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Chemistry of Heterocyclic Compounds, Vol. 33, No. 8, 1997

FORMATION OF A 4-QUINAZOLONE ON ATTEMPTING TO SYNTHESIZE A SYMMETRICAL AMIDINE OF
ANTHRANILONITRH+E.

CRYSTAL STRUCTURE OF 3-(2-CYANOPHENYL)-4QUINAZOLONE E. V. Babaev, S. V. Bozhenko, S. G. Zhukov, and V. B. Rybakov
Attempts to synthesize a sym-diarylformamidine by the reaction of anthranilonitrile and its N-formyl derivative led to theformation of 3-(2-cyanophenyl)-4-quinazolone. The structure of the substance obtained was confirmed by x-ray analysis.

On the basis of the simple heteroalternation rule, a 5 + 1 scheme has been proposed for the synthesis of a series of pyridines and quinolines by the cyclization of a 1,5-biselectrophilic CCCNC fragment and a 1,1-bisnucleophilic one carbon fragment [1]. The predicted reaction scheme was confirmed experimentally [2] by the reaction of an anthranilic acid amidine [namely, 2-(N,N-dimethylaminomethyleneimino) benzoic acid] with nitromethane. Somewhat later an analogous 5 + 1 synthetic scheme (with the san~ distribution of polarity in the reactants) was rediscovered in the example of the reaction of Ntrifluoroacetylanthranilic acid ester with a Wittig reagent [3]. Symmetrical amidines based on anthranilic acid derivatives are potential 1,5-biselectrophilic substrates useful for the synthesis of quinolines by this means. Either of the residues of the anthranilic acid derivative might emerge as leaving group in the reaction with a carbon bisnucleophile. One of the methods of synthesis of symmetrical amidines of aromatic amines (such as diphenylformamidine [4]) includes the condensation of an appropriate formanilide and an aniline. Up to the present time, anthranilic acid derivatives have not been used as substrates for such a reaction although several unsymmetrical amidines have been described [2, 5]. We found that 3-(2-cyanophenyl)-4-quinazolone was formed on attempting to obtain a symmetrical formamidine using anthranilonitrile as the aromatic amine.

H

HzN--

v

.

·"·0
Assignment of the substance obtained as a 4-quinazolone was confLrmed by IR spectral data, and the vibrational frequencies observed were typical of this class [6]. Peaks in the mass spectrum corresponded to the expected sequence of dissociation steps of the quinazolone fragment. The doublet in the PMR spectrum at 8.28 ppm was assigned probably to the M. V. Lomonosov Moscow State University, Moscow 119899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1105-1108, August, 1997. Original article submitted April 16, 1997.

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0009-3122/97/3308-0964518.00 9

Plenum Publishing Corporation


TABLE 1. Atomic Coordinates (xl04) and Equivalent Isotropic Displacement Parameters (Uec x 103) in the Investigated Structure
Atom
O(t) N(I) N(2) C(2) N(3) -208 (9) 3037(11) 2500(17) 4860(14) 5280(12) 3776(14) 4235 (16) 2801(16) 941 (17) 420(16) 1865(15) 1415(16) 2833 (14) 2557 (14) 2340(14) 2392(14) 2618(15) 2843 (I 4) 2504(18) 5848 5492 3104 14 -853 2161 2271 2624 2996 1363(9) 1304(9) 4011(12) 1580(11) 2368(9) 2986(11) 3919(13) 4525(13) 4272(13) 3351(13) 2702(11) 1714(12) 414(12) 1122(13) 270(12) -1230(13) -1970(12) -1138(13) 2705(16) 1183 4116 5149 4725 3164 745 -1785 -3021 -1635 ,3314 (6) 3280(7) 893(10) 3920(10) 5068(8)

Ueq
54(2) 34(2) 76(4) 40(3) 45(3) 38(3) 52(3) 54(3) 61 (4) 57 (4) 39(3) 37 (3) 37 (3) 38(3) 41(3) 44(3) 52(3) 47(3)

C(4)
C(5) C(o C(7) C(8) C(9) C(lo) C(zl) C(t2) C(13) C(t4) C(J.5) C(16) C(tT) H(2) H(5) H(6) H(7) H(a) H(13)

5624(9) 6800 (10)
7364(10) 6853(11) 5706(11) 5090(10) 3838(10) 2035(10) 843(10) -382(10) -399(10) 746(11) 1998(10) 85"7(11) 3511 7183 8143 7280
5352

33(4)
48 62 65 73 68 49 52 62 56

H(14) H(b3 H(t6)

-1179 -1219 706 2787

N3

Fig. 1. Numbering of atoms in the structure of the investigated compound. signal of the proton in the peri position to the 4-oxo group. Nevertheless the spectral methods did not permit a structure to be attributed unequivocally to the compound obtained. Final confirmation of the quinazolone structure was effected by x-ray analysis (see Fig. 1, Tables 1-3). As is evident, the aryl group (atoms C(11)-C(16) in Fig. 1) in the structure of the com.pound obtained is turned relative to the N(1)-C(10) fragment at the N(1)-C(ll) bond by 70 ~ The remaining geometrical parameters of the molecule (bond lengths and valence angles) are in good agreement with generally accepted values.

EXPERIMENTAL 3-(2-Cyanophenyl)-4-quinazolone. An excess of formic acid (54 mmole) was added to a solution of anthranilonitrile (5 mmole) in toluene (30 ml) and the mixture boiled for 2 h. The excess of formic acid and water were distiUed off using a 965


TABLE 2. Bond Lengths d (A) in the Investigated Compound
Bond O(z)--C(1o) N(z)--C..(Io) N(D--C(2) N(I)--CKID N(2)--C(17) C(2)--N(3) N(3)--C(4) ~
1,212(11) 1,375(11) 1,386(11) 1,432(11) 1,155(13) 1,312(I1) 1,394(11) 1,39"/(12) 1,400(13) 1,351(13) 1,357(14)

Bond
C('O--C(s) C(8)--C(9) C(9)--C0o) C(n)--C(16) C(11 )--C02 ) C (l 2)--C(13) C(12)--C(1"0 C(l 3)--C(14) C(14)--C(L~ C(~--C(~e)

a 1,376(13) 1,400(12) 1,486(12) 1,373(12) 1,392(12) 1,399(12) 1,41(2) 1,335(12) 1,358(13) 1,413(13)

C(4)--C(9) C(4)--C(s) C(s)--C(e C(6)--Cc'0

TABLE 3. Valence Angles co (deg) in the Investigated Compound
Angle co Angle w 122,7(9) 123,4(10) 113,7(10) 119,3(10) 121,4(10) 119,4(9) 120,3(10) 120,4(10) 119,3(10) 119,5(10) 122,0(11) 119,8(10) 119,2(10) 178,2(14)

C(lo)--N(1)--C(2) C(Io)--N(I)--C(11) C(2)--NcI)--C(u) No)--C(2)--N(D C(2)--N(3)--C(4) N(3)--C0)--C(9) N(3)--C(4)--C(s] C(9)--C(4)--C(s)

123,3(8) 119,7(8) 116,7(8) 124,1 (9)
I 16,0(9)

c(~)--C(s)--c(4)
C(s3--C(6)--C(v)

c(6)--cco--c(8) c.,c7)--c(a)--c(9)
Co)--C(9)--C(s) C(4)--C(9)--C(io) C(s)--C(9)--C(1o)

123,8(9) 117,0(10) 119,2(1) 118,2(10) 123,5(11) 120,3(11) 118,0(11) 120,9(I0) I18,2(I0) 120,9(10)

0 (I)--C(Io)--N(1) 0 (I)--C(i0)--C(9) N(I )--C(zo)--C(9) C(I 6)--C(11)--C(z2) C(l 6)--C(11)--N(I) C (12)--C(11)--N(1) C (11)--C(12)--C(13) C(l I)--C(12)--C(17) C (I3)--C(m)--C(I~) C(I 4)--C(~)--C(~.) C(t})--C(14)--C(b3 C(14)--C(u3--C(16) C(l I)--C(16)--C(L~) N (2)--C(17)--C(12)

Dean and Stark apparatus. Thionyl chloride (5 mmole) and anthranilonitrile (5 mmole) were added to the solution of Nformylanthranilonitrile obtained. The mixture was heated for i h and then evaporated in vacuum. The residue was treated with water. The aqueous solution contained unreacted N-formylanthranilonitrile. The insoluble residue (0.11 g, 9 %, mp 191-192~ was 3-(2-cyanophenyl)-4-quinazolone. IR spectrum (Nujol): 1617 (C=N), 1690 (C=O), 2247 cm -1 (CN). PMR spectrum (CD3CN, 200 MHz): 8.28 (1H, d, J = 8 Hz, 5-H); 8.15 (1H, s, 2-H); 7.8 (7H, m, Ar). Mass spectrum, m/z (I, %); 247 (I00) [M+], 219 (91) [M-CO] +, 192 (6) [M-CO-HCN] +, 129 (20) [NCC6H4NCH] +, 119 (16) [NCC6H4CO] +, 102 (40) [C6H4CN] +, 90 (20) [C6H4N] +, 76 (25) [C6H4] + The x-ray structural investigation of 3-(2-cyanophenyl)-4-quinazolone was carried out on a CAD-4 automatic monocrystal diffractometer using MoKoe radiation. Unit cell parameters were determined and refined from 25 reflections in the 0 angle range 12-13 ~ The crystals of the compound investigated were triclinic (space group P-l) with unit cell parameters a = 6.963(3), b = 8.845(9), c = 9.935(4) A, cx = 91.95(6) ~ /3 = 90.09(6) ~ 3' = 103.30(6) ~ Z = 2. The structure was solved by direct methods and refined by a full matrix least squares procedure with the SHELX [7] complex of programs in an anisotropic approach for the nonhydrogen atoms. The coordinates of hydrogen atoms were calculated from geometric considerations and refined to rigid binding with the corresponding carbon atoms. The final R factor was 8.81% from 1114 independent reflections with I > 2cr (I). The coordinates of atoms in the investigated compound and the isotropic thermal parameters equivalent to anisotropic are given in Table 1. The interatomic distances and the valence angles are given in Tables 2 and 3. The spatial disposition of atoms in the molecule and their numbering are shown in Fig. 1 [8]. The authors are grateful to the Russian Fund for Fundamental Investigations (RFFI) for financial support in paying for a license to use the Cambridge structural data bank (project No. 96-0%89187).

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2. 3. 4. 5. 6. 7.
.

E. V. Babaev, Khim. Geterotsild. Soedin., No. 7, 937 (1993). E. V. Babaev, Khim. Geterotsikl. Soedin., No. 7, 962 (1993). E. J. Latham, S. M. Murphy, and S. F. Stanforth, Tetrahedron Lea., 35, 3395 (1994). J. B. Shoesmith and J. Haldane, J. Chem. Soc., No. 7, 2704 (1923). D. A. Walsh, Synthesis, No. 9, 677 (1980). H. Culbertson, J. C. Decius, and B. E. Christensen, J. Am. Chem. Sot., 74, 4834 (1952). G. M. Sheldrick, SHELXL93. Program for the Refinement of Crystal Structures, University of Gottingen, Germany (1993). A. L. Spek, PLUTON92. Molecular Graphics Program, University of Utrecht, Netherlands (1992).

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