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Catalytic Hydrogenation of 7-Methoxy-6-methyl-8-nitro-1-isoquinolinecarbonitrile to Unusual Products.

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Synthesis of an N-Functionalized 1,3-Diaza- and
a P-Functionalized
1,3-Diphospha-2,4-disilacyclobutaneX*
By Uwe KlingebieP and Norbert Vater
Reactions of dichlorodiorganosilanes with ammonia
proceed with complete cleavage of hydrogen chloride to
afford six- and eight-membered cyclosilazanes and higher
condensation products"]. Sterically demanding substituents lead to short-chain acyclic silazanes[21.In this connection neither the formation of a four-membered ring
[R2Si-NHI2 nor of an intermediate product R2SiCI-NH2
has been observed.
Cyclosilaphosphanes were obtained by reaction of dichlorodiorganosilanes with lithium phosphide or metalated organoph~sphanes~'~.
The annelation can be attributed to the
marked tendency of the initially formed unstable diphosphinosilanes to rearrange, although bis(tert-butylphosphino)dimethylsilane, Me2Si(PHtBu),, has been isolated and
after lithiation used in the synthesis of cyclosilaphosphanes"].
By allowing difluorodiorganosilanes to react with lithium amide or lithium phosphide, we obtained the surprisingly stable N-(fluorosily1)amines 1 and 2, and the N(fluorosi1yl)phosphane 3 (b.p.=55 "C/18 torr, 38 "C/19
torr, and 70 "C/4 torr).
1, R = t B u
2, R = i P r
3, R = i P r
In an analogous fashion to the isoelectronic compound
(~Bu),S~F(OH)['~,
1 and 3 show no tendency to condense.
1,2 and 3 are readily N-and P-metalated by butyllithium,
and in the absence of reactants form 1,3-diaza- (7,8) and
1,3-diphospha-2,4-disilacyclobutanes 9,
respectively
(m.p.=93 "C, b.p.=55 "C/O.OI torr, and m.p.= 114 "C)
upon cleavage of lithium fluoride.
H
H
N
RzSi< >SiRz
N
H
with difluorodimethylsilane. All the novel compounds
were characterized by NMR spectroscopy.
Received: July 12, 1982 [Z 87/88 IEI
revised: August 24, 1982
German version: Angew. Chem. 94 (1982) 870
The complete version of this manuscript appears in:
Angew. Chem. Suppl. 1982, 1865-1874
CAS Registry numbers:
1, 83312-30-5; 2, 83312-31-6; 3, 83312-32-7; 7, 83312-33-8;8, 83312-34-9; 9,
83312-35-0; 10, 83312-36-1; 11, 83312-37-2;
[I] W. Fink, Angew. Chem. 78 (1966) 803; Angew. Chem. Int. Ed. Engl. 5
(1966) 760.
[2] L. H. Sommer, L. J. Tyler, J. Am. Chem. SOC.76 (1954) 1030.
[7] G. Fritz, R. Uhlmann, Z. Anorg. ANq. Chem. 442 (1978) 95.
(91 U. Klingebiel, Angew. Chern. 93 (1981) 696; Angew. Chern. Int. Ed. Engl.
20 (1981) 678.
Catalytic Hydrogenation of
7-Methoxy-6-methyl-8-nitro-l-isoquinolinecarbonitr~le
to Unusual Products
By Akinori Kubo*, Naoki Saito, Shinsuke Nakahara, and
Ryoichi lwata
There has recently been considerable interest in the crystal structures of 1,8-disubstituted naphthalenes with various nucleophilic groups (N(CH,),, OH, OCH3, NO2) at
one of the peri-positions and electrophilic groups (CO,
CN) at the other, which exhibit intramolecular nucleophilic-eiectrophilic interactions[']. However, few studies
have been reported on the chemical properties of this class
of compounds.
We now report the catalytic hydrogenation''] of the title
compound 1 in presence of 10% Pd/C (in anhydrous dimethylformamide (DMF), 3 h), which leads to formation
of the novel heterocyclic lactam 8-methoxy-7-methylpyrrolo[2,3,4-ijlisoquinoline-2(lH)-one 4 (5.7%) in addition to
the amines 2 (43%), 3 (13%)13],and 5 (17%)c31. Reduction of
1 in presence of Pt02 (anhydrous DMF, 4 h) affords 2
(8.0%), 3 (22.0%), and trace amounts of 4 and 5 . Compound 4 was obtained in quantitative yield by treating 3
with conc. HC1 (reflux, 30 min in ethanol).
/P\
(iPr)zSi\ ,Si(iPr)2
P
H
7, R = rBu; 8, R = i P r
9
NH, R'
1
Only one isomer was observed for 9 by NMR spectroscopy. The H atoms of the difunctional four-membered
rings 7 and 8 can be mono- or dilithiated by C4H9Li, so
that substitution reactions with elemental halides with retention of the ring framework are possible. For example, 8
forms N-mono- and N, N'-disubstituted products 10 and
11, respectively (b. p. = 52 "C/O.Ol torr, m. p. = 202 "C)
4
2 , R' = C N
3, R' = CONHz
5 , R' = H
CN
CN
The unexpected formation of lactam 4 can be rationalized by assuming that the oxygen atom of the nitro group
of 1 is transferred to the carbon atom of the cyano
groupL2].We, therefore, examined the catalytic hydrogena6. Under
tion of 2 and 5-nitro-1-isoquinolinecarbonitrile
[*] hiv.-Doz. Dr. U. Klingebiel, N. Vater
[**I
Institut fur Anorganische Chemie der Universitat
Tammannstrasse 4, D-3400 Gottingen (Germany)
This work was supported by the Forschungsmittel of the Land Niedersachsen and the Fonds der chemischen Industrie.
Angew. Chern. Int. Ed. Engl. 21 (I982) No. I 1
[*I
Prof. Dr. A. Kubo, N. Saito, S. Nakahara, R. Iwata
Department of Organic Chemistry, Meiji College of Pharmacy
1-35-23 Nozawa, Setagaya-ku, Tokyo 154 (Japan)
0 Verlag Chemie GmbH, 6940 Weinheim, 1982
0570-0833/82/1111-0857 $02.50/0
857
the same conditions as the reaction of 112],2 resisted hydrogenation and was recovered in 81% yield, whereas 6
furnished 5-amino- 1-isoquinolinecarbonitrile 7 in 72%
yield, but no amide.
These results provided additional evidence in support of
the proposed mechanism. Finally, we note that the orientaderition of nitration of 7-methoxy-6-methylisoquinoline
vatives is determined unambiguously without correlation
methods or spectroscopic analysis[51.
Received: July 20, 1981 [Z 197 IE];
revised: September 23, 1982
German version: Angew. Chem. 92 (1982) 875
cules. In the I R spectrum of 3 the C=O stretching vibration is observed at 1560 cm-', i. e. it is shifted by 167 cm-'
to lower wave numbers compared to that of 1. Thus, 1
should be coordinated to zinc via oxygen.
The X-ray structure determination shows that 3 crystallizes in the space group P j with a = b = 1190.1(1),
c=665.1(1) pm and Z = I, pca,,=2.37 Mgm-3. The structure was solved by direct methods and refined to
R = 0.046 and R , = 0.049 for 1498 independent reflections
with Fo > 30(F,,) and MoK,-radiation.
111 G. Procter, D. Britton, J. D. Dunitz, Helu. Chim. A c f a 64 (1981) 471, and
references cited therein.
[21 I (259 mg, 1.06 mmol) was hydrogenated in 10 mL anhydrous DMF with
201 mg 10% Pd/C (3 h). The catalyst was filtered off and removal of the
solvent gave 225 mg crude material, chromatography of which on 7 g silica gel (Kieselgel60) afforded 97 mg (43.0%) 2 , m.p.= 137.5-138.5 "C (nhexane). Elution with n-hexane/ethyl acetate (1 : l), and n-hexane/ethyl
acetate (I :1/1 :2) gave 84 mg of the eluate, which after preparative thin
layer chromatography on silica gel (CH2CI2/acetone 1 : 1) yielded 31 mg
(12.7%) 3, m.p.=104.5-106.O"C (benzene) 131, 13 mg (5.7%) 4, m.p.
262.5-264.O"C (acetone) [3] and 34 mg (17.2%) 5, m.p.=78.0-79.0 "C (nhexane).
131 3: 1R (KBr): 1560, 1630, 1658, 3340 cm-'; UV (EtOH): 1,,,=212 nm
(log&=4.59), 252 (4.42), 323 (sh, 3.50), 365 (3.58); 'H-NMR (CDCI,):
6=2.37 (s, 3H), 3.75 (s, 3H), 5.60 (br s, 2H, DAOexchangeable), 6.56 (br
s, 1 H, D20 exchangeable), 6.95 (s, 1 H), 7.43 (d, J = 8 Hz, 1 H), 7.52 (br s,
1 H, D 2 0 exchangeable), 8.13 (d, J = 8 Hz, 1 H); MS:m/z 231 ( M + 63%),
,
216 (54). 199 (loo), 171 (57).-4: IR (KBr): 1490, 1590, 1635, 1690,3190
c m - ' ; UV(EtOH):A,,,=217 nm(Iog&=4.39), 259(4.35), 345 (3.17), 392
(3.40); 'H-NMR ([D,]pyridine): 6= 2.37 (s, 3 H), 4.27 (s, 3 H), 7.25 (s, 1 H),
7.64 (d, J = 8 Hz, 1 H), 8.92 (d, J = 8 Hz, 1 H), 11.84 (s, 1 H, D20exchangeable); MS: m/z 214 ( M + ,
100%). 199 (63), 171 (56). I16 (15).
[41 H. Moll, H. Musso, H. Schroder, Angew. Chem. 75 (1963) 295; Angew.
Chem. Inr. Ed. Engl. 2 (1963) 212; H. Musso, H. Schroder, Chem. Eer. 98
(1965) 1526.
151 S. F. Dyke in S . Coffey: Rodd's Chemistry of Carbon?ompounds, 2nd ed.,
Elsevier, Amsterdam 1976, Vol. IV, Part F, Chapt. 27.
Synthesis and Structure of lZn(S2NzCO)611AsF61zSulfur-Nitrogen Rings as Ligands in Coordination
Compounds**
By Herbert W. Roesky*, Manfred Thomas,
Mathias Noitemeyer, and George M . SheIdrick
Dedicated to Professor Rudolf Hoppe on the occasion
of his 60th birthday
5-0x0-1,3h4,2,4-dithiadiazole1 can be prepared by reaction of [(CH3)2SnN2S2]2
with carbonyl difluoride[". In order to clarify whether the coordination of the ligand to a
metal atom takes place via oxygen, sulfur or nitrogen, we
have investigated the reaction of 1 with the zinc complex 2
in liquid SOa.
1
2
Fig. 1. Structure of [Zn(S2N2C0)6]2+,
atom numbering and interatomic distances [pm], standard deviations in brackets: C-N(1) 134.7(3), N(1)-S(I)
157.6(3), S(I)-N(2)
157.0(3), N(2)-S(2)
161.7(2), S(2)-C
178.9(3), 0-C
124.0(3).
In the Zn(SzN2COi+cation (Fig. 1) Zn is octahedrally
coordinated: The maximum distortion from 90" is 1.4". Zn
lies on the special position with 3 symmetry and As on a
threefold axis. The ligand 1I2]is planar within experimental error, and possesses no crystallographic symmetry. The
Zn-0-C
angle is 134.2'. The C-0 bond length in 3
(124.0(3) pm) is somewhat longer than in the free ligand
(122.2(7) pm). The remaining bond lengths within the
S2N2Cring show no significant change; the average S-N
bond length in the uncoordinated ligand 1 is 159.5 and in
3 158.8 pm.
Received: April 5, 1982 [Z 2 IEJ
revised: July 14, 1982
German version: Angew. Chem. 94 (1982) 861
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1982, 1813-1818
CAS Registry numbers:
2, 83416-63-1; 3, 83416-61-9.
[I] H. W. Roesky, H. Wiezer, Angew. Chem. 87(1975) 254: Angew. Chem. Inr.
Ed. Engl. 14 (1975) 258.
[21 H. W. Roesky, E. Wehner, E. J. Zehnder, H. J. Deiseroth, A. Simon,
Chem. Ber. 111 (1978) 1670.
3
After removal of SO,, 3 precipitates as a colorless solid.
3 (m. p. 150 "C) is recrystallized from liquid SO,; it is inso-
Tl(OtBu),Sn:
A Small Pentatomic Cage Molecule**
luble in CHZCl2.Owing to their modest donor properties,
the ligands 1 in 3 are very readily replaced by water mole-
By Michael Veith* and Richard Rosler
It is known that heavy main-group elements in low oxidation states can occur as essential constituents of cage
M. Thomas, Dr. M. Noltemeyer,
Prof. G. M. Sheldrick
Institut fur Anorganische Chemie der Universitat
Tammannstrasse. 3, D-3400 Gdttingen (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft, the
Fonds der Chemischen Industrie, and by Hoechst AG.
[*] Prof. Dr. H. W. Roesky,
858
0 Verlag Chemie GmbH, 6940 Weinheim. 1982
[*I Prof. Dr. M. Veith, R. Rosler
lnstitut fur Anorganische Chemie der Technischen Universitat
Pockelsstrasse 4, D-3300 Braunschweig (Germany)
[**I This work was supported by the Forschungsmittel of the Land Niedersachsen.
0570-0833/82/1111-0858
$. 02.50/0
Angew. Chem. Inr. Ed. Engl. 21 (1982) No. I 1
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