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(ProQuest: ... denotes formulae and/or non-USASCII text omitted; see image)
A direct entry and simple process for the synthesis of ......-spiroiminolactones present in a large number of natural products has been developed. In the first step, the synthesis of parabanic acid derivatives was commenced from the reaction of ......-disubstituted urea and thiourea with oxalyl chloride, then a three-component reaction was carried out with isocyanides, acetylenic esters, and ......-disubstituted parabanic acid derivatives. The method allows the construction of a variety of ......-spiroiminolactone structures in good to high yields starting from readily available precursors. It was found that in the case of ......-diphenyl thioparabanic acid, additional products of ......-dispiroiminolactones have been formed due to the higher electrophilicity of ......-dicarbonyl groups. The structures were fully established using spectroscopic analysis NMR, IR, and Mass spectrometry. The crystal structure of ......-dispiroiminolactone was confirmed from single-crystal X-ray diffraction study.
Mol Divers (2017) 21:6979 DOI 10.1007/s11030-016-9698-3
ORIGINAL ARTICLE
http://crossmark.crossref.org/dialog/?doi=10.1007/s11030-016-9698-3&domain=pdf
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Web End = One-pot synthesis of -spiroiminolactones and -dispiroiminolactones using N,N -disubstituted parabanic acid and thioparabanic acid derivatives
Sakineh Asghari1,2 Mohammad Qandalee3 Amir Ali Sarmadi1
Received: 11 April 2016 / Accepted: 6 September 2016 / Published online: 20 September 2016 Springer International Publishing Switzerland 2016
Abstract A direct entry and simple process for the synthesis of -spiroiminolactones present in a large number of natural products has been developed. In the rst step, the synthesis of parabanic acid derivatives was commenced from the reaction of N,N -disubstituted urea and thiourea with oxalyl chloride, then a three-component reaction was carried out with isocyanides, acetylenic esters, and N,N -disubstituted parabanic acid derivatives. The method allows the construction of a variety of -spiroiminolactone structures in good to high yields starting from readily available precursors. It was found that in the case of N,N -diphenyl thioparabanic acid, additional products of -dispiroiminolactones have been formed due to the higher electrophilicity of -dicarbonyl groups. The structures were fully established using spectroscopic analysis NMR, IR, and Mass spectrometry. The crystal structure of -dispiroiminolactone was conrmed from single-crystal X-ray diffraction study.
Keywords -spiroiminolactones -Dispiroiminolactones
Parabanic acid derivatives Dialkyl acetylenedicarboxylates
Isocyanide Zwitterionic intermediate
Introduction
Spirocyclic skeletons are found in the structure of many natural products [1]. Among the spirocyclic compounds, -spiroiminolactones are used as starting materials for the preparation of a wide range of compounds, such as antibacterial agents [2], aldosteroneinhibitors, and they can be used as convenient precursors for the synthesis of natural compounds [3,4]. Furthermore, a number of biologically active natural products, such as kijanolide, tetranolide, and chlorothricolide can be prepared from the hydrolysis of iminolactones that some pharmaceutical properties have been reported for this family of lactones [57].
One of the best approaches to iminolactone synthesis is the isocyanide-based reactions [828]. The reactive 1:1-intermediate generated in the reaction of isocyanide and acetylenic ester is trapped by an electron decient compound. Recently, a number of multicomponent reactions were carried out with different 1,2-dicarbonyl compounds, such as 1-methylindoline-2,3-dione [27], acenaphtylene-1,2-dione [29], phenantherene-9,10-dione, and aceanthrylene-1,2-dione which led to the monospiro and -dispiroiminolac-tones [30].
Our previously published reports described the synthesis of heterocyclic -iminolactones via multicomponent reactions of -halo ketones as active carbonyls [3133]. Herein, we have undertaken a thorough investigation of the addition of isocyanides to acetylenic esters and parabanic acid derivatives in which a number of -monospiroiminolactones and -dispiroiminolactones have been characterized.
Electronic supplementary material The online version of this article (doi:http://dx.doi.org/10.1007/s11030-016-9698-3
Web End =10.1007/s11030-016-9698-3 ) contains supplementary material, which is available to authorized users.
B Sakineh Asghari
1 Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar 47416-95447, Iran
2 Nano and Biotechnology Research Group, University of Mazandaran, Babolsar, Iran
3 Department of biology, Garmsar Branch, Islamic Azad University, Garmsar, Iran
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Results and discussion
Three-component reaction of parabanic acid derivatives 1, acetylenic esters 2, alkyl isocyanides 3 with a ratio of 1:1:1 was carried out in CH2Cl2 at room temperature, and product 4 was formed in good to high yields (Scheme 1).
When this reaction was carried out using parabanic acid derivatives, acetylenic esters, and alkyl isocyanides with a ratio of 1:2:2 at room temperature, only product 4 was formed, but for X=O only -monospiroiminolactone 4 was formed under reux condition in toluene, and in the case of X=S, the interesting -dispiroiminolactone 5 was formed in addition to compound 4 (Scheme 2).
In the rst step, three-component reaction of N,N -dimethyl parabanic acid 1a, diethyl acetylenedicarboxylate 2b, and tert-butyl isocyanide 3a was carried out with a ratio of
1:1:1 at room temperature, and the -spiroiminolactone product 4aba was formed in moderate yield (Table 1, entry 1). Then, the reactions of N,N -diphenyl parabanic acid 1b with dialkyl acetylenedicarboxylates 2ac and alkyl isocyanides 3ab were carried out which led to the corresponding products 4baa4bcb in higher yields (Table 1, entries 27). These results could be due to the higher electrophilicity of the carbonyl groups of compound 1b relative to compound 1a as a result of nitrogen resonance with phenyl groups. Similarly, N,N -diphenyl thioparabanic acid 1c was treated with dialkyl acetylenedicarboxylates 2ac and alkyl isocyanides 3ab to afford the desired products 4caa4ccb in high yields (Table 1, entries 813).
To obtain -dispiroiminolactone, the above reaction was performed with the ratio of 1:2:2 of the reactants. When the reactions were carried out using N,N -diphenyl parabanic acids 1ab, only the corresponding -spiroiminolactones
E X
R
X
R
R
+ +
CH2Cl2 R'-NCr.t. , 10-15 h
E
N R '
O O E
O
1 2 3
4
a: X= O, R= Me
b: X= O, R= Ph
c: X= S, R= Ph
a: E= CO2Me
b: E= CO2Et
c: E= CO2-t-Bu
a: R'= tBu
b: R'= cy-Hex
Scheme 1 Three-component reactions of parabanic acid derivatives, acetylenic esters, and alkyl isocyanides with a ratio of 1:1:1
X
X
X
E
R
R
Toluene R'-NC
R E
R'
+ +
1 2 2 +
4 5
reflux 2-4 h
E
N R '
R
N
O O E
O
E
E
1 2 3
N
R'
a: X= O, R= Me
b: X= O, R= Ph
c: X= S, R= Ph
a: E= CO2Me
b: E= CO2Et
c: E= CO2-t-Bu
a: R'= tBu
b: R'= cy-Hex
Scheme 2 Three-component reactions of parabanic acid derivatives, acetylenic esters, and alkyl isocyanides with a ratio of 1:2:2
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Table 1 Three-component reactions of N,N-disubstituted parabanic acid derivatives, acetylenic esters, and alkyl isocyanides (molar ratio 1:1:1)
Entry 1 2 3 4 Yield of 4 (%)
1 1a 2b 3a 4aba 58
2 1b 2a 3a 4baa 81
3 3b 4bab 85
4 2b 3a 4bba 75
5 3b 4bbb 79
6 2c 3a 4bca 71
7 3b 4bcb 73
8 1c 2a 3a 4caa 87
9 3b 4cab 90
10 2b 3a 4cba 82
11 3b 4cbb 85
12 2c 3a 4cca 74
13 3b 4ccb 76
Table 2 Three-component reaction of N,N -disubstituted parabanic acid derivatives, acetylenic esters, and alkyl isocyanides (molar ratio 1:2:2)
Entry 1 2 3 4 Yield of 4 (%)
5 Yield of 5 (%)
1 1a 2b 3a 4aba 63 5aba
2 1b 2a 3a 4baa 86 5baa
3 3b 4bab 88 5bab
4 2b 3a 4bba 79 5bba
5 3b 4bbb 83 5bbb
6 2c 3a 4bca 75 5bca
7 3b 4bcb 77 5bcb
8 1c 2a 3a 4caa 55 5caa 38
9 3b 4cab 54 5cab 43
10 2b 3a 4cba 50 5cba 35
11 3b 4cbb 53 5cbb 40
12 2c 3a 4cca 46 5cca 31
13 3b 4ccb 47 5ccb 33
4aba4bcb were formed without formation of any -dispiro products 5aba5bcb even in toluene reux condition (Table 2, entries 17). However, when the reaction was carried out using N,N -diphenyl thioparabanic acid 1c, -dispiroiminolactone 5 was formed in addition to product 4 (Table 2, entries 813). It can be postulated that the carbonyl groups of thioparabanic acid derivative 1c (X=S) are more electrophilic than those of parabanic acid derivatives 1ab (X=O), because the electron pair on nitrogen atom can be transferred readily to the sulfur atom of thiocar-
bonyl group relative to the oxygen atom of carbonyl groups [34].
The synthesis of these -spiroiminolactones can be rationalized by the initial formation of a highly reactive 1:1 zwitterionic intermediate 6 via the Michael-type reaction of isocyanide 3 with dialkyl acetylenedicarboxylate 2 [35 39]. Then, the attack of the negative charge of dipolar species 6 to one of the -dicarbonyl groups of compound 1 leads to the formation of intermediate 7, which undergoes intramolecular cyclization reaction to afford -spiroiminolactones 4. In the case of N,N -diphenyl thioparabanic acid, after the completion of the rst step, this reaction was continued with the second carbonyl group of the -monospiroiminolactone 4 by the formation of dipolar species 8. Then, by intramolecular cyclization reaction, -dispiroiminolactone derivatives 5 were obtained in moderate yields (Scheme 3).
The structures of 4aba4ccb were deduced from their IR, 1H NMR, 13C NMR, mass spectrometry, and elemental analysis. The 1H NMR spectrum of 4baa in CDCl3 displayed a singlet (s) at =1.38 ppm for the tert-butyl group and two singlets at =3.84 and 3.87 ppm for two methoxy groups. The signals of aromatic protons of two phenyl groups appeared at 7.267.56 ppm. The 13C NMR spectrum of 4baa showed 20 sharp lines in agreement with the proposed structure. The partial assignment of these resonances is given in the experimental section. The mass spectrum of 4baa exhibited molecular ion signals at m/z 491 (M+). The 1H and
13C NMR spectra of other derivatives of 4 were similar to that of 4baa except for different substituents which showed characteristic resonances in appropriate regions of the spectrum.
The structures of 5caa5ccb were deduced from their IR,
1H NMR, 13C NMR, and mass spectrometry and elemental analyses. The 1H NMR spectrum of 5cba in CDCl3 showed two triplets (t) at =1.22 and 1.28 ppm for the four methyl groups of the ethoxy moieties, a singlet at =1.43 ppm for the two tert-butyl groups, a AB quartet of quartet at =4.25 and 4.30 ppm for the two methylene groups of ethoxy moieties, and another AB quartet of quartet at =4.44 and 4.49 ppm for the other two methylene groups of ethoxy moieties. The aromatic protons appeared at =7.357.43 ppm. The
13C NMR spectrum of 5cba displayed 17 signals in agreement with the proposed structure. The mass spectrum of 5cba exhibited molecular ion signal at m/z=788 (M+).
Compound 5 has two chiral centers, which could lead to a mixture of diastereoisomers. For example, compound 5cba can exist as two diastereoisomers 5cba(I) and 5cba(II) or their enantiomers. In other words, 5cba is basically a mixture of dl/meso compound (Fig. 1), but 1H and 13C NMR spectra of 5cba showed only one diastereoisomer. Thus, the reaction is diastereoselective. To determine the stereochemistry of the obtained diastereoisomer, a single-crystal X-ray dif-
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Scheme 3 Proposed mechanismfor the reactions of parabanicacid derivatives, acetylenicesters, and alkyl isocyanides R N C C E
E
R N E
R'
N
X
E
X
O R'
R
O
7
E
S
R' C C
E N
C N R'
Ph
E
R'
E
E
If X=S,
R=Ph
X
4
S
R'
8
E
Ph
E
E
R'
5
N
R'
fraction analysis was performed for compound 5cba which conrmed the formation of only one diastereoisomer 5cba(I) or its enantiomer. The observed diastereoselectivity could be due to the steric effect of the two spiro rings in the dispiro iminolactone which prefer a trans-geometry, as shown in Fig. 1 (5cba(I) or its enantiomer). It is assumed that the generation of the rst chiral center in compound 4 is probably responsible for the diastereoselective formation of compound 5cba(I).
A 3D view of compound 5cba (I) with atom numbering is given in Fig. 2.
5cba (I) 5cba (II)
S
S
Ph
Ph
Ph
Ph
CO2
CO2
CO2Et
CO2Et
CO2Et
N
CO2Et
tBu
N
CO2Et
tBu
tBu
N
N
tBu
Fig. 1 Structures of the two possible diastereoisomers of compound 5cba
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Mol Divers (2017) 21:6979 73
singlet (s), doublet (d), triplet (t), and quartet (q). Elemental analyses were performed using a Costech ECS 4010 CHNS/O Elemental Analyzer. Single crystal was chosen for X-ray diffraction study. Crystallographic measurements were done at 298 K with a fourcircle CCD diffractometer Gemini of Oxford Diffraction, with mirrors-collimated Cu Ka radiation (k = 1.54184).
General procedure for the synthesis of compound 4
To a magnetically stirred solution of N,N -disubstituted (thio)parabanic acid (1.0 mmol) and dialkyl acetylenedicarboxylate (1.0 mmol), alkyl isocyanide (1.0 mmol) was added dropwise in dichloromethane (20 mL) at 0 C over 20 min.
The mixture was allowed to warm up to room temperature, and the reaction was monitored by the thin-layer chromatography (TLC) analysis. The mixture was stirred for more than 10 h and then was subjected directly to ash column chromatography on silica gel (200-300 mesh. n-pentane/diethyl ether 3:1) to yield the corresponding product.
Dimethyl-7-(tert-butylimino)-2,4-dioxo-1,3-diphenyl-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4baa)
Yield (0.40 g, 81 %). Mp 145148 C. IR (KBr) (max/cm1):
3073(Csp2H), 2976 and 2934 (Csp3H), 1801, 1748, and 1722 (4C=O), 1690 (C=N), 1659 (Cq), 1595 (C=C, aromatic), 1259 (Csp2O), and 1068 (Csp3O). 1H NMR (400.1 MHz, CDCl3) 1.38 (s, 9H, CMe3), 3.84 and 3.87 (2s, 6H, 2OCH3), 7.267.28 (m, 2H, ArH), 7.397.47 (m, 4H, ArH), and 7.527.56 (m, 4H, ArH). 13CNMR (100.6 MHz, CDCl3): 29.7 (CMe3), 53.2 and 53.4 (2OCH3), 55.9 (NCMe3),94.4 (Cspiro), 126.2 and 126.7 (4CHortho), 128.8 and 128.9 (2CHpara), 129.3 and 129.7 (4CHmeta), 131.1 and 132.6 (2Cipso), 133.6 and 142.6 (2Cq), 148.2 (C=N), and 153.2, 159.8, 160.7, and 164.9 (4C=O). MS: m/z (%) 491 (M+, 9), 476 (100), 444 (33), 293 (38), 197 (36), 165 (53), 119 (16), 77 (7), and 57 (37). Anal. Calcd for C26H25N3O7 (491.49):
C, 63.54; H, 5.13; and N, 8.55 %. Found: C, 63.31; H, 5.11; and N, 8.52 %.
Dimethyl-7-(cyclohexylimino)-2,4-dioxo-1,3-diphenyl-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4bab)
White Powder, yield (0.44 g, 85 %). Mp 141143 C. IR (KBr) (max/cm1): 3070 (Csp2H), 2937 and 2855 (Csp3
H), 1803, 1750, and 1724 (4C=O), 1695 (C=N), 1658 (C=C, iminolactone), 1597 (C=C, aromatic), 1261 (Csp2O), and 1079 (Csp3O). 1H NMR (400.1 MHz, CDCl3) 1.241.84 (m, 10H, 5CH2), 3.79 (tt, 3 JHH =10, 3 JHH =4.0, 1H, NCH),3.84 and 3.87 (2s, 6H, 2OCH3), 7.257.26 (m, 2H, ArH),
Fig. 2 3D view of 5cba (arbitrary atom numbering)
Conclusions
In summary, we have developed an efcient procedure for the preparation of -spiroiminolactones and diastereoselective synthesis of -dispiroiminolactones using N,N -disubstituted parabanic acid derivatives, alkyl isocyanides, and acetylenic esters. We envisioned that from many synthetic methods for the construction of these skeletons, multicomponent reaction would be highly appealing because of the control of the diastereoselectivity and stereochemistry of the reaction. In addition, the simplicity of this procedure introduces it as an interesting alternative to the other approaches.
Experimental Section
General
Dialkyl acetylenedicarboxylates and alkyl isocyanides were purchased from Fluka and Merck and used without further purication. Parabanic acid derivatives 1ac were synthesized from the reaction of N,N -disubstituted urea or thiourea with oxalyl chloride by known methods [40]. Melting points were measured on an Electrothermal 9100 apparatus and are uncorrected. Mass spectra were recorded on a FINNIGANMAT 8430 mass spectrometer operating at an ionization potential of 70 eV. IR spectra were recorded on a FT-IR BRUKER VECTOR spectrometer. 1H, and 13C NMR spectra were recorded on a BRUKER DRX-400 spectrometer at 400.13 and 100.61 MHz, respectively. NMR spectra were obtained on solution in CDCl3 using tetra methyl silane (TMS) as internal standard. The signals were reported as
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7.397.48 (m, 4H, ArH), and 7.527.55 (m, 4H, ArH). 13C
NMR (100.6 MHz, CDCl3): 24.5, 24.7, 25.6, 33.1, and 33.4 (5CH2), 53.3 and 53.4 (2OCH3), 57.5 (NCH), 95.0 (Cspiro), 126.2 and 126.7 (4CHortho), 128.8 and 128.9 (2CHpara), 129.3 and 129.7 (4CHmeta), 131.0 and 132.5 (2Cipso), 134.6 and 141.3 (2Cq), 150.6 (C=N), and 153.1, 159.8, 160.5, and 164.8 (4C=O). MS: m/z (%) 517 (M+, 19), 485 (17), 458(10), 420 (100), 333 (88), 165 (52), 119 (16), and 55 (20).
Anal. Calcd for C28H27N3O7 (517.53): C, 64.98; H, 5.26;
and N, 8.12 %. Found: C, 64.73; H, 5.24; and N, 8.09 %.
Diethyl-7-(tert-butylimino)-2,4-dioxo-1,3-diphenyl-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate(4bba)
White Powder, yield (0.39 g, 75 %). Mp 122125 C. IR (KBr) (max/cm1): 3069 (Csp2H), 2981 and 2938 (Csp3
H), 1800, 1747, and 1717 (4C=O), 1692 (C=N), 1656 (C=C, iminolactone), 1597 (C=C, aromatic), 1260 (Csp2O), 1058 (Csp3O). 1H NMR (400.1 MHz, CDCl3) 1.28 and 1.32 (2t, 3 JHH =7.2, 6H, 2CH3), 1.38 (s, 9H, CMe3), 4.27 and4.30 (AB quartet of quartet,2 JHH =10.8, 3 JHH =7.2, 2H, OCH2), 4.33 (q, 2H, 3 JHH =7.2, OCH2), 7.277.28 (m, 2H, ArH), 7.387.46 (m, 4H, ArH), and 7.517.58 (m, 4H, ArH). 13C NMR (100.6 MHz, CDCl3): 13.9 and 14 (2CH3), 29.7 (CMe3), 55.8 (NCMe3), 62.5 and 62.6 (2OCH2), 95.4 (Cspiro), 126.1 and 126.7 (4CHortho), 128.7 and 128.8 (2CHpara), 129.2 and 129.6 (4CHmeta), 131.1 and 132.6 (2Cipso), 133.5 and 142.7 (2Cq), 148.3 (C=N), and 153.2, 159.4, 160.3, and 165.0 (4C=O). MS: m/z (%) 519 (M+, 7), 504 (100), 458 (34), 293 (24), 197 (16), 151 (33), 119 (23), 77 (7), and 57 (20). Anal. Calcd for C28H29N3O7 (519.55): C, 64.73; H, 5.63; and N, 8.09 %. Found: C, 64.49;H, 5.61; and N, 8.06 %.
Diethyl7-(cyclohexylimino)-2,4-dioxo-1,3-diphenyl6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4bbb)
White powder, yield (0.43 g, 79 %). Mp 118120 C. IR (KBr) (max/cm1): 3068 (Csp2H), 2930 and 2856 (Csp3
H), 1802, 1746, and 1714 (4C=O), 1689 (C=N), 1653 (C=C, iminolactone), 1595 (C=C, aromatic), 1261 (Csp2O), and 1077 (Csp3O). 1H NMR (400.1 MHz, CDCl3) 1.231.84 (m, 10H, 5CH2), 1.28 and 1.31 (2t, 3 JHH =7.2, 6H,2CH3),3.79 (tt, 3 JHH =10, 3 JHH =4.0, 1H, NCH), 4.28 and 4.30 (AB quartet of quartet, 2 JHH =10.8, 3 JHH =7.2, 2H, OCH2), 4.34 (q, 3 JHH =7.2, 2H, OCH2), 7.257.28 (m, 2H, ArH), 7.387.47 (m, 4H, ArH), and 7.527.58 (m, 4H, ArH). 13CNMR
(100.6 MHz, CDCl3): 13.9 and 14 (2CH3), 24.4, 24.6,25.6, 33.1, and 33.4 (5CH2), 57.3 (NCH), 62.6 and 62.7 (2OCH2), 95.0 (Cspiro), 126.1 and 126.6 (4CHortho), 128.7 and 128.8 (2CHpara), 129.2 and 129.7 (4CHmeta), 131.1 and
132.6 (2Cipso), 134.6 and 141.4 (2Cq), 150.7 (C=N), and 153.1, 159.4, 160.0, and 164.9 (4C=O). MS: m/z %) 545 (M+, 9), 499 (12), 448 (78), 374 (85), 347 (100), 151 (24), 97(4), 77 (5), and 55 (7). Anal. Calcd for C30H31N3O7 (545.58): C, 66.04; H, 5.73; and N, 7.70 %. Found: C, 65.80; H, 5.71; and N,7.67 %.
Di-tert-butyl-7-(tert-butylimino)-2,4-dioxo-1,3-diphenyl-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4bca)
Light yellow crystals, yield (0.41 g, 71 %). Mp 169172
C. IR (KBr) (max/ cm1): 3070 (Csp2H), 2985 and 2934 (Csp3H), 1800, 1745 (4C=O), 1708 (C=N), 1661 (C=C, iminolactone), 1595 (C=C, aromatic), 1250 (Csp2O), 1066 (Csp2O). 1H NMR (400.1 MHz, CDCl3) 1.37 (s, 9H, NCMe3), 1.47 and 1.52 (2s, 18H, 2OCMe3), 7.297.31 (m, 2H, ArH), 7.367.46 (m, 4H, ArH), 7.517.55 (m, 2H, ArH), and 7.597.62 (m, 2H, ArH). 13C NMR (100.6 MHz, CDCl3): 28.0, 28.1, and 29.7 (3CMe3), 55.4 (NCMe3),84.2 and 84.5 (2OCMe3), 95.4 (Cspiro), 125.9 and 126.5 (4CHortho), 128.5 and 128.6 (2CHpara), 129.1 and 129.4 (4CHmeta), 131.3 and 132.9 (2Cipso), 133.2 and 142.5 (2Cq), 148.7 (C=N), 153.2, 158.6, 159.5, and 165.3 (4C=O). MS: m/z (%) 576 (M+, 15), 561 (13), 448 (36), 386 (14), 119 (13), 84 (4), and 57 (100). Anal. Calcd for C32H37N3O7 (575.65): C, 66.77; H, 6.48; and N, 7.30 %. Found: C, 66.52; H, 6.46; and N, 7.27 %.
Di-tert-butyl-7-(cyclohexylimino)-2,4-dioxo-1,3-diphenyl 6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4bcb)
Pale yellow powder, Yield (0.44 g, 73 %). Mp 133136
C. IR (KBr) (max, cm1): 3072 (Csp2H), 2978 and 2931 (Csp3H), 1799, 1747, and 1728 (4C=O), 1701 (C=N), 1667 (C=C, iminolactone), 1597 (C=C, aromatic), 1259 (Csp2O), 1076 (Csp3O). 1H NMR (400.1 MHz, CDCl3) 1.311.79 (m, 10H, 5CH2), 1.47 and 1.51 (2s, 18H, 2CMe3), 3.78 (tt,
3 JHH =9.2, 3 JHH =3.6, 1H, NCH), 7.277.29 (m, 2H, ArH),7.367.46 (m, 4H, ArH), 7.517.55 (m, 2H, ArH), and 7.597.61 (m, 2H, ArH). 13C NMR (100.6 MHz, CDCl3): 24.1,24.2, and 25.8 (3CH2), 28.0 and 28.1 (2CMe3), 33.2 and 33.4 (2CH2), 56.5 (NCH), 84.3 and 84.5 (2OCMe3), 95.1 (Cspiro), 126.0 and 126.5 (4CHortho), 128.5 and 128.6 (2CHpara), 129.1 and 129.5 (4CHmeta), 131.3 and 132.8 (2Cipso), 134.2 and 141.4 (2Cq), 150.8 (C=N), 153.2, 158.6, 159.2, and 165.2 (4C=O). MS: m/z (%) 602 (M+, 1), 489 (29), 374(92), 98 (100), and 57 (31). Anal. Calcd for C34H39N3O7 (601.69): C, 67.87; H, 6.53; and N, 6.98 %. Found: C, 67.63; H, 6.50; and N, 6.96 %.
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Diethyl-7-(tert-butylimino)-1,3-dimethyl-2,4-dioxo-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate(4aba)
Yellow oil, yield (0.23 g, 58 %). IR (KBr) (max/cm1): 2978 (Csp3H), 1795 and 1737 (4C=O), 1699 (C=N), 1663 (C=C, iminolactone), 1272 (Csp2O), and 1030 (Csp3O).
1H NMR (400.1 MHz, CDCl3) 1.26 (t, 3 JHH =7.2, 3H, CH3), 1.31 (s, 9H, CMe3),1.39 (t, 3 JHH =7.2, 3H, CH3),2.81 and 3.14 (2s, 6H, 2NCH3), 4.23 and 4.26 (AB quartet of quartet,2 JHH =10.8, 3 JHH =7.2, 2H, OCH2), 4.42 (q, 2H,
3 JHH =7.2, OCH2). 13CNMR (100.6 MHz, CDCl3): 13.8 and 14.0 (2CH3), 24.9 and 25.3 (2NCH3), 29.5 (CMe3), 55.8 (NCMe3), 62.4 and 62.6 (2OCH2), 94.9 (Cspiro), 133.1 and 143.0 (2Cq), 148.6 (C=N), 155.2, 159.0, 160.6, and 166.5 (4C=O). MS: m/z (%) 395 (M+, 11), 380 (100), 334 (49), 262 (30), 220 (9), 151 (10), 84 (4), 77 (7), and 57 (23). Anal.
Calcd for C26H25N3O7 (395.41): C, 54.68; H, 6.37; and N,10.63 %. Found: C, 54.47; H, 6.35; and N, 10.59 %.
Dimethyl-7-(tert-butylimino)-4-oxo-1,3-diphenyl-2-thioxo-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4caa)
White powder, yield (0.44 g, 87 %). Mp 186188 C. IR (KBr) (max/cm1): 3075 (Csp2H), 2976 and 2875 (Csp3
H), 1766, 1747, and 1722 (3C=O), 1690 (C=N), 1655 (C=C, iminolactone), 1595 (C=C, aromatic), 1326 (C=S), 1243 (Csp2O), and 1071 (Csp3O). 1H NMR (400.1 MHz, CDCl3)
1.37 (s, 9H, CMe3), 3.86 and 3.93 (2s, 6H, 2OCH3), 7.267.29 (m, 2H, ArH), 7.457.59 (m, 8H, ArH). 13CNMR (100.6 MHz, CDCl3): 29.7 (CMe3), 53.2 and 53.6 (2OCH3), 56.0 (NCMe3), 95.5 (Cspiro), 128.4 and 128.8 (4CHortho), 129.3 (2CHmeta), 129.6 (CHpara), 129.8 (2CHmeta), 129.9 (CHpara), 132.9 (Cipso), 133.6 (Cq), 134.1 (Cipso), 142.2 (Cq), 147.7 (C=N), 160.0, 160.6, and 165.7 (3C=O), and 182.8 (C=S).MS: m/z (%) 507 (M+, 65), 492 (54), 460 (13), 226 (51), 197 (50), 165 (100), 77 (26), and 57 (62). Anal. Calcd for
C26H25N3O6S (507.56): C, 61.53; H, 4.96; N, 8.28; and S,6.32 %. Found: C, 61.30; H, 4.94; N, 8.24; and S, 6.30 %.
Dimethyl-7-(cyclohexylimino)-4-oxo-1,3-diphenyl-2-thioxo-6-oxa-1,3-diazaspiro[4.4]-non-8-ene-8,9 dicarboxylate (4cab)
White powder, yield (0.48 g, 90 %). Mp 146149 C. IR (KBr) (max/cm1): 3066 and 3007 (Csp2H), 2933 and 2856 (Csp3H), 1772, 1760, and 1723 (3C=O), 1694 (C=N), 1657 (C=C, iminolactone), 1595 (C=C, aromatic), 1324 (C=S), 1253 (Csp2O), and 1076 (Csp3O). 1H NMR (400.1 MHz,
CDCl3) 1.381.80 (m, 10H, 5CH2), 3.79 (tt, 3 JHH =9.6,
3 JHH =4.0, 1H, NCH), 3.86 and 3.93 (2s, 6H, 2OCH3),7.277.29 (m, 2H, ArH), and 7.457.59 (m, 8H, ArH).
13CNMR (100.6 MHz, CDCl3): 24.4, 24.6, 25.6, 33.1, and 33.3 (5CH2), 53.3 and 53.6 (2OCH3), 57.6 (NCH), 95.0 (Cspiro), 128.5 and 128.6 (4CHortho), 129.3 (2CHmeta), 129.7 (CHpara), 129.8 (2CHmeta), 129.9 (CHpara), 132.9 and 134.1 (2Cipso), 134.6 and 140.9 (2Cq), 150.3 (C=N), 159.9, 160.3, and 165.7 (3C=O), and 182.7 (C=S). MS: m/z (%) 533 (M+,20), 436 (100), 273 (9), 241 (24), 194 (26), 165 (50), 111(16), 83 (17), and 55 (20). Anal. Calcd for C28H27N3O6S (533.60): C, 63.03; H, 5.10; N, 7.87; and S, 6.01 %. Found: C, 62.80; H, 5.08; N, 7.84; and S, 5.98 %.
Diethyl-7-(tert-butylimino)-4-oxo-1,3-diphenyl-2-thioxo-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4cba)
White Powder, Yield (0.44 g, 82 %). Mp 121123 C. IR (KBr) (max/cm1): 3067 (Csp2H), 2975 and 2932 (Csp3
H), 1775, 1743, and 1721 (3C=O), 1705 (C=N), 1657 (C=C, iminolactone), 1595 (C=C, aromatic), 1324 (C=S), 1249 (Csp2O), and 1071 (Csp3O). 1H NMR (400.1 MHz, CDCl3)
1.31 and 1.36 (2t, 3 JHH =7.2, 6H, 2CH3), 1.37 (s, 9H, CMe3), 4.31 and 4.33 (AB quartet of quartet,2 JHH =10.8,
3 JHH =7.2, 2H, OCH2), 4.36 and 4.40 (AB quartet of quartet,2 JHH =10.8, 3 JHH =7.2, 2H, OCH2), 7.287.30 (m, 2H, ArH), 7.467.59 (m, 8H, ArH). 13CNMR (100.6 MHz, CDCl3): 14.0, 14.1 (2CH3), 29.8 (CMe3), 55.9 (NCMe3),62.5 and 62.8 (2OCH2), 95.5 (Cspiro), 128.4 and 128.8 (4CHortho), 129.2 (2CHmeta), 129.6 (CHpara), 129.7 (2CHmeta), 129.8 (CHpara), 133.0 (Cipso), 133.6 (Cq), 134.2 (Cipso), 142.3 (Cq), 147.8 (C=N), 159.6, 160.1, and 165.8 (3C=O), and 182.8 (C=S). MS: m/z (%) 535 (M+, 92), 520 (100), 474 (17), 255 (17), 225 (63), 151 (68), 107 (5), 77(11), and 57 (25). Anal. Calcd for C28H29N3O6S (535.61): C, 62.79; H, 5.46; N, 7.85; and S, 5.99 %. Found: C, 62.57; H, 5.44; N, 7.82; and S, 5.96 %.
Diethyl-7-(cyclohexylimino)-4-oxo-1,3-diphenyl-2-thioxo-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4cbb)
White powder, yield (0.48 g, 85 %). Mp 135137 C. IR (KBr) (max/cm1): 3069 (Csp2H), 2932 and 2856 (Csp3
H), 1772, 1758, and 1724 (3C=O), 1693 (C=N), 1653 (C=C, iminolactone), 1595 (C=C, aromatic), 1332 (C=S), 1276 (Csp2O), 1078 (Csp3O). 1H NMR (400.1 MHz, CDCl3)
1.231.84 (m, 10H, 5CH2), 1.30 and 1.35 (2t, 3 JHH =7.2, 6H,2CH3), 3.78 (tt, 3 JHH =9.2, 3 JHH =4.0, 1H, NCH), 4.32 and 4.33 (AB quartet of quartet, 2 JHH =10.8, 3 JHH =7.2, 2H, OCH2), 4.36 and 4.41 (AB quartet of quartet, 2 JHH =10.8,
3 JHH =7.2, 2H, OCH2), 7.357.38 (m, 4H, ArH), and 7.407.43 (m, 6H, ArH). 13CNMR (100.6 MHz, CDCl3): 13.9 and 14.1 (2CH3), 24.5, 24.6, 25.6, 33.1, and 33.3 (5CH2),57.4 (NCH), 62.6 and 62.8 (2OCH2), 95.4 (Cspiro), 128.4 and
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128.8 (4CHortho), 129.2 (2CHmeta), 129.3 (CHpara), 129.4 (2CHmeta), 129.6 (CHpara), 130.0 (Cipso), 133.8 (Cq), 134.4 (Cipso), 143.3 (Cq), 147.5 (C=N), 159.8, 160.2, and 165.1 (3C=O), and 182.6 (C=S). MS: m/z (%) 561 (M+, 9), 464(43), 400 (35), 354 (18), 327 (24), 301 (18), 272 (28), 226(42), 199 (23), 135 (100), and 77 (60). Anal. Calcd for C30H31N3O6S (561.65): C, 64.15; H, 5.56; N, 7.48; and S,5.71 %. Found: C, 63.91; H, 5.54; N, 7.45; and S, 5.69 %.
Di-tert-butyl-7-(tert-butylimino)-4-oxo-1,3-diphenyl-2-thioxo-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4cca)
Light yellow powder, yield (0.44 g, 74 %). Mp 175178
C. IR (KBr) (max/ cm1): 3067 (Csp2H), 2978 and 2933 (Csp3H), 1776, 1736, and 1712 (3C=O), 1708 (C=N), 1662 (C=C, iminolactone), 1596 (C=C, aromatic), 1371 (C=S), 1253 (Csp2O), and 1087 (Csp2O). 1H NMR (400.1 MHz,
CDCl3) 1.35 (s, 9H, NCMe3), 1.50 and 1.55 (2s, 18H, 2OCMe3), 7.307.33 (m, 2H, ArH), 7.447.46 (m, 3H, ArH), and 7.487.60 (m, 5H, ArH). 13CNMR (100.6 MHz, CDCl3): 28.0, 28.1, and 29.8 (3CMe3), 55.4 (NCMe3), 84.2 and84.6 (2OCMe3), 95.6 (Cspiro), 128.4 and 128.7 (4CHortho), 129.1 (2CHmeta), 129.4 (CHpara), 129.5 (2CHmeta), 129.7 (CHpara), 133.0 and 133.1 (2Cipso), 134.4 and 142.0 (2Cq), 148.3 (C=N), 159.0, 159.3, and 166.1 (3C=O), and 182.8 (C=S). MS: m/z (%) 591 (M+, 23), 464 (80), 318 (14), 226(31), 151 (163), 135 (15), 97 (9), and 57 (100). Anal. Calcd for C32H37N3O6S (591.72): C, 64.95; H, 6.30; N, 7.10; and
S, 5.42 %. Found: C, 64.70; H, 6.27; N, 7.07; and S, 5.40 %.
Di-tert-butyl-7-(cyclohexylimino)-4-oxo-1,3-diphenyl-2-thioxo-6-oxa-1,3-diazaspiro[4.4]non-8-ene-8,9-dicarboxylate (4ccb)
Pale yellow powder, yield (0.47 g, 76 %). Mp 173175 C. IR (KBr) (max, cm1): 3069 (Csp2H), 2980 and 2935 (Csp3
H), 1764, 1739, and 1721 (3C=O), 1685 (C=N), 1621 (C=C, iminolactone), 1595 (C=C, aromatic), 1327 (C=S), 1276 (Csp2O), 1072 (Csp3O). 1H NMR (400.1 MHz, CDCl3)
1.181.72 (m, 10H, 5CH2), 1.48 and 1.59 (2s, 18H, 2CMe3),3.66 (m, 1H, NCH), 7.307.32 (m, 2H, ArH), 7.387.43 (m, 3H, ArH), and 7.497.55 (m, 5H, ArH). 13CNMR (100.6 MHz, CDCl3): 23.4, 23.5, and 25.4 (3CH2), 27.9 and28.0 (2CMe3), 32.2 and 32.4 (2CH2), 68.0 (NCH), 83.9 and85.8 (2OCMe3), 96.0 (Cspiro), 128.4 and 128.7 (4CHortho), 129.4 (2CHmeta), 129.5 (CHpara), 129.6 (2CHmeta), 129.7 (CHpara), 133.0 and 133.1 (2Cipso), 134.8 and 142.0 (Cq), 148.4 (C=N), 159.0, 160.0, and 165.3 (3C=O), and 183.6 (C=S). MS: m/z (%) 618 (M+, 1), 561 (1), 516 (2), 417 (4), 197 (17), 165 (9), 135 (19), 83 (24), and 56 (100). Anal. Calcd for C34H39N3O6S (617.76): C, 66.10; H, 6.36; N, 6.80; and
S, 5.19 %. Found: C, 66.07; H, 6.35; N, 6.81; and S, 5.20 %.
General procedure for the synthesis of compound 5 in reux condition
To a magnetically stirred solution of N,N -diphenyl thioparabanic acid (0.28 g, 1.0 mmol) and dialkyl acetylenedicarboxylate (2.0 mmol) in 25 mL dry toluene was added dropwise, alkyl isocyanide (2.0 mmol) at 0 C over 30 min.
Then, the mixture was reuxed for 2 h. After the completion of the reaction, the mixture was subjected directly to ash column chromatography on silica gel (200300 mesh, n-pentane/diethyl ether 3:1). Solvent was removed under vacuum to yield the corresponding product.
Tetramethyl-2,8-bis(tert-butylimino)-11,13-diphenyl-12-thioxo-1,7-dioxa-11,13-diazadispiro[4.0.4.3]trideca-3,9-diene-3,4,9,10-tetracarboxylate (5caa)
Yield (0.28 g, 38 %). Mp 205208 C. IR (KBr) (max/cm1): 3068 (Csp2H), 2964 and 2928 (Csp3H), 1761, 1737 (4C=O), 1694 (2C=N), 1659 (2C=C, iminolactone), 1594 (C=C, aromatic), 1339 (C=S), 1242 (Csp2O), 1072 (Csp3
O). 1H NMR (400.1 MHz, CDCl3) 1.18 (s, 18H, 2CMe3),3.81 and 4.02 (2s, 12H, 4OCH3), 7.307.33 (m, 4H, ArH),7.417.43 (m, 6H, ArH). 13CNMR (100.6 MHz, CDCl3): 29.5 (2CMe3), 53.0 and 53.1 (4OCH3), 55.5 (2NCMe3), 104.3 (2Cspiro), 129.3 (4CHortho), 129.5 (2CHpara), 130.0 (4CHmeta), 134.5 (2Cipso), 135.5 and 140.8 (4Cq), 146.7 (2C=N), 160.3, 161.0 (4C=O), and 182.8 (C=S). MS: m/z (%) 732 (M+, 12), 424 (35), 394 (9), 364 (22), 197 (100), 165(22), and 57 (36). Anal. Calcd for C37H40N4O10S (732.80): C, 60.64; H, 5.50; N, 7.65; and S, 4.38 %. Found: C, 60.42; H, 5.48; N, 7.62; and S, 4.36 %.
Tetramethyl-2,8-bis(cyclohexylimino)-11,13-diphenyl-12-thioxo-1,7-dioxa-11,13diazadispiro-[4.0.4.3]trideca-3,9-diene-3,4,9,10-tetracarboxylate (5cab)
Pale yellow powder, yield (0.34 g, 43 %). Mp 226229 C. IR (KBr) (max/cm1): 3069 (Csp2H), 2933 and 2856 (Csp3
H), 1758 and 1736 (4C=O), 1694 (2C=N), 1662 (2C=C, iminolactone), 1595 (C=C, aromatic), 1335 (C=S), 1253 (Csp2O), 1077 (Csp3O). 1H NMR (400.1 MHz, CDCl3)
1.251.79 (m, 20H, 10CH2), 3.47 (tt, 3JHH =9.6, 3JHH =4.0, 2H, 2NCH), 3.82 and 4.05 (2s, 12H, 4OCH3), 7.337.35 (m, 4H, ArH), and 7.427.44 (m, 6H, ArH). 13CNMR (100.6 MHz, CDCl3): 24.6, 24.7, 25.5, 33.0, and 33.1 (10CH2),53.1 and 53.2 (4OCH3), 57.8 (2NCH), 104.4 (2Cspiro), 129.3 (4CHortho), 129.5 (2CHpara), 129.8 (4CHmeta), 134.5 (2Cipso), 136.7 and 139.0 (4Cq), 149.3 (2C=N), 160.3 and 160.5 (4C=O), and 182.8 (C=S). MS: m/z (%) 784 (M+, 22),
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364 (37), 279 (62), 225 (9), 197 (100), 165 (93), 111 (5), 83(23), and 55 (17). Anal. Calcd for C41H44N4O10S (784.87): C, 62.74; H, 5.65; N, 7.14; and S, 4.09 %. Found: C, 62.50;H, 5.63; N, 7.11; and S, 4.07 %.
Tetraethyl-2,8-bis(tert-butylimino)-11,13-diphenyl-12-thioxo-1,7-dioxa-11,13-diazadispiro[4.0.4.3]-trideca-3,9-diene-3,4,9,10-tetracarboxylate (5cba)
Pale yellow powder, yield (0.28 g, 35 %). Mp 194197 C. IR (KBr) (max/cm1): 3067 (Csp2H), 2979 and 2935 (Csp3
H), 1751, 1727 (4C=O), 1700 (2C=N), 1664 (2C=C, iminolactone), 1595 (C=C, aromatic), 1332 (C=S), 1240 (Csp2O), 1070 (Csp3O). 1H NMR (400.1 MHz, CDCl3) 1.22 and1.28 (2t, 3JHH =7.2, 12H, 4CH3), 1.43 (s, 18H, 2CMe3), 4.25 and 4.30 (AB quartet of quartet,2JHH =10.8, 3JHH =7.2, 4H, 2OCH2), 4.44 and 4.49 (AB quartet of quartet,2JHH =10.8,
3JHH =7.2, 4H, 2OCH2), 7.357.38 (m, 4H, ArH), and 7.417.43 (m, 6H, ArH). 13CNMR (100.6 MHz, CDCl3): 13.9 (2CH3), 14.2 (2CH3), 29.7 (2CMe3), 55.4 (2NCMe3), 62.2 (2OCH2), 62.4 (2OCH2), 104.4 (2Cspiro), 129.2 (4CHortho), 129.3 (2CHpara), 129.9 (4CHmeta), 134.7 (2Cipso), 135.6 and 140.9 (4Cq), 147.0 (2C=N), 160.0 and 160.7 (4C=O), and 182.8 (C=S). MS: m/z (%) 788 (M+, 15), 452 (25), 378(25), 225 (100), 179 (34), 151 (18), and 57 (33). Anal.
Calcd for C41H48N4O10S (788.91): C, 62.42; H, 6.13; N,7.10; and S, 4.06 %. Found: C, 62.19; H, 6.11; N, 7.07; and S, 4.04 %. X-Ray crystal structure of 5cba: C41 H48
N4 O10 S, Mr 788.89, Orthorhombic; unit cell parameters: a = 12.106(2), b = 17.620(4), c = 20.064(4),
V = 4279.6(15) 3, and Z = 4. The nal R indices
[I>2sigma (I)] R1=0.0482, wR2=0.1249, R indices (all data), R1=0.0739, wR2=0.1349, T 298(2) K.
Tetraethyl-2,8-bis(cyclohexylimino)-11,13-diphenyl-12-thioxo-1,7-dioxa-11,13-diazadispiro[4.0.4.3]trideca-3,9-diene3,4,9,10-tetracarboxylate (5cbb)
Pale yellow powder, yield (0.34 g, 40 %). Mp 217220 C. IR (KBr) (max/cm1): 3069 (Csp2H), 2931 and 2856 (Csp3
H), 1759, 1732 (4C=O), 1694 (2C=N), 1656 (2C=C, iminolactone), 1595 (C=C, aromatic), 1333 (C=S), 1276 (Csp2O), 1078 (Csp3O). 1H NMR (400.1 MHz, CDCl3) 1.201.80 (m, 20H, 10CH2), 1.27 and 1.47 (2t, 3JHH =7.2, 12H,4CH3),3.52 (tt, 3JHH =9.6, 3JHH =4.0, 2H, 2NCH), 4.26 and 4.31 (AB quartet of quartet, 2JHH =10.8, 3JHH =7.2, 4H, 2OCH2),4.45 and 4.50 (AB quartet of quartet, 2JHH =10.8, 3JHH =7.2, 4H, 2OCH2), 7.357.38 (m, 4H, ArH), 7.407.43 (m, 6H, ArH). 13CNMR (100.6 MHz, CDCl3): 13.8 (2CH3), 14.3 (2CH3), 24.5, 24.6, 25.5, 32.9, and 33.1 (10CH2), 57.7 (2NCH), 62.3 (2OCH2), 62.4 (2OCH2), 103.4 (2Cspiro), 129.2 (4CHortho), 129.4 (2CHpara), 129.6 (4CHmeta), 134.7 (2Cipso), 136.8 and 139.4 (4Cq), 149.5 (2C=N), 159.8 and
160.2 (4C=O), and 182.5 (C=S). MS: m/z (%) 840 (M+, 12), 378 (21), 307 (45), 225 (100), 179 (58), 151 (25), 83 (16), and 55 (10). Anal. Calcd for C45H52N4O10S (840.98): C,64.27; H, 6.23; N, 6.66; and S, 3.81 %. Found: C, 64.02; H,6.21; N, 6.63; and S, 3.79 %.
Tetra-tert-butyl-2,8-bis(tert-butylimino)-11,13-diphenyl-12-thioxo-1,7-dioxa-11,13-di-aza-spiro[4.0.4.3]trideca-3,9-diene-3,4,9,10-tetracarboxylate (5cca)
Light yellow powder, yield (0.28 g, 31 %). Mp 173 175 C. IR (KBr) (max/ cm1): 3069 (Csp2H), 2975 and 2928 (Csp3H), 1752, 1726 (4C=O), 1705 (2C=N), 1654 (2C=C, iminolactone), 1596 (C=C, aromatic), 1369 (C=S), 1282 (Csp2O), 1107 (Csp2O). 1H NMR (400.1 MHz,
CDCl3) 1.08 (s, 18H, 2NCMe3), 1.47 and 1.59 (2s, 36H, 4OCMe3), 7.337.35 (m, 4H, ArH), and 7.447.46 (m, 6H, ArH). 13CNMR (100.6 MHz, CDCl3): 27.8, 27.9, and28.0 (6CMe3), 57.9 (2NCMe3), 83.6 and 85.6 (4OCMe3), 104.6 (2Cspiro), 127.9 (4CHortho), 129.5 (2CHpara), 129.6 (4CHmeta), 132.5 (2Cipso), 134.0 and 148.1 (4Cq), 152.1 (2C=N), 159.5 and 160.1 (4C=O), and 182.6 (C=S). MS: m/z (%) 901 (M+, 5), 479 (33), 423 (60), 379 (57), 276 (100), 199(28), 119 (13), and 57 (63). Anal. Calcd for C49H64N4O10S (901.12): C, 65.31; H, 7.16; N, 6.22; and S, 3.56 %. Found: C, 65.06; H, 7.13; N, 6.20; and S, 3.54 %.
Tetra-tert-butyl-2,8-bis(cyclohexylimino)-11,13-diphenyl 12-thioxo-1,7-dioxa-11,13-diazaspiro[4.0.4.3]trideca-3,9-diene-3,4,9,10-tetracarboxylate (5ccb)
Pale yellow powder, yield (0.32 g, 33 %). Mp 204208 C. IR (KBr) (max, cm1): 3066 (Csp2H), 2977 and 2933 (Csp3H), 1753 and 1721 (4C=O), 1697 (2C=N), 1656 (2C=C, iminolactone), 1595 (C=C, aromatic), 1330 (C=S), 1278 (Csp2O), 1074 (Csp3O). 1H NMR (400.1 MHz,
CDCl3) 1.201.70 (m, 20H, 10CH2), 1.48 and 1.59 (2s, 36H, 4CMe3), 2.84 (m, 2H, 2NCH), 7.337.36 (m, 4H, ArH), and 7.457.48 (m, 6H, ArH). 13CNMR (100.6 MHz, CDCl3): 23.4, 23.6, 25.4 (6CH2), 27.9 and 28.0 (4CMe3), 32.1 and 32.3 (4CH2), 67.7 (2NCH), 83.9 and 85.7 (4OCMe3), 105.1 (2Cspiro), 128.0 (4CHortho), 129.5 (2CHpara), 129.6 (4CHmeta), 132.4 (2Cipso), 134.3 and 148.1 (4Cq), 152.1 (2C=N), 161.2 and 163.0 (4C=O), and 183.5 (C=S). MS: m/z (%) 952 (M+, 1), 505 (21), 461 (32), 340 (56), 265 (79), 210 (100), 98 (71), and 57 (44). Anal. Calcd for C53H68N4O10S (953.19): C, 66.78; H, 7.19; N, 5.88; and S, 3.36 %. Found: C, 66.53; H, 7.16; N, 5.85; and S, 3.34 %.
Acknowledgements We gratefully acknowledge the nancial support from the Research Council of Mazandaran University.
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