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Oxidative Amination of Toluhydroquinone.

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and the cycloadduct (11) to the thermally unstable cyclonona[cd]azulene derivative (12) resulting in cyclobutene
ring opening; renewed valence isomerization of (12) to (23)
and subsequent elimination of diethylamine affords a 75 %
yield of the hitherto inaccessible l0-methylbenzo[a]cyclopent[cd]azulene ( 1 4 ) (yellow-brown platelets, m. p. 136-
Ha
H2
137oC)181.
In analogous manner, the tetracyclic hydrocarbon
( 2 5 ) can be transformed in 21 % yield into 4,9-dimethyl-1,2-
dihydrobenzo[l,2]dicyclopent[cd,ij]azulene
colored needles, m. p. 144 "C).
( I 6)
(bronze
Received: December 1 I , 1975 [ Z 363d IE]
German version: Angew. Chem. 88,125 (1976)
CAS Registry numbers:
(1),209-42-7: /31,58150-65-5; ( 4 J , 58150-66-6; ( S ) , 58150-67-7; ( 5 ) , 3,5,8,10tetramethyl derivative, 58150-68-8; (6). 17597-70-5, (i), 58150-69-9; ( 8 ) ,
58150-70-2; (9), 581 50-71-3; ( / I 1.58150-72-4; ( 1 2 ) . 58150-73-5; ( 1 3 ) , 5815074-6: (14),58150-75-7:(15), 1143-34-6; (16). 58150-76-8;dimethyl acetylenedicarboxylate. 762-42-5: N,N-diethyl- 1 -propynylamine, 4079-68-9
- ~-
K . Hufiier, H . Diehl, and H . C'. Siiss, Angew. Chem. 88, 121 (1976);
Angew. Chem. Int. Ed. Engl. I S . 104 (1976).
H . Diehl and K . H u f i w r , Angew. Chem. 88, 124 (1976); Angew. Chem.
Int. Ed. Engl. 1 5 , 107 (1976).
K . H U ~ J WPure
.
Appl. Chem. 28. 153 (1971).
( 1 ) and its alkyl derivatives also undergo Diels-Alder reaction with
maleic anhydride and tetracyanoethylene; K . Hafnrr and J . Sfhneider.
Justus Liebigs Ann. Chem. 624, 37 (1959); K . Hufiler and G. Schnridrr,
h i d . 672. 194 (1964).
Correct elemental analyses, UV, NMR, and MS spectra were obtained
for all compounds described.
Cf. [3] and K . Hufiier, G. H a j w r - S d m e l d e r , and F. Bauer, Angew. Chem.
80, 801 (1968); Angew. Chem. Int. Ed. Engl. 7, 808 (1968).
A . G. Aiidrrson, Jr., A. F. Monranu, A . A . MucDoriald, and G. M. Musurla,
J. Org. Chem. 38, 1445 (1973); C h . J u t ; and E . S c h w i g r r , Synthesis
IY74. 193.
7 ,5-Dimethyl- [4] and 3,5,8.10-tetramethylaceheptylene ( 6 ) 161 react
with N.N-diethyl-I -propynylamine to give 68',',, of 3.5-dimethyl- and 92",,
of the 3.5,7,9-tetramethyl derivative, respectively, of ( 1 4 ) .
Oxidative Amination of Toluhydroquinone[**]
By Suresh C. Srivastava and Utfert Hornemann"]
Schafer and Aguado"] have reported that the interaction
of a variety of hydroquinones with arylamines and sodium
iodate constitutes a facile route for the preparation of bis(ary1amino)-I ,4-benzoquinones including ( 3 ) , for which they gave
O
(1). R = hIIc6IIs
( 4 ) . K = OH
a decomposition point of 147°C but no data to prove its
structure. During our attempts to prepare 3,6-dianilinotoluquinone (3) by this route using 10 mmol of toluhydroquinone,
20 mmol of aniline (each dissolved in 75 ml of methanol) and
30mmol of sodium iodate (dissolved in 75ml of water) and
stirring the mixture for 24 h at room temperature, we observed
that the predominant reaction product is 5-anilinotoluquinone
( 1 ) (50% yield), that (3) is obtained in only 26% yield,
and that the novel 6-anilinotoluquinone (2) is formed in
10% yield.
( 1 ) is also the predominant or a major reaction product
when the relative amounts of the reactants are varied. With
10 instead of 20mmol of aniline the yields of ( I ) , (2) and
(3) are 70 %, 15 % and 10 %, respectively, while when 30 mmol
instead of 10mmol of toluhydroquinone is used the yields
of (1) and (2) are 40 % and 50 %, respectively, and no (3)
can be detected. In contrast to these observations, but presumably in accord with results obtained by Zincke"', it was found
that a reaction mixture containing 30 mmol toluquinone and
20 mmol aniline in ethanol yielded ( I ) and (3) in 60% and 307(,
yield, respectively, and no detectable quantity of (2).
The composition of the reaction mixtures in most cases is
5&70% of (1) cersus 3(r500/, of (2) plus (3). This may be
explained as follows: Assuming that it is the sole function of
the iodate to generate toluquinone, the product ratio reflects
the difference in the reactivity of position 5 cersus 6 of toluquinone towards attack by the nucleophilic aniline. Moreover,
once any (21 has formed it can give rise to (3) and the extent
of this conversion is dependent on the amount of aniline
and the amount of oxidizing agent present in the reaction
mixture. This explanation holds for most of the reaction mixtures except for that in which toluhydroquinone and sodium
iodate were used in excess of aniline. The observed increase in
the amount of (2) formed in this case is reproducible but is
not readily explained. We suggest that partial formation of a
quinhydrone, which would be expected to have the methyl
groups oriented in a "para" arrangement, may lead to increased
accessibility of the 6 position.
Table I . Physical data for compounds ( 1 ) t o (6). All compounds gave
the molecular ion In the mass spectrum.
Cpd.
M.p.["C]
(dec.)
'H-NMR (6 values, in CDCl,)
(1)
150-151
(2)
155-156
(3)
(4)
(5)
24k242
127-141
110-120 [a]
(6)
166-171
2.05 (d, 3H, J2,=1.5Hz), 6.13 (s, IH), 6.52 (hr.,
IH), 7.24 (br., 5H)
2.12(d,3H, J2,=2.0Hr), 6.18 (d, IH, J3g=2.5Hz),
6.58 (m. lH), 7.32 (br., 5H)
1.59 (s, 3H), 6.03 (s, IH), 7.30 (br., 10H)
2.03(d, 3H, J,,=1.5 Hz).6.05(s, lH).6.60(hr.. I H )
2.10(d. 3H, J2,=1.5 H~).6.20(d.1H, J , , = 2 0 Hz)
6.60 (m, IH)
1.97 (s, 3H), 7.24 (s, IH)
[b]
_______
[a] M.p. 117-127'C
-
(dec.) IS]; [b] M.p. 173-175"C
[6].
0
(21, R
= KHCcH5
( 5 1 , R = OH
(31, R = S H C s H s
16). R = OH
__~_
['I
Dr. S. C. Srivastava and Prof. Dr. U. Hornemann
Department of Medicinal Chemistry and Pharmacognosy, School of
Pharmacy and Pharmacal Sciences
Purdue University
West Lafayette, Indiana 47907 (USA)
[**] This work was supported by NIH Research Grant CA 14378.
A n g e n . Chem. I n t . Ed. Engl. j
&I/.
I5 ( 1 9 7 6 ) No. 2
3,6-Dianilinotoluquinone ( 3 ) (Table 1) precipitated from
the reaction mixture as a yellow brown powder and was
recrystallized from chloroform; the compound is presumably
identical with the dianilinotoluquinone (m.p. 232-233 "C)
prepared by Zincke[']. The filtrate obtained after removal
of (3) was evaporated to dryness, the residue extracted with
methanol and the extract concentrated to yield ( I ) (Table
1) as red crystals; this material is presumably identical with
the reaction product obtained by Schafer and Aguado"] and
with Zincke's monoanilinotoluquinone, (m. p. 144-145 "C).
(2) (Table 1) was obtained as red crystals after chrobatography of the mother liquor on a silica gel column which was
109
developed with chloroform. The 'H-NMR spectra of (1)-(3)
are in accord with the proposed structures (cf. [3]).
Further proof for the identity of the anilinoquinones (1)(3) was obtained by converting them into the known hydroxyquinones ( 4 ) l41, (5)[51 and (6)[,1, respectively, with refluxing
10 % H,SOJmethanol (1 : 1) for 10min (Table 1). Each reaction mixture was poured into water, the product extracted
with chloroform, the chloroform layer dried with Na2S04
before evaporation, and the resulting hydroxyquinones purified by sublimation.
Received: November 12, '1975 [Z 348 IE]
German version: Angew. Chem. 88, 87 (1976)
CAS Registry numbers:
( I ) , 57674-09-9; ( 2 ) , 57674-10-2; ( 3 ) , 21111-68-2; 14J. 615-91-8;
(S), 2446-75-5; (61, 2207-58-1
[I1
__
121
r3i
[4]
[5]
[6]
K Schafer and A . Ayuado, Angew. Chem. 83,441 (1971); Angew. Chem.
Jnt. Ed. Engl. 10, 405 (1971).
7: Zincke, Ber. Dtsch. Chem. Ges. 16, 1555 (1883).
S. Berger and A . Rieker in S. Patai: The Chemistry of Quinoid Compounds. Wiley, New York 1974, Part I, p. 163ff.
R . B. Woodward, F . Sondheimer, D.Taub, K. Heusler, and W H . McLamore,
J. Am. Chem. SOC. 74, 4223 (1952).
H . Musso, Chem. Ber. 91, 349 (1958).
K G . Hanger, W C. Howell, and A . K Johnson, J. Chem. SOC. 1958,
496.
Fluorosulfinyl Isocyanate[**]
By Hans-Joackim Krannich and Wolfgang Sundermeyer[']
All previous attempts to prepare halosulfonyl pseudohalides,
OSXY, and sulfinyl bispseudohalides, OSY (X =halogen;
Y = pseudohalogen) have failed"]. We have now succeeded
in synthesizing the first compound of type OSXY by reaction
of fluorocarbonyl bromide"] with bis(sulfony1amido)mercury(11)1~].
The fluorosulfinyl isocyanate (2) is formed in a rearrangement reaction-to our knowledge formerly unobservedfrom the expected intermediary fluorocarbonylsulfinylamine
(1 ) ; the CF bond becomes an SF bond.
the transition 109-67 is evidenced by a metastable peak
at 41 (calc. 41.18). The I9F-NMR spectrum shows a singlet
at - 55.5 ppm (CFC13ext. standard), which can be attributed
to an OSF bond in contrast to an OCF bond14](for comparison : CH,O-S(0)F
(- 55.6ppm)["I, (CF,),N-0-S(0)F
(-59.5ppm[5b1). In the IR spectrum there are no carbonyl
bands. Bands do occur, however, at 2245 (vs, v,,NCO), 2192 (m,
sh), 1348 (s, v,NCO), 1281 (vs, vSO), 753 (vs, vSF), 716 (vs,
vSN), 610 (vs, 6NCO), and 488 cm ' (m) (gas spectrum). Also
present is the combination band of the two NCO vibrations
at ca. 3580cm-'. In the Raman spectrum the intensity ratio
of the two NCO bands is typically reversed.
Our redistribution experiments on carbonyl halides and
pseudohalides[6]indicatearelatively high mobility of the fluorine atom in the neighborhood of a carbonyl group. An intermolecular exchange of the fluorine atom between the two C
atoms, observable in the case of fluorocarbonyl isocyanate
OC(F)NCO by a broad I9F-NMR signal at room temperaturel7I,leads in the case of ( I ) to an irreversible rearrangement
to (2).
~
Received: November 5, 1975 [ Z 353 IE]
German version: Angew. Chem. 88,88 (1976)
CAS Registry numbers:
OCFBr, 753-56-0; HglNSO),, 25682-06-8; fluorosulfinyl isocyanate.
57789-32-9
111 G . Jander and D. Ullmann, Z. Anorg. Allg. Chem. 230, 405 (1937);
C . S. Forbes and H. H . Anderson, J. Am. Chem. SOC. 65, 2271 (1943);
P. W Schenk and H . Bloching, Chem. Ber. 92, 2333 (1959).
[2] G. Siegemund, Angew. Chem. 85, 982 (1973); Angew. Chem. Int. Ed.
Engl. 12, 918 (1973).
[3] W Verbeek and W Sundermeyer, Angew. Chem. 81, 330 (1969); Angew.
Chem. Int. Ed. Engl. 8, 376 (1969).
[4] H . 4 . Horn, Fluorine Chem. Rev. 6, 135 (1973).
[5] a) F. See/, J . Boudier, and W Gombler, Chem. Ber. 102, 443 (1969);
b) J . A . Loft, D. P . Babb, K . E . Pullen, and J . M . Shreeoe, Inorg.
Chem. 7, 2593 (1968).
[6] Chr. Jackh and W Sundermeyer, Chem. Ber. 106, 1752 (1973).
[7] 0.Glemser. Li. Biermann, and M . Field, Chem. Ber. IOf), 1082 (1967).
,>
[Ir (2,4,6-C,H2(CH,) (CO)(PPh,),]-The First Example of cis-fvans Isomerism in Complexes of the
Vaska Type[**]
By Lutz Dahlenburg and Reinhard Nasd']
OCFBr (ca.27 g) is condensed via a high-vacuum apparatus
onto Hg(NSO), (5.1g) in a 200ml Duran glass ampoule;
the ampoule is then sealed and shaken for 48 h at 10--15°C.
After removal of the volatile reaction products in a high
vacuum the excess OCFBr serving as reaction medium is
separated from the product at normal pressure for further
use. The combined product after five such treatments afforded
4.5 g of (2) (yield.26.7%) as an almost colorless liquid (b. p.
60.5 "C) which slowly turns yellow at room temperature.
While elemental analysis merely affords evidence of the
presence of ( 1 ) or (2), the mass spectrum clearly indicates
presence of the isomer ( 2 ) : m/e= 109 molecular ion (rel. int.
57.8%), 90 0s-NCO (12.5), 67 OSF (loo), 64 SO2 (6.3),
48 SO (25), 46 NS (18.8), 42 NCO (14.0), and 32 S (7.8);
p]
Prof. Dr. W. Sundermeyer and Dipl.-Chem. H. J. Krannich
Anorganisch-chemisches Institut der Universitat
6900 Heidelberg 1, Im Neuenheimer Feld 270 (Germany)
[**] We thank Prof. Dr. H . Siebert for helpful discussion of the vibration
spectra. This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
I10
The cis-trans isomerism frequently found in planar platinum@) complexes of the type [Pt(L),(X)(Y)] has so far not
been observed in the numerous comparable iridium(1) complexes of the Vaska type IrA(CO)L, (A=univalent anion
ligand, L=tertiary phosphane or arsane). On the basis of
their 'H- and ,lP-NMR spectra and their dipole moments
all these compounds prove to have a trans configuration,
which, in two cases [A, L=CI, P(o-C,H,CH,),; C6F5,
P(C,H,),] has also been confirmed by X-ray structure analysis[', The postulated existence of cis-[IrA(CO)(PPh,),]
[A=H, C(CN),] is doubtful[31,if not already ruled
We are now able to show that the o-mesityl complex ( 2 ) .
which is accessible according to
'.
M e s = 2,4,6-CsH,(CH,),
[*] Prof. Dr. R. Nast and Dr. L. Dahlenburg
Institut fur Anorganische und Angewandte Chemie der Universitat
Martin-Luther-King-Platz 6, 2000 Hamburg 13 (Germany)
[**] This work was supported by the Fonds der Chemischen Industrie.
Angew. Chem. Inr. Ed. Engl. J Vol. I S ( 1 9 7 6 ) No. 2
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