CC BY
20
УДК 547.867
Sh. М. Salikhov, R. R. Zaripov, S. А. Krasko, L. R. Latypova, N. М. Gubaidullin, I. B. Abdrakhmanov, G. E. Zaikov, S. Yu. Sofina
EFFICIENT SYNTHESIS OF A BISSPIRO-3,1-BENZOXAZIN-4,1'-CYCLOPENTANES
Keywords: 3,1-benzoxazine, ortho-(cyclopent-1-enyl)-aniline, intramolecular heterocyclization.
The new data on the directed synthesis of bisspiro-3,1-benzoxazine based on dicarboxylic acid 2 - (1-cyclopentenyl) aniline were obtained. The influence of various substituents in the benzene ring of ortho tsiklopentenilarilamidov on the reaction of their intramolecular heterocyclization was studied.
Ключевые слова: 3,1-бензоксазин, орто-(циклопент-1-енил)-анилин, внутримолекулярная гетероциклизация.
Получены новые данные о направленном синтезе бис-спиро-3,1-бензоксазина на основе дикарбоновой кислоты 2 - (1-циклопентенил) анилина. Изучено влияние различных заместителей в бензольном кольце в орто-циклопентенилариламидов на реакцию их внутримолекулярной гетероциклизации.
Introduction
Benzoxazines are the most promising compounds for the synthesis of a new generation of organic substances with pronounced biological activity. Major effective and widely used approaches to create 3,1-benzoxazines based on the classical condensation methods of amines with carboxylic acids derivatives and further cyclization of products by various regents and catalysts [1]. Previously, we have developed a method of the available synthesis of 3,1-benzoxazine, which allowed to include amino-Claisen rearrangement products in this process [2]. Initiating systems based on these compounds and their metal complexes have found practical substantiation as polymer molecular weight regulators in controlled radical polymerization [3] and antioxidants of radical chain oxidation of polyisobutylene.
In order to expand the combinatory library of 3,1-benzoxazines by the proposed approach [4] we continue studying synthetic capacity of available dicarboxylic acids.
4C-R-C' + 2
1. HCl„, CH,Cl,
2 10% NaHC°3
J-R-U
о о . и и
NH-C—R—C—NH
2 R=no 6 R=(CH2)4
3 R=CH2 7 R=1,3-C6Hj
4 R=(CH2)2 8 R=1,4-C6Hj
5 R=(CH2)3
9 R=(CH2)3
10 R=(CH2)4 || 11 R=1,3-C6H4
12 R=1,4-C6H4
So, the reaction of chloranhydride with the or-tho-(cyclopent-1-enyl)-aniline 1 in the presence of K2CO3 led the amides 2-8. The reaction of compounds 5-8 with HCl(g) and the subsequent treatment with 10% NaHCO3 gives benzoxazines 9-12. In the case of amides 2-4 formation of 3,1-benzoxazine cycle is not observed. Probably insignificant length of methylene bridge is a steric hindrance to the formation of two 3,1-benzoxazinone cycles at a short distance from each other.
COCl
4
+ 1
R
13 R = 2-N °2
14 R = 3-N°2
15 R = 2-O CH3
16 R = 2-I
17 R = 3-I
18 R = 2-C l 4-Cl
19 R = 2-N O
20 R = 3-N°2
21 R = 2-O CH3
22 R = 2-I
23 R = 3-I
24 R = 2-C l 4-Cl
Further the range of 3,1-benzoxazine synthesized from monocarboxylic acids was extended. It is established that the chloroanhydrides of benzoic acids react with ortho-(cyclopent-1-enyl)aniline 1 at mild conditions to form amides 13-18 in high yelds. The treatment of these amides by HCl(g) led to benzoxazines 19-24.
K2CO3
Benzoxazines based on pyridinecarboxylic acids, where the introduction of an electron-deficient pyri-dine ring favours the formation of the conjugated system in which there are two coordinating center to form a donor-acceptor bond with ions of metals are also of practical interest. Benzoxazin 26 was obtained from amide 25 using a method described above.
о и
NH— C^
A
HCl
Cl
NH
C
-HCl
R
+ 1
CHCl
22
Cl
Cl
R
R
B
Cl
R
R
D
Intramolecular heterocyclization of arylamides A to 3.1-benzoxazines is initiated by the proton-catalyzed addition of cyclopentadiene ring to the double bond and the generation of carbenium ion of benzyl-type B; the subsequent intramolecular stabilization ions by nucleophilic oxygen atom of an amide fragment gives heterocyclic ions C - precursors of neutral products of the rearrangement D. Since, the cyclization reaction is probably limiting stage, the introduction of donor substituents into the benzene ring of the initial substrate promotes the intramolecular heterocyclization of ortho-cyclopentanedione. The cyclization of amides under the electron impact mass spectrometry conditions [5] confirmed this fact.
Experimental Section
1 13
Spectra of 'H and 1 NMR were recorded on Bruker AM-300 (300.13 and 75.47 MHz) and Bruker Avance III 500 (500.13 and 125.75 MHz), using CDCl3, and acetone-d6 as solvents. Chemical shifts are reported in units of parts per million and all coupling constants are reported in hertz. All reaction were monitored by TLC analysis on plates "Sorbfil PTLC-A-AF".
General synthetic procedure for carboxylic acid amides
To a solution of chloroanhydride (0.014 mol) in CH2Cl2 under stirring at room temperature ortho-(cyclopent-1-enyl)-aniline (0.01 mol) and K2CO3 (0.02 mol) was added. The reaction mixture was stirred for 24 hours. After completion of the reaction (control by TLC), the precipitate was filtered off, the filtrate was washed with water (1 x 25 mL), 10% NaHCO3 (2 x 25 mL), dried over MgSO4. The solvent was evaporated, the residue was purified by column chromatography (petroleum ether: ethyl acetate).
N,W-bis(2-cydopent-1-en-1-ylphenyl)ethanediamide (2): white solid (54%); mp 202-204°C. 1H NMR (CDCl3 +acetone - d6): 1.90 m (2H, C4H), 2.46 m (2H, C5H), 2.54 m (2H, C3H), 5.84 t (2H, J = 2.0, C2H), 6.97 - 7.08 (3H, m, Ar), 8.19 (1H, d, J = 7.3, Ar), 9.73 (1H, br, NH). 13C NMR (CDCl3 +acetone - d6): 22.96 (C4), 33.53 (C5), 36.33 (C3), 119.66 (C2), 124.54 (Ar), 127.23 (Ar), 127.69 (Ar), 128.79 (C1), 131.27 (Ar), 132.72 (Ar), 139.22 (Ar), 156.95 (C=O).
N,W-bis(2-cydopent-1-en-1-ylphenyl)malonamide (3): orange oil (40%); 1H NMR (CDCl3): 2.0 (2H, m, C4H), 2.18 (1H, s, COCH2CO), 2.53 (2H, m, C5H), 2.71 (2H, m, C3H), 6.0 (1H, J = 2.0, t, C2H), 6.775-7.15 (4H, m, Ar). 13C NMR (CDCl3): 23.23 (C4), 33.47 (CH2), 33.98 (C5H), 36.44 (C3H), 117.38 (Ar), 120.23 (Ar), 125.62 (C2H), 127.66 (Ar), 128.35 (Ar), 129.41 (C2H), 135.84 (Ar), 140.51 (Ar), 140.93 (C=O).
N,W-bis(2-cydopent-1-en-1-ylphenyl)succinamide (4): yellow oil (50%). 1H NMR (CDCl3): 1.85 (2H, m, C4H), 2.34 (2H, m, C5H), 2.48 (2IH, m, C3H), 2.77 (2H, s, CH2), 5.57 (1H, J = 2.0, t, C2 H), 7.0-7.30 (4H, m, Ar). 13C NMR (CDCl3): 23.74
(C4H), 28.59 (CH21), 33.59 (C5H), 35.78 (C3H), 126.48 (C2), 127.84 (Ar), 128.62 (Ar), 129.19 (Ar),
129.30 (C1), 129.36 (Ar), 137.15 (Ar), 140.45 (Ar), 176.54 (C=O).
N,N'-Ms(2-cydopent-1-en-1-ylphenyl)pentanediamide (5): yellow oil (66%). 1H NM/IR (CDCl3): 1.81 MH, m, CH2), 2.02 (2H, m, C4H), 2.49 (2H, m, C H), 2.57 (2H, m, C2H), 2.70 (2H, m, CH2), 5.88 (1H, J=1.8, t, C2 H), 6.73 (1H, td, J=1.6, 7.6, C4H), 7.10-7.25 (4H, m, Ar), 8.25 br. (1H, NH). 13C NMR (CDCl3): 22.99 (CH2), 23.20 (C4H), 33.69 (C3H), 36.14 (C5H), 36.58 (CH2), 115.70 (Ar), 118.10 (Ar), 127.57 (Ar), 128.13 (Ar), 128.55 (C1), 130.47 (C2), 134.37 (Ar), 140.47 (Ar), 170.43 (C=O).
N,W-bis(2-cydopent-1-en-1-ylphenyl)hexanediamide (6): yellow oil (38%). 1H NMR (CDCl3): 1.19 (4H, s, CH2), 2.02 (2H, m, C4H), 2.48 (2H, m, C5H), 2.61 (2H, m, C2H), 2.76 (4H, s, CH2), 5.87 (1H, J = 2.0, t, C2H), 6.60-7.07 (4H, m, Ar). 13C NMR (CDCl3): 23.23 (C4H), 29.73 (C3H), 30.95 (C5H), 33.83 (CH2), 36.63 (CH2), 123.75 (C1),
125.31 (Ar), 126.82 (Ar), 127.53 (Ar), 125.74 (C2), 127.97 (Ar), 128.29 (Ar), 141.32 (Ar), 146.57 (Ar), 161.13 (C=O).
N,N'-bis(2-cydopent-1-en-1-ylphenyl)isophthalamide (7): white solid (68%). mp. 105-107°C. 'H NMR (CDCl3): 1.95 (4H, m, C11H2, C11aH2), 2.50 (4H, m, C10H2, C10aH2), 2.72 (4H, m, C9H2 C9aH2), 6.03 (2H, J = 2.1, t, C8H, C8aH), 7.15 (2H, t, J = 7.4, C4H, C4aH), 7.27 (2H, d, J = 7.9, C6H, C6aH), 7.32 (2H, t, J = 7.4, C5H, C5aH), 7.68 (1H, t, J = 7.7, C5H), 7.95 (2H, d, J = 6.9, C6H, C6aH), 8.15 (2H, d, J = 7.9, C6H, C4H), 8.50 (1H, s, C2H), 9.45 (2H, br, NH). 13C NMR (CDCl3): 23.27 (C10, C10a), 33.78 (C11, C11a), 36.77 (C9, C9a), 121.25 (C6, C6a), 124.288 (C4, C4a), 125.64 (C2), 127.65 (C8, C8a), 127.72 (C6', C4), 129.02 (C1, C1a), 129.28 (C5), 129.74 (C5, C5a), 130.86 (C3, C3a), 134.31 (C2, C2a), 135. 52 (C7, c7a), 140.77 (C1', C3'), 163.72 (C=O).
N,W-bis(2-cydopent-1-en-1-ylphenyl)terephthalamide (8): white solid (44%). mp. 205-207°C. 'H NMR (CDCl3): 2.29 (4H, m, C^H2, C11aH2), 2.45 (4H, m, C10H2, C10aH2), 2.84 (4H, m, C9H2, C9aH2), 5.69 (2H, t, J = 2.1, C9H, C8aH), 6.42 (2H, t, J = 7.4, C4H, C4aH), 7.27 (2H, d, J = 7.9, C6H, C6aH), 7.40 (2H, t, J = 7.4, C5H, C5aH), 7.44 (1H, t, J = 7.7, C5H), 7.94 (2H, d, J = 6.9, C6H2, C6aH), 8.31 (2H, d, J = 7.9, C H, C4H), 9.19 (2H, br, NH). 13C NMR (CDCl3): 25.89 (C10, C10a), 27.54 (C11, C11a), 29.66 (C9, C9a), 119.39 (C6, C6a), 124.39 (C4, C4a), 126.51 (C2'), 127.31 (C8, C8a), 127.83 (C6, C4'), 131.85 (C2, C2a), 135.13 (C7, C7a), 141.26 (C1', C3'), 161.07 (C=O).
N-(6-cydopent-1-en-1-ykyclohexa-1,5-dien-1-yl)-2-nitrobenzamide (13): yellow solid (65%). mp. 91-93°C. 'H NMR (CDCl3): 1.95 (2H, m, H5a, H5b), 2.48 (2H, m, H4a, H4b), 2.67 (2H, m, H3a, H3b), 5.91 (1H, t, 3J = 1.8, H2'), 7.15 (1H, t, 3J4-3 = 7.3, J4-5 =
7.3, H4), 7.22 (1H, d, 3J3-4 = 7.3, = 7.3, 3J5-4= 7.3, H5), 7.62 (2H, t, 3Jm_p = 7.4, 3Jm_o = 7.4, Hm), 8.1, Hm), 8.33 (1H, d, 3Ja-5 = (CDCl3): 23.31 (C5), 33.89 (C4' (C6), 124.85 (C4), 124.89 (Cm'). (C3), 128.26 (C0), 130.82 (C2')
H3), 7.31 (1H, t, 3J5-6 m, Ho, Hp), 7.772 (1H, 8.11 (1H, d, 3Jm'-p = 7.3, H6). 13C NMR ), 36.78 (C3'), 121.73 127.86 (C5), 127.87
130.89 (Cp), 132.51 (C1), 133.08 (Cp'), 133.99 (Cm), 140.59 (C2), 146.50 (C0), 164.14 (C=O).
N-(6-cydopent-1-en-1-ykyclohexa-1,5-dien-1-yl)-3-nitrobenzamide (14): yellow solid (68%). mp. 94-95°C. 1H NMR (CDCI3): 2.09 (9H, m, H5a, H5'b), 2.66 (2H, m, H4a, H4b), 2.73 (2H, m, H3a, H3b), 6.0 (1H, t, 3J = 1.8, H2'), 7.15 (1H, dd, 3J4_3 = 7.3, 3J4-5 = 7.3, H4), 7.25 (1H, d, 3J3-4 = 7.3, H3), 7.31 (1H, d, J 4 = 7.3, 3J5-6 = 7.3, H5), 7.71 (1H, dd, 3Jm'_p = 7.9, 3Jm'_ 0' = 7.9, H-m), 8.23 (1H, d, 3J0'-m' = 7.9, H°'), 8.40 (1H, d, 3Jp-m' = 7.9, Hp), 8.43 (1H, d, 3J6-5 = 7.3, H6), 8.61 (1H, br, NH), 8.63 (1H, s, H°). 13C NMR (CDCI3): 23.641 (C5), 24.750 (C5'), 33.91 (4C4), 37.09 (Co3), 120.08 (C®5), 121.51 (C0), 134.62 (C4), 126.30 (C°), 127.86 (C3), 127.99 (C5), 128.85 (C1'), 130.26 (Cm'), 131.31 (C°), 134.09 (C1), 136.61 (Cp), 141.11 (C2), 148.32 (Cm), 162.26 (C=O).
N-(6-cydopent-1-en-1-ykyclohexa-1,5-dien-1-yl)-2-methoxybenzamide (15): brown oil (79%). 1H NMR (CDCI3): 2.03 (2H, m, H5'a, H5'b), 2.58 (2H, m, H4a, H4b), 2.70 (2H, m, H3a, H3b), 3.95 (3H, s, OCH3), 5.97 (1H, t, 3J2-3' = 2.0, H2'), 7.01 (d, 1H, J m = 8.4, Ho) 7.08 (1H, t, 3J4-5 = 7.5, 3J4-3= 7.5, H4), 7.13 (1H, t, 3Jp-m = 7.6, 3Jn-m' = 7.6, Hp), 7.20 (1H, dd, 3J3-4 = 7.5, 4J3-5 = 1.2, H3), 7.28 (1H, dt, 3J5-6 = 8.2, 3J5-4 = 7.5, J5-3 = 1.2, H5), 7.48 (1H, dt, 3Jm-° = 8.4, 3Jm-p= 7.6, 3Jm-m' = 1.6, Hm), 7.30 (1H, dd, 3Jm'-p = 7.6, 3Jm-m = 1.6, Hm), 8.44 (1H, d, 3J6-5 = 8.2, H6). 13C NMR (CDCI3): 23.56 (C5), 33.92 (C4), 36.56 (C3), 55.86 (OCH3), 111.40 (Co), 121.57 (Cp), 122.15 (C6), 127.67 (C5), 128.0 (C3), 129.48 (C1), 130.49 (C2'), 132.71 (Cm), 133.14 (Cm), 135.54 (Cp'), 141.04 (C2), 157.15 (C°), 163.26 (C=0).
N-(6-cydopent-1-en-1-ykydohexa-1,5-dien-1-yl)-2-iodobenzamide (16): dark solid (61%). mp. 85-87°C. 1H NMR (CDCI3): 2.03 (2H, m, H5'a, H5'b), 2.56 (2H, m, H4a, H ), 2.74 (2H, m, H3a, H3b), 5.98 (1H, t, 3J = 2.0, H2'), 7.191 (2H, m, H4, Hp), 7.28 (1H, dd, 3J3-4 = 7.4, J3-5 = 1.4, H3), 7.35 (1H, ddd, 3J5-6 = 8.2, 3J5-4 = 7.4, 4J5-3 = 1.4, H5), 7.47 (1H, t, 3Jm-° = 7.4, 3Jm-p = 7.4, Hm), 7.52 (1H, d, 3J°-m = 7.4, H°), 7.95 (1H, d, 3Jm'-p = 8.0, Hm), 7.97 (1H, br, NH), 8.48 (1H, d, 3J6-5 = 8.2, H6). 13C NMR (CDCI3): 23.34 (C5), 33.90 (C4'), 37.11 (C3'), 92.29 (C°'), 121.34 (C6), 124.53 (Cp), 127.80 (C°), 127.95 (C5), 128.11 (C3), 128.45 (Cm), 129.08 (C1'), 131.02 (C2'), 131.47 (C4), 134.31 (C), 134.31 (C), 140.23 (Cm), 140.51 (C2), 142.39 (Cp), 167.19 (C=0).
t, 3J = 2.0, H2')37.17 (1H, dd, 3J3-4=7.5, 4J3-5=1.2, H3), 7.24 (1H, dd, 3Jm-° = 8.0, 3Jm-p = 7.4, Hm), 7.28 (1H, dd, J4-5 = 7.5, 3J4-3=7.5, H4), 7.34 (1H, ddd, J5-6 = 7.5, 3J5-6 = 7.5, 3J5-4 = 7.5, 4J5-3 = 1.2, H5), 7.82 (1H, d, 3Jp-m = 7.4, Hp), 7.91 (1H, d, 3J°-m = 8.0, H°), 8.21 (1H, s, H°), 8.45 (1H, d, 3J6-5 = 7..5, H6); 8.50 (1H, br, NH). 13C NMR (CDCI3): 23.44 (C5), 29.73 (C4), 33.94 (C3'), 94.58 (Cm'), 120.91 (C6), 124.32 (C3), 126.07 (Cp), 127.79 (C5), 127.92 (C4), 130.54 (Cm), 130.94 (C2'), 134.39 (C2), 136.21 (C°), 138.97 (Cp), 140.59 (C°), 141.05 (C1), 142.33 (C1), 169.10 (C=0).
2,4-dichloro-.N-(6-cydopent-1-en-1-ylcyclohexa-1,5-dien-1-yl)benzamide (18): white solid (65%). mp. 78-79°C. 1H NMR (CDCI3): 2.05 (2H, m, H5a, H5b), 2.58 (2H, m, H4a, H4b), 2.72 (2H, m, H3'a, H3b), 5.92 (1H, t, J = 18, H2'), 7.20 (2H, m, H4, H3), 7.35 (1H, dt, 3J5-4= 7.6, 3J5-6 = 7.6, H ), 7.4-0 (1H, dd, 3Jm-°= 8.3, 4Jm-m' = 1.4, Hm), 7.51 (1H, d, 4Jm'-m= 1.8, Hm), 7.77 (1H, d, 3J°-m= 8.3, H°), 8.46 (1H, br, NH), 8.48 (1H, dd, 3J6-5= 7.6, 4J6-4 ^ 1.0, H6). 13C NMR (CDCI3): 23.37 (C5), 33.87 (C4'), 37.14 (C3'), 121.15 (C6), 124.52 (C4), 127.79 (Cm), 127.82 (C5), 128.02 (C3), 129.21 (Cp), 130.28 (Cm'), 131.20 (C2'), 131.59 (C°), 133.77 (C°'), 134.37 (C2), 137.15 (Cp'), 140.43 (C1), 163.27 (C=0).
^-(2-cyclopent-1-en-1-ylphenyl)pyridine-2-carboxamide (25): yellow solid (79%). mp. 85-87°C. 1H NMR (CDCI3): 2.10 (2H, m, C11H2), 2.65 (2H, m, C10H2), 2.75 (2H, m, C9H2), 6.05 (1H, t, J = 2.2, C8H), 7.20 (1H, t, C4H, J = 7.5), 7.28-7.35 (2H, m, C3H, C6H), 7.48 (1H, t, J = 7.5, C5H), 7.80 (1H, t, J = 6.0, C4H), 8.30 (1H, d, J = 8.0, C6H), 8.05 (1H, d, J = 8.0, C3H), 8.10 (1H, t, J = 8.0, C5H). 13C NMR (CDCI6): 23.51 (C10), 33.91 (C9), 36.68 (C115), 120.32 (C6), 122.26 (C3), 123.76 (C4), 126.13 (C), 127.61 (C8), 128.24 (C5), 128.93 (C2), 131.39 (C33), 134.74 (C1), 137.48 (C4), 139.94 (C7), 148.03 (C6), 150.22 (C2), 161.63 (C=O).
General synthetic procedure for benzoxazines
To a solution of the amide (0.01mol) in CH2CI2 was bubbled HCI(g). After completion of the reaction (control by TLC) was treated 5% NaHCO3, washed with water (1 x 25 mL), dried over MgSO4. The solvent was evaporated, the residue was purified by column chromatography (petroleum ether: ethyl acetate).
2,2'-propane-1,3-diylbisspiro[3,1-benzoxazine-4,1'-cyclopentane] (9): yellow oil (38%). 1H NMR (CDCI3): 2.0 (5H, m, C2 H, C4H, CH2), 2.45 (2H, m, CH2), 2.53 (2H, m, C5H), 2.74 (2H, m, C3H), 7.04-7.38 (4H, m, Ar). 13C: NMR (CDCI3): 23.54 (C2, C5'), 25.35 (CH2), 36.14 (CH2), 40.78 (C3, C4'), 88.44 (C1), 122.10 (Ar), 123.85 (Ar), 125.91 (Ar), 126.19 (Ar), 127.29 (Ar), 134.90 (Ar), 162.10 (C1).
N-(6-cydopent-1-en-1-ykydohexa-1,5-dien-1-yl)-3-iodobenzamide (17): dark solid (63%). mp. 86-88°C. 1H NMR (CDCI3): 2.11 (2H, m, H5'a, H5b); 2.68 (2H, m, H4a, H4b); 2.77 (2H, m, H3a, H3b); 6.01. (1H,
2,2'-butane-1,4-diylbisspiro[3,1-benzoxazine-4,1'-cyclopentane] (10): yellow oil (42%). 1H NMR (CDCI3): 1.68 (4H, m, C2H, C5H), 1.70 (4H, m, C3H, C4H), 2.10 (2H, m, CH2), 2.21
(2H, m, CH2), 6.95-7.15 (4H, m, Ar). 13C NMR (CDCl3): 23.945 (C2, C5'), 25.99 (CH2), 35.34 (CH2), 40.87 (C3', C4'), 88.42 (C1), 122.21 (Ar), 124.12 (Ar), 126.22 (Ar), 128.32 (Ar), 128.86 (Ar), 139.01 (Ar), 162.33 (C1).
2,2'-(1,3-phenylene)bisspiro[3,1-benzoxazine-4,1'-cyclopentane] (11): white solid (82%). mp. 120-122°C. 'H NMR (CDCl3): 1.91 (4H,
m, C11H, C11'aH), 2.05 (8H, m, C12H, C13H, C13'aH,
C12aH), 2.35 (4H, m, C14H, C14'aH), 7.19-7.30 (8H, m, C7H, C7aH, C8H, C8aH, C9H, C9aH, C10H, C10aH), 7.50 (1H, t, J = 7.8, C5H), 8.27 (2H, d, J = 7.8, C4H, C6H), 8.27 (1H, s, C2H). 13C NMR (CDCl3): 23.80 (C12, C13, C12a, C13a), 40.20 (C11, C14, C11a, C14a), 89.16 (C4, C4a), 122.06 (C9, C9a) 124.99 (C2), 126.59 (C7, C7a), 127.166 (C5), 128.18 (C10, C10a), 128.38 (C4', C6'), 129.19 (C1', C3'), 130.56 (C8, C8a), 133.41 (C5, C5a), 139.59 (C6, C6a), 156.20 (C2, C2a).
2,2'-(1,4-phenylene)bisspiro[3,1-benzoxazine-4,1'-cyclopentane] (12): yellow oil (62%). 'H NMR (CDCl3): 1.82 (iH, m, C2H), 2.0 (4H, m, C2H, C4H), 2.25 (2H, m, C^'HW^^^ (6H, m, Ar)). 13C NMR (CDCl3): 23.80 (C2', C5), 40.14 (C3', C4), 89.08 (C1), 122.04 (Ar), 123.04 (Ar), 126.74 (Ar), 127.59 (Ar), 128.39 (Ar), 129.23 (Ar), 135.62 (Ar), 139.52 (Ar), 156.15 (C1).
2-(2-nitrophenyl)spiro[3,1-benzoxazine-4,1'-cyclopentane] (19): yellow solid (82%). mp. 79-81°C. 'H NMR (CDG3): 1.90 (2H, m, H4a, H4b), 2.16 (4H, m, H3a, H3b, H5a, H5b), 2.41 (2H, m, H2'a, H2'b), 7.18 (1H, d, 3J5_6 = 7.5, H5), 7.20 (1H, dd, 3J6-5 = 7.5, 3J6-7 = 8.0, H6), 7.30 (2H, m, H7, H8), 7.62 (1H, m, Hm), 7.80 (1H, dt, 3Jp-m' = 8.0, 4Jn.m = 8.0, 4Jp_o = 1.7, Hp), 8.27 (1H, dd, 3Jm'-p = 8.0, 3Jm'_m = 1.7, H-Arm), 8.89 (1H, dd, 3Jo-m = 7.8, 4Jo-p = 1.77, Ho). 13C NMR (CDCl3): 24.0 (C3', C ), 40.65 (C2', C5'), 89.80 (C4), 122.02 (C5), 123.45 (Co), 125.32 (C8), 127.31 (C6), 128.59 (C7), 131.52 (Cm), 133.43 (Cp), 134.11 (Cm'), 135.46 (Cp), 138.93 (C8a), 146.85 (Co), 159.15 (C2).
2-(3-nitrophenyl)spiro[3,1-benzoxazine-4,1'-cyclopentane] (20): brown oil (90%). 'H NMR (CDCl3): 1.92 (2H, m, H4a, H4b), 2.12 (4H, m, H3a, H3b, H , H5'b), 2.35 (2H, m, H2a, H2b), 7.16 (1H, d, 3J5-6 = 7.5, H5), 7.22 (1H, dd, 3J6-5 = 7.5, 3J6-7 = 8.0, H6), 7.31 (2H, m, H7, H8), 7.61 (1H, t, 3Jm-o' = 8.0, 3Jm'-p = 8.0, H-Arm), 8.32 (1H, dt, 3Jo'-m' = 8.0, 4Jo'-p = 1.7, 4Jo'-o = 1.7, H-Aro), 8.45 (1H, dt, 3Jp-m' = 8.0, 4Jp-o' = 1.7, 4Jp-o = 1.7, H-Arp), 8.92 (1H, dd, 4Jo-o' = 1.7, 4Jo-p = 1.7 , H-Ar5). 13C NMR (CDCl3): 23.99 (C3', C4'), 40.62 (C2', C5), 89.86 (C4), 122.31 (C5), 122.71 (Co), 1255.24 (C8), 127.34 (C6), 128.64 (C7), 129.27 (C5a, Cm'), 133.43 (Cp), 135.16 (Cp'), 138.93 (C8a), 148.33 (Cm), 154.40 (C2).
2-(2-methoxyphenyl)spiro[3,1-benzoxazine-4,1'-cyclopentane] (21): brown oil (69%). 1H NMR (CDCl3): 1.85 (2H, m, H5a, H5b), 2.02 (4H, m, H2a, H2b, H4a, H4b), 2.43 (2H, m, H3a, H3b), 3.76 (3H, s, OCH3), 6.94 (1H, d, 3Jm-p = 8.3, Hm), 6.99 (1H, t, 3Jm-
p = 7.5, 3Jm-o = 7.5, Hm), 7.12 (1H, d, J5-6 = 8.3, H5), 7.18 (1H, m, H6) 7.27 (1H, m, H7, H8), 7.40 (1H, ddd, 3Jp-m' = 8.3, 3Jp-m = 7.5, 4Jp-o = 1.7, Hp), 7.65 (1H, dd, 3Jo-m = 8.4, 7.5, 4Jo-p = 1.7, Ho). 13C NMR
(CDCl3): 24.19 (C, C5'), 40.47 (C3', C4'), 55.68 (OCH3), 89.47 (C4), 120.39 (Cm), 122.06 (C5), 123.44 (Cp'), 124.83 (C7), 128.56 (C6), 128.28 (C8), 129.39 (C5a), 131.08 (Co), 131.85 (Cp), 139.75 (C8a), 158.21 (Co'), 158.54 (C2).
2-(2-iodophenyl)spiro[3,1-benzoxazine-4,1'-cyclopentane] (22): brown oil (81%). 'H NMR (CDCl3): 1.82 (2H, m, H5a, H5b), 2.05 (4H, m, H2a, H2b, H4a, H4b), 2.48 (2H, m, H , H3b), ^.02 (1H, t, 3Jm-p = 7.5, 3Jm-o = 7.5, Hm), 7.14 (1H, d, 3J5-6 = 8.3, H5), 7.19 (1H, m, H6), 7.29 (1H, m, H7, H8), 7.40 (1H, m, Hp), 7.58 (1H, dd, 3Jo-m = 8.4, 3Jm-p= 7.5, 4Jo-p = 1.7, Ho), 7.90 (1H, d, 3Jm-p = 7.9, H"1'). 13C NMR (CDCl3): 224.19 (C2', C55), 40.47 (C3', C4'), 89.47 (C4), 92.80 (Co'(), 122.53 (C5), 124.83 (C7), 128.28 (C8), 128.56 (C6), 129.18 (Cm), 129.42 (C5a), 130.24 (Co), 131.36 (Cp), 133.76 (Cp'), 139.10 (Cm'), 139.45 (C8a), 159.74 (C2).
2-(3-iodophenyl)spiro[3,1-benzoxazine-4,1'-cyclopentane] (23): brown oil (82%). 1H NMR (CDCl3): 1.59 (2H, m, H5a, H5b), 2.11 (4H, m, H2a, H2b, H4a, H4b), 2.35 (2H, m, H3a, H3b), 7.18-7.26 (3H, m, H5, H8, Hm), 7.34 (2H, m, H6, H7), 7.86 (1H, ddd, 3Jo-m = 6.9, 3Jo-o' = 1.6, 4Jo-p = 1.1, H7), 8.11 (1H, ddd, 3Jp-m = 7.8, 4Jp-o' = 1.4, Hp), 8.51 (1H, dd, 4Jo'-o = 1.6., 4Jo-p = 1.4, Hrf). 13C NMRR (CDCl3): 233.96 (C2', C5^, 40.37 (C3', C4'), 89.37 (C4), 93.99 (Cm'), 122.19 (C"), 125.03 (C5), 126.89 (C7), 126.98 (Cp), 128.52 (Cm), 129.33 (C5a), 129.91 (C8), 135.29 (Cp), 136.66 (Co'), 139.37 (C8a), 140.04 (Co), 155.22 (C2).
2-(2,4-dichlorophenyl)spiro[3,1-benzoxazine-4,1'-cyclopentane] (24): colorless oil (70%). 'H NMR (CDCl3): 1.62 (2H, m, H5a, H5b), 2.18 (4H, m, H2a, H2 , H4a, H4b), 2.37 (2H, m, H3'a, H3'b), 7.22 (1H, dt, 3J4-3 = 7.6, 3J4-5 = 7.6, 4J4-6= 1.0, H4), 7.28 (1H, dd, 3J3-4= 7.6, 3J3-5 = 1.4, H3), 7.32 (1H, m, H5, H6), 7.44 (1H, dd, 3Jm-o= 8.3, 4Jm-m' = 1.4, Hm), 7.61 (1H, d, 3Jo-m= 8.3, Ho), 7.85 (1H, d, 4Jm'-m= 1.8, Hm'). i3C NMR (CDCl3): 24.24 (C2', C5'), 40.56 (C3', C4'), 90.12 (C4), 122.08 (C5), 125.96 (C7), 126.71 (Cp'), 127.14 (Co), 128.12 (C"), 129.34 (C8), 129.49 (C5a), 130.34 (Co), 131.59 (^m), 133.17 (Co'), 136.67 (Cp), 138.56 (C8a), 159.62 (C2).
2-pyridin-2-ylspiro[3,1-benzoxazine-4,1'-cyclopentane] (26): yellow oil (75%). 1H NMR (CDCl3): 1.60 (2H, m, H4'), 2.0 (4H, m, H2', H5'), 2.30 (2H, m, H3'), 7.13 (1H, t,J = 7.5, H6), 7.20 (1H, t, J = 7.5, H7), 7.32 (2H, m, H5, H11), 7.47 (1H, d, J = 7.5, H8), 7.75 (1H, t, J = 7.8, H12), 8.06 (1H, d, J = 7.8, H10), 8.79 (1H, d, J = 7.8, H13). 13C NMR (CDCl3): 23.59 (C-2', C-5'), 40.10 (C-3', C-4'), 89.35 (C-4), 121.94 (Ar), 123.04 (Ar), 125.09 (Ar), 125.67 (Ar), 127.08 (Ar), 128.31 (Ar), 129.42 (Ar), 136.53 (Ar), 139.04 (Ar), 149.66 (Ar), 150.65 (Ar), 155.25 (C=N).
References
1. Grovachevskaya Е. V., Kvitkovsky F. V., Kosulina T.P. Russian Journal of Chemical Heteroatom Compounds (in Rus.). 2003. №2. 161-320.
2. Kazaryantz S. А., Salikkhov Sh. М., Abdrakhmanov I. B., Ivanova S. R. Bashkirian Chemical Journal (in Rus.). 2009. v.16. №4. 19-24.
3. Kazaryantz S. А., Ivanova S. R. Salikkhov Sh. М., Abdrakhmanov I. B., Islamova R. M. Bashkirian Chemical Journal (in Rus.). 2010. v.17. №3. 42-45.
4 Kazaryantz S. А., Ivanova S. R. Zaripov R. R., Yakupova L. R., Salikhov Sh. M. Herald of Bashkirian University Journal (in Rus.). 2010. v.15. №3. 581-584.
5. Galkin Е. G., Еrastov А. Q, Vyrypaev Е. М., Furley I. I Abdrakhmanov I. B Salikhov Sh. M., Krasko S. А. Russian Journal of Chemical Heteroatom Compounds (in Rus.). 2013. №7. 1160-1165.
© Sh. М. Salikhov - Ph.D. in Chemistry, Research Fellow, Institute of Organic Chemistry Ufa Scientific Centre of Russian Academy of Sciences; R. R. Zaripov - Instructor, Bashkir State Agrarian University; S. А. Krasko - Ph.D. in Chemistry, Assistant Professor, Ufa State Petroleum Technological University; L. R. Latypova- graduate student, Institute of Organic Chemistry Ufa Scientific Centre of Russian Academy of Sciences; N. М Gubaidullin - Doctor of Science, Full Professor, Bashkir State Agrarian University;
1 B. Abdrakhmanov - Academician, Doctor of Science, Institute of Organic Chemistry Ufa Scientific Centre of Russian Academy of Sciences; G. E. Zaikov - Doctor of Science, Full Professor, Kazan National Research Technological University; S. Yu. Sofina - Ph.D. in Science, Associate Professor, Kazan National Research Technological University, ov_stoyanov@mail.ru.
© Ш. М. Салихов - к.х.н., научный сотрудник, Федеральное государственное бюджетное учреждение наук Институт органической химии УНЦ РАН; Р. Р. Зарипов - ассистент, ФГБОУ ВПО Башкирский государственный аграрный университет; С. А. Красько - к.х.н., старший преподаватель, ФГБОУ ВПО Уфимский государственный нефтяной университет; Л. Р. Латыпова - магистрант, Федеральное государственное бюджетное учреждение наук Институт органической химии УНЦ РАН; Н. М. Губайдуллин - д-р с/хх наук, профессор, ФГБОУ ВПО Башкирский государственный аграрный университет; И. Б. Абдрахманов - акад. АН РБ, д-р хим. наук, Федеральное государственное бюджетное учреждение наук Институт органической химии УНЦ РАН; Г. Е. Заиков - д.х.н., проф. каф. ТПМ КНИТУ; С. Ю. Софьина - к. т.н., доцент каф. ТПМ КНИТУ, ov_stoyanov@mail.ru.
