ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 9, pp. 1252–1253. © Pleiades Publishing, Ltd., 2012. Original Russian Text © R.I. Khusnutdinov, N.A. Shchadneva, Yu.Yu. Mayakova, U.M. Dzhemilev, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 9, pp. 1252–1253.
SHORT COMMUNICATIONS
Unusual Reaction of Adamantane-1-carboxylic Acid and Adamantane-1-carbonyl Chloride with Acetonitrile and Carbon Tetrachloride in the Presence of VO(acac)2 R. I. Khusnutdinov, N. A. Shchadneva, Yu. Yu. Mayakova, and U. M. Dzhemilev Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia e-mail:
[email protected] Received October 29, 2011
DOI: 10.1134/S1070428012090187 The presence of an electron-withdrawing group at the bridgehead position of adamantane molecule is known to considerably reduce its reactivity in substitution reactions, for that substituent somewhat restricts introduction of a second functional group into the adamantane core. This relation is clearly demonstrated by the reactions of adamantane-1-carboxylic acid (I) with PCl3 and SOCl2, which lead to the formation of adamantane-1-carbonyl chloride (II) instead of chlorination at the skeletal carbon atoms [1]. The chlorination of adamantane-1-carbonyl chloride (II) with the use of AlCl 3 resulted in replacement of the COCl group with formation of 1-chloroadamantane [2]. Disubstituted adamantane derivatives containing a halogen atom together with another electronwithdrawing group are usually prepared via multistep procedures [3, 4]. We now report on simultaneous chlorination at the bridgehead position and replacement of the COOH or COCl group by cyano in adamantane-1-carboxylic acid (I) or adamantane-1-carbonyl chloride (II) by the action of carbon tetrachloride and acetonitrile in the presence of vanadyl acetoacetonate VO(acac)2 as catalyst. The product of this reaction was 3-chloroadaman-
tane-3-carbonitrile (III) (Scheme 1). The reaction time depended on the temperature. The reaction carried out at 125°C was complete in 3 h, at 140°C in 1.5 h, and at 150°C in 1 h. Prolonged heating of the reactants in the presence of VO(acac) 2 is undesirable because of tarring. Regardless of the initial compound (I or II), the second product was chloroform, i.e., the chlorinating agent is carbon tetrachloride. Excess carbon tetrachloride also acts as solvent. No reaction occurred in the absence of CCl 4 . The molar reactant ratio VO(acac) 2 –AdR–CCl 4 –MeCN was 1 : (100–1000) : (200–2000) : (100–1000). High efficiency of the process and low consumption of the catalyst should be noted. When the reaction was carried out in the presence of water, the only reaction product was 3-chloroadamantane-1-carboxamide (IV, 93–95%) (Scheme 2). Compound IV was synthesized previously by successive treatment of difficultly accessible 3-hydroxyadamantane-1-carboxylic acid with excess thionyl chloride and ammonia [3, 4]. Scheme 2. CONH2
Scheme 1. + MeCN + CCl4
CN
+ MeCN + CCl4 R
R
VO(acac)2 150°C, 1–3 h –CHCl3
I, II
I, II
Cl III, ~95%
I, R = COOH; II, R = COCl.
VO(acac)2, H2O 125–150°C, 1 h Cl IV
The reactions were carried out in a glass ampule or in a stainless-steel high-pressure microreactor. The results of parallel runs differed insignificantly. A reac1252
UNUSUAL REACTION OF ADAMANTANE-1-CARBOXYLIC ACID
tor (or ampule) was charged with 0.01 mmol of VO(acac)2, 10 mmol of freshly distilled acetonitrile, 10 mmol of compound I or II, and 20 mmol of CCl4 (1.8 ml of water was added in the synthesis of IV). The reactor was hermetically closed (the ampule was sealed), and the mixture was heated for 1–3 h at 125– 150°C under stirring. When the reaction was complete, the reactor (ampule) was cooled to room temperature and opened, the mixture was filtered through a layer of Al2O3, unreacted acetonitrile and carbon tetrachloride were distilled off, and the residue was distilled under reduced pressure using an air condenser or recrystallized from methanol. 3-Chloroadamantane-1-carbonitrile (III). mp 208.5–209°C (from MeOH); published data [5]: mp 208–209°C. IR spectrum, ν, cm–1: 2248 (C≡N), 763 (C–Cl). 1H NMR spectrum, δ, ppm: 1.84 br.s (2H, CH 2 ), 1.97 br.s (2H, CH 2 ), 2.05 br.s (4H, CH 2 ), 2.14 br.s (2H, CH), 2.33 br.s (4H, CH 2 ). 13 C NMR spectrum, δC, ppm: 27.94 (C5, C7), 29.09 (C3), 30.21 (C6), 39.25 (C4, C10), 45.52 (C8, C9), 47.15 (C2), 65.92 (C1), 123.95 (C≡N). Mass spectrum, m/z (Irel, %): 195 (12) [M]+, 168 (7.1), 161 (12), 160 (100), 159 (7), 128 (6.5), 118 (10), 105 (6.3), 104 (14), 93 (13.4), 92 (10), 91 (13), 79 (10), 77 (13), 65 (11), 55 (6), 53 (8.1), 51 (7.3), 41 (21.4), 39 (25). 3-Chloroadamantane-1-carboxamide (IV). mp 137–138°C. IR spectrum ν, cm–1 : 3580–3300, 2900, 2365, 1675, 1440, 1415, 765. 1H NMR spectrum, δ, ppm: 1.65–1.73 m (4H, CH2), 1.84 br.s (2H, CH 2 ), 2.01 br.s (2H, CH), 2.14 br.s (2H, CH 2 ), 2.31 br.s (4H, CH2), 5.70 br.s and 6.27 br.s (1H each, NH2). 13C NMR spectrum, δC, ppm: 28.74 (C5, C7), 37.45 (C6), 38.34 (C4, C10), 49.07 (C8, C9), 51.02 (C3), 55.16 (C2), 67.63 (C1), 162.02 (C=O). Mass spectrum, m/z (Irel, %): 213 (39) [M]+, 178 (17), 177 (12), 169 (100), 171 (33), 133 (24), 93 (15), 91 (42), 79 (18), 77 (5), 67 (10), 65 (15), 55 (12), 53 (8), 41 (20), 39 (23).
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Found, %: C 61.93; H 7.48; Cl 16.45; N 6.54. C 11 H 16 ClNO. Calculated, %: C 61.97; H 7.51; Cl 16.43; N 6.57. The purity of the products was checked, and composition of the reaction mixtures was monitored, by GLC on a Khrom-5 chromatograph using a 1.2-m × 3mm column packed with 5% of SE-30 on Chromaton N-AW–HMDS (0.125–0.160 mm); carrier gas helium, flow rate 50 ml/min; oven temperature programming from 50 to 270°C at a rate of 8 deg/min. The IR spectra were measured in the range 550–3600 cm–1 on a Bruker Vertex 79V spectrometer from samples dispersed in KBr or mineral oil. The 1H and 13C NMR spectra were measured on a Bruker Avance-400Q instrument at 400.13 and 100.62 MHz, respectively, from solutions in CDCl3. The mass spectra were run on a Shimadzu QP-2010 Plus GC–MS system (Supelco PTE-5 capillary column, 30 m × 0.35 mm). The elemental compositions were determined on a Carlo Erba 1106 analyzer. This study was performed under financial support by the Ministry of Education and Science of the Russian Federation (state contract no. 02.740.11.0631). REFERENCES 1. Sasaki, T., Shimizu, K., and Ohno, M., Chem. Pharm. Bull., 1984, vol. 32, no. 4, p. 1433. 2. Yagrushkina, I.N., Zemtsova, M.N., and Moiseev, I.K., Russ. J. Org. Chem., 1995, vol. 31, p. 579. 3. Stetter, H. and Mayer, J., Chem. Ber., 1962, vol. 95, p. 667. 4. Stepanov, F.N. and Srebrodol’skii, Yu.I., Sintezy prirodnykh soedinenii, ikh analogov i fragmentov (Syntheses of Natural Compounds and Their Analogs and Fragments), Moscow: Nauka, 1967. 5. Petrov, K.A., Repin, V.N., and Sorokin, V.D., Zh. Org. Khim., 1992, vol. 28, p. 129.
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