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Heterocyclic Systems with 12 -Electrons.

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Aromatic aliphatic ethers are also cleaved by ( I ) , although
in lower yield. Prolonged heating (24h) of ( 2 a ) , (2bJ, and
( Z c ) , respectively, with the reagent gives 48% phenol, 22"/;
o-cresol, and 40% 1-naphthol. Aliphatic ethers are stable under
these conditions. The reactions proceed after the manner of a
preferred "hardsoft" interaction, which also explains the
known cleavage of ethers with HI.
ane at room temperature afforded the 2-bromo-5-ethoxynaphtho[ 1,8-bc]thiolylium tetrafluoroborate (5 a ) as exceptionally
moisture-sensitive, black-red crystals (Table 1).
Procedure for ester cleavage
(
A mixture of an appropriate ester (5 mmol) and iodotrimethylsilane (2.0g, 10mmol) is heated td 100°C, with exclusion
of atmospheric moisture, for the time period specified in Table
1 . The cooled reaction mixture is diluted with ether (25ml),
washed with 0.5 N sodium hydroxide (2 x 30ml), the alkaline
sollitions are acidified and extracted with chloroform
(2 x 30 ml). The dried extracts give TLC-pure carboxylic acid
upon solvent removal.
(7)iI"
CHzCl
Ii5CZO
,
Received: September 20. 1976 [Z 568 IE]
German version: Angew. Chem. 8X. 847 (1976)
CAS Registry numbers:
( I ) . 16029-98-4; ( 2 0 ) . 100-66-3; ( l b / , 578-58-5; ( 2 c ) . 2216-69-5;
methyl benzoate, 93-58-3; methyl 2-bromobenzoate. 610-94-6;
methyl benzeneacetate. 101-41-7; methyl decanoate, 110-42-9:
methyl 2.2-dimethylpropanoate. 598-98-1 ; ethyl benzoate, 93-89-0;
ethyl benzeneacetate, 101-97-3; benzyl benzoate, 120-51-4;
benzyl cyclohexanecarboxylate, 22733-94-4: benzoic acid. 65-85-0
.-
E. fifscbrrn. and B. Lihrrrk, R O C ~Chem.
.
30. 323 (1956); F. Elsirigrr.
J . Schwihvr. and A. E S C ~ Y I I I I ~ OHelv.
S P ~ . Chim. Acta 43, I13 (1960).
T-L. Ho and C. M . W(ni~g.Synth. Commun. 5 . 305 (1975): cf. E. W
7lrorrro.s and T I. Cloivrll, J . Org. Chem. 37. 744 (1972).
J. C . Slrodrcrrr and G. D. D " w , Jr.. J. Org. Chem. 29, 2006 (1964);
P . A . Borrlefr and W S. Jolr~i.sori.Tetrahedron Lett. 1970, 4459: N.
K~ir~rhlirm
and A. Scott. J . Am. Chem. Soc. 96. 590 (1974); T - L. Ho
and C . M. Worig. Synth. Commun. 4. 307 (1974): 1 - L . H o . Synthesis
1974. 715: 1975, 510.
B . 0.Pro!.. L. H . Soriirwr. G. M . Goldhrr~g.C . 7: Krrr. P. A. DiCior(qio.
and F. C . Wlritrriore J. Am. Chem. SOC. 70. 433 (1948): U . Kriirrke,
Chem. Ber. 95, I74 (1962).
Heterocyclic Systems with 12 x-Electrons[**]
[I1
By Richard Nridleiri and Hartmut See/[*]
Dedicated to Professor Erich Hiickel 011 the occasion of his
80th birthday
Heterocyclic systems with 12 n-electrons which are iso-nelectronic with phenalenium ions were previously unknown.
We report here on the first representatives of this class of
compounds, uiz. the heterocyclic cations of type ( 5 ) .
Using the preparative route outlined in the scheme below
we obtained the orange 2-bromo-5H-naphtho[1,8-b~]thiophen-5-one ( 4 a ) from 3-(chloromethyl)-l-benzothiophene ( 1 ) l 2 ] ria the intermediates ( 2 ) and (3). Reaction of
( 4 a ) with triethyloxonium tetrafluoroborate in dichlorometh[*] Prof. Dr. R. Neidlein and Dr. H. See1
Pharmazeutisch-Chemisches lnstitut der UniversitPt
Im Neuenheimer Feld 364. D-6900 Heidelberg (Germany)
[**I Part I of Heterocyclic 12 n-and 14 rr-Systems.-This work was supported
by the Fonds der Chemischen Industrie and the Deutsche Forschungseemeinschaft.
Table I . Physical properties of compounds (41 and 1 5 ) .
(401: M.p. 163--164"C: 'H-NMR ICDCIj): 6=7.56ppm (d. Hj, J = IOHz).
6.66 (d, H+. J = I O H z ) . 8.14 (d Of d, Hh. J l l r t h r , = 8 H ~J,,,,,,=I
.
Hz). 7.60 (t.
H,. J = S H z ) , 7.96(d of d. H8. J ,,,,r,.=8Hz, J,,,,,.=I Hz): I R ( K B r ) : C=O
1625 cm-'. (CHCI.,): C=O 1635 c m - ' : U V ( C H 3 0 H ) : F.,,,=236nm
(& = 8640). 265 ( I 2 830). 275 ( I I 750). 369 ( I6 620).
(4h1: M.p. 137---138"C: 'H-NMR (CDCI,): 6=7.65ppm (d, H.3. J = IOHz),
6.55 (d. H4. J = I O H z ) , 8.13 (d of d. He, J ,,,,,,,,=7Hz. J",',m = I Hz). 7.47 (1.
H,).7.90(dofd. Ha.J,,,,,,,,=8Hz,J,,,,,,,=I Hz):IR (KBr):C=O 1635cm-I.
(CHCI,): 1630 c m - l : U V (CH,OH): ).,,,=388 nni (I:= 12630).
1 5 0 1 : 'H-NMR ( C D j C N ) : 6 = 1.68 ppm(t,CH,-. J = 7 Hz).4.78 Iq. -CH2--.
5=7Hz).7.5-8.8IH,. H4. Hh-He): UV(CH2C12):h,,,=434nm (&=9200).
( 5 h 1 : M.p. 160--162"C: 'H-NMR ICF,COOH): b = 1.67ppni (t. CH,--.
J = 7 Hz). 4.84 (q. -CHz-.
J = 7 Hz). 7.6--9.0 (CeHS-. Hj. Ha, H,--H,):
U V (CH2C12):h.,,=456nm (&= 12800).
- ~ . .
-
~~
( 5 a ) reacts with C- or N-nucleophiles in the presence of
Hunig basef3]to give compounds of type (6). With hydrazine
the violet azine ( 7 ) is formed.
Reaction of 2-phenyl-SH-naphtho[ 1,8-bc]thiophen-5-one
(4b)I4] with triethyloxonium tetrafluoroborate at 35 to 40°C
leads to the orange-red, very stable salt ( 5 b ) in 71 % yield.
This reacts with C- or N-nucleophiles in the presence of
Hunig base[31with elimination of the C z H s O group to give
products of type (8). The compounds ( 8 a ) and (8b) are
iso-n-electronic with phenafulvenes['] (Table 2).
775
Table 2 . Physical data or compounds ( 6 ) to (X).
~~
X
(6Cl)
(6h)
(61.)
(611)
(61,)
(b/)
(hl)
(6h)
(hi)
lhl, I
(61)
(6111)
1611)
Ih<iJ
(611
INCliC
pCH,--C,,H,-N
C,,Hs-N
/I-H;C>OZC-C,H,-N
p-CI-CbH,-N
I?-Br-C,>H,-N
p-NC-C,H,-N
p-O,N-C,H,-N
CoH5-CO-NH-N
3-Pyridyl-CO-NH-N
C,H5-CH-CO-NH-N
NC-CH2-CO-NH-N
C,,H,-NH-N
p-02N-C,,H4-NH-N
3.5-(02NI>C,H3-N H -N
17)
(Xtl)
(
x /I )
(X1.)
("1)
(NCIIC
2.4.6-Trioxopel.liydroI .3-diariti-5-ylidene
C,>HS--C'O-NH-N
1.4-lOrN)iC,H3-NH-N
M.p.
["CI
Yield
Color
249- -250
15X 159
55
18
17
34
4x
37
35
52
54
54
26
53
49
36
51
red
bright yellon
bright yellow
yellow
yellon
yellow
119
1x2
184
204
I84
203
237
226
201
128
134
234
280
130
279
266
256
270
[<'<>I
120
183
I85
205
I X5
204
238
127
202
229
135
235
28 I
yellow
Received: August 30. 1976 [Z 569 IE]
revised: October 4. 1976
German version: Angew. Chem. XX. XI0 11976)
CAS Registry numbers:
I / ). 3216-47-5: ( 2 1 , . 26461-80-3: / 3 ) , 10245-72-4: ( 4 ~ ) 60788-83-2:
.
(4h).
10245-71-3: f.511). 60788-85-4: ( 5 h ) . 60788-87-6. ( 6 ~ 0 .60788-88-7: ( f i b ) .
yellow
yellow
yellow
yellou
yellow
yellow
biolet
60788-894: ( 6 ~ 1 60788-90-1:
.
(611). 60788-91-2: ( h i , ) . 60788-92-3: ( 6 / ) .
60788-93-4: f/i<q).60788-94-5: ( f i l l ) , 60788-95-6: ( 6 ; ) . 60788-96-7: ( O X ) .
60788-974: ( 6 1 ) . 60788-9X-9: ( 6 i i i ) . 60788-99-0: (611). 60789-00-6: ( 6 t i ) .
60789-0 1-7: ( 6 /I 1.60789-02-8: f 7 1.60789-03-9: (<'t[f ).60789-04-0: ( X h ). 6078905- I : (XC.). 60789-06-1: ( X d ) . 60789-07-3: 2-bromo-3.4-dihydro-5-oxo-5Hnaplitho[I.H-h~~]thiophene. 10245-73-5: triethyloxoninm tetrafluoroborate.
368-39-X
\,lolet
132
39
16
\
167
257
271
96
black-red
red-ye1low
\w~let
79
92
Synthesis of ( X u ) : A mixture of ( 5 b ) (1 mmol) and monosodiomalononitrile ( I mmol) in anhydrous tetrahydrofuran
(10ml) is heated under reflux for 24 h. The solvent is removed
and the residue chromatographed with benzene an a column
packed with silica gel 60 (Merck). After removal of benzene
from the eluate ( X u ) is obtained in 16 x) yield.
lolet
red-violet
[I]
[2]
[3]
Esprriiiieiitd:
Synthesis of ( 3 ) : (2) is dissolved in 90'%, acetic acid (3.5
liters) and the solution warmed to 75°C. A solution of Br2
( I mol) in 90'%, acetic acid is then added dropwise and the
mixture stirred for 30min at 75°C. The cooled solution is
poured into 15 liters of water and the resulting precipitate
of (3) dried and recrystallized from methanol; yield 90
m.p. 116-1 17°C.
Synthesis of ( 4 u ) : A mixture of (3) (0.653mol) and S0Cl2
(640ml) is heated under reflux for I h. Excess SO2CI2 is
removed, the residue taken up in 4.18 liters anhydrous CH2C12
and the resulting solution cooled to - 10°C and treated portionwise with AIC13 (0.848mol). The mixture is stirred for
3 h at -5°C. treated with 60g N a 2 S 0 4 . 1 0 H 2 0 and stirred
for a further 4 h at -5°C. I t is then washed with H20.
three times with N a H C 0 3 solution, and the CH2C12 solution
finally dried over MgS04. After removal of CH2CI2the residue
(orange-yellow crystals) is recrystallized from acetic acid : yield
84 m.p. 108-1 10°C.0.0754mol of this substance is heated
under reflux for 3 h with 0.468 mol chloranil in 1.5 liters /cr'tbutanol. The reaction mixture is then filtered, the tert-butanol
removed, and the residue taken up in CHCI,; the resulting
solution is washed four times with H 2 0 , four times with
5 NaOH, a further two times with water, and finally dried
over MgS04. After removal of CH2CI2the remaining orange
crystals are recrystallized from acetic acid; yield 75
m.p.
163--164°C.
Synthesis of ( 5 u ) : A stirred solution of ( 4 u ) (1.89mmol)
in anhydrous dichloroethane is treated at 35-40°C with
1.89mmol triethyloxonium tetrafluoroborate. The resulting
deep ruby-red solution is stirred for 20min. cooled to O"C,
and treated with anhydrous ether, whereupon ( 5 u ) precipitates as a finely crystalline salt which is used immediately
in further reactions. Yield 70 to 80%.
Synthesis of ( 5 h ) : A stirred solution of (4h)14] (1.91 mmol)
in anhydrous dichloroethane (4ml) is treated at 35 to 40°C
with 1.91 mmol triethyloxonium tetrafluoroborate. After 1 h
aqueous ethanol is added, whereupon the orange-red salt
( 5 h ) precipitates. Yield 71 %, m.p. 160-162°C.
Synthesis of ( 6 a ) : CH2(CN)2(1.89mmol) is added to a
stirred solution of ( 5 u ) (1.89mmol) in anhydrous CH3CN
( I 0 ml) at room temperature. Hunig base (3.78 mmol) is added
to the mixture, which is stirred for 1 h and then allowed to
stand overnight at - 15°C. Red crystals.precipitate; yield 55%.
[4]
[5]
Based o n lectures by R . Nridiriii in Haifa. Hamburg, Heidelberg. Jerusalem. Rehovot. and Tel-Aviv.
E. Cmpmqiw and E. S. Nc&s. J. Heterocycl. Chem. 2, 231 11965): P.
Cqqmorir, Bull. Soc. Chim. Fr. l Y 4 Y . 382: F . F . B l i d r and G. S/irc,ts.
J. A m . Chem. Soc. 70. 3768 (1948): S. .4tdi1111, J . Mo.>\, and G. J
.Wor.fiil. ihrtl. 70. 3075 11948).
S. Hiitit</and E . i W / l . Justus Liebigs Ann. Chem. 732. 7'(1970).
D. G. H~~II~I/I(?~IIc
and Q . N . Ptwrrr.. Aust. J. Chem. / Y . 1909 (1966).
See C J . ~ S.
.
ffiiiiiq and E . W ~ J / /Justus
/.
Liebigs Ann. Chem. 732. 26
I19701.
Structure and Absolute Configuration of an Organo-Iron
Compound Having Iron as Chiral Center[']
'I<),
By M. George R e i ~ i i ~l r, m Beriia/, Hrnri Bruriner, and
Mui?fred Muschio/[*]
The absolute configurations are known of optically active
organo-Mo compounds with square pyramidal coordination
around the metal atom['] and of ferrocene derivative^'^] in
which the metal atom is not the chiral center. We now describe
the structure and absolute configuration of compound (1 ),
in which the iron atom is bonded to four different ligandsf4].
'z,,
x,
I%,,
776
Compound ( I )crystallizes in the orthorhombic space group
P21212twith u= 11.201(3), b=14.817(7), and c= 18.976(3)A;
V=3149.36A3; d,,,=1.12(2) and d,,,,=1.10 g/cm3 for a unit
cell with four molecules. A total of4422 independent reflections
was collected with a computer-controlled diffractometer using
monochromatized Mo-Ka radiation .;( = 0.71069 A) to
2 0 1 6 0 " . The structure was solved and refined using 2194
reflections for which I ( h k / ) > 3g[I(hk/)]. The final R ( F ) and
R,(F) values were, respectively, 0.066 and 0.072. The absolute
configuration of ( 1 ) was determined by- refinement of the
entire data set with the two possible enantiomeric configura~~
.
[*] Dr. M. G. Reisner a n d Prof. Dr. 1. Bernal [**]
Chemistry Department. University of Houston
Houston, Texas 77004 ( U S A )
Prof. Dr. H. Brunner a n d M. Muschiol
lnstitut Iur Chemie der UniversitPt
Universitiitsstrasse 3 I , D-8400 Regensburp (Germany)
[**I Recipient o f a US Senior Scientist Award administered by the Alexander
von Humboldt-Foundation: present address(1976-1977): lnstitut fur Chemie
der Universitiit. Universitiitsstrasse 3 I . D-8400 Regensburg,lGerman,y~.
A i l g t w . Chriii. lilt.
E d . Em)/. 1 V i l . / 5 ( 1 9 7 6 ) No. I 2
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