close

Вход

Забыли?

вход по аккаунту

?

The First Clamped and Strongly Deformed Adamantane.

код для вставкиСкачать
l-Butyl-2,3,4-tri-terr-butyl-l,3,2,4-diazadiboretidine,4. Compound 1
(0.80 g) and butyl azide (0.39 g) were combined in 10 mL of pentane at 0 "C and
the resulting solution was stirred for 30 min at room temperature. Distillative
workup gave 4 (0.70 g, 65%) as a colorless liquid at 70 'C/O.Ol Torr.
size and shape of cyclophanes and host compounds. Comparison of the angles in adamantane and benzene (Scheme 1)
shows that the bridgehead bonds in 1,3-position, like the
m-phenylene bonds, form an angle of ca. 120".
Received: April 17, 1990 [Z 3912 IE]
German version: Angew. Chem 102 (1990) 910
CAS Registry numbers:
1, 109976-00-3; 2, 128270-57-5; 3, 128270-58-6; 4, 128270-59-7; Fe(CO),.
13463-40.6.
111 R. Boese, B. Krockert, P. Paetzold, Chem. Ber. 120 (1987) 1913.
[2] 2: NMR (CDCI,; 25°C; 60 MHz/TMS ('H), 32.08 MHz/Et,O. BF, ("B),
67.88MHz/TMS (I3C)): 6('H) = 0.72, 1.12, 1.29 (3s. 1 : l : l ; 3tBu);
=)28.7, 28.9, 30.8 (3 q ; Me of 3 tBu),
6("B) = 28.4, 48.1 (2 s, 1 : 1); c ~ ( ' ~ C
53.5 (s; C1 of NrBu); the two expectedly broad BC-' ,C singlets could not be
found. MS (70eV): m / z 470 (Me, 68%), 413 (Me - C,H,, 70), 357
(Me - C,H9 - C,H,, SO), 301 (Ma - CaH9- 2C4H8,100).
[3) Single crystals of 2 were obtained from pentane; a = 9.3161(18),
b = 9.666(2), C = 10.7385(17)A, z = 69.941(14), j3 = 80.517(13), 7 =
62.474(13)", V = 805.5(2) A3, 2 = 1, eCalcd
= 0.969 g cm-,, PI (No. 2);
crystal dimensions 0.12 x 0.25 x 0.13 mm3; T = 155 K; measuring range
3 < 2 8 I 4 5 " ; 2113 unique reflections, 1323 observed with F, 2 4.0 o ( F J ;
anisotropic temperature factors for the non-hydrogen atoms; 181 refined
parameters R = 0.071, R, = 0.070. Further details of the crystal structure
investigation my be obtained from the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH.
D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository
number CSD-320105, the names of the authors, and the journal citation.
[4] P. Paetzold, Adv. Inorg. Chem. 3 f (1987) 123.
[5] A. Pelter, K. Smith, H. C. Brown: Borane Reagents, Academic Press, London 1988, p. 239.
[6] 3:NMR(cf.[Z]):&('H) =0.99, 1.06, 1.14(3s, 1:1:1;3tBu);d(iiB) =37.0,
46.3 (2 s. 111); 6(',C) = 28.5, 29.0, 32.3 (3 q; Me of 3 rBu), 55.3 (s; CI of
NrBu), 146.5 (s; BCN); further BC-13C singlets were not observed.
MS (70eV): m / z 470 (Ma, 96%). 413 (Ma - C,H,, 70). 357
(Ma - C,H9 - C4H8,50), 301 (Me - C4H9- 2 C,H8, 100).
17) Single crystals of 3 were obtained from pentane; a = 8.164(2),
b = 19.250(5), c = 10.190(5)A, j3 = 109.39(3)", V = 1510.6A3, 2 = 2,
ecllsd= 1.033 g ern-,, P2Jc (No. 14); crystal dimensions 0 . 1 2 ~ 0 . 1 4 ~
0.21 mm3; T = 103 K; measuring range 3 9 2 8 2 44'; 1861 unique reflections, 1348 observed with F, 5 40(F); anisotropic temperature factors for
the non-hydrogen atoms; 190 refined parameters, R = 0.05, R, = 0.063.
For further details, see [3], CSD-320104.
[8] 4: NMR (Cf. [2]): 6(lH) = 0.80 - 1.20 (4H; C-CH,-CH,C of Bu), 0.89 (t,
3H; CH3 of Bu), 1.06 (s, 18H; 2 BrBu), 1.21 (s, 9 H ; NrBu), 2.99 (t. 2 H ;
NCH,);b("B) = 42.7;6(13C) = 14.3(q;C40fBu),20.5(t;C3ofBu),29.4
(4; C2 of BtBu), 34.4 (4; C2 of NtBu), 37.4 (t; C2 of Bu), 42.7 (t; C1 of Bu),
48.8 (s; C1 of NrBu); the BC-"C singlet was not found. MS: m / z 278 (Me,
39%), 263 (Me - CH,, loo), 235 ( M e - C,H,, 71), 221 (Me - C4H9,
36).
[9] P. Paetzold, E. Schroder, G. Schmid, R. Boese, Chem. Ber. 118 (1985) 3205;
P. Paetzold, C. von Plotho, G. Schmid, R. Boese, B. Schrader, D. Bougeard,
U. Pfeiffer, R. Gleiter, W. Schafer, ibid. 117 (1984) 1089.
Scheme 1
The stereochemistry of the new hydrocarbon phane 1,
which we designed with this consideration in mind, was expected to be fundamentally different from that of the known
[2.2]metacyclophane2, since three intraannular Hi hydrogen
atoms project into the interior of the ten-membered ring.
2
1
The synthesis of 1 (m.p. 78-79.5") was accomplished via
the dithia[3.3]cyclophane route, starting from 1,3-bis(mercaptomethy1)benzene and 1,3-bis(bromomethyl)adamantane,"] to give dithia[3.3]phane 3 (40 % yield),''] followed by
sulfone pyrolysis (50 % yield)13' (Scheme 2).
Br
Br
L.4-
1
4
Scheme 2. a) High-dilution technique, 2 equiv. NaOH, EtOH/C6H6(4: l), 78 h
reflux, 12 h room temperature, 40%; b) HOAc, H,O, (30%), 5 h reflux, 65%;
c)
Torr, 550°C. 50%.
The First Clamped and Strongly Deformed
Adamantane **
B y Fritz VogtIe,* Joachim Dohm, and Kari Rissanen
Can benzene rings in strained macrocycles be replaced by
adamantane building blocks? If so, this would offer a general
approach to varying the lipophilicity, ring strain, and cavity
[*I Prof. Dr. F. Vogtle, DiplLChem. J. Dohm
Institut fur Organische Chemie und Biochemie der Universitlt
Gerhard-Domagk-Strasse 1
D-5300 Bonn 1 (FRG)
[**I
902
The "[2.2](1,3)adamantanometacyclophane" lL4I exhibits
an intense molecular peak in the mass spectrum ( m / z 266)
and characteristic 'H and I3C NMR spectra. The signals of
HI and HI' are strongly shifted upfield (6 = - 0.10 and
+ 0.06),r51 whereas Hi of the benzene ring absorbs at
6 =7.75. The signals of dithiaphane 3 and disulfone 4 are
even more strongly shifted upfield (up to 6 = - 2.18; cf.
Table 1).
Dr. Kari Rissanen
Department of Chemistry
University of Jyvaskyla
Kyllikinkatu 1 - 3
SF-40100 Jyvaskyla (Finnland)
This work was supported by the Deutsche Forschungsgemeinschaft (Sonderforschungsbereich 334: Interactions in Molecules), the Fonds der
Chemischen Industrie (doctoral fellowship for .f D.), and Bayer AG,
Leverkusen (donation of adamantane). We thank Dr. G. Eckhardr and C.
Schmidt for the EI mass spectra and NMR spectra, respectively.
0 VCH VerlagsgeselischaJi mbH. 0-6940 Weinheim. 1990
0570-0833/90/0808-0902 S 3.50+.25/0
3
5
Angew. Chem. Int. Ed. Engl. 29 (1990) No. 8
P
Table 1. ‘H NMR shifts of intraannular protons in 1, 3, and 4 as well as 5
and 2.
Compd
6 (H,)
6(H’,)
6 (H”,)
TVC]
1
1.15
3
4
5
7.63
1.67
7.43 [d]
-0.10
-0.18
-0.27
-0.07
-0.12
1.41
1.95
-0.18
>0.50
0.06
-0.04
0.29
0.27
0.50
-2.18
-1.12
-0.18
-1.33
2
4.25
25
25
126
25
116
25
25
25
-73.5
25
Solvent
A
[a] 200 MHz. [b] 90 MHz. [c] Cf. [2]. [d] 100 MHz, cf. [6]. [el 60 MHz, cf. [6].
The ’H N M R spectrum of 1 remains largely unchanged
even at 116 “C (90 MHz, [DJtoluene) and 126 “C (90 MHz,
C,D,Cl,); the AB splitting pattern of the signals of HI and
HI’ is merely transformed into an AM pattern, whereby the
signal of the more strongly shielded Hi’ is shifted to higher
field, that of the less shielded HI’ to lower field (cf. Table 1).
The increase in temperature apparently affects the interaction of the solvent with the aromatic system and thus influences the ring-current effect, which causes the opposite shifts
of the HI and HI’ signals. From these observations we conclude that 1 is conformationally rigid and is present in the
anti conformation.
Comparison of these findings with the ‘H N M R results
for the corresponding [7]metacycIophane 5,r61for which a
ring inversion has a barrier of only AGS = 48 kJ mol-’,
reveals that the conformational rigidity of adamantanophane 1 is remarkable. In contrast to 5, compound 1 has a
stiffened aliphatic “chain”. The two aliphatic bridges in 1
and 5 therefore differ strongly in their steric demands and, in
particular, in their interaction with the aromatic Hi proton.
The X-ray structure analysis reveals that, despite the
“spherical” adamantane moiety, 1 adopts the anti conformation (Fig. l), as observed for the [2.2]metacyclophane 2.1’3 ‘1
Fig. 1. Molecular structure of 1 (stereoview).
Fig. 2. Molecular structure of 1 (side view); the parts of the molecule in the
“back” are exactly covered by those 1n the front, since this allows the intraannular atoms (hatched) and the deformations to be optimally shown.
and 150.5, respectively. This is all the more remarkable, since
known adamantane compounds encumbered sterically with
substituents (e.g., biadamantane and biadamantylidene) are
much less deformed.[g]
The bond lengths and angles in the benzene ring of 1 are
more strongly distorted than in the [2.2]metacyclophane 2
(values in parentheses): for example, C18-CI9 141.6 pm
(138.2 pm), C17-Cl8 136.0 pm (138.7 pm), and C18-Cl9C20 116.4” (117.3”).Furthermore, the boat-shaped deformation of the benzene ring characteristic of the [2.2]metacyclophane is even more pronounced in 1 : C20 is displaced
by 16.7 pm (14.3 pm) and C17 by 7.4 pm (4.2 pm) from the
ring plane and the corresponding angles are 14.3” for C20
and 6.5” for C17 (11.9’ and 3S0, respectively, in 2)! Finally,
the CH,-CH, bridges (157.0 and 157.8 pm) are longer in 1
than in [2.2]metacyclophane (1 55.9 pm).
The increased strain in 1 (compared with 2) caused by the
adamantane moiety is thus compensated by deformation of
both the rigid adamantane and the benzene ring. According
to MM2(85) calculations, the strain energy of 1 is nearly a
factor of 2.5 higher than that of [2.2]metayclophane (2).[1°1
The investigation shows that the rigid adamantane framework can be significantly distorted by bridging; such distortion was previously not achieved by substitution with bulky
substituents. In addition, the study shows that it is possible
to replace benzene rings, even in strained ring compounds,
by adamantane units serving as “rigid” building blocks.
These findings open up new possibilities, especially within
phane chemistry, where arene units (benzene, naphthalene,
pyridine, thiophene, etc.) might be replaced by adamantane
and related hydrocarbons and heteropo1ycycles.r”.
Furthermore, transannular chemical reactions should be possible in these new “aliphane~”[~’
and might lead-as usual for
[2.2]phanes-to new polycyclic hydrocarbons hardly accessible via other routes.
Received: March 19, 1990 [Z 3862 IE]
German version: Angew. Chem. 102 (1990) 943
Especially striking is the strong distortion of the adamantane framework in 1. In order to reduce the steric interactions in the interior of the macrocycle, C11 is bent away from
the aromatic ring (distance C11-C20 278.6 pm, cf. Fig. 2),
resulting in a flattening of the cyclohexane chair of the
adamantane moiety and a decrease in the angles ClO-C3C11 and C8-C7-C11 to unusually smalI values (100.6” and
100.3”, respectively) for sp3 carbon atoms (normal value:
109.5”).At the same time, the adamantane bonds C7-C8 and
C3-C10 are lengthened to 154.8 and 154.5 pm, respectively,
whereas the bonds C5-C6 and C4-C5 are shortened to 150.8
Angew. Chem. Int. Ed. Engl. 29 (1990) No. 8
0 VCH
CAS Registry numbers:
1,128191-75-3;3, 128191-76.4; 4, 128191-77-5; 1 3bis(brornomethy1)adernantane, 1078-87-1; 1,l-bis(merceptomethyI)benzene,41563-69-3.
[l] a) S . Landa, Z. Kamycek, Collect. Czech. Chem. Commun. 24(1959) 1320;
b) an improved synthesis is described in [2].
[2] F. Vogtle, J. Dohm, M. Nieger, K. Rissanen, Chem. Ber., in press.
[31 a) F. Vogtle, L. Rossa, Angew. Chem. 91 (1979) 534; Angew. Chem. Int. Ed.
Engl. 18 (1979) 514.
[41 In a strict sense, the name “adamantanophane” is not in accord with phane
nomenclature, since, according to this name, the aliphatic adamantane is
treated as an “aromatic” unit. Although in violation of the rules, this name
is nonetheless useful because it is short and descriptive. For comparison.
Verlagsgesellschaft mbH, 0-6940 Weinherm, 1990
0570-0833/90~0808-0903
$3.50+ .25/0
903
pentacyclo[9.3.3.1.14.*.113. ‘6]eicosa-4,6.8(20)-triene(IUPAC name), pentacyclo[0.16.11.5.1 1.7.13-7.13,7.1 14]eicosane-10,12,14(20)-triene(nodal
nomenclature[l3]), [13~7.13~9.15~7][ll]metacyclophane
(usual phane
nomenclature[l4]), [2.2](1,3jadamantanometacyclophane (“araliphane”
name). For this reason, corresponding names of compounds (e.g.,
triquinacenophane[l5], cyclooctatetraenophane[16]) have already been
coined in the literature. I t seems reasonable to classify uraliphatic compounds such as I , 3, and 4 as “uraliphanes” and completely uliphatic phane
analogues as “uliphanes” (from uliphatic).
[5] Spectroscopic data for 1 (numbering shown in formula: ‘H NMR
(200 MHz, CD,CI,, TMS): 6 =7.75 ( s , 1 H ; 20-Hj; 7.20 (t, 3 J = 7 . 4 Hz,
1 H; 17-H); 6.96 (d, ’J=7.4 Hz, 2 H ; 16,18-H); 3.14, 2.65 (AB,
’J = 13.6 Hz, ’ J = 12.113.6 Hz, 4 H , 1-H,,,,,. 14-Hsx,eq),2.53, 1.29 (AB,
’J= 12.0 Hz,4H;4,6-H,,,4,6-H,);2.23(m,
1H;S-H); 1.98(m. 1H;9-H);
1.65 (tt. ’J= 3.2Hz, 4 J =1.0 Hz, 2H; 12-H); 1.41, 0.87 (AB,
’3 = 12.6 Hz, ’J = 12.013.6 Hz, 4 H ; 2-H.,,,,, 13-Hax!eq);
1.36 (m, 4 H ; 8H, 10-H); 0.06 (dt, ’J = 16.6 Hz, ‘J = 3.0 Hz, 1 H ; ll-HGq);- 0.10 (d,
’J = 16.6 Hz, 1 H; ll-HaJ. ”C NMR (50.32 MHz, CDCI ): 6 = 145 7
(C-15, C-19); 140.5 (C-20): 130.0 (C-17); 127.4 (C-18, C-12); 50.6 (C-8,
C-l0);42.6(C-2. C-13);41.1 (C-11); 39.2(C-l2); 37.3 (C-6.C-4); 32.3 (C-1,
C-14); 32.2 (C-9), 31.4 (C-3. C-7); 29.0 (C-5). The assignment was made by
H,H- and C,H-COSY, spin-echo, and IH{ ‘H) NOE difference NMR spectroscopy. MS (70 eV): mjr 266.2027 ( M a , 100%) (calcd 266.2028).
161 S . Hirano, H. Hara, T. Hiyama, S. Fujita, H. Nozaki, Tetrahedron 31
(1975) 2219.
[7] Crystal structure analysis of 1: monoclinic, space group P2Jc (No.
14); a = 1149.6(1). h = 1558.7(2), c = 916.7(1)pm, B = 112.30(1).; Y =
1519.713)~1 0 6 p m 3 ; Z= 4 ; ~= ~
1.164gcm-’;
~ , ~ ~
Mo,,(1 = 0.70930A);
p = 0.06 mm-’; F&)
= 584; T = 296 k 1 K , crystal dimensions,
0.20 x 0.18 x 0.24 mm; CAD4 diffractometer (Enraf-Nonius); corrections:
Lorentz polarization, linear 5 % decrease (corrected with factors 1.000 to
1.024011I); 2 8 = 4 - 50.; hklrange: h = - 13-12, k = - 1 8 4 , I = 0-10:
2179 measured, unique reflections, 1417 with I > 3.0 01. The structure was
solved using MULTAN (least-squares Fourier method). Refinement:
R = 0.045, R, = 0.055, non-hydrogen atoms refined anisotropically, H
atoms determined using the AF map and refined with fixed, isotropic
temperature factors (SDP and PLUTO programs). Further details of the
crystal structure investigations are available on request from the Director
of the Cambridge Crystallographic Data Centre. University Chemical
Laboratory, Lensfield Road, Cambridge CB2 1EW (UK), on quoting the
full journal citation.
(81 The dithiaphane 3 was also characterized by X-ray structure analysis: cf.
[21.
[9] a) S. C. Swen-Walstra, G. J. Visser, Chem. Commun. 197f, 82; b) R. A.
Alden, J. Kraut, T. G. Traylor, J Am. Chem. Soc. 90 (1968) 74: c) 0.
Ermer,ibid. 110(1988)3747;d)O.Ermer,C.-D.Bodecker,Chem.
Ber. 114
(1981) 652; e) M. A. Flamm-ter Meer, H.-D. Beckhaus, K. Peters, H.-G.
von Schnering, C. Ruchardt, ihid. ff8 (1985) 4665.
[lo] MM2(85)/MMP2 calculations (on an HP 9000/825S SRX) gave a 0 strain
energy of 217 kJ mol-’ for 1 and 85.5 kJ mol-’ for 2; semiempirical
calculations using AM1 (on a CONVEX C 220) gave an SCF standard
enthalpy of formation of 50.9 kJ mol-’ for 1 and 182 kJ mol-’ for 2. We
thank DipLChem. P.M . Windschef for the calculations. For strain energies of other small cyclophanes cf. F. Bickelhaupt, Pure Appl. Chem. 62
(1990) 373.
[ I l l This was further substantiated by our synthesis of macrocycles of type 6 ,
formally obtained by replacement of two benzene rings by adamantane
’’.
6 : R = H, C H j , CH2COOEt
units in hexa-m-phenylene[17]. The poor solubility of hexa-m-phenylene
was still exhibited even after incorporation of the adamantane framework.
The following macrocycles were identified by mass spectrometry: 6
(R = H): EI-MS, m/z calcd 636.3228, found 636.3259 (M”); 6 (R = CH,):
EI-MS, m/z 692 (M”); 6 (R=CH,COOC,H,): EI-MS, m/z 980 (M”).
[12] Unstrained macrocyclic polyethers containing an adamantane unit. A. A.
Chaikovskaya, T. N. Kudrya, A. M. Pinchuk, Zh. Org: Khim. 25 (1989)
2000.
[13] N. Lozac’h, A. L. Goodson, Angew. Chem. 96 (1984) 1; Angew. Chem. Int.
Ed. Engl. 23 (1984) 1.
[14] F. Vogtle, P. Neumann, Tetrahedron 26 (1970) 5847.
1151 W. P. Roberts, G. Shoham, Tetrahedron Lett. 22 (1981) 4895.
[16] L. A. Paquette, M. A. Kesselmayer, J Am. Chern. SOC.1 f 2 (1990) 1258.
117) H. A. Staab, F. Binning. Chem. Ber. 100 (1967) 293.
904
0 VCH
Verlugsgesdlschuff mbH, 0-6940 Weinheim, 1990
CsNa,(OH), * 6 H,O : Structural Differentiation
in the Hydrate of a Ternary Alkali-Metal
Hydroxide **
By Dietrich Mootz* and Heinz Riitter
Dedicated to Professor Dietrich Babel on the occasion
of his 60th birthday
The structures of most hydrates of the lighter alkali-metal
hydroxides were determined some time ago.[’*21 More recently, structural characterizations have also been carried
out for such compounds of the heavy alkali
as well
as for anhydrous ternary alkali hydroxides.[41 Hydrates,
however, of ternary alkali hydroxides, to our knowledge,
have so far not been subjected to crystal structure analysis.
Only one phase of this kind, to which the composition
CsOH . 2 NaOH .4H,O has been assigned, can be found in
the literature.[’] Our structure determinationt6] unmistakably shows that the compound in question, melting congruently at 46.5 “C, is a hexahydrate dominated in a characteristic way by differentiation between the cations of unequal size
as well as between the H,O molecules and the OH@ions.[71
In the crystal structure of CsNa,(OH), .6H,O the Nae
ions are coordinated by the six H,O molecules to form distorted octahedra (Na-0 distances between 2.275(3) and
2.688(3) A). The octahedra are linked by common faces to
form columns parallel to the crystallographic b axis. These
are arranged according to the pattern of closest packing of
cylindrical rods[’’ and connected with each other by a complex system of hydrogen bonds with the H,O molecules as
twofold proton donors and the OHe ions as fourfold
proton acceptors (0..‘ 0 distances between 2.633(4) and
2.798(4) A). Thus, each OHe ion bridges two octahedron
edges in adjacent columns. Each column, together with two
further ones and the associated OH@ ions, encloses in a
Fig. 1. Perspective drawing of the structure of CsNa,(OH), . 6H,O, projected
down the h axis (atomic thermal-vibration ellipsoids at the 25% probability
level, ORTEP plot[lO]). Ellipsoids without equators, OHe ions; ellipsoid with
equator, Cse ion; bold lines, hydrogen bonds. One sees the pseudotrigonal
arrangement of three columns of the face-linked Na(H,O), octahedra and,
between them and the bridging OHe ions, the large cavities containing the Cse
ions. For completion of the three small cavities another column each (not
shown in the figure) has to be added.
[*] Prof. Dr. D. Mootz, DipLChem. H. Rutter
Institut fur Anorganische Chemie und Strukturchemie der Universitat
Universitatsstrasse 1, D-4000 Dusseldorf (FRG)
[**I
This work was supported by the Minister fur Wissenschaft und Forschung
des Landes Nordrhein-Westfalen, the Fonds der Chemischen Industrie,
and the Dr. Jost Henkel-Stiftung. It is part of the doctoral dissertation in
progress of H. Riitfer, Universitdt Dusseldorf.
0570-0833/90j0808-0904$3.50+ .25/0
Angew. Chem. Int. Ed. Engl. 29 (1990) N o . 8
Документ
Категория
Без категории
Просмотров
2
Размер файла
380 Кб
Теги
deformed, clamped, first, strongly, adamantane
1/--страниц
Пожаловаться на содержимое документа