et.sub.2O 1:1). There was thus obtained the title compound
with a yield of 33%.
[0056] B.p. 32-43.degree. 0.07 mbar
[0057] .sup.1H-NMR: 2.03 (s, 3H); 3.03 (s, 2H); 4.85 (s, 1H); 6.44
(s, 1H); 7.09 (dd, J=7, J=7, 1H); 7.11 (d, J=7, 1H); 7.22 (m, 1H)
7.41 (d, J=7, 1H)
[0058] .sup.13C-NMR: 145.9(s); 143.9(s); 141.8(s); 128.7(d);
128.4(d); 124.6(d); 123.7(d); 120.1(d); 84.9(d); 51.8(q);
14.1(q)
b) Preparation of 2-methyl-1H-inden-1-yl acetate via cyclization of
the acylal
[0059] A solution of FeCl.sub.3 anhydrous (21 mg, 0.125 mmol) in
BuOAc (2 ml) was added dropwise during 5 minutes to a stirred
solution of the 2-methyl-3-phenyl-2-propenylidene diacetate (3.1 g,
12.5 mmol) in BuOAc (8 ml) at 123.degree.. After 2 h at 123.degree.
the reaction was stopped and worked-up as above. Chromatography
(SiO.sub.2, cyclohex/AcOEt 9:1) of the crude product allowed the
isolation of the title acetate (62% yield). Identical spectra as
previously described.
Example 3
Synthesis of 2,6-dimethyl-1H-inden-1-yl acetate from the
corresponding aldehyde
[0060] A solution of (2E)-2-methyl-3-(4-methylphenyl)-2-propenal
(100.0 g, 0.62 mol) in cyclohexane (300.0 g) was added dropwise in
2 hours to a stirred solution of zinc chloride (3.1 g, 22 mmol) in
acetic anhydride (188.4 g, 1.85 mol) at 80.degree. C. The reaction
mixture was stirred further at 80.degree. C. for 18 hours and then
cooled to 25.degree. C. The mixture was washed twice with water
(100.0 g) and a 5% aqueous solution of sodium carbonate (100.0 g)
and concentrated under reduced pressure. The crude product was
flash-distilled (B.p.: 75-90.degree. C./0.1 mbar) affording 88.5 g
of the desired acetate (69%) as a yellow liquid (purity: 97.1%
GC).
[0061] .sup.1H-NMR: 7.19 (s, H); 7.03 (d, J=7.9, H); 6.99 (d,
J=7.9, H); 6.37 (s, H); 6.11 (s, H); 2.31 (s, 3H); 2.17 (s, 3H);
1.95 (s, 3H).
[0062] .sup.13C-NMR: 171.5 (s); 143.3 (s); 142.3 (s); 141.0 (s);
134.8 (s); 143.3 (s); 129.2 (d); 125.2 (d); 120.0 (d); 78.4 (d);
21.3 (q); 21.1 (q); 14.0 (q).
Example 4
Synthesis of 2,6-dimethyl-1H-inden-1-yl acetate from the
corresponding aldehyde
[0063] General Procedure
[0064] A solution of (2E)-2-methyl-3-(4-methylphenyl)-2-propenal
(100.0 g, 0.62 mol) in acetic anhydride (100.0 g) was added
dropwise in 2 hours to a stirred solution of the catalyst in acetic
anhydride (88.4 g, 1.85 mol in total) at 80.degree. C. The reaction
mixture was stirred further at 80.degree. C. until the complete
conversion of the starting material and then cooled to 25.degree.
C. The mixture was diluted with methyl tert-butyl ether (300.0 g),
washed successively with water (twice 100.0 g) and a 5% aqueous
solution of sodium carbonate-(100.0 g) and concentrated under
reduced pressure. The crude product was flash-distilled (B.p.:
75-90.degree. C./0.1 mbar) affording the desired acetate as a
yellow liquid.
[0065] The results obtained are listed in the following table:
1 Catalyst Reaction time Isolated yield H.sub.3PO.sub.4 (0.072 eq.)
22 h. 51% BF.sub.3.OEt.sub.2 (0.036 eq.) 19 h. 37% ZnBr.sub.2
(0.036 eq.) 5 h. 55% eq. = molar equivalents in respect to the
starting material h = hours
Example 5
Synthesis of 1-ethoxy-2-butyl-1H-indene from the corresponding
aldehyde
[0066] A mixture of 2-butylcinnamic aldehyde (5 g, 26.7 mmol.),
triethyl orthoformate (5.9 g, 40 mmol.), absolute ethanol (10 g,
217 mmol.) and Amberlyst.RTM. 15 (0.52 g) was heated at reflux
(85.degree. C. oil bath). After three days, the mixture was
filtered and concentrated under vacuum. The residue % as subjected
to silica gel flash chromatography (hexane/ethyl acetate 98:2),
yielding 3.8 g (17.6 mmol., 66% yield) of the indenyl ethyl
ether.
[0067] .sup.1H-NMR: 0.95 (t, J=7.4, 3H), 1.15 (t, J=6.9, 3H),
1.46-1.36 (m, 2H), 1.70-1.50 (m, 2H), 2.45-2.30 (m, 2H), 3.27-3.15
(m, 2H), 4.95 (s, 1H), 6.41 (s, 1H), 7.1 (t, J=7.2, 1H), 7.13 (d,
J=7.2, 1H), 7.21 (t, J=7.2, 1H), 7.42 (d, J=7.2, 1H).
[0068] .sup.13C-NMR: 14.0 (q), 15.7 (q), 22.7 (t), 28.1 (t), 30.5
(t), 60.0 (t), 83.4 (d), 120.2 (d), 123.7(d), 124.6 (d), 126.9 (d),
128.3 (d), 142.5 (s), 143.6 (s), 151.3 (s).
* * * * *