close

Вход

Забыли?

вход по аккаунту

?

Synthesis and Characterization of New 134-Oxadiazolines Synthese und Charakterisierung neuer 134-Oxadiazoline.

код для вставкиСкачать
837
1.3.4-Oxadiazolines
Synthesis and Characterization of New 1,3,4-Oxadiazolines
Synthese und Charakterisierung neuer 1,3,4-Oxadiazoline
Nedime Ergenq', Sevim Rollas', Yalqin Topaloglu, and Gulten Otiik
University of Istanbul, Faculty of Pharmacy. Beyazit 34452, Istanbul
'University of Marmara. Faculty of Pharmacy
Received May 29, 1989
In connection with our previous research on the synthesis
of azo-substituted five membered heterocycles'") we repon
here the synthetic route and the spectral characteristics of
2-aryl substituted-3-acetyl-5-[4-(1-phenyl-3,5-dimethyl-4pyrazoly1azo)-phenyll-1,3,4-oxadiazolines 2a-2h. 4-( 1 -Phenyl-3.5-dimethylpyrazoly1azo)-N2-(substituted benzylideobtained from the reaction of
ne)benzohydrazidesla-lhSe8),
1-phenyl-3,5-dimethyl-4-(4-hydrazinocarbonylphenylazo)pyrazole (1)9' with various aldehydes, were reacted with
Ac20, but no acetyl derivatives of hydrazones were formed,
instead, cyclization occured and compounds 2a-2h were obtained (Scheme).
The structures of compounds 2a-2h were confirmed by means of elemental analysis and spectral data. Instead of the UV absorptions of la-lh
between 348-352 run, 2a-2h showed maxima between 359-367 run. The
NH-absorptions of la-lh occured at about 3200 cm", whereas 2a-2h had
Ph
I
no absorptions in this region. Because both the starting compounds la-lh
and the cyclization products 2a-2h have carbonyl functionalities the ab
sorptions of 2a-2h at 1654-1674 cm-' (compounds 2b and 2c showed an
additional C=O absorption at 1769 cm-' due to the acetylation of the OH
group of the aromatic ring) could not help in structure elucidation. The 5substituted-3-acetyloxadiazolinestructure was supported by the 'H-NMR
spectra of 2a-2h. Signals due to -CONH-N= at about 12 ppm disappeared
after cyclization. Furthermore, the Ar-CH=N- protons of l a - l h which
show a one proton singlet at about 8.10-8.70 ppm region were shifted to the
7.06-7.13 ppm region. Although this proton would be expected at a little bit
higher field, the inductive effect of 0 and N and the phenyl ring attached to
the same C-atom shift this one proton signal more downfield than expected.
The molecular structure of the compounds was further elucidated by EIMS data. Molecular ions at m/z = 566; 508: 498; 482; 509 and 507 confirmed the molecular weights of 2c-2h, respectively. M' of 2a was not detectable, whereas 2b showed the M-1 peak at m/z = 551. Common m/z values
Compound 1
ArCHO
Compounds la-lh
Comp.
2a
Compounds
Ar
O O C " ,
Comp.
Ar
2c
2b
21
2c
29
2d
2h
Arch. Pharm. (Weinheim)322.837-838 (1989)
2a -2h
OVCH VerlagsgesellschaftmbH, D-6940 Weinheim, 1989
0365-6233/89/1111-0837$02.50/0
838
Ergen$ and coworkers
Table. Some data of 2-9
Comp.
Nr.
m.p.
"C
Yield
2a
162-163
73
2b
138
65
2c
116-118
75
2d
167-168
66
2e
175
53
2f
160(dec)
73
2g
197
68
2h
139-141
47
z
Molecular
formula
(Mol. Wt)
C
C~Hd'h.03
(494.6)
C3OHBN605
(552.6)
C31H30N605
(566.6)
Ca&..&604
(508.5)
C27H23N602C1
(499.0)
C27H23N602F
(482.5)
Cz7Hz3N704
(509.5)
C2gH2gN702.1R H2O
(516.6)
ofthe main fragments of 2a-2h are 77; 106, 118; 171; 199 and 303. The assignments of 2a-2h were in accordance with the ms data of oxadiazolines") and az~pyrazoles"-'~'.
Experimental Part
M.p.: Biichi melting point apparatus. uncorr.- IR spectra (KBr): Perkin
Elmer 577 spectrometer.- NMR and mass spectra were obtained at the Institute of Pharmaceutical Chemistry. Wesfdische Wilhelms Universit&
Miinster. F.RG, (NMR Varian A 60 NMR Spectrometer, Mass: Varian
MAT 44 S). Electronic spectra: Shimadzu W-260 spectrophotometer. Microanalyses: Perkin-Elmer, Model 240 Elemental Analyzer.
General procedure for the synthesis of Za-Zh
A mixture of 0.0025 mol la-lh and 5 ml of Ac2O was refluxed for 30
min at 130-140°C. Excess of Ac2O and by-product AcOH were distilled
off under reduced pressure and the residue was recrystallized from EtOH.
Testingfor biological activities
Compounds 2a-2h are king screened for insecticidal, herbicidal, fungicidal and plant growth regulant activities by Organic Chemistry Division,
Sittingbourne Research Centre, U.K., in accordance with the protocol of
Shell Company.
2a-2h were also tested preliminarily by diffusion method for their antimicrobial activities against Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 8739. Pseudomonas aeruginosa ATCC 1539, Klebsiella
68.0
67.5
65.2
65.3
65.7
65.9
66.1
65.9
65.0
65.3
67.2
66.7
63.6
63.6
67.4
67.2
Elemental analysis
Calcd.Bund
H
5.29
5.51
5.10
5.25
5.33
5.44
4.75
4.76
4.64
4.64
4.80
5.00
4.55
4.60
5.85
5.72
N
17.0
16.9
15.2
15.5
14.8
14.7
16.5
16.4
16.8
16.5
17.4
17.7
19.2
20.0
19.0
18.7
pneumoniae UJ 57, Bacillus subtilis ATCC 6633, Micrococcus luteus
ATCC 9341, Candida albicuns KUEN 931: they have no remarkable activities.
References
1
6
I
8
9
10
11
12
13
N.Ergeng, S.Rollas, S.Demir, and Fdzdemir, J. Fac. Pharm. Istanbul
11,183(1975); C.A.87,68224~(1977).
Eidem, ibid. 13,98 (1977); C.A. 89,6269 d (1978).
N.Ergen$ and F.t)zdemir, ibid. 16.17 (1980); C.A. 96,84813k (1982).
N.Ergen$ and H.t)qeki$, Pharmazie 43,832 (1988).
S.Rollas, J. Fac. Pharm. Istanbul 17, 41 (1981); C.A. 97, 55729c
(1982).
N.Ergen$, S.Rollas. and Y.Topalo&, Arch. Pharm. (Weinheim) 319.
545 (1986).
N.ErgenC, S.Rollas, Y.Topaloglu, and G.@pan, J. Fac. Pharm. Istanbul 22.29 ( I 986); C.A. 108,5069h (I 988).
N.Ergenq, S.Rollas, G.Capan, N.Do&m, and Y.t)zger, Pharmazie, in
press.
N.Ergen$ and S.Rollas, J. Fac. Pharm. Istanbul 11, 117 (1975); C.A.
87,68222 a (1977).
].&her, I.SElenyi, and W.Schunack, Arch. Pharm. (Weinheim) 320,
120 (1987).
H.Wilde, R.Herzschuh, P.Lepom, and G.Mann, J. F'rakt. Chem. 323,
13 (19811.
BMar&iec, Pharmazie 40,110 (1985).
J. ,pacep-.
~ ~ o l l aN.&geng,
s,
~.~ankaogVl~,
and ~ . ~ a r i ~ &
Istanbul 18,107 (1982); C.A. 101,90819e (1984).
[Kphsll]
Arch. Pharm. (Weinheim)322,837-838 (1989)
Документ
Категория
Без категории
Просмотров
6
Размер файла
129 Кб
Теги
134, synthesis, synthese, charakterisierung, characterization, oxadiazolin, neues, new, und
1/--страниц
Пожаловаться на содержимое документа