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Aza [18]annulenes.

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bullvalenes with two equal substituents. For such bullvalenes
one can formulate twelve positional isomers, i. e. four each
of the 1,2-, 1,3-, and 1 , 4 - i ~ o r n e r s [ ~The
, ~ ~ring
.
size in the
macrocyclic moiety of the "breathing" crown ethers ( I ) and
(2) varies between the limiting values 11 and 13 and 20
and 22, respectively.
Q,
R
R
(31, R
(4), R
is), R
(6), R
= Br
= CN
= CHO
= CHzOH
ticularly strongly dependent upon temperature are the
resonance signals of the bullvalene protons and, in the case
of ( I ) , (2), and ( 6 ) , also those of the protons of the methylene
groups attached to the bullvalene system. In contrast to all
other substituents the CH20H-, CH20CH3-, and CH20Acgroups display no pronounced preference for definite positions
at the bullvalene skeleton['! This finding, together with the
ring size (which, according to model considerations, is sufficiently large for 'the macrocyclic moiety in ( I ) and (2)),
and the temperature-dependence of the 'H-NMR spectra are
convincing enough reasons for us to describe ( 1 ) and (2)
as "breathing" crown ethers''].
A study of the temperature-dependent 'H-NMR spectra
of ( I ) and (2) in the presence of alkali-metal ions would
be interesting. We presume that (2 ), in particular, is capable
of adapting itself to cations of various sizes.
Received: December 29, 1978 [Z 180a IE]
German version: Angew. Chem. 91, 331 (1979)
The syntheses of (1) and (2) follow the conventional routes
used for the preparation of crown
The key compound
is bullvalenedimethanol (6). Reaction of dibromobullvalene
(3)15] with sodium dicyanocuprate[61 in dimethylformamide
in the molar ratio 1 : 2.4, followed by extraction with ether
and chromatography on silica gel (ether/pentane 3 : 2) afforded
the dinitrile ( 4 ) . Reduction of ( 4 ) with 2.2 equivalents of
diisobutylaluminum hydride in toluene at 40°C led to formation of ( 5 ) in almost quantitative yield. Reduction of (5)
with a suspension of 0.56 equivalents of LiAIH4 in ether
at -4O"C, hydrolysis at -25°C and chromatography on
silica gel (ether) generated bullvalenedimethanol ( 6 ) .
(6) is allowed to react with 1.0 equivalent of diethylene
glycol ditosylate and 2.2 equivalents of NaH in dimethyl
sulfoxide (DMSO) (4 days at 40°C). Extraction with dichloromethane and chromatography on silica gel (ethyl acetate)
led to ( I ) . The crown ether (2) was obtained analogously
by reaction of ( 6 ) with pentaethylene glycol ditosylate.
W uon E. Doering, W R . Roth, Tetrahedron 19, 715 (1963).
First indications on the expected properties of macrocycles with annelated
bullvalene groups, see J . F. M . Oth, R. M e r h y i , H . Rottele, G . Schroder,
Chem. Ber. 100, 3538 (1967).
G. Schroder, J . F . M . Oth, Angew. Chem. 79, 458 (1967): Angew. Chem.
Int. Ed. Engl. 6, 414 (1967).
C. J . Pedersen, J. Am. Chem. SOC.89, 2495 (1967): see e.g. D. J . Cram,
J . M . Cram, Acc. Chem. Res. 1 1 , 8 (1978); D. A . Laidler. J . F . Stoddart,
J. Chem. SOC.Chem. Commun. 1977, 481; W Hain, R . Lehnert, H .
Rottele, G . Schroder, Tetrahedron Lett. 1978, 625.
J . F. M . Oth, R . Merbnyi, G . Engel, G . Schroder, Tetrahedron Lett.
1966, 3377.
L. A . Paquette, G. H . Birnberg, J. Org. Chem. 40, 1709 (1975).
G. Schroder, H . Focke, J . F. M . Oth, Tetrahedron Lett. 1975, 2403.
Our argument is as follows: the inductive effect of these three groups
is virtually zero and therefore similar to the case of hydrogen.
In this connection, the relatively rapid mixing process of the proton
resonance signals of the bullvalenedicarboxylic anhydride should be
mentioned. Because of the size of the anhydride ring the exchange
process can only involve 1,2- and no 1,3- or 1,4-positional isomers:
E . Vogel, 19: Grimme, W Meckel, H . J . Riebel, J . F . M . Oth, Angew.
Chem. 78, 599 (1966); Angew. Chem. Int. Ed. Engl. 5, 590 (1966).
Table 1. Physical data of compounds ( I ) , ( 2 ) , ( 4 ) , ( 5 ) , and (6).
(1 ):colorless crystals, m.p. 84°C (from ether/pentane); yield 9 % ; 'H-NMR
(160"C, [D,]-DMSO): 6=4.18 (br. s, XH, bullvalene-H), 3.91 (s, 4H, methylene-H), 3.60 (m, XH, ethylene-H); 'H-NMR (-4O"C, CD2CI2): 6=5.85
(narrow m, 4.3H, olef, H), 4.35-2.92 (m of many narrow bands of differing
intensity, 12H, methylene- and ethylene-H), 2.78 (m, 0.9 H, aliph. bullvalene-H),
2.19 (m, 2.8H, aliph. bullvalene-H); IR (KBr): 3030, 2940-2840, 1650cm-';
UV (methanol): 1.=230nm ( ~ = 3 8 0 0 )
( 2 ) : colorless, highly viscous oil, b. p. 1 10"C/10-3 tom; yield 20 %; 'H-NMR
(120"C, [D6]-DMSO): 6=4.18 (br. s, XH, bullvalene-H), 3.83 (s, 4H, methylene-H), 3.58 (s, 2OH, ethylene-H); 'H-NMR (-4O"C, CDzCIz): 6=5.85
(m,4.5H,olef.H),4.40-3.80(m,4H,methylene-H),
3.58(m,20H,ethylene-H),
2.65 (m, 0.8H, aliph. bullvalene-H), 2.20 (m, 2.7H, aliph. bullvalene-H); IR
(film): 3020, 2860, 1630 cm-'; UV (methanol): 1=230nm (&=3500)
( 4 ) : colorless needles, m. p. 134°C (from ether); yield 45 %; 'H-NMR (120"C,
ID,]-DMSO): 6=4.68 (br. s); 'H-NMR (-3O"C, CD2C12): 6=7.20-6.65
(m, 2H, olef. H), 6.35-5.70 (m, 2H, olef. H), 3.05-2.40 (m, 4H, aliph.
(&=6300), 255
H); IR (KBr): 2200, 1615cm-'; UV (methanol): i.,,,=245
sh nm (5600)
( 5 ) : colorless crystals, m.p. 119°C (from toluene); 'H-NMR (120"C, [D6]DMSO): 6=9.13 (s, 2H, aldehyde-H), 4.80 (br. s, 8 H, bullvalene-H); 'H-NMR
(-3O"C, CD2C12):6=9.30 (s, 0.3H, aldehyde-H), 9.10 (s, 1.7H, aldehyde-HI,
7.02-6.68 (m,2H,olef. H), 6.15-5.55 (m, 2H, olef. H), 4.16 (split d, J=XHz,
0.6H, aliph. H), 3.50 (m, 0.6H, aliph. H), 2.95-2.50 (m, 2.8H, aliph. H);
IR (KBr): 3010, 1670, 1625 cm-'
( 6 ) : colorless oil, b.p. 100"C/10-3 tom; yield 92 % based on 1 4 ) ; 'H-NMR
(120"C, [D6]-DMSO): 6=4.25 (s, 10H, bullvalene-H and OH), 3.78 (s, 4H,
methylene-H): 'H-NMR (-40°C, CD2CIZ):6=5.83 (m, 4 S H , olef. H), 4.82
(br. s, 2H, OH), 4.25-3.56 (5 overlapping pseudo-s of differing intensity,
4H, methylene-H), 2.65-1.90 (m, 3.5H, aliph. bullvalene-H); IR (film): 3300,
3010, 2900, 2850, 1630 cm-': UV (methanol): i = 2 3 0 n m (&=3200).
Aza [1 8 ] a n n u l e n e s [ * * I
By Walter Gilb and Gerhard Schroder"]
Dedicated to Professor Horst Pommer on the occasion of his
60th birthday
Higher membered monocyclic vinylogs of pyridine with
(4n 2) x-electrons were hitherto unknown. It may, however,
be expected-as previously assumed[']-that the range of
validity of the Huckel rule in these compounds and in the
carbocyclic annulenes is very similar.
Vigel et aLL21and Muchowski et
recently described
bridged aza[lO]annulenes. We now report on the synthesis
and properties of the aza[l8]annulene (1). The key step is
the photolysis of the tetracyclic azide (8 ).
+
(3), R = COOH
( 4 ) , R = CON3
( S j , R = N=C=O
::
(6), R = NH-C-NHz
Yo Q
(7), R = N--C-NHz
(8). R
N3
I*]
Like precursors (3) to (6), the crown ethers ( I ) and (2)
show temperature-dependent 'H-NMR spectra (Table 1).Par-
312
Prof. Dr. G. Schroder, DipLChem. W. Gilb
Institut fur Organische Chemie der Universitat
Richard-Willstatter-Allee 2, D-7500 Karlsruhe 1 (Germany)
[**I This work was supported by BASF AG, Ludwigshafen.
Aiigew. Chem. I n t . Ed. Engl. 18 ( 1 9 7 9 ) No. 4
0 Verlag Chemie, GmbH, 6940 Weinheim, 1979
0570-083~~/79/'0404-0312
$ 02.5(110
Reaction of the 2:2 dimer of cyclooctatetraene with diazoacetic ester in the presence of copper powder furnishes four
isomeric monoadducts, of which (2) is the major product[41.
The carboxylic acid (3)[4] is allowed to react firstly with
triethylamine and ethyl chloroformate and then with aqueous
sodium azide solution to give the acid azide ( 4 ) (95%). Its
transformation into the azide (8) proceeds analogously to
the synthesis of cyclopropyl azide from cyclopropanecarbonyl
azideU5'.Heating of ( 4 ) in benzene for 2h leads to the isocyanate ( 5 ) (96 %), which is converted via the urea derivative
(6) (94 %, ether solution and NH3) into the N-nitrosourea
(7) (not isolated; with N Z 0 4in ether). Reaction of (7) with
lithium azide in methanol, followed by column chromatography ( S O 2 , pentane/ether= 19: 1) affords (8) as a colorless
oil [25 % based on ( 6 ) ] .
Irradiation of (8) at - 80°C in pentane (5 x
M) with
a mercury low-pressure lamp yields, after concentration of
the pentane phase and column chromatography (SiOz, pentane/ether = 19: 1) of the liquid residue, dark-green crystalline
aza[l8]annulene ( I ) (28 %) (see Table 1).
Table 1. Physical data of the compounds (1 ), ( 4 ) , (S), (6), ( 8 ) , ( 9 ) * ( 1 0 ) .
( 1 ): black-green needles, m. p. z 200°C (dec., from pentane); 'H-NMR (28"C,
CDC13): 6= -1.84 (m, 5H,), 8.86 (m, iOH,), 10.05 (d, J=5.2Hz, 2H0=2H,);
UV (dioxane): i,,,=276
(~=7400),329 (sh, 20200), 349 (sh, 43000), 374
(140000), 410 (sh, 11400), 467 (11400), 611 (720), 682 nm (580); IR (CHC13):
3005, 1310, 950 c m - '
( 4 ) : m.p. 74°C (dec.); 'H-NMR (CDCla): 6 ~ 1 . 2 5(m, 1H), 2.20 (m, 3H),
3.40 (m, 3H), 5.20-6.30 (m, 10H); UV (dioxane): i = 2 2 7 n m (sh, c = 1600);
IR (CHCI3): 2140, 1690 cm-'
( 5 ) : yellowish oil, 'H-NMR (CDC13): 6=1.73 (m, 2H), 2.28 (m, 1 H), 3.38
(m, 4H), 5.12-6.16 (m, 10H); UV (dioxane): 1=260nm (sh, c=3250); IR
(CCI,): 2255cm-'
( 6 ) : m. p. 213°C (dec., From dioxane); 'H-NMR (CDCl3): 6=1.78 (m, 2H),
2.25 (d of a t, 5 ~ 4 . 2and 1.0Hz, 1 H), 3.46 (m, 4H), 4.62 (br. s, 2H, NH?),
4.77 (br. s, 1 H, NH), 5.45-6.05 (m. 10H); U V (dioxane): E.=249nm (sh,
1:=2100); IR (KBr): 3480, 3180, 1674cm-'
( 8 ) : colorless oil, 'H-NMR (CDC13): 6=1.69 (m, 2H), 2.56 (m, 2H),
3.42 (m, 3H), 5.13-6.40 (m, 10H); UV (methanol): i = 2 5 1 nm (sh, r:=4000);
IR (CHC13):2090cm-'
( 9 ) + / 1 0 ) : violet-black crystals, m.p. z 180°C (dec.); 'H-NMR ([D],dimethylformamide, - 50°C): 6= -4.24 (m, 5Hi), -3.60 (pseudo-t, J = 12 Hz,
0.8HJ. -0.81 (br. s , 0.1-0.2H, inner NH), 9.76-10.71 (m, lOH,), 10.90
(dd. J=12.6 and 5.5Hz, 0.8HO=0.8H,), 11.49 (dd, J=13.5 and 6.5Hz, 0.4
Ho=0.4 H,), 19.0 (br. s, ca. 0.8 H, exterior NH)
__
- ____
-
The 'H-NMR spectrum confirms the structure of ( I ) . The
difference between the resonance signals for the 5 inner (Hi)
and 12 outer protons (H,) is ca. 11 ppm. Like [18]ann~lene[~]
the molecule is strongly diatropic. The doublet of the two
outer protons arises from the protons in the a-position to
the nitrogen. The couplingconstant proves the cis arrangement
of H , and Hg; the nitrogen thus occupies an internal position
in the aza[l8]annulene. The 'H-NMR spectrum of ( I ) is
practically temperature-independent. (1 ) thus behaves like
1,2-disubstituted [I 8lannulene~~~I.
gen chloride derivative which is stable at room temperature
in the absence of moisture (see Table 1).
The lower the temperature the more structured are the
two broad singlets around 6 = -0.81 and 19.0 in the 'H-NMR
spectrum of the hydrogen chloride derivative. On irradiation
at the frequency of these signals the double doublets at 6 = 11.49
and 10.90each change to one doublet with J = 6.5 and 12.6 Hz,
respectively. D 2 0addition leads to the same result; in addition
the two broad singlets disappear. The coupling constant
J = 6.5 Hz corresponds to a cis-, that of J = 12.6 Hz to a transrelationship between H, and Hg. The 'H-NMR spectrum
thus provides proof of the structure of the aza[l8]annulenium
ions (9) and ( l o ) , which presumably are present in equilibrium with each other (1.4 mixture). Addition of NH3 at
- 50°C leads to deprotonation. A 'H-NMR spectrum
recorded immediately thereafter at this temperature revealed
the presence of only ( I ). Apparently the conjugate base of
(10) rapidly isomerizes to the more stable (I).
Received: December 29, 1978 [Z 180b IE]
German version: Angew. Chem. 91, 332 (1979)
CAS Registry numbers:
( I ) , 69622-60-2; ( 2 ) , 42339-87-7; (3), 42339-91-3; (4). 69622-61-3; ( 5 ) ,
69622-62-4; (61, 69622-63-5; ( 7 ) , 69622-64-6; (8) (isomer A), 69622-65-7;
( 8 ) (isomer B), 69684-56-6; ( 9 ) , 69622-66-8
[I] G . Schriider, Pure Appl. Chem. 44,925 (1975).
[2] M . Schafer-Ridder, A . Wagner, M. Schwamborn, H . Schreinrr, E . Deurout,
E . Vogel, Angew. Chem. 90, 894 (1978); Angew. Chem. Int. Ed. Engl.
17, 853 (1978).
[3] H:J. Gdiz, J . M . Muchowski, M. L. Maddox, Angew. Chem. 90, 896
(1978); Angew. Chem. Int. Ed. Engl. 17, 855 (1978); Note added i n
proof. see also W J . Lipo, H . 7:Cruxford, P. C . Radlick, G . K . Helmkamp,
J . Org. Chem. 43, 3813 (1978).
[4] P. HiIdenbrand, G . Plinke, J. F. M . Oth, G . Schrdder, Chem. Ber. 1 I I ,
107 (1978).
[5] W Kirmsr, H . Schiitte, Chem. Ber. 101, 1674 (1968).
161 R. Woiousky, E. P . Woo, F . Sondheimer, Tetrahedron 26, 2133 (1970).
[7] R. Neuberg, J. F . M. Oth, G . Schrdder, Justus Liebigs Ann. Chem.
1978. 1368.
The Double Salt Na2S205.NaOOCH as Intermediate
in the Formation of Sodium Dithionite by Reduction
of SO2 with Sodium Formate
By Gert Ertl, Volker Kiener, Werner Ostertag, and Gerd
Wunsch"]
Dedicated to Professor Horst Pommer on the occasion of his
60th birthday
Sodium dithionite is of importance in vat dyeing and in
bleaching. One method of industrial production consists in
the reduction of sulfur dioxide by formate in aqueous methanol[' -31:
NaOH
+ 2 S 0 2 + NaOOCH -+
Na2S204
+ COz + H 2 0
Little has been reported on the mechanism of this reaction
which proceeds in a three-phase system (solid, liquid, gaseous).
Yoshio et a/. assumed the intermediacy of Na2S205.HCOOH
in the dithionite formation processi2! We were unable to
detect this compound, but found instead that the reaction
proceeds via the isolable double salt Na2S205.NaOOCH.
Our experiments were conducted in the following way:
all the NaOH and half the amount of NaOOCH required
--__
Feeding dry hydrogen chloride into an etheral solution
of (I ) leads to precipitation of a black-violet crystalline hydroAngew. Chem. Ifzt. Ed. Engl. I8 ( I 979)
p] Dr. G. Ertl, Dr. V. Kiener, Dr. W. Ostertag, Dr. G. Wunsch
Hauptlaboratorium der BASF AG
D-6700 Ludwigshafen (Germany)
No. 4
IC Vwlaa Chemie, GmbH, 6940 Weiriheim, 1979
313
0570-0833/7910404-0313 $ 02.50/0
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