1,4-Addition of lithium organyls to para-quinols / structure determination of 2,6-Di-tert-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1-one

Article abstract of DOI:10.1515/znb-1996-0314

Addition of lithium organyls to sterically hindered para-quinols leads to 1,2-or 1,4-adducts. The 1,4-addition prevails, if the 4-substituents in the quinol and the organic group in the lithium organyl are large. Four 1,4-addition products (2-cyclohex-2-en-1-ones) are synthesized and their structures investigated by NMR spectroscopy. The aryl groups at C-4 and C-5 acquire equatorial positions, the alkyl group at C-6 is bisectional. These results are confirmed by X-ray analysis of 2,6-di-tert-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1-one, revealing a twist boat conformation of the cyclohexene ring.

Full text of DOI:10.1515/znb-1996-0314

1,4-Addition of Lithium Organyls to /?ara-Quinols / Structure Determination
of 2,6-Di-te/t-butyl-4-hydroxy-4,5-diphenyIcyclohex-2-en-l-one
Gerhard Henesa, Anton Rieker*,a, Markus Neumayerb, Wolfgang Hiller*,b
Institute for Organic Chemistry, University of Tübingen, Auf der Morgenstelle 18,
D-72076 Tübingen
b Institute for Inorganic Chemistry, Technical University of Munich, Lichtenbergstr. 4,
D-85747 Garching
Z. Naturforsch. 51 b, 381-387 (1996); received August 11, 1995
Crystal Structure, Quinol, 1,4-Addition, Lithium Organyl, Cyclohex-2-en-l-ones
Addition of lithium organyls to sterically hindered para-quinols leads to 1,2- or 1,4-adducts.
The 1,4-addition prevails, if the 4-substituents in the quinol and the organic group in the lithium
organyl are large. Four 1,4-addition products (2-cyclohex-2-en-l-ones) are synthesized and
their structures investigated by NMR spectroscopy. The aryl groups at C-4 and C-5 acquire
equatorial positions, the alkyl group at C-6 is bisectional. These results are confirmed by X-
ray analysis of 2,6-di-terr-butyl-4-hydroxy-4,5-diphenylcyclohex-2-en-1-one, revealing a twist
boat conformation of the cyclohexene ring.
Introduction
conditions [1 - 6]. The reaction sequence generally
is in the order 2 - ^ 4 —> 6 ^ 7 or 2 —> 6 ^ 7 . The
step 4 —>6 can also be performed thermally without
acid [3]. Meantime, similar observations have been
reported by other authors [7 -1 0 ].
In this paper, we wish to discuss the factors deter-
mining the ratio of 1,2:1,4-addition and to confirm
the structure and configuration of the 1,4-addition
products.
We have reported earlier that /?«ra-quinols 1 add
lithium-organic compounds (2.0 - 2.5 equivalents,
di-/7-butyl-ether, 60 - 120 °C) to give mainly 1,2-
addition products 2 (6 - 92%), besides 1,4-addition
products
[1 - 6]. With 1.0 equivalent of lithium-organic com-
pounds or potassium tert-butylate quinones are
3 (4-20%) and oxepins 4 (up to 20%)
5
obtained via base-catalyzed acyloin rearrangement
of the quinolate anions (53 - 100%) [4].
1.2- vs 1,4-Addition
Influence o f the substituents R and R l
It is expected that the 1,2-addition to the sterically
hindered carbonyl group in 1 depends on the steric
requirements of the group R 1of the lithium organyl.
If we use the small MeLi, steric effects in the
quinol 1 should not play a decisive role, i. e. 1,2-
addition to the carbonyl group should not be at a dis-
advantage with respect to the 1,4-addition. Indeed,
after alcaline hydrolysis of the reaction mixture, the
1.2-adducts 2 (R 1=Me) are isolated in 84-92% yield
[3, 6]. With larger groups in the lithium organyls
(phenyl, 4-tolyl, 3-tolyl) the yields of 1,2-adducts
2 are smaller (generally 45-60%) [3 - 6], and the
1,4-adducts are formed as byproducts (8-13%) (see
Table I); with 2-tolyl- or mesityllithium neither pri-
mary 1,2- nor 1,4-adducts could be obtained; the
structure of the reaction products has not yet been
determined.
The 1,2-addition products 2 can be transformed
by acid either into the oxepins 4 , the ortho-cyclo-
hexadienones 6 or the phenols 7, depending on
the amount of acid present and on the reaction
* Reprint requests to these authors.
0939-5075/96/0300-0381 $ 06.00 (c) 1996 Verlag der Zeitschrift für Naturforschung. All rights reserved.
K
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382
G. Henes et al. • 1,4-Addition of Lithium Organyls to para-Quinols
Table I. 2,6-Di-f£rf-butyl-4-hydroxy-4-R-5-R'-cyclohex-2-en-l-ones 3
No
R
R1
m. p.
[°C]
Yield
[%]
1H NMR Spectra (<5ppm)
/Bu R1
R
=CH
6.56
H5/H6 [J = 7-8 Hz]
3.08/2.75
OH
a
b
c
d
Me
169
206
15
0.84a 1.18 7.25 - 7.42
1.27
0.82b
1.24
c 6h 5
1.40
Me
12
4-MeC6H4
c 6h 5
1.17 7.10 - 7.18C 6.47
2.32
3.02/2.71
1.40(br)
1.24
fBu
118-119 20d, 66e 0.87b
— 7.18 - 7.33c—
6.28
3.49/2.65
1.25
4f
c 6h 5
148
0.86b
1.30
c 6h 5
— 6.97 - 7.26g— 6.79
3.35/2.90
2.03
J 60 MHz, CDCI3; b 400 MHz, CDCI3; c broad multiplet; d 0.16 molar CöHs-Li; in addition 46% 2c (R = fBu,
R1 = CftHs);e 0.56 molar CöHj-Li; in addition 9% 2c (R = fBu, R1 = CöHs); 1 in addition 48% 2d (R = R1 = CöHs);
g multiplet, partly broadened.
In addition, the size of the substituent R in 4-
position of the quinol is of influence. Large groups
R, as phenyl or fm -butyl, shield the carbon atom 5
of the ring more than a methyl group. Thus, under
comparable conditions, the yields of the 1,4-adducts
are highest with R = Me (12-15%, see Table I).
In the reaction of quinol la (1: R = Me) with 4-
tolyllithium in addition to 3b (3: R = Me, R 1 =
4-Tolyl) the exomethylene adduct 8 is formed in
8% yield, presumably by dehydration of the corre-
sponding 1,2-adduct.
If only 1.5 equivalents of phenyllithium are used
to react with Id (1: R = C6H5) at 37°C in diethylether
for 12 h, the initially formed lithium salt of Id pro-
duces about 47% of the quinone 5 via acyloin rear-
rangement. In addition, 44% of 2,4-diphenyl-6-ferf-
butylphenol 7d(7: R = R' ^C öH s) are also obtained
after acidic hydrolysis, due to acid-catalyzed rear-
rangement of the 1,2-adduct 2d (2: R = R 1 = C6H5)
[4]. In agreement with this assumption, the same
compound 5 is formed, if Id (R = CöH^) is treated
with 1.5 equivalents of methyllithium under other-
wise identical conditions. The quinone 5 can also
be obtained by photolysis of Id (1: R = CöHs) [5],
where the mechanism, however, must be different.
Influence o f the concentration o f R 1Li
The relative amount of 1,2:1,4-addition depends
also on the actual concentration of the lithium or-
ganyl. Thus, the reaction of lc (1: R = fBu) and Id
(1: R = C6H5) with 0.16 M phenyllithium (2.5 equiv-
alents) in di-/2-butylether at 60°C produces after 4h
46% 2c (2: R = fBu, R 1 = C6H5)/20% 3c (3: R = fBu,
R 1 = C6H5) and 48% 2d (2: R = R 1 = C6H5)/4% 3d
(3: R = R 1 = C6H5), respectively. With a 0.56 M
phenyllithium solution (again 2.5 equivalents), the
yields starting with lc are 9% 2c/66% 3c.
The given molarities of phenyllithium refer to
the situation at the beginning of the experiment,
immediately after mixing the solution of 1 in di-n-
butylether with phenyllithium in diethylether. Due
to evaporation of some of the diethylether and use-
up of the reagent, the concentration will vary with
time. The results are probably due to steric effects,
Structure of the Reaction Products
The structure of the 1,2-adducts 2, the oxepins
4 and cyclohexadienones 6 has already been dis-
cussed [3]. The 1,4-adducts 3 are isomers of 2,
as shown by elemental analysis and mass spectro-
metry. In the IR spectra, there is an OH-absorption
between 3440 and 3550 cm -1 which is character-
istic of a non-hindered OH-group. In addition, a
carbonyl-absorption at 1654-1670 cm -1 excludes a
diol-structure. In the 'H NMR spectra the absorp-
tion of two tert-butyl groups (6 = 0.82-0.87 and
1.24-1.30 ppm), of an olefinic proton (6 = 6.28-6.79
ppm) and an OH-group (6 = 1.24-2.03 ppm) is in
agreement with structure 3. The tert-butyl signal at
low field must be attributed to the tert-butyl group
since phenyllithium is more strongly associated at at the alkene carbon C-3, the one at higher field
higher concentrations, corresponding to a larger
“size”, favoring the 1,4-addition [11, 12].
belongs to the group at C-6. In addition, AB type
spectra of the two vicinal aliphatic protons H'' and
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383
G. Henes et al. ■1,4-Addition of Lithium Organyls to /?ara-Quinols
H6 (J = 7-8 Hz) are also observed. For the related
compound 9, obtained by reduction of Id (1: R =
C6H5) with NaBH4 in methanol [13], iH6/H5e - 4.2
Hz, ^h6/H5a - 13.5 Hz. As a consequence, both pro-
tons in 3 must be arranged axially.
The H5-signal is shifted to lower field (3.02 -
3.49 ppm) by the paramagnetic anisotropy of the
5-aryl ring. The high-field shift of the signal of H6
(2.65-2.90 ppm) may be explained by a diamag-
netic anisotropic effect of the neighbouring car-
bonyl group which seems to overcompensate the
inductive effect of that group. From 2D-NMR spec-
tra it can be seen that the shifts of C-5 (6 = 46-54
ppm) and C-6 (<§ = 60-64 ppm) follow the opposite
order. The assignment of H5/H 6 is further supported
by the fact that the doublet of H5 is somewhat broad-
ened. Actually, one would expect an additional cou-
pling of H3 with H5. Such a coupling (J = 2.2 Hz)
is observed in the compound 9, however, only with
the equatorial H3e. This again supports the above
assumption that in 3d H5 is in axial position.
Fig. 1. Plot of molecule 3d along with the atomic num-
bering scheme. The ellipsoids represent 50% probability.
A v ab is diminished (from both sides) and is small-
est for 3a and 3b (R = Me). Apparently, the large
substituent 4-rBu in 3c not only causes the above
mentioned twisting of the 5-aryl ring but also an in-
tramolecular van-der-Waals interaction with proton
H5, responsible for an additional low-field shift of
the A signal. If 4-rBu is replaced by the smaller Me
group, the van-der-Waals repulsion is diminished
and, simultaneously, the 5-aryl ring is less twisted
with respect to the cyclohexene ring. Both effects
cause a high-field shift of the H5-signal and a low-
field shift of the signal of H6 (smaller diamagnetic
anisotropy effect of 5-aryl), in agreement with the
1H NMR spectra.
The total configuration of the 1,4-adducts 3 can-
not definitely be determined by 1H NMR. Accord-
ing to Dreiding models, there are at least twelve
possible arrangements, eight of them can be ex-
cluded for steric reasons, two are ruled out due to
the size of the dihedral angle. The two stereoiso-
mers I and II remain from these considerations as
the most probable ones.
The rotation of the 5-aryl ring is hindered, as can
be seen from dynamic NMR effects (line broaden-
ing, coalescene) at room temperature for the ortho-
and m^ta-protons and carbon atoms of the ring, de-
pending on the frequency (60, 250,400 MHz) used.
The activation barriers were not determined quanti-
tatively. Comparison of the spectra of 3c - d, how-
ever, reveals that the barrier is highest with 3c. This
result agrees well with the above considerations.
In order to prove the structural conclusions defi-
nitely, the crystal structure of 3d (R = R 1 = C6H5)
was determined. The compound 3d crystallizes in
the monoclinic space group P2]/c with 4 molecules
in the unit cell. It is present as the racemic form due
to the centrosymmetric space group.
9
I
3
II
For 3c with a large group R (R = tBu), the most
probable configuration will be I: the 6-tert-buty\
group as well as R and R 1 are arranged equatori-
ally. Moreover, the 5-aryl ring is “perpendicular”
with respect to the cyclohexene ring and thus ar-
ranged symmetrically between the adjacent tert-
butyl groups. Hence, the 'H NM R signals of 4-rBu
and 6-rBu practically coincide even at 400 MHz (in
the l3C NMR spectra their signals are separated by
14 Hz at 100 MHz), which would not be expected
for configuration II. With a configuration similar to
I it is also possible to explain the characteristic trend
of zAz/ab of HVH6 in 3a - d (R is an aryl ring in each
case). The largest difference is observed with 3c,
/. e. for a large R (= rBu). With decreasing size of R,
The cyclohexenone ring exhibits the twist boat
conformation 2T4 [14] confirmed by the pucker-
ing parameters
<P = 199.6° [15] and the endocyclic torsion an-
gles (see Fig. 2). In the parent cyclohexene
Q
=
56.3 pm,
0
= 79.5° and
a
twisted half-chair conformation [16] was observed.
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G. Henes et al. ■1,4-Addition of Lithium Organyls to /?ara-Quinols
01
(temperature 200 - 300°C), ionisation energy 70 eV. -
TLC was performed on silica gel HF254,346 (Merck) - For
column chromatography silica gel Merck (0.05-0.20 mm)
was used as adsorbent. The petroleum ether used had bp.
50 - 70°C.
Phenyllithium was prepared from bromobenzene and
Li in ether [20]: 0.2 mol batches in 200 ml ether gave 0.9 -
1.0 M solutions. 2-, 3-, 4-Tolyllithium were obtained from
Li and the corresponding bromo-toluene in ether; 1 mol
batches gave 0.6 - 0.7 M solutions.
General methodfor the preparation of2,6-di-tert-butyl-l-
R1-4-R-cyclohexa-2,5-dien-l,4-diols (2) and 2,6-di-tert-
butyl-4-hydroxy-4-R-5-R' -cyclohex-2-en-1 -ones (3)
2.5
Equivalents of the lithiumorganyl in ether were
added, drop by drop, to 3.0 g of the 2,6-di-rm-butyl-4-
R-4-hydroxy-cyclohexa-2,5-dien-l-one 1 {para-quinol)
in 50 ml of di-fl-butylether with stirring under N2-
atmosphere at 60°C. After 4 h of stirring at this temper-
ature, the solvent was evaporated in vacuo. The residue
was dissolved in a small amount of methanol, treated
with saturated aqueous NH4CI solution until a pH of 8
was reached, and cooled to 0 - 5°C. The reaction products
were filtered off or extracted with ether and recrystallized
from petroleum ether or methanol.
The deviation of the conformation of 3d can
be explained by steric effects, since the simi-
lar but less-hindered 2,4,5,6-tetramethyl-4,5,6-tri-
nitro-cyclohex-2-en-1 -one [17] still shows a slightly
twisted half-chair arrangement. The aryl groups at
C-4 and C-5 in 3d are in equatorial positions, the
alkyl group at C-6 is bisectional [18]. An interest-
ing aspect for the interpretation of the NMR spectra
are the dihedral angles [19] H 5-C 5-C 6-H 6 with
-150.6° and C 17-C 5-C 6-H 6 with -32.70°. From
the dihedral angle of ca. -151° a coupling constant
7H5H6 between 7 and 11 Hz can be derived from
the Karplus curve, which agrees well with the value
of 7-8 Hz found experimentally. Furthermore, in-
termolecular H-bonds 0 2 -H 2 - 0 1 ' are observed
with a distance 02- - 0 1 ' of 298 pm and an angle
02-H 2- • 0 1 ’of 152.8° (see Fig. 3).
2.6-Di-tert-butyl-4-hydroxy-4-methyl-3-phenyl-cyclo-
hex-5-en-l-one (3a)
3.0 g (13 mmol) of para-quinol la (R = Me), treated
with 2.5 equivalents of phenyllithium as described above,
gave 0.4 g (13%) of 3a, colorless needles, m. p. 169 -
170°C. - IR (KBr): 3550/3460 cm’ 1 (OH), 2950 (rBu),
1668 (C=0).
C21H30O2 (314.4)
Calcd C 80.21 H 9.62%,
Found C 80.07 H 9.82%.
Experimental Part
General:
2.6-Di-tert-butyl-4-hydroxy-4-methyl-3-(4-tolyl)-
cyclohex-5-en-1 -one (3b) and 2,6-di-tert-butyl-l-
(4-tolyl)-4-exomethylene-cyclohexa-2,5-diene (8)
IR spectra were obtained with a Perkin-Elmer 21 spec-
trometer. - NMR spectra were performed with Varian
A-60 (60 MHz), Bruker AC 250 (250 MHz) and WM 400
(400 MHz) spectrometers using TMS as standard. Mass
spectra were recorded with a MS9 of AEI. direct insert
2.0 g (8 mmol) of para-quinol la (R = Me), treated
with 2.5 equivalents of 4-tolyllithium as described above.
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G. Henes et al. • 1,4-Addition of Lithium Qrganyls to /7ara-Quinols
385
Table II. Crystal data and structure refinement for 3d.
gave an oil, which lead to 0.35 g (12%) of 3b after re-
crystallization from petroleum ether, m. p. 206°C. - IR
(KBr): 3550 cm' 1 (OH), 2960 (/Bu), 1667 (C=0). - MS
(70 eV), m/e = 328 (M+). - 13C NMR (C D C I3, 62.9 MHz):
6 = 20.98 (Me), 29.07 (C-/Bu), 29.37 (Me), 29.91 (C-
rBu), 34.77 (C-rBu), 35.63 (C-/Bu), 51.21 (C-5), 60.87
(C-6), 68.27 (C-4), 129.10 (C-Ar), 129.0 - 130.0 (br, C-
Ar), 136.42 (C-Ar), 138.43 (C-Ar), 142.38 (C-3), 152.38
(C-2), 203.84 (C-l).
Empirical formula
Formula weight
Temperature
C26H31O1
376.52
293(2)K
71.073 pm
Wavelength
Crystal system
Space group
monoclinic
P2i/c
Unit cell dimensions
a = 1147.0(1) pm, ct = 90°
b = 1826.0(1) pm,
0 = 115.19(1)°
c= 1182.8(1) pm, 7 = 90°
2.2417(3) nm
4
C22H32O2 (328.5)
Calcd C 80.44 H 9.82%,
Found C 80.49 H 9.75%.
Volume
Z
From the mother liquor, a second fraction was ob-
tained: 0.2 g (8%) 8, m. p. 148-149 °C (from petroleum
ether). - IR (KBr): 3450 cm“ 1 (OH), 2950 (?Bu), 1650
(=CH2). - MS (70 eV), m/e = 310 (M+).
Density (calculated)
Absorption coefficient 0.069 mm-1
F(000)
Crystal size
6 Range for data
collection
1.116 g/cm3
816
0.25 x 0.20 x 0.07 mm
C22H30O (310.5)
3 to 23°
Calcd C 85.11 H 9.74%,
Found C 84.78 H 9.88%.
Index ranges
0 < h < 12, 0 < k < 20,
-12 < / < 11
3263
Reflections collected
Independent reflections 3092 (Rm = 0.0340)
2.4.6-Tri-tert-butyI-4-hydroxy-3-phenyl-cyclohex-5-en-
1-one (3c)
Reflections observed
Refinement method
Data, parameters
Goodness-of-fit
Final R indices
1352
Full-matrix least-squares on F2
3091,261
1.044
a) 40.3 g (145 mmol) of para-quinol lb (R = fBu) in
1.4 1of di-n-butylether were treated with 2.5 equivalents
of phenyllithium in ether as described above (molarity of
phenyllithium: 0.16). The reaction product was dissolved
in methanol, whereupon 10.2 g (20%) of 3c deposited as
crystals, m. p. 118 - 119°C (from methanol). - IR (KBr):
3440 cm“ 1 (OH), 2950 (/Bu), 1670 (C=0). - MS (70 eV),
m/e = 356 (M+). - l3C NMR(CDC13, 100.6 MHz): 6 =
R 1= 0.0470, wR2 = 0.1046
[F0 > 4cr(F„)]
R indices (all data)
Extinction coefficient
Largest diff. peak,
hole
R\ =0.1967, wR2 = 0.1413
0.006(2)
187 e x nm' 3
-164 e x nm-3
25.57
(C-rBu), 29.33 (C-rBu), 29.47 (C-rBu), 34.38 (C-
phenyllithium in ether as described above to give 1.7 g (45
%) 2d, m. p. 166 °C (from petroleum ether); for analytical
data see ref. [3], The mother liquor of 2d was evaporated.
The resulting light brown syrup was chromatographed
(silica gel, petroleum ether). Elution (solvent in paren-
thesis) gave the following fractions: 1 + 2 (petroleum
ether): biphenyl (yield ca. 5 % of the applied phenyl-
lithium); 2-4 (petroleum ether:benzene = 10:1.5): 1.39 g
(46%) 2-rm-butyl-4,6-diphenylphenol (7d); 5 (petroleum
ether:benzene = 3:7): 151 mg (4 %) 3d, m. p. 116 °C. -
IR (KBr): 3500 cm' 1 (OH), 2950 (/Bu), 1654 (C=0). -
MS (m/e): 376 (M+). - ,3C NMR (CDC13, 100.6 MHz):
6 = 28.94 (C-rBu), 29.93 (C-rBu), 35.07 (C-rBu), 35.88
(C-rBu), 53.96 (C-5), 59.89 (C-6), 73.09 (C-4), 125.27
(C-Ar), 126.32 (C-Ar), 126.82 (C-Ar), 127.50 (C-Ar),
127.76 (C-Ar), 130.0 (br, C-Ar), 139.98 (C-Ar), 143.13
(C-3), 146.63 (C-Ar), 153.46 (C-2), 203.46 (C-l).
rBu), 35.08 (C-rBu), 41.34 (C-rBu), 45.80 (C-5), 63.51
(C-6), 74.45 (C-4), 126.72 (C-Ar), 127.83 (br, C-Ar),
128.11 (br, C-Ar), 128.79 (br, C-Ar), 132.24 (br, C-Ar),
138.66(C-3), 144.65 (C-Ar), 151.14(C-6),204.34(C-1).
C24H36O2 (356.5)
Calcd C 80.85 H 10.18%,
Found C 80.90 H 10.11 %.
The mother liquor of 3c was evaporated and the residue
crystallized from petroleum ether to give 23.0 g (45%) of
2c (R = R1 = fBu); for the analytical data see ref. [3].
b) If the reaction was performed in 200 ml of di-n-
butylether (molarity of phenyllithium: 0.56), but all other
conditions identical as under a), the yields were: 34.0 g
(66%) 3c and 4.7 g (9%) 2c.
2.6-Di-tert-butyl-4-hydroxy-4,5-diphenyl-cyclohex-5-en-
1-one(3d)
C26H32O2 (376.5)
3.0 g (10 mmol) of para-quinol lc (R = Phenyl) in 50
ml of di-n-butylether were treated with 2.5 equivalents of
Calcd C 82.94 H 8.57%,
Found C 82.65 H 8.69%.
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G. Henes et al. ■1,4-Addition of Lithium Organyls to /?«ra-Quinols
386
Table III. Atomic coordinates [x 104] and equivalent Table IV. Selected bond lengths [pm] and angles [°]for 3d.
isotropic displacement parameters [pm: x 10"'] for 3d.
U(eq) is defined as one third of the trace of the orthogo-
nalized U,, tensor.
0(1)-C(1)
C(l)-C(2)
C(2)-C(3)
C(3)-C(4)
C(4)-C( 11)
C(5)-C( 17)
122.7(4) 0(2)-C(4)
148.5(5) C( 1)-C(6)
132.8(5) C(2)-C(7)
144.2(4)
151.7(5)
152.4(5)
156.6(4)
154.8(4)
157.3(5)
x/a
U(eq)
Atom
y/b
z/c
C(4)-C(5)
C(5)-C(6)
149.5(5)
152.0(5)
4361(2)
6787(2)
5275(4)
5056(4)
5941(4)
7121(3)
7680(3)
6638(3)
3804(4)
3213(4)
2832(4)
4006(5)
8123(3)
8482(4)
9433(4)
10047(4)
9683(4)
8734(4)
8898(4)
10097(4)
11219(4)
11155(5)
9967(5)
8856(4)
6848(4)
8249(4)
5957(5)
6600(4)
4597(1)
3917(1)
4171(2)
3385(2)
3088(2)
3476(2)
3949(2)
4448(2)
2996(2)
3282(3)
3131(2)
2174(2)
2933(2)
2352(2)
1869(2)
1964(2)
2528(2)
3005(2)
4334(2)
4044(2)
4367(3)
4997(3)
5288(2)
4967(2)
4604(2)
4857(2)
5223(2)
3924(2)
776(2)
- 569(2)
1116(3)
763(3)
459(3)
537(3)
1757(3)
1859(3)
546(4)
1408(4)
-819(4)
733(6)
59(1)
55(1)
48(1)
47(1)
54(1)
43(1)
44(1)
46(1)
62(1)
92(2)
88(2)
127(2)
43(1)
52(1)
62(1)
64(1)
61(1)
49(1)
47(1)
59(1)
70(1)
74(1)
71(1)
57(1)
55(1)
78(1)
92(2)
74(1)
0(1)
0(2)
C(l)
C(2)
C(3)
C(4)
C(5)
C(6)
151.9(5) C(6)-C(23)
0(1)-C(1)-C(2) 120.1(4) 0(1)-C(1)-C(6) 120.3(3)
0(2)-C(4)-C(3) 108.9(3) 0(2)-C(4)-C(5) 111.9(3)
0(2)-C(4)-C(l 1) 105.6(3) C(l)-C(2)-C(3)
C( 1)-C(2)-C(7) 122.2(4)
C(l)-C(6)-C(5)
C(2)-C(l)-C(6) 119.6(3) C(2)-C(3)-C(4)
C(3)-C(2)-C(7) 122.5(4) C(3)-C(4)-C(5) 108.9(3)
C(3)-C(4)-C( 11) 110.9(3)
C(6)-C(5)-C(4) 111.7(3)
114.4(4)
113.5(3)
124.5(4)
C(7)
C(8)
C(9)
110.5(3)
C(5)-C(4)-C(l 1)
C(10)
C (ll)
C( 12)
C(13)
C( 14)
C(15)
C( 16)
C( 17)
C(18)
C( 19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
data were collected with 9/n? scan. During the exposure
time of 56 h no significant loss of intensity was observed.
The structure was solved by direct methods, which
revealed the positions of all non-H atoms. The refinement
with unique merged data, reflections with F > 4 cr(F) and
isotropic displacement factors led to an R-value of R1
= 0.122. The final least squares refinement (on F2) with
anisotropic displacement parameters for all non-H atoms,
positions of the H atoms as riding model with SHELXL-
93 defaults, converged to R values of R 1= 0.047 and wR2
= 0.1046.
Calculations were performed with the programs CAD-
SHEL [21], SIR92 [22], SHELXL-93 [23], SHELXTL-
PLUS package [24] and PLATON-94 [15]. A summary of
the crystal data, data-collection and structure-refinement
parameters is given in Table II. Final atomic coordinates
are listed in Table III, selected bond distances and angles
in Table IV. A graphic representation of the molecule is
given in Fig. 1, the shape of the six-membered cyclohex-
ene ring in Fig. 2. In Fig. 3 the intermolecular H-bridges
are shown [25].
532(3)
1376(3)
1434(4)
664(4)
- 183(4)
-232(3)
1868(3)
2608(4)
2692(4)
2032(4)
1287(4)
1209(4)
3241(3)
4014(4)
3263(4)
3849(4)
Crystal structure determination of 3d
All X-ray investigations were performed on an au-
tomated four-circle diffractometer CAD4-T (ENRAF-
NONIUS, Delft) with graphite-monochromated MoKa-
radiation at room temperature. A colorless single crystal
of approximate dimensions 0.25 x 0.20 x 0.07 mm was
mounted on a glass fibre. The lattice parameters were
determined by refinement of the diffraction geometry of
100 precisely centered high-angle reflections. Intensity
Ackknowledgement
We thank the Deutsche Forschungsgemeinschaft,
Fonds der Chemischen Industrie, and Hewlett-Packard
for their support.
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via free access