摘要:

N O Me 1e N O Me 4 S 2 N O Me 5 Cl + S2Cl2 (2) N R2 R1 N R2 R1 S S N R1 R2 S2Cl2 1a R1 = R2 = H b R1 = Me, R2 = H c R1 = H, R2 = Me 2a b c 1 2 3 4 5 6 7 8 9 10 11 12 13 14 (1) J. CHEM. RESEARCH (S), 1997 435 J. Chem. Research (S), 1997, 435 J. Chem. Research (M), 1997, 2601–2613 Dithiines Annulated by Heterocycles. Part 2.1 Reaction of Disulfur Dichloride with Various Quinolines Thorsten Link, Martin Oberjat and G�unter Klar* Institut f�ur Anorganische und Angewandte Chemie der Universit�at Hamburg, Martin-Luther- King-Platz 6, D-20146 Hamburg, Germany The reaction of sulfur dichloride with the quinoline derivatives 1a–c gives the dithiinodiquinolines 2a–c, whereas with 1e other products, namely quinolinyl sulfide 4 and chloroquinoline 5, are formed.For more than 100 years the reaction of disulfur dichloride with quinoline (1a) to give a dithiinodiquinoline3b has been known, although the structure has only been correctly assigned5,6 as 1,4-dithiino[2,3-c;5,6-cp]diquinoline (2a) for 20 years.In this paper it is clearly shown by MS and 1H NMR spectroscopy that from 6- and 8-methylquinoline (1b,c) the corresponding dithiinodiquinolines 2b,c are obtained, thus disproving the former postulation3d,f that during the reaction with disulfur dichloride the methyl group of 1c is lost. In its sulfuration reactions disulfur dichloride can behave both as a nucleophile and an electrophile, as is seen from the reactions with quinolines 1a–c [eqn.(1)] or with 1,2-dimethoxybenzene. 7 According to the general reaction (n+1)SnCl2mCl2+nSn+1Cl2 disulfur dichloride can also act as a chlorinating agent, i.e. 8-hydroxyquinoline is chlorinated giving 5,7-dichloro- 8-hydroxyquinoline.3d From this it can be understood that the reaction of disulfur dichloride with 6-methoxyquinoline (1e) leads to two products, namely 6,6p-dimethoxybis(quinolin-5-yl) sulfide (4) and 5-chloro-6-methoxyquinoline (5), both formed by the electrophilic attack of S2Cl2 and Cl2, respectively, at the C6 ring of 1d.Having carried out an X-ray analysis of 4 the structure assignment for 5 was made on the basis of the NMR data of both compounds. The X-ray study showed 4 to have the so-called butterfly conformation and that all bond lengths and angles lie in the normal ranges. Crystal Data for 4.·C20H16N2O2S, Mr=348.4, F(000)= 728, monoclinic P, a=1011.7(1), b=1186.9(1), c= 1446.5(1) pm, b=95.49(1)°, V=1702.7Å106 pm3, space group P21/c (no. 14), Dx=1.36 g cmµ3, m(CuKa)=17.1 cmµ1. The experimental data were collected at room temperature on an Enraf Nonius CAD4 diffractometer using a graphite monochromator with CuKa radiation (l=154.178 pm), and in addition an absorption correction14 was applied. The structure was solved by direct methods.15 The final R value R(F)obs was 0.0686 [wR2(F2)obs=0.2471].16 The estimated standard deviations for the geometrical parameters involving nonhydrogen atoms lie within the following ranges: bond lengths 0.3–0.6 pm; bond angles 0.1–0.3°). Atomic coordinates, bond lengths, bond angles and thermal parameters have been deposited with the Fachinformationszentrum (FIZ) Karlsruhe GmbH, D-76344 Eggenstein-Leopoldshafen, and can be ordered by quoting the authors, the journal and depositing number CSD 406842.We thank the Fonds der chemischen Industrie for financial support. Full text in German Techniques used: MS, 1H and 13C NMR, X-ray diffraction References: 27 Tables: 7 Fig. 2: Two views of the unit cell of 4 Received, 11th June 1997; Accepted, 11th August 1997 Paper G/7/06116A References 1 Part 1: S. Friederichs, T. Link and G. Klar, Phosphorus Sulfur Silicon Relat. Elem., 1995, 107, 279. 3 (b) A. Edinger and H. Lubberger, J. Prakt. Chem., 1896, 54, 340; (d) A. Edinger, J. Prakt. Chem., 1897, 56, 273; (f) A. Edinger and J. B. Ekeley, J. Prakt. Chem., 1902, 66, 209. 5 I. Baranowska and W. Karmi�nski, Pol. J. Chem., 1976, 50, 785. 6 A. Ma�slankiewicz and K. Pluta, Rocz. Chem., 1980, 54, 33. 7 K. W. Stender, N. W�olki and G. Klar, Phosphorus Sulfur Silicon Relat. Elem., 1989, 42, 111. 14 N. Walker and D. Stuart, Acta Crystallogr., Sect. A, 1983, 39, 158. 15 G. M. Sheldrick, SHELXS-90, Acta Crystallogr., Sect. A, 1990, 46, 467. 16 G. M. Sheldrick, SHELXL-93, Crystal Structure Refinement, Universit �at G�ottingen, 1993. *To receive any correspondence. Fig. 1 Molecular structure of 6,6p-dimethoxybis(quinolin-5-yl) sulfide (4) and atom

ISSN:0308-2342    

DOI:10.1039/a706116a

出版商:RSC    

年代:1997

数据来源: RSC

摘要:

R 1. CB, Rh complex 2. H2O2, NaOH R OH R OH + cis trans cis : trans = 2.3–13.3 : 1 84–94% 1 2 3 (1) 436 J. CHEM. RESEARCH (S), 1997 J. Chem. Research (S), 1997, 436 J. Chem. Research (M), 1997, 2665–2678 Stereoselective Metal Catalysed Hydroboration of 4-Substituted 1-Methylidenecyclohexanes Xue-Long Hou,* Quan-Cheng Xie and Li-Xin Dai Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China Rhodium catalysed hydroboration of 4-substituted 1-methylidenecyclohexanes gives cis-hydroboration products with high stereoselectivity; the effects of influencing the stereochemistry are discussed.Transition metal catalysed hydroboration differs greatly from conventional hydroboration in its chemo-, regio- and stereoselectivities. Excellent asymmetric induction is realized when only a catalytic amount of chiral metal complex is used in catalytic reactions. These results are complementary to conventional hydroboration and have found applications in organic synthesis.3 We reported previously the regio- and stereo-selective hydroboration of styrene derivatives5a,b and the regioselective hydroboration of allylsulfones6 under catalytic conditions.Now we disclose that metal catalysed hydroboration of 4-substituted 1-methylidenecyclohexanes affords cis-4-substituted cyclohexane-1-methanols in high yield. It provides another example in which the stereoselectivity is greatly changed in the metal catalysed hydroboration compared with the conventional one.13,14 Reaction of methylidenecyclohexanes 1 with catecholborane (CB)† at room temperature in the presence of a rhodium complex gave rise to the cis- and trans-cyclohexane derivatives 2 and 3 in high yields after usual hydrogen peroxide oxidation [eqn.(1)]. The results showed that the stereoselectivity is higher under metal catalytic conditions than those of conventional hydroboration.The ratio of cis to trans is increased to 13.3:1 under catalytic conditions, compared to a cis to trans ratio of around 1–2:1 for conventional hydroboration, which is in accord with results reported by Lichtenberg13 and Brown.14 The ratio of cis to trans products is determined from their 1H NMR spectra. From the results of the reactions of 1 with BH3, CB and 9-BBN it can be rationalised by assuming that the conventional hydroboration of 1 is controlled by both kinetic and thermodynamic effects.When BH3 is used, less hindered equatorial attack would be favoured and more cis products would be obtained. In the case of a bulkier reagent, such as 9-BBN, the trans product arising from axial attack is more stable thermodynamically, so that the reaction gives less cis products compared with those when BH3 is used as a reagent. When the reaction is carried out under catalytic conditions, the steric effect plays a more important role because the reaction proceeds through an intermediate rhodium complex coordinated with the carbon–carbon double bond and kinetic effects control the stereochemistry of the reaction.For substrates with heteroatom substituents the ratio of cis to trans products is lower than those with alkyl and phenyl substituents in both cases of conventional and catalytic hydroboration because there is a greater number of conformers in which the R group is in an axial position15 and the favourable equatorial attack at these heteroatom-substituted methylidenecyclohexanes gives rise to more trans products compared with those cases in which R is an alkyl or phenyl group.The state of the catalyst plays an important role in the reaction. The best results are obtained when the catalyst is produced in situ from the action of [Rh(COD)Cl]2 and 4 equiv. of PPh3. When Wilkinson’s complex was employed as catalyst the ratio of cis to trans decreased significantly since some of the catalyst would be oxidised when allowed to stand for a period of time.Besides, Lewis acids5b and solvents16 also have an effect on the stereochemistry of the reaction. Financial support from the National Natural Foundation of China and Chinese Academy of Sciences is gratefully acknowledged. Techniques used: 1H NMR, MS, HRMS References: 16 Table 1: Hydroboration of 4-substituted 1-methylidenecyclohexanes Table 2: Thermodynamics vs. kinetic reaction control Table 3: Influence of catalyst on the stereochemistry of the reaction Fig. 1: Kinetic and thermodynamic controlled reactions Received, 23rd July 1997; Accepted, 28th August 1997 Paper E/7/05335E References cited in this synopsis 3 (a) K. Burgess and M. J. Ohlmeyer, Chem. Rev., 1991, 91, 1179; (b) D. A. Evans, G. C. Fu and A. H. Hoveyda, J. Am. Chem. Soc., 1992, 114, 6671; (c) D. A. Evans, J. R. Gage and J. L. Leighton, J. Am. Chem. Soc., 1992, 114, 9434; (d) P. Kocienski, K. Jarowicki and S. Marczak, Synthesis, 1991, 1191. 5 (a) J. Zhang, B. Lou, G. Guo and L. Dai, J. Org. Chem., 1991, 56, 1670; (b) J. Zhang, B. Lou, G. Guo and L. Dai, Chin. J. Chem., 1992, 50, 913. 6 X. L. Hou, D. G. Hong, G. B. Rong, Y. L. Guo and L. X. Dai, Tetrahedron Lett., 1993, 34, 8513. 13 J. Klein and D. Lichtenberg, J. Org. Chem., 1970, 35, 2654. 14 H. C. Brown, R. Liotta and I. Brener, J. Am. Chem. Soc., 1977, 99, 3427. 15 F. R. Jensen, C. H. Bushweller and B. H. Beck, J. Am. Chem. Soc., 1969, 91, 344. 16 (a) F. A. L. Anet, J. Am. Chem. Soc., 1962, 84, 1053; (b) J. Reisse, J. C. Celotti and G. Chiurdoglu, Tetrahedron Lett., 1965, 397. *To receive any correspondence (e-mail: xlhou@pub.sioc.ac.cn). †Systematic name: 1,3,2-benzodioxaborole.

ISSN:0308-2342    

DOI:10.1039/a705335e

出版商:RSC    

年代:1997

数据来源: RSC

摘要:

O OR Y HN Me OH 7 8 6 5 1 2 14 + X– 1a–h O OR Y N Me X 2a–h TPP, DEAD or DIAD O OR Y HN Me OH + X– 3a–h TPP, DEAD or DIAD O OR Y N Me X 4a–h J. CHEM. RESEARCH (S), 1997 437 J. Chem. Research (S), 1997, 437 J. Chem. Research (M), 1997, 2734–2742 The First Preparation of 6b-Bromo Codeine and Morphine Derivatives. Kinetic vs. Thermodynamic Control† Csaba Simon,a S�andor Hosztafia and S�andor Makleit*b aAlkaloida Chemical Company Ltd., Tiszavasv�ari, H-4440 Hungary bDepartment of Organic Chemistry, L.Kossuth University, P.O. Box 20, Debrecen, H-4010 Hungary Starting from the hydrogen halide salts of morphine and codeine derivatives, 6a-halogeno(Cl, Br)-substituted codeine and morphine derivatives have been prepared under Mitsunobu conditions. In a previous paper1 we reported that the hydrogen halide produced in the Mitsunobu reaction2–5 acts as an acid reactant. To obtain further proof of this, the reaction of the hydrochloride salt of a tertiary amine (viz.codeine hydrochloride) with diethyl azodicarboxylate and triphenylphosphine was investigated. It was found that this reaction readily proceeds at room tempreature to result in the displacement of the alcoholic hydroxy group by chlorine with inversion of con- figuration to give the known 6b-chloro-6-deoxycodeine (2a). We have now investigated the applicability of the hydrogen halide salts of codeine and morphine derivatives in the Mitsunobu reaction. Utilizing the Mitsunobu reaction, attempts were made at synthesizing 6b-bromo-6-deoxycodeine and its derivatives, compounds hitherto reported as only hypothetical intermediates in the transformations.14 The codeine and morphine derivatives were first converted into the corresponding hydrogen halide salts, and these were allowed to react in benzene or toluene suspension with diethyl or diisopropyl azodicarboxylate (DEAD or DIAD) and triphenylphosphine. With the compounds having D7,8 double bonds the reaction was complete within ca. 1 h at room temperature, affording the 6b-halogeno derivatives (2a–h) in acceptable yields. Analogous conversions of compounds with a saturated ring C proceeded much slower (3–4 h) and with lower yields to give 4a–h. In the case of the hydrogen iodide salts the reaction did not give clear-cut results. This work was financially supported, in part, by a grant (OTKA reg. no. TO13991) obtained from the National Science Foundation (Budapest, Hungary). Techniques used: 1H NMR, mass spectrometry. References: 23 Table 1: Mps, yields and analytical data for the compounds prepared Table 2: Formulae and mass spectral data for the compounds prepared Table 3: 1H NMR spectral data for the compounds prepared Received, 26th June 1997; Accepted, 1st September 1997 Paper E/7/04502F References cited in this synopsis 1 Cs. Simon, S. Hosztafi and S. Makleit, Tetrahedron Lett., 1993, 34, 6475. 2 O. Mitsunobu, Synthesis, 1981, 1. 3 B. R. Castro, Org. React., 1983, 29, 1. 4 D. L. Hughes, Org. React., 1992, 42, 335. 5 D. L. Hughes, Org. Prep. Proced. Int., 1996, 28, 127. 14 G. Stork and F. H. Clarke, J. Am. Chem. Soc., 1956, 78, 4619. †‘Morphine Alkaloids, Part 138.’ For Part 137, see J. Marton, Cs. Simon, S. Hosztafi. Z. Szab�o, � A. M�arki, A. Borsodi and S. Makleit, Bioorg. Med. Chem., 1997, 5, 3

ISSN:0308-2342    

DOI:10.1039/a704502f

出版商:RSC    

年代:1997

数据来源: RSC

摘要:

OAc O 1 OAc 5 Cl R AcO 10 11 R Cl R = O R = a-H, b–OAc 8 14 R = O R = a-H, b–OAc O R 15 16 R Cl R = O R = a-H, b–OAc 17 18 R = O R = a-H, b–OAc O O O HO J. CHEM. RESEARCH (S), 1997 439 J. Chem. Research (S), 1997, 439 J. Chem. Research (M), 1997, 2847–2859 The Preparation of 4-Chloroandrosta-3,5-dien-7-ones Caroline Y. M. Bourban, James R. Hanson* and Ismail Kiran School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton, Sussex BN1 9QJ, UK Routes are described for the preparation of 4-chloroandrosta-3,5-diene-7,17-dione and the corresponding 17b-acetate starting from the readily available testosterone and dehydroisoandrosterone acetates.The introduction of halogen into a steroid is a common structural modification which alters steroidal biological activity. Androst-4-ene-3,17-dione is a natural substrate for aromatase whilst 4-chloroandrost-4-ene-3,17-dione shows moderate activity as an inhibitor of this system.1 A C-4 chloro substituent in a 4,6-dichloro-4,6-dien-3-one is labile under the conditions of a Michael addition in which the vinyl halide is converted into a reactive secondary halide.2 Compounds possessing an unsaturated ketone on ring B such as androst- 5-en-7-ones have attracted interest as aromatase inhibitors.4 The biological activity of 4-chloroandrosta-3,5-dien-7-ones became of interest in this context and their synthesis forms the subject of this paper. 17b-Acetoxyandrost-4-en-3-one (1) was converted into its 4-chloride with sulfuryl chloride6 and thence by reduction with sodium tetrahydroborate and cerium chloride7 and treatment with methanesulfonyl chloride to the 3,4-dichloride.Elimination of the 3-chloride with collidine or with lithium bromide and lithium carbonate in dimethylformamide gave 17b-acetoxy-4-chloroandrosta-3,5-diene (5) which was then hydrolysed to the 17b-alcohol. However, although allylic oxidation at C-7 with tert-butyl chromate or with the chromium trioxide–3,5-dimethylpyrazole complex occurred, the yield was not satisfactory. A better route (see Scheme 1) involved the allylic oxidation at C-7 of 3b-acetoxyandrost-5-en-17-one (10) and the corresponding 17b-acetate (11).Acid-catalysed elimination of the 3b-acetoxy group afforded the known 3,5-dienones.9,10 These were converted into the 3a,4a-epoxides 15 and 16 and thence by diaxial hydrolysis with hydrochloric acid to the 3a-hydroxy-4b-chloro steroids 17 and 18.Elimination of the 3a-hydroxy groups by treatment of their methanesulfonates with collidine gave the chlorodienones 8 and 14 in satisfactory overall yield. I. K. thanks the Turkish Government for financial support. Techniques used: 1H and 13C NMR, IR, UV Table 1: 13C NMR data for compounds 5, 7, 8, 14, 17 and 18 Schemes: 2 References: 11 Received 14th August 1997; Accepted, 10th September 1997 Paper E/7/05960D References cited in this synopsis 1 D. A. Marsh, H. J. Brodie, W. Garrett, C.-H. Tsai-Morris and A. M. H. Brodie, J. Med. Chem., 1985, 28, 788. 2 R. A. Le Mahieu, M. Carson, D. E. Maynard, P. Rosen and R. W. Kierstead, J. Am. Chem. Soc., 1971, 93, 1664. 4 M. Numazawa, M. Tachibana and Y. Takeda, J. Steroid Biochem., 1996, 58, 431. 6 C. Y. M. Bourban, J. R. Hanson and P. B. Hitchcock, J. Chem. Res., 1990, (S) 274; (M) 2050. 7 J. L. Luche, L. Rodriguez-Hahn and P. Crabbe, J. Chem. Soc., Chem. Commun., 1978, 601. 9 H. B. Hagan and J. Jacques, Bull. Soc. Chim. Fr., 1960, 1551. 10 K. Yasuda and H. Mori, Chem. Pharm. Bull., 1967, 15, 179. *To receive any correspondence. Scheme 1

ISSN:0308-2342    

DOI:10.1039/a705960d

出版商:RSC    

年代:1997

数据来源: RSC

摘要:

442 J. CHEM. RESEARCH (S), 1997 J. Chem. Research (S), 1997, 442–443 J. Chem. Research (M), 1997, 2647–2664 Molecular Complex of C60 with the Concave Aromatic Donor Dianthracene: Synthesis, Crystal Structure and Some Properties Dmitry V. Konarev,a Eduard F. Valeev,b Yury L. Slovokhotov,b Yury M. Shul’gaa and Rimma N. Lyubovskaya*a aInstitute of Chemical Physics RAS, Chernogolovka, 142432, Russia bInstitute of Organoelement Compounds RAS, 28 Vavilov St, Moscow, 117334, Russia A new molecular complex dianthracene C60 (C6H6)3, with a layered structure and a strong van der Waals interaction which is favoured by the concave donor molecule, is obtained by diffusion methods.Fullerene C60 is able to form charge transfer (CT) complexes1,3,7,8 basically with a weak CT degree owing to its being a weak acceptor.3 The interactions in these complexes are van der Waals interactions. The planarity of p-donors is less preferential for the coordination with spherical fullerene molecules since steric compatibility between C60 and the donor molecules is needed for effective van der Waals interaction. Possibly donors with an initially concave shape correspond to C60 spheres well and can form complexes with stronger van der Waals interactions between the components.Such donors are cyclotriveratrylene7 and trans-9,9p-bis- (telluraxanthenyl) (BTX).8 Dianthracene also has a ‘concave’ shape and was chosen for preparing the C60 complex. Here we report the synthesis, crystal structure and some characteristics of the new C60 molecular complex DAN C60 (C6H6)3 with the donor dianthracene (DAN).† DAN C60 (C6H6)3 (1) was prepared by the filtration of DAN and C60 benzene solutions (1 mmol dmµ3 and 0.1 mmol dmµ3 respectively) into one flask (DAN:C60=1:1) and evaporation down to 50 ml by heating. The solution became colourless after standing overnight and a polycrystalline precipitate was formed with a quantitative yield.Fullerene C70 does not form a crystalline complex with DAN even after complete evaporation of the benzene solution.High-quality single crystals of 1 were obtained by a diffusion method from saturated benzene solutions of C60 and DAN during 2 months and were washed with benzene. IR spectroscopy of 1 showed that the frequencies of the absorption bands attributed to C60 remained practically unchanged with respect to the individual C60 which showed an absence of a noticeable CT. The shifts of the DAN main absorption bands with respect to an individual donor in the 400–1500 cmµ1 range do not exceed 2 cmµ1 but the positions of the C·H absorption bands have larger shifts (1–6 cmµ1).There are absorption bands attributed to the basic electron transition of C60 at 265, 342 and a shoulder at 450 nm in the UV–VIS–NIR optical absorption spectrum of 1. The electron transition of DAN (the absorption band maximum is less than 220 nm in any individual donor) was not observed.No charge transfer band was found in the 500–1000 nm range. C1s X-ray photoelectron spectra of 1, C60, and DAN are presented in Fig. 1. The satellite structure which can be represented by two peaks (P1 and P2) was observed in all spectra to the side of higher binding energy from the P0 peak. In the case of DAN the distance between P0 and the most intensive satellite peak P1 is equal to 6.6 eV. This satellite peak originates from the excitation of php* transitions in the phenyl rings.For satellite structures of C60 and 1 the intensity is substantially larger and the distances between the P0 and P1 peaks are smaller than those in the spectrum of DAN. All these facts testify that the natures of the satellites are different for DAN and for C60 and 1. The php* transitions which are characteristic of DAN phenyl rings were not manifested in the spectrum of 1. This is obviously associated with the strong interaction of the p-electrons of the C60 and the DAN phenyl rings.The thermogravimetry revealed that the benzene is removed from the complex crystals starting at 425 K. A partial decomposition of DAN was observed from 605 K, and the loss of mass after 1075 K is due to C60 sublimation. Single crystal X-ray diffraction data showed that the fullerene, dianthracene and three solvent molecules reside in special positions on the symmetry plane. The projection of the crystal structure along the b axis is shown in Fig. 2.A mutual orientation of the DAN and C60 molecules is shown in Fig. 3. The C60 molecules are arranged in layers lying in the ab plane. The closest distance between the centres of the fullerene spheres is along the ab diagonal and is equal to 10.08 Å. However, the layer arrangement is far from being hexagonal dense packing. The centre–centre distances along the a and b axes are much larger and are equal to 13.260 and 15.117 Å, respectively. The concave shape of the DAN molecules allows its efficient packing with the C60 spheroids.Thus, each C60 molecule is sandwiched between two DAN molecules, which form two-dimensional layers parallel to the ab plane. The whole packing pattern may be described as alternating sheets made up of C60 and DAN molecules. The shortest C(C60)–C(DAN) intermolecular contacts (13.4 Å) shown in Fig. 3 are close to the sum of the van der Waals radii of sp2 carbon atoms (3.35 Å).18 Two-thirds of the C6H6 molecules on the symmetry plane fill the gaps in the slack layers of the DAN molecules.One third of the benzene molecules are incorporated in voids of layers of fullerene molecules. A relatively high R-factor value reached (0.069) and a significant variance in C·C bond lengths (1.04–1.84 Å) indi- *To receive any correspondence. †Systematic name: 5,6,11,12-tetrahydro-5,12[1p,2p]:6,11[1P,2P]-dibenzenodibenzo[ a,e]cyclooctene. Fig. 1 C1s X-ray photoelectron spectra of 1 (1), C60 (2) and DAN (3)J. CHEM.RESEARCH (S), 1997 443 cate some degree of disorder of the fullerene molecules in this compound. This disorder was not later clarified from the difference electron density map. Therefore 1 is to be considered as a van der Waals compound without noticeable charge transfer. This is associated with the weak donor properties of DAN and the weak acceptor properties of fullerene. The interaction is mainly of van der Waals character and is realized through the polarization interaction of C60 and DAN molecules.The close approach of the donor to C60 is attained due to the correspondence of a spherical C60 molecule and a concave donor one. As a result, a complex with close contacts and a strong interaction between its components was obtained. The strong interaction results in a quantitative formation of 1 in solution. The unique ability of this donor to form a complex with C60 which is quantitatively precipitated from even dilute benzene solutions can be used to isolate C60 from different mixtures. The elongated shape of C70 does not allow formation of a complex with DAN. This can therefore be used as a method for the partial separation of C60 from C70.Fullerene C60 is easily isolated from the complex by its dissolution in hot toluene. Crystal Data for 1.·C106H38, M=1311.36, F(000)= 1188.0, monoclinic, a=13.260(5), b=15.177(4), c=15.764(5) Å, b=110.97(2)°, V=2926(2) Å3, space group Cm, Z=2, Dc=1.470 g cmµ3, m(MoKa)=0.74 cmµ1.The experimental data were collected at room temperature on a Siemens P3 diffractometer using a graphite monochromator with MoKa radiation (l=0.71073 Å). The structure was solved by direct methods using SHEHLXS-86 and refined using SHELXL-93 with anisotropic thermal parameters for all atoms. All hydrogen atoms were located on the difference Fourier map and added to the refinement with fixed positional and thermal parameters. The final R value was 0.069 (Rw=0.189). The estimated standard deviations for the geometrical parameters involving non-hydrogen atoms lie within the following ranges: in dianthracene molecules bond lengths 0.010–0.017 Å; bond angles 0.60–0.91°, in C6H6 and C60 molecules bond lengths 0.02–0.05 Å; bond angles 1–5°.We thank Dr V. N. Semkin and Dr A. Graja for help with IR and UV–VIS spectra investigations and Dr B. P. Tarasov for thermogravimetric analysis. This work was supported by the Foundation of Intellectual Collaboration in the framework of the Russian Programme ‘Fullerenes and Atomic Clusters’ (grants 95087 and 94018).Techniques used: X-ray diffraction, IR, UV–VIS–NIR, X-ray photoelectron spectroscopy, thermogravimetric analysis References: 19 Table 1: Crystal data and structure refinement for 1 Table 2: Atomic coordinates and equivalent isotropic displacement parameters for 1 Table 3: Bond lengths and angles for 1 Appendix: Anisotropic displacement parameters, hydrogen coordinates and isotropic displacement parameters for 1 Received, 8th July 1997; Accepted, 27th August 1997 Paper E/7/04862I References cited in this synopsis 1 A. Izuoka, T. Tachikawa, T. Sugawara, Y. Suzuki, M. Konno, Y. Saito and H. Shinohara, J. Chem. Soc., Chem. Commun., 1992, 1472. 3 G. Saito, T. Teramoto, A. Otsuka, Y. Sugita, T. Ban, M. Kusunoki and K. Sakaguchi, Synth. Met., 1994, 64, 359. 7 J. W. Steed, P. C. Junk, J. L. Atwood, M. J. Barnes, C. L. Raston and R. S. Burkhalter, J. Am. Chem. Soc., 1994, 116, 10 346. 8 D. V. Konarev, R. N. Lyubovskaya, O. S. Roshchupkina, Y. M. Shul’ga, M. G. Kaplunov, I. N. Kremenskaya, L. P. Rozenberg, S. S. Hasanov and R. P., Shibaeva, Mendeleev Commun., 1996, 3. 18 J. Emsley, The Elements, Oxford University Press, Oxford, UK, 3rd edn., 1996. Fig. 2 Projection of the crystal structure along the b axis Fig. 3 A mutual orientation of DAN and C60 molecules

ISSN:0308-2342    

DOI:10.1039/a704862i

出版商:RSC    

年代:1997

数据来源: RSC

摘要:

Me NAr NHAr PhCOC CCOPh + N Ph O COPh Ar H COPh COPh NHAr + 1a–c 2 8a–c 9a–c N Ph H COPh O Ar a Ar = 4-MeC6H4 b Ar = 4-MeOC6H4 c Ar = 4-CIC6H4 10 Me NAr NHAr PhCOC CCOPh + 1a–c 2 H COPh NAr Ph O Me NAr 3a–c H COPh NAr Ph O NHAr 4a–c 5a–c NAr H COPh Ph –O NHAr 6a–c NAr H COPh Ph HO NAr –H2O NAr H COPh NAr Ph +H2O NAr + ArNH2 H COPh O Ph 8a–c 7a–c ArNH2 + 2 COPh H COPh NHAr 9a–c a Ar = 4-MeC6H4 b Ar = 4-MeOC6H4 c Ar = 4-CIC6H4 444 J. CHEM. RESEARCH (S), 1997 J. Chem. Research (S), 1997, 444–445 J.Chem. Research (M), 1997, 2679–2687 Reaction of N1,N2-Diarylacetamidines with Alkynic Dienophiles: Synthesis of New Pyridin-2-one Derivatives Mohsen Abdel-Motaal Gomaa* Chemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt 6-Benzoyl-1-aryl-4-phenylpyridin-2(1H)-ones 8a–c together with the corresponding 2-aryl-1,4-diphenylbut-2-ene- 1,4-diones 9a–c were obtained from the reaction of N1,N2-diarylacetamidines 1a–c with dibenzoylacetylene 2, while reaction of 1a,b with dimethyl acetylenedicarboxylate 11a and methyl propiolate 11b afforded only the acetamidine– dimethyl maleate adducts (E)-12a,b and the acetamidine–methyl acrylate adduct (E)-12c respectively.Recently we have investigated the behaviour of N1,N2-diarylformamidines and -acetamidines towards electron-poor compounds such as 2,3,5,6-tetrachloro-1,4-benzoquinone, 2 , 3 - d i c h l o r o - 1 , 4 - n a p h t h o q u i n o n e, 2 - ( d i c y a n o m e t h y l i d e n e ) - indane-1,3-dione, 3-(dicyanomethylidene)indolone, 2,3-dicyano- 1,4-naphthoquinone and 9-dicyanomethylidene-2,4,7- trinitrofluorene.1–4 We have synthesized several new heterocyclic compounds with the amidines.As a continuation of this work, we selected some alkynic dienophiles in order to investigate their behaviour towards N1,N2-diarylacetamidines. It has been reported that free acetamidine and trichloroacetamidine react with dimethyl acetylenedicarboxylate to give a low yield of a 4-hydroxypyrimidine- 6-carboxylic ester via an isolable intermediate adduct.5 N-Aryl-acetamidines and -benzamidines react similarly with ethyl propiolate to furnish pyrimidone derivatives.6 A 2,6-disubstituted pyrimidone has also been prepared analogously from N-o-chlorophenylbenzamidine and 4-ethylphenyl propiolate.7 A literature survey did not reveal any report on the reaction of N1,N2-diarylacetamidines with dibenzoylacetylene.Therefore the present work was undertaken to study the behaviour of N1,N2-diarylacetamidines towards benzoylacetylene (2) as a dienophile, as well as, for comparison, to dimethyl acetylenedicarboxylate (DMAD, 11a) and methyl propiolate (11b).First, the reaction of acetamidines 1a–c with dibenzoylacetylene 2 was investigated. Thus a solution of 2 (2 mmol) in ethyl acetate was added to solutions of 1a–c (1 mmol) in the same solvent. After 1 h at room temperature, work-up gave the 6-benzoylpyridin-2(1H)-ones 8a–c in 37–73% yield along with arylamino-1,4-diphenylbut-2-ene-1,4-diones 9a–c in 18–27% yield (Scheme 1).The 6-benzoylpyridin-2(1H)-one structure 8a–c was preferred over the alternative structure 10 on the basis of the spectral data. 1H NMR spectroscopy showed two doublets at 6.75 and 6.85 ppm, which were assigned as the two olefinic protons 5-H and 3-H respectively (long range coupling) with !4J! 1.3 Hz for the structures 8a–c. 13C NMR spectroscopy showed signals at 157.6 ppm for (C-2, i.e.C�O) for the structures 8a–c. In the reaction product 10 it would be difficult to assign these signals. The structures of 9a–c were identified by comparison of their melting points with those reported in the literature.8µ10 Compounds 8a–c may be rationalized as being formed by nucleophilic addition of the N2 of 1a–c on the C-1 of 2, forming 3a–c, being in equilibrium with 4a–c (Scheme 2). The nucleophilic methylene carbon of the latter obviously prefers attacking at C-4 (C�O) instead of at C-3 of the enamine moiety in 4a–c to form 5a–c and thus 6a–c.The latter undergo spontaneous dehydration to give 7a–c, which in turn hydrolyse to give 8a–c and the corresponding amines. Consequently, the amines formed add to dibenzoylacetylene (2) to give the adducts 9a–c. Hydrolysis of the acetamidine [which should generate the acetanilide ArNHCOCH3 and the free amine ArNH2 which in turn would attack the dibenzoyl acetylene (2)] prior to the reaction with 2 is considered unlikely, because there is no change in the acetamidines 1a–c under similar conditions but where 2 is absent.Moreover, the acetanilide failed to react with 2 under the same conditions. *E-mail: rumenia@enstinet.eg.net Scheme 1 Scheme 2Me NAr NHAr + a Ar = 4-MeC6H4 b Ar = 4-MeOC6H4 R R¢ MeOH R R¢ NAr Me ArN 1a, b a R = R¢ = CO2Me 11a, b b R = H, R¢ = CO2Me a Ar = 4-MeC6H4, R = R¢ = CO2Me 12a-c b Ar = 4-MeOC6H4, R = R¢ = CO2Me c Ar = 4-MeC6H4, R = CO2Me, R¢ = H J.CHEM. RESEARCH (S), 1997 445 Next, the reaction of 1a,b with dimethyl acetylenedicarboxylate 11a and methyl propiolate 11b was investigated in order to compare their reactivity with 2 towards 1a,b. The reaction of 1a with 11b in methanol at room temperature overnight did not reveal any change in the reaction mixture; thus when heated at reflux for 1 h, it gave the acetamidine– methyl acrylate adduct 12c as the E-form. This trans-structure was assigned on the basis of the 1H NMR spectrum, where the two olefinic protons show up as two doublets (at d 4.65 and 8.95 with |3J| 14 Hz).11 Similarly 1a,b reacted with DMAD 11a in methanol at reflux for 2 h to provide the acetamidine–dimethyl maleate adducts (E)-12a,b in 80–81% yield.These adducts 12a–c failed to cyclize as in the case of dibenzoylacetylene (2), even at higher temperatures: this was probably due to electronic and steric reasons. This is because of the difference in the reactivity of the carbonyl carbon atom of 2 and 11a,b, where it has been reported that in ab-unsaturated carbonyl compounds (like 3a–c and 12a–c) nucleophilic addition (like the active methylene in our case) is preferred at C�O rather than at C�C, in the sequence aldehydeaketoneaester.12 Therefore 3a–c cyclizes readily rather than 12a–c.Moreover, owing to the formation of 12a–c in the E-form, attack of the active methylene carbon atom of the amidine moiety at the carbonyl carbon atom of the ester is made difficult.The author is deeply indebted to Professor Dr D�opp, Division of Organic Chemistry, Gerhard-Mercator Universit�at, GH Duisburg, Germany, for measuring mass and NMR spectra and elemental analyses. Techniques used: IR, 1H and 13C NMR, mass spectrometry References: 12 Schemes: 3 Received, 2nd May 1997; Accepted, 28th August 1997 Paper E/7/03014B References cited in this synopsis 1 D. D�opp, M. A.-M. Gomaa, G. Henkel and A. M. Nour El-Din, J. Heterocycl. Chem., 1995, 32, 603. 2 D. D�opp, M. A.-M. Gomaa, G. Henkel and A. M. Nour El-Din, J. Chem. Soc., Perkin Trans. 2, 1996, 573. 3 M. A. Gomaa, S. K. Mohamed and A. M. Nour El-Din, J. Chem. Res. (S), 1997, 284. 4 M. A. Gomaa and D. D�opp, unpublished results. 5 L. P. Prikazchikova, L. I. Rybchenko and V. M. Cherkasov, Khim. Geterotsikl. Soedin., 1977, 831 (Chem. Abstr., 1977, 87, 184 452). 6 K. A. Gupta, A. K. Saxena and P. C. Jain, Synthesis, 1981,905. 7 K. A. Gupta, A. K. Saxena, P. R. Dua, R. C. Srimal and B. N. Dhawan, Indian Pat., 158 084 (1986) (Chem. Abstr., 1987, 107, 59051). 8 E. Van Loock, G. L’abb�e and G. Smets, Tetrahedron Lett., 1970, 20, 1693. 9 N. Jolles, Gazz. Chim. Ital., 1938, 68, 488. 10 P. Barraclough, M. Edwards, T. L. Gilchrist and C. J. Harris, J. Chem. Soc., Perkin Trans. 1, 1976, 716. 11 Atta-ur-Rahmen, Nuclear Magnetic Resonance, Springer-Verlag, New York, 1986. 12 P. Sykes, A Guidebook to Mechanism in Organic Chemistry, Longman, Ha

ISSN:0308-2342    

DOI:10.1039/a703014b

出版商:RSC    

年代:1997

数据来源: RSC

摘要:

n R R 1 3bR = H 4 R = Me 5 R = OMe 4 X 2 7 9 (O.S. IV 623) i 2 20 iii 21 Br i 10 X = I 14 X = Br ii or iii O v 15 R R Br ix, iv, i 24 R = H 25 R = OMe R R X X 38 X = I; R = Me X X i 37 X = I 39 X = Br 40 X = Br; R = Me 59 X = Br; R = OMe 63 X = Br; R = OCHPh2 R R Y X vii vii R R X X vii 64 Ar = Ph 65 Ar = m-C6H4Me 66 Ar = p-C6H4- tert-C5H11 67 Ar = p-C6H4OMe R = Me 73 Ar = Ph 74 Ar = p-C6H4-Bu t 75 Ar = p-C6H4OMe 76 Ar = 3,5-di-Bu tC6H3 R = OMe 26 X = Bu t, Y = H R = Me 27 X = OMe, Y = H 29 X = Y = tert -C5H11 R = OMe O 68 Ar = 69 Ar = O 64 70 v Ar = p-C6H4COMe 70 71 x Ar = p-C6H4CO2H Br O 89 R R X 78 Ar = Ph R = OCHPh2 R R X 10 vii or viii vii 14 or 24 33 R = Me, X = H 35 R = OMe, X = H 36 R = H, X = tert-C5H11 ii or iv 19 X = Me vi 446 J.CHEM. RESEARCH (S), 1997 J. Chem. Research (S), 1997, 446–447 J. Chem. Research (M), 1997, 2701–2733 Synthesis of Bridged Oligophenylenes from Fluorene. Part 1. Ter- and Quater-phenyls Charles J. Kelley,*a Alem Ghiorghisa and Joel M.Kauffmanb aMassachusetts College of Pharmacy and Allied Health Sciences, 179 Longwood Ave, Boston MA 02115-5804, USA bPhiladelphia College of Pharmacy and Science, 600 South 43rd Street, Philadelphia PA 19104-4495, USA Alkylation and halogenation of fluorene give halogenated 9,9-dialkylfluorenes, which are converted by Pd-catalysed coupling with aryl Grignard reagents into a series of ter- and quater-phenyls exhibiting strongly efficient fluorescence, useful solubility and photochemical stability. By virtue of their high quantum efficiency of fluorescence and their photochemical stability, the p-oligophenylenes are the premier class of ultraviolet laser dyes.2 The utility of the parent series of p-oligophenylenes 1 is compromised by high crystallinity and, when na1, low solubility.To synthesise compounds 1 for a study of their uses as fluorescent agents, we recognised the need to build solubilising factors into the molecules. While a soluble series of ring-alkylated com- *To receive any correspondence (e-mail: ckelley@mcp.edu). Scheme 1 Reagents: i, ButOK–XCH2CH2R, DMSO; ii, I2–HIO4; iii, NBS–propylene carbonate; iv, Br2–CH2Cl2; v, RCOCl–AlCl3, CH2Cl2; vi, MeMgCl–PdCl2 (dppb)–14; vii, preformed ArpMgX-PdCl2 (dppb)–fluorenyl halide; viii, Mg, heat (THF); ix, AlMe3; x, NaOBr–H2O–THFJ.CHEM. RESEARCH (S), 1997 447 pounds 1 was known,4 the presence of alkyl groups on nonterminal rings diminished fluorescence by sterically preventing ring coplanarity.We have prepared a series of 1 in which one or two adjacent rings are bridged by dialkylmethylene groups. This functionality lowers crystallinity and melting points whilst improving the solubility and ensuring the coplanarity of pairs of bridged benzene rings. These strongly fluorescent, bridged oligophenylenes have been prepared by the clean, efficient dialkylation of fluorene 2 to 9,9-dialkylfluorenes (3b,4) or for enhanced alcohol solubility to 9,9-bis(2-methoxyethyl)fluorene 5.As shown in Scheme 1, the synthesis of bridged terphenyls 26, 27 and 29 and quaterphenyls 33, 35, 36, 64–69 and 73–77 was carried out in a three-step sequence comprised of the one-pot dialkylation of 2 at C-9, the selective iodination or bromination at C-2 (and C-7) and the coupling of the 9,9-dialkylhalofluorenes with preformed Grignard reagents catalysed25 by the palladium chloride complex with 1,4-bis(diphenylphosphino)butane (dppb).The use of 1 mol% or less of this air-stable coupling agent in concentrated THF solutions routinely gave excellent yields. Delayed strong exotherms exhibited by the reaction were controlled by the portionwise addition of the halofluorene derivative (mixed with the catalyst) to the Grignard solution. Since fluorescence properties are often affected by impurities, special attention was paid to the purification of each intermediate. Difficulties encountered in the preparation of bromofluorene 14, free from its 2,7-dibromo analogue 40, were resolved by spinning-band distillation of liquid 21 and its alkylation to 14.We found that fluorescence lifetimes were lengthened in bridged oligophenylenes by the inclusion of tert-alkyl groups in p- (and pp-) positions,7c–e e.g., 26, 36, 66 and 74. Shifts of fluorescent maxima to longer wavelengths were achieved by placing alkoxy groups in p- (and pp-) positions, 7b e.g., 27, 67–69 and 75. To prepare the intermediates needed to produce ringsubstituted bridged oligophenylenes, we employed literature methods for the direct introduction of halo, nitro, acetyl and halomethyl substituents into the 2- or 2,7-positions of 4 and its halogenated derivatives 10 and 14.Other standard methods allowed the conversion of those substituents into amino, dimethylamino, methoxy, cyano, carboxy, tert-pentyl, and diethylphosphonomethyl substituents. Acylation of quaterphenyl 64 gave its diacetyl derivative 70 which was oxidised to dicarboxylic acid 71.Synthesis of the bromoaryl cyclic ether 89, which was converted into its Grignard reagent for coupling with 40 in the preparation of 69, is fully described. The methodology and materials described in this paper have been used to prepare a series of soluble higher oligophenylenes, quinque- to deci-phenyl. The fluorescence properties of these compounds have been reported7e and their synthesis will be published.8 References: 36 Table 1: Mps of 9,9-dialkylfluorenes Received, 12th August 1997; Accepted, 1st September 1997 Paper E/7/05889F References cited in this synopsis 2 (a) M.Rinke, H. Gusten and H. J. Ache, J. Phys. Chem., 1986, 90, 2661 (and references cited therein); (b) M. Rinke, H. Gusten and H. J. Ache, J. Phys. Chem., 1986, 90, 2666. 4 (a) H. O. Wirth, K. H. Gonner and W. Kern, Makromol. Chem., 1963, 63, 30; (b) H. O. Wirth, K. H. Gonner, R. Stuck and W. Kern, Makromol. Chem., 1963, 63, 53; (c) H. O. Wirth, G. Waese and W. Kern, Makromol. Chem., 1965, 86, 139. 7 (a) J. M. Kauffman, C. J. Kelley, A. Ghiorghis, E. Neister, L. Armstrong and P. Prause, Laser Chem., 1987, 7, 343; (b) J. M. Kauffman, C. J. Kelley, A. Ghiorghis, E. Neister and L. Armstrong, Laser Chem., 1988, 8, 335; (c) P. A. Fleitz, C. J. Seliskar, R. N. Steppel, J. M. Kauffman, C. J. Kelley and A. Ghiorghis, Laser Chem., 1991, 11, 99; (d) C. J. Seliskar, D. A. Landis, J. M. Kauffman, M. A. Aziz, R. N. Steppel, C. J. Kelley, Y. Qin and A. Ghiorghis, Laser Chem., 1993, 13, 19; (e) J. M. Kauffman, P. Litak, J. A. Novinski, C. J. Kelley, A. Ghiorghis and Y. Qin, J. Fluorescence, 1995, 5, 295. 8 J. M. Kauffman and C. J. Kelley, in preparation. 25 A. Minato, K. Tamao, T. Hayashi, K. Suzuki and M. Kumada, Tetrahedron Lett., 1981, 22, 5319.

ISSN:0308-2342    

DOI:10.1039/a705889f

出版商:RSC    

年代:1997

数据来源: RSC

摘要:

ArSO2 C H R 1 – H R ArSO2 H DMC K2CO3 CO2Me C R ArSO2 H 2 4 CO2Me C R ArSO2 – CO2Me R ArSO2 Me 5 DMC H R ArSO2 Me 3 K2CO3 448 J. CHEM. RESEARCH (S), 1997 J. Chem. Research (S), 1997, 448–449 J. Chem. Research (M), 1997, 2688–2696 Dimethyl Carbonate as a Methylating Agent. The Selective Mono-C-methylation of Alkyl Aryl Sulfones Andrea Bomben, Maurizio Selva* and Pietro Tundo* Dipartimento di Scienze Ambientali del’Universit`a di Venezia, Calle Larga S. Marta 2137, 30123, Venezia, Italy At 180–210 °C, a-methylene sulfones (both benzyl aryl and alkyl aryl sulfones, RCH2SO2AR: R=Ph, p-ClC6H4, Ar=Ph, p-ClC6H4, p-MeC6H4, and R=Me, Ar=Ph, p-ClC6H4, p-MeC6H4) react with dimethyl carbonate to yield the corresponding mono-C-methyl derivatives [RCH(CH3)SO2Ar] in a selectivity a99%, at conversions of 76–99% (isolated yields: 97–92%).a-Sulfonyl carbanions, e.g. 1, may react with a number of different electrophiles yielding, for example, condensation with esters, aldehydes and isocyanates, though their most widely used reaction is by far nucleophilic displacement with alkyl halides [eqn. (1)].RPX RCH2SO2ArhRCH(RP)SO2Ar (1) Base(µ78 to µ33°C) R=aryl, alkyl; base=BuLi; MNH2 (M=Li, Na, K) However, the generation of carbanions 1 necessitates very strong bases.1,3–5 Only in the case of triflones (RCH2SO2CF3)7 may mild bases act efficiently to promote alkylations; however, triflones themselves are not always accessible.1 An alternative route for alkylation processes can be conceived with the use of dialkyl carbonates (DAlCs) as alkylating agents.In particular, dimethyl carbonate (DMC) is an excellent methylating agent which allows unprecedented high mono-C- and mono-N-methyl selectivities: derivatives of both aryl- and aryloxy-acetic acid derivatives and primary aromatic amines [XCH(CH3)W: X=Ar and ArO, W=CN and CO2Me, and ArNHCH3, respectively] have been obtained in 90–99% selectivity at substantially quantitative conversions (up to 99%).12–16,17 This paper reports that also sulfones bearing a-methylene groups (benzyl aryl and alkyl aryl sulfones: ArCH2SO2Arp and RCH2SO2Arp) can be effectively mono-C-methylated (selectivity a99%) by DMC, even when a mild base (K2CO3) is used.Batchwise reactions are performed in an autoclave by loading a mixture of the substrate, K2CO3 and DMC in a 1:2:130–210 molar ratio, respectively, DMC acting both as the methylating agent and the solvent. At 180–210 °C, mono-C-methylations of benzyl aryl and alkyl aryl sulfones [ArCH2SO2Arp, 2a–c and 2g–h: Ar\Ph, p-ClC6H4; Arp=Ph, p-ClC6H4, p-MeC6H4, and RCH2SO2Arp, 2d–f: R=Me; Arp=Ph, p-ClC6H4, p-MeC6H4) proceed with a selectivity a99% (at conversions of 95–99%), and afford good to high yields (77–92%) of isolated products [3a–h; eqn.(4)]. K2CO3 RCH2SO2Ar+MeOCO2MehRCH(Me)SO2Ar 180–210 °C +MeOH+CO2 (4) R Ar T/°C Yield (%) 3a 3b 3c 3g 3h 3d 3e 3f Ph p-ClC6H4 p-MeC6H4 Ph p-ClC6H4 Ph p-ClC6H4 p-MeC6H4 Ph Ph Ph p-ClC6H4 p-ClC6H4 Me Me Me 180 180 180 180 180 200 200 210 78 76 92 80 81 85 77 76 A major influence on reactivity arises from the different aryl and alkyl groups directly bound to the methylene reacting group: thus benzyl aryl sulfones (ArCH2SO2Arp: 2a–c,g– h) are efficiently mono-methylated at 180 °C while alkyl aryl sulfones (MeCH2SO2Ar: 2d–f) do not, and actually require a more elevated reaction temperature of 200–210 °C for the reaction to go to completion.Such a behaviour seems to be clearly related to the stabilization of aryl sulfonyl carbanions [ArSO2�CHArp formed during the reactions] induced by the resonance with the adjacent Arp group. The methylation of the sulfones 2a–h follows, in all likelihood, the mechanistic pattern reported for aryl- and aryloxyacetic acid derivatives.14–16 Accordingly, the monomethyl selectivity is explicable through the occurrence of two consecutive nucleophilic displacements (Scheme 1): (i) a methoxycarbonylation of the initially formed sulfonyl carbanion [ArSO2�CHR] (BAc2 mechanism) followed by (ii) a methylation of the resulting intermediate [ArSO2CH(CO2Me)R (4)] yielding the methyl derivative [ArSO2C(Me)(CO2Me)R, (5); BAl2 mechanism].Finally, compound 5 undergoes a de-methoxycarbonylation reaction to the final product [ArSO2CH(Me)R]. *To receive any correspondence (e-mail: selva@unive.it). Scheme 1 Suggested mechanism for the mono-C-methylation of alkyl aryl sulfones with dimethyl carbonatefbJ.CHEM. RESEARCH (S), 1997 449 Both intermediates 4 and 5 are detected during the reaction of DMC with sulfones 3a–h (maximum amount of 10–30%, by GC; structures assigned by GC–MS). Also, methyl aryl sulfones (ArSO2CH3) react with DMC as in Scheme 1: the formation of methoxycarbonylated compounds (ArSO2CH2CO2Me) as intermediates, allows the homologation of the methyl group to a isopropyl one. Thus, PhSO2Me yields PhSO2CHMe2 and PhSO2C(CO2Me)Me2 (6) (12 and 81%, respectively; 14 h at 180 °C; conversion 93%).Likewise, PhCH2SO2Me affords PhCH(Me)SO2- CHMe2 and PhCH(Me)SO2C(CO2Me)(Me)2 (7) (14 and 50%, respectively; 21.5 h at 180 °C; conversion 98%). Compounds 6 and 7 have been isolated in 63 and 34% yields, respectively (characterized by 1H and 13C NMR spectra). 1H NMR and GC–MS spectra are given in the full text for all products. The synthesis here discussed has both synthetic advantages and remarkable environmental benefits: (i) it affords selectively only mono-methyl derivatives; (ii) it uses an intrinsically safe methylating agent (DMC) in place of the toxic methyl chloride (or dimethyl sulfate); (iii) it gives neither organic nor inorganic by-products (alkylation procedures using alkyl halides cannot avoid the formation of stoichiometric amounts of inorganic salts to be disposed of); (iv) it does not require additional solvents.Moreover, the procedure discloses intriguing perspectives of the chemistry of sulfonyl carbanions since it shows that these anionic moieties can actually be generated also in the presence of very mild bases.Techniques used: 1H and 13C NMR, GC and GC–MS References: 24 Table 1: Yields, reaction temperature and times, purification for products 3a–h Received, 21st May 1997; Accepted, 1st September 1997 Paper E/7/03510A References cited in this synopsis 1 P. D. Magnus, Tetrahedron, 1977, 33, 2019. 3 K. Kondo and D. Tunemoto, Tetrahedron Lett., 1975, 1007. 4 C. R. Hauser and T. M. Harris, J. Am. Chem. Soc., 1957, 79, 6342. 5 E. M. Kaiser and C. R. Hauser, Tetrahedron Lett., 1967, 3341. 7 J. B. Hendrikson, A. Giga and J. Wareing, J. Am. Chem. Soc., 1974, 96, 2275. 12 F. Trotta, P. Tundo and G. Moraglio, J. Org. Chem., 1987, 52, 1300. 13 P. Tundo, F. Trotta and G. Moraglio, J. Chem. Soc., Perkin Trans. 1, 1989, 1070. 14 M. Selva, C. A. Marques and P. Tundo, J. Chem. Soc., Perkin Trans. 1, 1994, 1323. 15 P. Tundo and M. Selva, Chemtech, 1995, 25, 31. 16 A. Bomben, C. A. Marques, M. Selva and P. Tundo, Tetrahedron, 1995, 51, 11573. 18 M. Selva, A. Bomben and P. Tundo, J. Chem. Soc., Perkin Trans. 1, 1997, 1

ISSN:0308-2342    

DOI:10.1039/a703510a

出版商:RSC    

年代:1997

数据来源: RSC

摘要:

450 J. CHEM. RESEARCH (S), 1997 J. Chem. Research (S), 1997, 450–451 J. Chem. Research (M), 1997, 2743–2757 New Hippurins from the Indian Ocean Soft Coral Sarcophyton crassocaule Ammanamanchi S. R. Anjaneyulu,* Moturu V. R. Krishna Murthy and Nidasanametla S. Kameswara Rao Department of Organic Chemistry, School of Chemistry, Andhra University, Visakhapatnam 530 003, India Four new hippurins, (22S,24S)-24-methyl-22,25-epoxyfurost-5-ene-3b-20b-diol (1), (22R,24S)-24-methyl-22,25-epoxyfurost- 5-ene (2) and their respective 3b-acetates (3 and 4), have been isolated for the first time from the Indian Ocean soft coral Sarcophyton crassocaule.As a part of our continuing work on the bioactive secondary metabolites of soft corals of the Indian Ocean we have examined the soft coral species Sarcophyton crassocaule, and the results are reported here. The organism was collected from the Andaman and Nicobar Islands of the Indian Ocean, cut into pieces and percolated repeatedly with methanol.The concentrate from the methanolic extract was fractionated into ethyl acetate. The residue from the ethyl acetate extract on chromatography over a column of silica gel using gradients of solvent mixtures from light petroleum to ethyl acetate furnished four pure compounds 1–4. Compounds 1–4 were found to be new spiroketal steroids with 28 carbons, like hippurins and hippuristanols isolated from the marine gorgonian Isis hippuris6–9 collected from different sea waters.However at the same time they differ from hippurins,6–9 which are saturated 3a-hydroxy derivatives, being 3b-hydroxy-5-enes similar to the 27-carbon steroid sapogenins of plant origin.10–15 Compound 1 had mp 213–216 °C, [a]D 25 µ38.0° (c, 0.001 in CHCl3), and analysed for C28H44O4, supported by its molecular ion M+ 444 (+ve FABMS). It exhibited hydroxylic absorption at 3472(s), 3350(sh), 1023(s), 971(s) and 924(m) in its IR spectrum but no conjugation in its UV spectrum.Its 1H NMR spectrum (Table 1), reminiscent of a sterol and in particular of hippurins,6–9 showed two tertiary methyls at d 0.96 and 1.10 and three tertiary methyls connected to oxygenated carbons at d 1.02, 1.28 and 1.30 in addition to a secondary methyl at d 0.92. Further, it exhibited a carbinolic methine proton at d 3.5 and a trisubstituted olefinic proton at d 5.3 characteristic of a 3b-hydroxy steroidal 5-ene, together with another carbinolic methine proton at d 4.4 characteristic of a 16a-hydrogen in taccagenin10–13 and hippurin derivatives. 6–9 Its 13C NMR spectrum showed all 28 carbons, the substitution pattern of which was decided by its DEPT spectrum.Olefinic carbons characteristic of a 5-ene were shown at d 140.9 and 121.3.14,15 For the four oxygens of the molecule it showed five oxygenated carbons at d 71.7, 79.3, 82.6, 84.2 and 118.6, the last one being characteristic of a C-22 spiro ketal carbon, as in hippurin and hippuristanol derivatives from I.hippuris6–9 or taccagenin and others10–15 from plant sources. These spiroketal derivatives are known to occur in both the epimeric forms at C-22 (R or S) which can be distinguished by IR, 1H and 13C NMR spectral data.6–9 The 13C NMR values for compound 1 were compared with those for 22-epihippuristanol9 (6) and taccagenin12 (5) (Table 2). From the diagnostic 13C value of C-22 (d 118.0) as well as the absence of hydrogen bonding between the 20b-hydroxy and the 22,25-epoxy oxygen, the 22-S configuration was fixed in compound 1 as in epihippuristanol9 (6).The 13C values of C-16, -17, -20, -21, -22 and -23 are nearly identical with the corresponding values of epihippuristanol in support of the S configuration at C-22. However, the C-18 in taccagenin (5) resonated at d 18.8 compared with at d 23.0 in 1 and at d 27.2 in epihippuristanol. This difference could be attributed to the fact that in hippuristanol the C-18 is subjected to deshielding both by the 11b-hydroxy and the 20b-hydroxy groups, while in compound 1 only the latter has any effect and in taccagenin neither of these have any influence.While hippurins and hippuristanols are saturated stanols with a 3a-hydroxy group, plant sapogenins like taccagenin (5) are 3b-hydroxy-5-enes. The 13C NMR values of compound 1 from C-1 to C-12 agreed perfectly with those of taccagenin, in support of their identity *To receive any correspondence. Table 1 Comparative 1H NMR spectral data of new hippurins 1–4 Assignment 1a 2b 3a 4b 5c 6d 7d 18-H3 19-H3 21-H3 26-H3 27-H3 28-H3 3-H 11-H 16-H 24-H 21-OH 6-H OAc 0.96 (s) 1.10 (s) 1.02 (s) 1.28 (s) 1.30 (s) 0.92 (d, J 7 Hz) 3.50 (m, w1/2 30 Hz) — 4.40 (q, J 6 Hz) 2.27 (m) — 5.30 (d, J 4 Hz) — 1.08 (s) 1.25 (s) 1.18 (s) 1.28 (s) 1.32 (s) 0.96 (d, J 7 Hz) 3.50 (m, w1/2 30 Hz) — 4.35 (q, J 6 Hz) 1.90 (m) 3.10 (s) 5.3 (d, J 4 Hz) — 0.92 (s) 1.06 (s) 0.99 (s) 1.20 (s) 1.25 (s) 0.88 (d, J 7 Hz) 4.53 (m, w1/2 30 Hz) — 4.36 (q, J 6 Hz) 2.27 (m) — 5.30 (d, J 4 Hz) 1.96 (s) 1.00 (s) 1.15 (s) 1.08 (s) 1.32 (s) 1.30 (s) 1.95 (d, J 7 Hz) 4.50 (m, w1/2 30 Hz) — 4.30 (q, J 6 Hz) 1.90 (m) — 5.40 (d, J 4 Hz) 2.02 (s) 0.80 (s) 1.03 (s) 1.02 (d) ——— — — 4.50 (q, 2 H) — — 5.35 (d) — 1.34 (s) 1.03 (s) 1.30 (s) 0.98 (s) 1.27 (s) 0.94 (d, J 7.0) 4.01 (br s, w1/2 10 Hz) 4.28 (m) 4.43 (ddd, J 7, 7, 5 Hz) 2.26 (ddq, J 13, 6, 7 Hz) ——— 1.38 (s) 1.03 (s) 1.32 (s) 1.20 (s) 1.22 (s) 0.98 (d, J 7.0) 4.04 4.30 (m) 4.30 (m) 1.88 (ddq, J 9.5, 9, 7 Hz) 3.19 (s) aSpectra recorded at 200 MHz in CDCl3 with Me4Si as reference.bSpectra recorded at 90 MHz in CDCl3 with Me4Si as reference. cFrom ref. 12. dFrom ref. 9.O O RO OH 1 R = H 3 R = Ac 1 2 3 4 6 7 8 9 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 O O RO OH 2 R = H 4 R = Ac O O HO OH 6 O O HO OH 7 HO HO O O HO CH2OH CH2OH 5 21 22 23 24 25 26 27 20 J. CHEM. RESEARCH (S), 1997 451 in this part of the molecule.The structure of compound 1 could thus be elucidated as (22S,24S)-24-methyl- 22,25-epoxyfurst-5-ene-3b,20b-diol. The 1H–1H and 13C–1H spectra of 1 revealed the following, though not all, partial connectivities in favour of the proposed structure: in the 1H–1H spectrum 6-H (5.30), with 7a-H (1.75) and 7b-H (1.80); 16a-H (4.40) with 15-H (1.05) and 17-H (1.7); 24a-H (2.27) with 28-H3 (0.92): in the 13C–1H spectrum C-6 (121) with 6-H (5.34); C-24 (42.3) with 24a-H (2.27); C-27 (29.1) with 27-H3 (1.30); C-26 (26.6) with 26-H3 (1.28); C-21 (16.4) with 21-H3 (1.02; C-18 (23.0) with 18-H3 0.96; C-19 (19.4) with 19-H3 (1.10); C-28 (14.0) with 28-H3 (0.92).In its NOESY spectrum the following important connectivities were noticed: 16a-H with 21a-H3 and 14a-H, 28-H3 with 23b-H (2.10) and 23a-H (2.35). Compound 2, C28H44O4, m/z 426 (M+ µH2O, EIMS), mp 198–200 °C, [a]D 25 µ23.3° (c, 0.002 in CHCl3), was recognised as the 22R epimer of compound 1 from its IR, 1H and 13C NMR spectral data (see Tables 1 and 2).Compounds 3, [a]D 25 µ74.4° (c, 0.002 in CHCl3), mp 180–184 °C, C30H46O5, M+ 486 (EIMS), and 4 [a]D 25µ61.5° (c, 0.002 in CHCl3), oil, C30H46O5, M+ 486 (CIMS) were found to be the respective 3b-monoacetates of compounds 1 and 2 with 22S and 22R configurations respectively by comparison of their IR, 1H and 13C NMR spectral data with those of compounds 1 and 2 (see Tables 1 and 2). The mass-spectral fragmentations of compounds 1–4 agreed with the reported patterns.8,9 It is interesting to note that no spiroketal derivative has been isolated from a soft coral so far and this is the first report from S.crassocaule. The same species from Australian sea waters was reported earlier to give five cembranoid derivatives, 16 of which sarcophine and sarcophytoxide released into the sea water were regarded as allelochemicals.17 We are grateful to the Department of Ocean Development, New Delhi, for financial support. Techniques used: Polarimetry, IR, UV, 1H and 13C NMR including 2D NMR (1H–1H, 1H–13C COSY and 1H–1H NOESY), EIMS, CIMS and FABMS References: 17 Tables: 2 Received, 19th March 1997; Accepted, 2nd September 1997 Paper E/7/01937H References cited in this synopsis 6 R.Kazlauskas, P. T. Murphy, R. J. Quinn, R. J. Wells and P. Schonholzer, Tetrahedron Lett., 1977, 4439. 7 T. Higa, J. Tanaka and K. Tachibana, Tetrahedron Lett., 1981, 22, 2777. 8 C. Bheema Sankara Rao, K.V. Ramana, D. Venkata Rao, Eoin Fahy and D. J. Faulkne, J. Nat. Prod., 1988, 51, 954. 9 T. Higa, J. Tanaka, Y. Tsukitani and H. Kikuchi, Chem. Lett., 1981, 1647. 10 A. M. E. Abdel-Aziz, K. R. Brain, G. Blunden, T. Crabb and A. K. Bashir, Planta Med., 1990, 56, 218. 11 M. H. Yang, G. Blunden, A. Patel, T. A. Crabb and W. J. Griffin, Phytochemistry, 1989, 28, 3171. 12 A. Abdel-Aziz, K. Brain, G. Blunden, T. Crabb and A. K. Bashir, Phytochemistry, 1990, 29, 1643. 13 J.Munarulire, R. M. Munabu, C. Murasaki, T. Eguchi, Y. Fujimoto, K. Kakinuma, K. Kobayashi, M. Uramoto and N. Ikakawa, Chem. Pharm. Bull., 1993, 31, 411. 14 P. K. Agrawal, D. C. Jain, R. K. Gupta and R. S. Thakur, Phytochemistry, 1985, 24, 2479. 15 P. K. Agrawal, D. C. Jain and A. K. Pathak, Magn. Reson. Chem., 1995, 33, 923. 16 B. F. Bowden, J. C. Coll and S. J. Micheil, Aust. J. Chem., 1980, 33, 879. 17 J. C. Coll, B. F. Bowden, D. M. Tapidas and W. C. Dunlop, J. Exp.Mar. Biol. Ecol., 1982, 60, 293. Table 2 Comparative 13C NMR spectral data for new hippurins 1–4 Carbon 1a 2a 3a 4a 4b 6c 7c C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 C-16 C-17 C-18 C-19 C-20 C-21 C-22 C-23 C-24 C-25 C-26 C-27 C-28 COCCH3 CO 37.3 31.7 71.7 41.0 140.9 121.3 31.9 30.6 50.1 36.7 20.5 40.3 42.4 56.9 31.7 79.3 65.4 23.0 16.4 82.6 19.4 118.6 39.8 42.3 84.2 26.6 29.1 14.0 —— 37.2 31.6 71.7 42.3 141.0 121.3 32.1 30.3 50.2 36.7 20.5 40.7 42.7 55.7 31.9 79.8 65.2 23.0 16.4 80.6 19.4 115.2 41.2 41.9 84.5 26.6 29.0 14.0 —— 37.0 30.6 73.9 41.1 139.8 122.3 31.9 29.1 50.0 36.7 20.4 40.2 42.5 56.9 31.9 79.3 65.5 23.0 16.5 82.6 19.3 118.6 38.1 39.8 84.2 26.5 27.8 14.0 21.4 170.4 37.0 30.3 73.9 41.0 139.8 122.2 31.9 29.1 50.0 36.7 20.5 39.8 41.9 56.8 30.6 79.4 65.2 23.0 16.4 80.6 19.3 115.2 40.3 40.8 82.5 27.8 28.5 14.0 21.3 170.4 36.8 31.2 70.3 41.9 140.8 120.2 31.4 30.8 49.4 36.0 20.2 39.1 39.8 55.5 31.1 80.5 61.2 18.8 19.3 37.4 14.2 119.6 36.8 32.9 87.2 65.8 64.9 ——— 32.5 28.8 66.4 35.5 40.1 28.0 31.7 30.4 58.5 36.4 68.2 49.0 42.3 58.3 31.9 79.0 66.7 27.2 19.3 82.7 19.5 118.5 40.1 41.1 84.1 23.0 29.2 14.0 —— 32.6 28.7 66.4 35.3 40.0 27.9 31.7 30.2 58.3 36.3 68.1 49.8 42.2 57.2 34.0 80.1 66.1 28.4 15.5 79.2 18.6 115.2 40.9 41.9 84.5 22.9 29.0 14.7 —— aSpectra recorded at 22.5 MHz with Me4Si as reference. bFrom ref. 12. cFrom ref. 9.

ISSN:0308-2342    

DOI:10.1039/a701937h

出版商:RSC    

年代:1997

数据来源: RSC

摘要:

N Ar CN Ar¢ NH2 1 CH(OEt)3 (MeCO)2O N Ar CN Ar¢ N 2 CHOEt N N N Ar NH NH2 Ar¢ 3 NH2NH2•H2O aq. EtOH N NH N Ar NH NH2 Ar¢ CHOH N N N Ar HNNH2 Ar¢ 4 N NH N Ar Ar¢ CHOH HNNH2 (A) (B) 4 N N N Ar CI Ar¢ 5 a Ar = C6H4CI-4 b Ar = C6H4F-4 (Ar¢ = C6H4Me-4) N N N Ar NH Ar¢ 3 NH2 N N N Ar Ar¢ 6 N N CH(OEt)3 (MeCO)2O N N N Ar Ar¢ 7 N N Me 6, 7a Ar = C6H4CI-4 b Ar = C6H4F-4 MeCO2H (MeCO)2O N N N Ar Ar¢ N N Me 8a R = C4H3O-2, Ar = C6H4CI-4 b R = C4H3S-2, Ar = C6H4CI-4 c R = C4H3O-2, Ar = C6H4F-4 d R = C4H3S-2, Ar = C6H4F-4 Ar¢ = C6H4Me-4 NH2NH2•H2O RCHO 452 J.CHEM. RESEARCH (S), 1997 J. Chem. Research (S), 1997, 452–453 J. Chem. Research (M), 1997, 2771–2789 Pyrrolo[2,3-d]pyrimidines. Part 3.1 Synthesis of Some Novel 4-Substituted Pyrrolo[2,3-d]pyrimidines and Their Related Triazolo Derivatives Wahid M. Basyouni,* Hanaa M. Hosni and Khairy A. M. El-Bayouki Pesticide Chem. Dept., National Research Centre, Dokki, Cairo, Egypt Syntheses and rearrangements of 3-amino-5-aryl-4-imino-7-(p-tolyl)-4,7-dihydro-3H-pyrrolo[2,3-d]pyrimidines 3 to the 4-hydrazino-7H-pyrrolo[2,3-d]pyrimidines 4 were carried out; the 2-(unsubstituted or substituted) 9-aryl-7-(p-tolyl)- 7H-pyrrolo[3,2-e][1,2,4]triazolo[1,5-c]pyrimidines 6–12 and 14, ureas 13a–c and thioureas 13d–h were obtained from 3 and the hydrazones 15 from 4.Treatment of the 2-ethoxymethylideneamino-4-aryl-1-(ptolyl) pyrrole-3-carbonitriles 2 with hydrazine hydrate afforded the 3-amino-5-aryl-4-imino-7-(p-tolyl)-4,7-dihydro- 3H-pyrrolo[2,3-d]pyrimidines 3, rather than the expected 4-hydrazino-7H-pyrrolo[2,3-d]pyrimidine 4.13 Products 4 were obtained by Dimroth rearrangement of 3 upon prolonged heating in aqueous ethanol.16 Upon heating 3 under reflux with triethyl orthoformate or acetic acid in acetic anhydride, the corresponding 9-aryl- 7-(p-tolyl)-7H-pyrrolo[3,2-e][1,2,4]triazolo[1,5-c]pyrimidines 6 and 9-aryl-2-methyl-7-(p-tolyl)-7H-pyrrolo[3,2-e][1,2,4]- triazolo[1,5-c]pyrimidines 7 were afforded respectively.Also, 9-aryl-2-(2-furyl or 2-thienyl)-7-(p-tolyl)-7H-pyrrolo[3,2-e]- [1,2,4]triazolo[1,5-c]pyrimidines 8 were synthesized by heating 3 with 2-furfuraldehyde or thiophene-2-carbaldehyde in the presence of piperidine (Scheme 1). Upon treating 3a with ethyl chloroformate–DMF, the pyrrolo[ 3,2-e][1,2,4]triazolo[1,5-c]pyrimidine derivative 6a was smoothly obtained,17,18 rather than the expected 9-(p-chlorop h e n y l ) - 7 - ( p- t o l y l ) - 7 H- p y r r o l o [ 3 , 2 - e] [ 1 , 2 , 4 ] t r i a z o l o [ 1 , 5 - c] - pyrimidin-2(3H)-one 9.20,21 Also, when 3a was treated with ethyl chloroformate in the presence of pyridine drops, the 3- e t h o x y c a r b o n y l - 9 - ( p- c h l o r o p h e n y l ) - 7 - ( p- t o l y l ) - 7 H - p y r r o l o - [ 3 , 2 - e] [ 1 , 2 , 4 ] t r i a z o l o [ 1 , 5 - c] p y r i m i d i n - 2 ( 3 H) - o n e 10 was afforded without isolation of the triazolone derivative 9.The 2-substituted 9-(p-chlorophenyl)-7-(p-tolyl)-7H-pyrrolo[ 3,2-e][1,2,4]triazolo[1,5-c]pyrimidines 12 were obtained in good yields by reacting 3a with acyl chlorides.Moreover, when 3a was left to react with some isocyanate derivatives in methylene dichloride at room temperature, the corresponding N-substituted Np-[5-(p-chlorophenyl)- 4-imino-7-(p-tolyl)pyrrolo[2,3-d]pyrimidin-3-yl]urea deriva- *To receive any correspondence. Scheme 1N N N Ar NH Ar¢ N CH N(Me)2 6a N N NN(H)CO2Et Ar NH Ar¢ N N N Ar Ar¢ NH N O N N NN(H)CO2Et Ar NCO2Et Ar¢ N N N Ar Ar¢ N N O C O OEt N N NN(H)COR Ar NH Ar¢ N N N Ar NH Ar¢ N C R OH N N N Ar Ar¢ N N R 9 10 12 3a (C) 11 CICO2Et DMF R COCI 12a R = CH2CI, b R = CH2Ph c R = Ph, d R = C6H4Cl- p N N N Ar NH Ar¢ N C X NR H H N N N Ar Ar¢ N N NR 14 14a R = Me b Et c CH2Ph d COPh H 13 13R X 13R X a C3H7- n O e Et S b C4H9- n O f C4H9- n S c Ph O g Ph S d Me S h CH2Ph S (Ar = C6H4Cl-4 ; Ar¢ = C6H4Me-4) N N N F Me HNN R¢ R R¢ R 15 R¢ R a H C6H4CI-4 d Me C6H4OMe-4 b H C4H3S-2 e Me C6H4Me-4 c Me C6H4F-4 f Me C4H3O-2 15 15 N N N F Me HNN R¢ R 15 N N N F Me HNN CHR¢¢ 15a, b EtOH–HCl EtOH–HCl R¢¢CHO EtOH–HCl 4b 15c–f R1R2C O + RR¢C O J.CHEM. RESEARCH (S), 1997 453 tives 13a–c were afforded in good yields. In comparison, reaction of 3a with isothiocyanates in methylene dichloride afforded the 2-substituted 9-(p-chlorophenyl)-7-(p-tolyl)- 7H-pyrrolo[3,2-e][1,2,4]triazolo[1,5-c]pyrimidines 14, without isolation of their thiourea derivatives, whereas, when the same reaction was carried out by using n-butylisothiocyanate, the N-(n-butyl)-Np-[5-(p-chlorophenyl)-4-imino-7-(p-tolyl)- 4,7-dihydro-3H-pyrrolo[2,3-d]pyrimidin-3-yl]thiourea 13f was obtained.Meanwhile, the thiourea derivatves 13d–h were synthesized from reacting 3a with the appropriate isothiocyanate in dry benzene containing drops of triethylamine (Scheme 2). Condensation of the hydrazine 4b with 4-chlorobenzaldehyde, thiophene-2-carbaldehyde, 4p-fluoro-, 4p-methoxy-, 4p-methyl-acetophenones and 2-acetylfuran in absolute ethanol containing drops of concentrated hydrochloric acid, was found to afford the corresponding hydrazones 15a–f.When the hydrazones 15b–f were heated under reflux with 4-chlorobenzaldehyde in absolute ethanol containing concentrated hydrochloric acid, the hydrazone 15a was obtained (mp and mixed mp with the product obtained from 4b and 4-chlorobenzaldehyde). Also, reaction of the hydrazones 15a,c–f with thiophene-2-carbaldehyde under the same reaction conditions afforded the hydrazone 15b (mp and mixed mp with the product obtained from 4b and thiophene-2- carbaldehyde).However, upon heating the hydrazones 15a,b,d–f with 4p-fluoroacetophenone, 15a–c,e and f with 4p-methoxyacetophenone, 15a–d and f with 4p-methylacetophenone and 15a–e with 2-acetylfuran under the same reaction conditions, the hydrazones 15 were recovered unchanged. Moreover, when the hydrazones 15 were heated under reflux in absolute ethanol containing concentrated hydrochloric acid (reaction medium), the hydrazones 15 were also recovered unchanged (Scheme 3).Techniques used: IR, MS, 1H NMR, elemental analysis References: 24 Tables 1–3: Characterization and spectral data for the products Received, 24th December 1996; Accepted, 3rd September 1997 Paper E/6/08610A References cited in this synopsis 1 Part 2, W. M. Basyouni, Kh. A. M. El-Bayouki, M. M. El-Sayed and H. Hosni, J. Chem. Res., 1996, (S) 127; (M) 0801. 13 R. S. Hosmane, B. B. Lim and F. N. Burnett, J. Org. Chem., 1988, 53, 382. 16 E. C. Taylor and P. K. Leoffler, J. Am. Chem. Soc., 1960, 82, 3147. 17 Kh. A. M. El-Bayouki, A. S. El-Sayed and W. M. Basyouni, Gazz. Chim. Ital., 1989, 119, 163. 18 Kh. A. M. El-Bayouki, W. M. Basyouni and M. M. El-Sayed, An. Quim., 1991, 87, 899. 20 A. Dornow and D. Wille, Chem. Ber., 1965, 98, 1505. 21 W. J. Jrwin and D. G. Wibberley, Adv. Heterocycl. Chem., 1969, 10, 149. Scheme 2 Scheme 3

ISSN:0308-2342    

DOI:10.1039/a608610a

出版商:RSC    

年代:1997

数据来源: RSC