P. Frohberg, G. Drutkowski, C. Wagner
FULL PAPER
(62), 77 (56). C15H15N3O2 (269.31): calcd. C 66.90, H 5.61, N 15.60;
found C 66.61, H 5.63, N 15.33.
Table 7. Crystallographic data for 1d and 1k
1d
1k
[1]
[1a] A. S. Shawali, J. Heterocyclic Chem. 1980, 17, 833Ϫ854. [1b]
Empirical formula
Formula mass
Crystal system
Space group
C28H22Cll4N6O2
616.32
monoclinic
P21/a
C18H13Cl2N3O
358.21
monoclinic
P21/c
[1c]
A. S. Shawali, Chem. Rev. 1993, 93, 2731Ϫ2777.
G. Brog-
gini, G. Molteni, G. Zecchi, Heterocycles 1998, 47, 541Ϫ557.
[1d]
A. S. Shawali, M. A. Abdallah, Adv. Heterocycl. Chemistry
Temperature [K]
Cell dimensions
293
220
1995, 63, 277Ϫ338.
[2] [2a]
N. Prasad, A. Sahay, J. Prasad, K. R. K. Singh, Asian J.
˚
[2b]
a [A]
20.836(4)
4.870(3)
29.398(3)
110.265(11)
2798.4(18)
4
1.463
1.95Ϫ24.95
0.462
Ϫ25 Յ h Յ 24
0 Յ k Յ 5
Ϫ34 Յ l Յ 34
9474/4898
7.906(2)
22.452(6)
9.402(2)
96.92(3)
1656.8(7)
4
1.436
2.60Ϫ25.00
0.401
Ϫ9 Յ h Յ 9
Ϫ26 Յ k Յ 26
Ϫ11 Յ l Յ 11
11750/2835
Chem. 1996, 8, 357Ϫ360.
N. Prasad, A. Sahay, J. Prasad,
˚
b [A]
K. R. K. Singh, Asian J. Chem. 1996, 8, 65Ϫ74.
˚
[3] [3a]
c [A]
B. I. Buzykin, M. P. Sokolov, V. A. Pavlov, V. N. Ivanova,
β [°]
L. F. Chertanova, T. A. Zyablikova, Zh. Obshch. Khim. 1990,
3
˚
[3b]
Volume [A ]
Z
60, 546Ϫ555.
B. I. Buzykin, Z. S. Titova, V. D. Cherepin-
skii-Malov, N. G. Gazetdinova, A. P. Stolyarov, I. A. Litvinov,
Yu Struchkov, Yu Kitaev, Izv. Akad. Nauk SSSR, Ser. Khim.
1983, 541Ϫ549.
C. Reichardt, K. Halbritter, Chem. Ber. 1973, 106, 1661Ϫ1667.
A. F. Hegarty, M. T. McCormack, B. J. Hathaway, L. Hulett,
J. Chem. Soc., Perkin Trans. 2 1977, 9, 1136Ϫ1141.
R. C. Seccombe, C. H. L. Kennard, Aust. J. Chem. 1970, 23,
395Ϫ397.
ρ [g·cm3]
θ range [°]
µ [mmϪ1]
Limiting indices
[4]
[5]
[6]
Reflections
[7] [7a]
collected/unique
Reflections with
I Ͼ 2σ(I)
R(int)
parameters
V. D. Cherepinskii-Malov, B. I. Buzykin, A. I. Gusev, Izv.
[7b]
3416
2387
Akad. Nauk SSSR Ser. Khim. 1981, 2716Ϫ2719.
V. D.
Cherepinskii-Malov, B. I. Buzykin, J. P. Kitajev, J. T.
Strutschkov, Izv. Akad. Nauk SSSR Ser. Khim. 1975, 805Ϫ811.
J. E. Rowe, D. A. Papanelopoulos, Aust. J. Chem. 1995, 48,
2041Ϫ2046.
0.0358
449
0.0447; 0.0970
0.0781; 0.1138
0.202; Ϫ0.286
0.0352
269
0.0355; 0.0848
0.0429; 0.0886
0.453; Ϫ0.432
[8]
R1; wR2 [I Ͼ 2σ(I)]
R1; wR2 (all data)
[9]
J. E. Rowe, A. F. Hegarty, J. Org. Chem. 1984, 49, 3083Ϫ3087.
O. Exner, J. Smolikova, V. Jehlicka, A. S. Shawali, Collect.
Czech. Chem. Commun. 1979, 44, 2494Ϫ2506.
Ϫ3
˚
[10]
ρmax; ρmin [eA
]
[11] [11a]
M. O. Lozinskii, P. S. Pel’kis, Zh. Org. Khim. 1965, 1,
[11b]
1415Ϫ1422, 1871Ϫ1875, 1976Ϫ1980.
M. O. Lozinskii, P.
S. Pel’kis, Zh. Org. Khim. 1966, 2, 692Ϫ697.
[12]
R. Fusco, R. Romani, Gazz. Chim. Ital. 1948, 78, 342Ϫ355.
(1Z)-2-Anilino-N-methyl-2-oxo-N-phenylethanehydrazonoyl Chlor-
ide (2): This compound was synthesised according to a published
procedure.[37] 2-(2-Methyl-2-phenyl)hydrazino-2-oxoacetanilide (9,
7 mmol, 2.0 g) was suspended in 80 mL of toluene. Phosphorus
pentachloride (14 mmol, 2.9 g) was added to the stirred suspension
at room temperature. The mixture was stirred at 50 °C until the
reaction was complete (monitored by TLC; hexane/ether, 7:3) and
then poured onto crushed ice. The organic layer was separated, and
the aqueous layer was washed twice with ether. The organic solu-
tion was dried, the solvent was removed, and the crude product
was purified by dry column chromatography, with toluene as elu-
ent. Yield: 0.9 g, (46%) of light yellow needles from heptane, m.p.
126Ϫ131 °C. 1H NMR ([D6]DMSO): see Table 5; additional sig-
nals: δ ϭ 3.72 (s, 3 H, CH3), 7.06Ϫ7.70 (10 H, arom. H). 13C NMR
([D6]DMSO): see Table 5; additional signals: δ ϭ 41.1 (s, 1 C,
CH3), 117.5Ϫ147.9 (12 C, arom. C). MS (70 eV): m/z (%) ϭ 287
(45) [Mϩ], 105 (100), 77 (51). C15H14ClN3O (287.75): calcd. C
62.61, H 4.90, Cl 12.32, N 14.60; found C 62.30, H 4.91, Cl 12.36,
N 14.52.
[13] [13a]
L. J. Powers, S. W. Fogt, Z. S. Ariyan, D. J. Rippin, R. D.
Heilmann, R. J. Matthews, J. Med. Chem. 1981, 24, 604Ϫ609.
[13b]
Patent, Kumiai Chemical Industry Co., Ltd. EP 200134;
Chem. Abstr. 1987, 106, 33062.
[14]
A. J. Hodgkinson, B. Staskun, J. Org. Chem. 1969, 34,
1709Ϫ1710.
[15] [15a] P. Frohberg, C. Kupfer, P. Stenger, U. Baumeister, P. Nuhn,
[15b]
Arch. Pharm.(Weinheim, Ger.) 1995, 328, 505Ϫ516.
A. S.
Shawali, N. M. Elwan, A. M. Awad, J. Chem. Res. Synop. 1997,
[15c]
8, 268Ϫ269.
A.S. Shawali, A. Osman, Tetrahedron 1971,
27, 2517Ϫ2528.
[16]
[17]
[18]
L. F. Audrieth, J. R. Weisiger, H. E. Carter, J. Org. Chem. 1941,
6, 417Ϫ420.
Patent, I. G. Farbenind. A.-G., DE 463140; Chem. Abstr. 1929,
22, 4130a.
D. G. Kuhn, J. A. Furch, D. A Hunt, M. Asselin, S. P. Baffic,
R. E. Diehl, T. P. Miller, Y. L. Palmer, M. F. Treacy, S. H.
Trotto, ACS Symp. Ser. 1998, 686, 185Ϫ193.
B. Vickery, G. R. Willey, M. G. B. Drew, J. Chem. Soc., Perkin
Trans. 2 1981, 155Ϫ160.
Tables of interatomic distances and configuration in molecules
and ions, supplement 1956Ϫ59, The Chemical Society, Special
Publication number 2, London, 1965.
T. D. Petrova, A. G. Ryabichev, T. I. Savchenko, V. E. Platonov,
V. I. Mamatyuk, Yu. V. Gatilov, I. Yu. Bagryanskaya, Zh. Org.
Khim. 1986, 22, 1297Ϫ1306.
T. Pilati, M. Simonetta, Acta Crystallogr., Sect. C: Cryst.
Struct. Commun. 1986, 42, 1425Ϫ1428.
A. Sahay, Asian J. Chem. 1994, 6, 476.
F. Kaberia, B. Vickery, G. R. Willey, M. G. B. Drew, J. Chem.
Soc., Perkin Trans. 2 1980, 11, 1622Ϫ1626.
Publication in preparation.
H. V. Patel, K. A. Vyas, S. P. Pandey, P. S. Fernandes, Tetrahed-
ron 1996, 52, 661Ϫ668.
[19]
[20]
2-(2-Methyl-2-phenyl)hydrazino-2-oxoacetanilide (9): The synthesis
was based on ref.[38] 1-Methyl-1-phenylhydrazine (0.02 mol, 2.4 g)
and 2-anilino-2-oxoacetyl chloride (0.02 mol, 3.7 g) in toluene were
stirred at room temperature until completion of reaction, as mon-
itored by TLC (hexane/ethyl acetate, 7:3). Yield: 2.7 g (50%) of an
amorphous solid from chloroform/heptane, m.p. 229Ϫ231 °C. IR
(KBr): ν˜ ϭ 3300, 3244 (NH ass.), 1755 (CϭO, amide, hydrazide),
1H NMR ([D6]DMSO): δ ϭ 3.13 (s, 3 H, CH3), 6.77Ϫ7.83 (10 H,
arom. H), 10.69 (s, 1 H, CONH, amide), 11.00 (s, 1 H, CONHN,
hydrazide). 13C NMR ([D6]DMSO): δ ϭ 39.9 (CH3), 112.7Ϫ149.3
(12 C, arom. C), 158.8 (CONH, amide), 159.9 (CONHN,
hydrazide). MS (70 eV): m/z (%) ϭ 269 (100) [Mϩ], 148 (53), 121
[21]
[22]
[23]
[24]
[25]
[26]
1662
Eur. J. Org. Chem. 2002, 1654Ϫ1663