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Dehydrobenzene from Aromatic Diazonium Salts.

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Vinyl trifluoromethanesulfonates, prepared by methods 1 and 2.
Ketone or
aldehyde
Trifluoromethanesulfonate [a]
Reaction time (days)
Yield
method 1
( %)
I
method 2
I
n= 3
n=4
n= 5
n= 3
n= 4
5
n=6
n=
n= 6
B. p.
("C/torr)
NMR
(vinyl-H, T)
__
40
50
45
40
21-2310.5
78-80/12
71-7314
84-87/4
28
74-7615
35
4.41 (m, 1 H)
4.22 (m, 1 H )
4.10 (t, 1 H)
4.36 (t, 1 H)
1660 (CC14)
1690 (CC14)
1680 (CHC13)
1680 (CC14)
1710 (film)
I96--197/760
1695 (CCI,)
40
46-47/0,5
4.59;4.50
(2d 2 H )
1650 (film)
18
40-45/10
-
1701 (film)
2.98 (s, 1 H)
1630 (film)
45
138- l40/2.5
[a] OTf = O S O Z C F ~ .
12 203 IE]
Received: March 6,1970; revised April 17, 1970
German version: Angew. Chem. 82, 517 (1970)
['I Th. E. Dueber and Prof. Dr. P. J. Stang
Department of Chemistry, University of Utah
Salt Lake City, Utah 84112 (USA)
W. D. Pfeifer (Nato Fellow), R. H. Summerville (NSF
Predoctoral Fellow), M. A. Imhoff (NIH Fellow), and
Prof. Dr. P. v. R. Schleyer
Department of Chemistry, Princeton University
Princeton, N.J. 08 540 (USA).
Dip1.-Chem. K. Hummel, Dipl.-Chem. S. Bocher, Dr. C. E.
Harding (Stipendiat der Alexander von Humboldt-Stiftung), and Prof. Dr. M. Hanack
Chemisches Institut der Universitat
74 Tubingen, Wilhelmstrasse 33 (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, the National Science Foundation, and the Petroleum Research Fund
(Grant No. 1801-GI). We wish to thank Dr. R. L. Hansen,
Minnesota Mining and Manufacturing Co., for providing us
with a sample of barium trifluoromethanesulfonate.
[l] Trifluoromethanesulfonic anhydride was prepared by
treating barium trifluoromethanesulfonate with fuming sulfuric acid followed by several distillations of the product over
P205. J . Burdon, J . Farazman, M . Stacey, and J . C. Tatlow,
J. chem. SOC.(London) 1957, 2574.
[2] R . L. Hansen, J. org. Chemistry 30, 4322 (1965); A . Streitwieser,j r . , C. L . Wilkins, and E. Kielmann, J. Amer. chem. SOC.
90,1598 (1968); T . M . Su, W . F. Sliwinski, and P . v. R . Schleyer,
ibid. 91, 5386 (1969).
[3] P . J . Stung and R. SummerviIle, J. Amer. chem. SOC.91,
4600 (1969).
141 W . M. Jones and D . D . Maness, J. Amer. chem. SOC.91,
4314 (1969).
[5] R . Sustmann, J . E. WiNiams, M . J . S . Dewar, L. C . Allen,
and P. v. R . Schleyer, J. Amer. chem. SOC.91, 5350 (1969).
161 Review: M . Hanack, Accounts chem. Res., in press.
[7] The preparation of cyclic vinyl tosylates and mesylates has
been reported by N . Frydman, R . Bixon, M . Sprecher, and
Y.Mazur, Chem. Commun. 1969, 1044.
Dehydrobenzene from Aromatic Diazonium Salts [I]
By Christoph Ruchurdt and C. C . T a n [ * ]
Not long ago we showed that benzenediazonium p-chlorobenzoate, which is prepared by isomerization of p-chloro-Nnitrosobenzanilide in CC14, reacts with tetracyclone in CC14
at 70°C to give tetraphenylnaphthalene ( I ) in 46% yieldrzl.
522
Compound ( 1 ) may be synthesized more readily and in
better yields by portionwise addition of crystalline benzenediazonium tetrafluoroborate or chloride (10 mmoles) t o a
vigorously stirred mixture of tetracyclone (1.92g, 5.0mmoles),
glacial acetic acid (0.1 g), and anhydrous potassium acetate
in benzene at 60 O C . Evolution of nitrogen ceases within 2.5 h.
After the product had been washed neutral and chromatographed o n acidic A1203, 1.52 g (3.52 mmoles, 70%) or 1.60 g
(3.70 mmoles. 74%) of tetraphenylnaphthalene ( I ) could be
detected by gas chromatography. The compound was isolated
in good yield by concentration and crystallization from dioxane/ethanol. The structure was confirmed by comparison
of melting points 1197 OC ([31: 197 "C) and 202 "C(141: 204 "C)]
and IR spectra, and by C, H analysis.
The analogous reactions of anthracene were found to give
9 % and 4;% (36 % isolated) of triptycene [m.p. 249-25TOC
(131: 254 "C)].
We interpret this synthesis in terms of formation of dehydrobenzene in a n Ez elimination which is initiated even by the
weak base acetate ion owing t o the favorable leaving group
properties of Nz.
1-co
CcH,
The success of the above reaction suggested that the synthesis
of ( I ) (17-34 %) and triptycene (1-3 %) from N-nitrosoacetanilide described by Cadogan et al. proceeds not via an
"arynoid intermediate", as was originally suspected, but
rather via dehydrobenzene [51. However, its precursor,
benzenediazonium acetate, undergoes rapid, competitive
decomposition by a chain reaction in the presence of Nnitrosoacetanilide[*b. 61. If this decomposition is suppressed by slow, dropwise addition of an ice-cold benzene
solution of N-nitrosoacetanilide (10mmoles,30 ml or 15 ml,
respectively) to a solution of tetracyclone (5 mmoles/30 ml)
Angew. Chem. internat. Edit.
1 Vol. 9 (1970) 1 No. 7
or anthracene (5 mmoles 15 ml), to which solid potassium
acetate has been added, at 60 "C over a period of 20 min, then
8 8 7 ; of l l ) (96Xfound bygaschromatography)or14 --18%of
triptycene (according t o gas chromatography) may beisolated.
dried with MgS04 and vacuum distilled. UV: A,,
= 2921 A;
IR: 0 = 3000, 1700, 1365, 1300-1275 cm-1: N M R : T = 5.43,
5.70, 4.70, 3.27, (H-2, H-3, H-5, and H-6, respectively),
J 2 , 3 = 6.0, J5.6 = 7.0 Hz, b.p. 110 "CjO.0014 torr, yield 55 %.
Received: April 16, 1970
[Z 209 IE]
German version: Angew. Chem. 82, 547 (1970)
Publication delayed at authors' request
Received: April 7 , 1970
[ Z 207 1El
German version: Angew. Chern. 82, 518 (1970)
[*] Prof. Dr. Ch. Ruchardt and Dip1.-Chem. C. C. Tan
Organisch-chemisches Institut der Universitiit
44 Miinster, Orleans-Ring 23 (Germany)
[ l ] This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.
[2] a) Ch. Riichardt, C. C. Tan, and B. Freudenberg, Tetrahedron Letters 1968, 4019; b) Ch. Riichardt and C. C. Tan,
Chem. Ber. 103, 1774 (1970).
[3] L. Frredmann and F. M . Logullo, J. org. Chemistry 34,
3089 (1969).
[4] H . Herwig, W. Metlesics, and H . Zeiss, J. Amer. chem. SOC.
81, 6203 (1959).
(51 D. L. Brydon, J . I . G. Cadogan, D. M . Smith, and J . B.
Thoinson, Chem. Commun. 1967, 721; see also R. W. Franck
and K . Yanagi, J. Amer. chem. SOC.90, 5814 (1968); J . I . G.
Cadogan, J . Cook, M. J . P. Harger, and J . T . Sharp, Chem.
Commun. 1970, 299.
[6] G. R. Chalfont and M . J . Perkins, J. Amer. chem. SOC.89,
3054 (1967).
One-Step Synthesis of 2-Substituted
N-Ethoxycarbonyl-1,2-dihydropyridinest * *I
By Gideon Fraenkel, J. W. Cooper, and C . M . Fink[*]
Pyridine derivatives react only slowly with Grignard compounds t o give poor product yields [ I ] . The same applies t o
N-acylpyridinium salts 121.
We have now found that pyridine derivatives ( I ) react with
ethyl chloroformate and Grignard compounds to give 2alkyl-1-ethoxycarbonyl-1,Z-dihydropyridines (3), the reaction presumably proceeding via the pyridinium chloride (2).
[*I Prof. Dr.
G . Fraenkel, Dr. J. W. Cooper, and C. M. Fink
Department of Chemistry, The Ohio State University,
140 West 18th Avenue, Columbus, Ohio 43210 (USA)
[ * *] This work was supported by the National Science Foundation.
[I] N . Goetz-Luthy, J. Amer. chem. SOC.71, 2254 (1949); W. v.
E. Doering and P. Z. Pasternack, ibid. 72, 145 (1950); R. A .
Benkeser and D. S. Holton, ibid. 73, 5861 (1951).
[2] A . D. Miller and R. Levine, J. org. Chemistry 22, 168 (1957).
[3] C. Fraenkel and J . W. Cooper, Tetrahedron Letters 1968,
7 825.
A New Synthesis of the Quinazoline System
By Gerhard Simchen, Giinfher Entenmann, and
Rolf Zondler [*I
We recently reported on the synthesis of aza and 1,3-thiaza
heterocyclic compounds by cyclizing acylation of a-cyano
and w-thiocyanato carbonyl halides [I]. We have now found
that 1,3-diaza heterocyclic compounds are also accessible by
this method. Reaction of o-cyanophenyl isocyanates ( I ) ,
Z = 0, and o-cyanophenyl isothiocyanates ( I ) , 2 = S, with
hydrogen halide at room temperature in di-n-butyl ether
initially affords carbamoyl and thiocarbamoyl halides (2),
Z = 0 and Z = S, resp.[21, which cyclize at about 7 0 ° C
in the presence of a n excess of hydrogen halide t o the hitherto
and 4undescribed 4-halogeno-2-quinazolones(3u)-(3c)
halogeno-2-quinazolinethiones(3d), respectively.
(34
(36)
(3c)
(3d
Treatment of (3b) with n-butyllithium in hexane gave a red
solution which was found t o contain 2,4-di-terf-butyl-l,2dihydropyridyl-1-lithium by N M R spectroscopy 131. It is
converted into 2,4-di-tert-butylpyridine when the solution is
heated. The low-temperature N M R spectrum of (36) indicates the presence of two rotational isomers.
I-Ethoxycarbonyl-2,4-di-fert-bufyl-1,2-dil~ydropyridine
(3b):
To a mixture of 4-fert-butylpyridine (1.01 g, 7.5 mmoles) and
20 ml of a 0.75 M solution of rert-butylmagnesium chloride in
tetrahydrofuran (15 mmoles) is added ethyl chloroformate
(0.81 g, 7.5 mmoles) a t 0 ° C over a period of 10 min. The
reaction mixture is hydrolyzed with 1 ml of water at O°C,
filtered, and the white precipitate is washed with tetrahydrofuran. The washings are added t o the filtrate which is then
Angew. Chem. infernat. Edit. J Vol. 9 11970) No. 7
H
c1
H
Br
Br
H
CI
C1
0
0
0
S
21 3
348-350
> 350
295-296
87
78
77
70
Ring closure proceeds by nucleophilic attack of the intermediate nitrile-hydrogen halide adducts o n the carbamoyl or
thiocarbamoyl halide (2). The 4-chloro-2-quinazolines (3a)
t o (3c) can also be synthesized without isolation of intermediates by successive passage of phosgene (ca. 1 h) and
hydrogen chloride (cu. 7 h) through a suspension of 2-cyanoanilinium chloride (4) in di-n-butyl ether a t 120'C and at
80 O C respectively. Nucleophilic substitution of the halogen
atoms attached t o C-4 of (3) proceeds readily.
General procedure:
Compound ( I ) , 2 = 0 or S, (0.01 mole) is suspended in
di-n-butyl ether (50 ml). HCl or HBr is passed into the suspension at 80°C for 7 hours. The resulting precipitate is
523
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