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Methylene-P-Toluenesulfonamide (−)-Carvone Is Spearmint Oil, Whereas the (S)-(+)- a B Enantiomer Is a Constituent of Dill and Caraway Oils

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Methylene-P-Toluenesulfonamide (−)-Carvone Is Spearmint Oil, Whereas the (S)-(+)- a B Enantiomer Is a Constituent of Dill and Caraway Oils Note 351 Synthesis and Analgesic-like Effect diterpene skeletons. Among the monoterpene starting − of (6R,4S)-p-Mentha-1,8-dien-6-yl- materials, probably the (+)- and ( )-forms of car- vone are the most versatile. The best source of (R)- methylene-p-toluenesulfonamide (−)-carvone is spearmint oil, whereas the (S)-(+)- a b enantiomer is a constituent of dill and caraway oils. Dami˜ao P. de Sousa , Franklin F. F. Nobrega ´ , The cost of (R)-(−)-carvone is usually much lower Reinaldo N. de Almeidab,andTimothyJ.Brocksomc than that of the (+)-isomer, but both enantiomers of a Laborat´orio de Qu´ımica de Produtos Naturais e Sint´eticos carvone have been used as chirons in the synthesis of Bioativos (LAPROBIO), Departamento de Fisiologia, Universidade Federal de Sergipe, diverse intermediates and natural compounds, princi- CEP 49100-000 S˜ao Crist´ov˜ao, Sergipe, Brazil pally terpenoids [1 – 4]. b Laborat´orio de Tecnologia Farmacˆeutica, Universidade The range of pharmacological activity that has been Federal da Para´ıba; Caixa Postal 5009, CEP 58051 – 970, recorded for terpenes is remarkably wide. They are Jo˜ao Pessoa, Para´ıba, Brazil c Laborat´orio de Qu´ımica Bio-Orgˆanica, Departamento de found to function as anticonvulsant, antinociceptive, Qu´ımica, Universidade Federal de S˜ao Carlos, sedative, and anxiolytic agents [5 – 11]. The range Caixa Postal 676, 13565-905 S˜ao Carlos, SP, Brazil of pharmacological effects of this family of natu- Reprint requests to Dr. Dami˜ao P. de Sousa. ral products is apparently due to a variety of ac- E-mail: damiao [email protected] tion mechanisms. Terpene derivatives also have been shown to have several effects on the central ner- Z. Naturforsch. 2009, 64b, 351 – 355; vous system (CNS), including antinociceptive [12, 13] received October 19, 2008 and sedative [14] activity. These facts led us to The synthesis of a monoterpene-based para-toluenesulf- verify in mice the psychopharmacological profile onamide is reported starting from naturally occurring (R)- of (6R,4S)-p-mentha-1,8-dien-6-yl-methylene-p-tolu- − ( )-carvone (1), by 1,2-addition of HCN followed by reduc- enesulfonamide (4), an intermediate prepared from tion with lithium aluminum hydride to afford the amino alco- − hols 3a and 3b. Tosylation of this mixture with p-toluenesulf- (R)-( )-carvone (1) in our terpene total synthesis onyl chloride furnished sulfonamide 4 in 55 % overall yield. studies. Compound 4 was evaluated in behavior animal models to in- vestigate its effects on the central nervous system. It showed Results and Discussion low toxicity and sedative action in mice, indicating it to be psychoactive. It also caused a decrease in the spontaneous (R)-(−)-Carvone (1) is an excellent, cheap and com- motor activity of mice. This depressant effect was confirmed in the acetic acid-induced writhing test, which demonstrated mercially available, chiral enantiopure starting mate- a significant antinociceptive response more potent than 1. rial for the synthesis of natural occurring compounds. The present results provide evidence that sulfonamide 4 has We have already reported the synthesis of a chiral analgesic-like psychopharmacological activity. synthetic intermediate for perhydroazulene terpenoids, − Key words: p-Toluenesulfonamide, Carvone, starting from (R)-( )-carvone (1) with initial 1,2- Monoterpene, Analgesic Activity, addition of the nucleophile trimethylsilyl cyanide [3]. Antinociceptive Activity In the present paper we report the synthesis of a p-toluenesulfonamide beginning with 1,4-addition of cyanide to (R)-(−)-carvone (1), a reaction already known to furnish selectively the adduct 2 in 90 % yield, isolated by crystallization [15, 16]. Introduction Thus, the reaction of (R)-(−)-carvone (1) with The total synthesis of naturally occurring terpenes potassium cyanide and acetic acid in ethanol under has always been an important research area, with the the published conditions [16] produced the nitrile 2 use of simple, chiral, enantiopure monoterpenes as (Scheme 1). Reduction of compound 2 with LiAlH4 starting materials being a relevant option [1, 2]. These gave a 95 : 5 mixture of amino alcohols 3a and 3b in monoterpene starting materials are readily available, 89 % yield. The constitution of the 3a/3b mixture was frequently in both enantiomeric forms, and contain sig- confirmed by micro-analysis of the L-(+)-tartaric acid nificant scaffolds of the desired mono-, sesqui-, and salts. Sulfonylation of these amino alcohols using p- 0932–0776 / 09 / 0300–0351 $ 06.00 c 2009 Verlag der Zeitschrift f¨ur Naturforschung, T¨ubingen · http://znaturforsch.com 352 Note CN O O HO CH2NH2 KCN, EtOH, H O 2 LiAlH4, THF acetic acid, 0 oC, 90 % r. t., 89 % % 9 6 1 o 2 C, 20 3a: a-OH 1 y, P 3b: β -OH Cl, Ts O CH2NH S O Scheme 1. Synthesis of (6R,4S)-p- mentha-1,8-dien-6-yl-methylene-p-tolu- 4 enesulfonamide (4). Fig. 1. Effect of sulfonamide 4 on spon- taneous motoric activity in mice. n =8; * p < 0.05, ** p < 0.01 significantly dif- ferent from control. Fig. 2. Effect of sulfonamide 4,(R)- (−)-carvone, morphine on acetic acid- induced writhing in mice. n =8;*p < 0.01 significantly different from control. toluenesulfonyl chloride afforded the easily purified p- ioral screening were suggestive of a central depres- toluenesulfonamide 4, in 69 % yield. TLC analysis of sant effect. The animals were found to show de- the reaction product suggested that both aminoalco- creased locomotive activity and an increase in sedation hols, 3a and 3b, had reacted. Noteworthy in this re- at 0.5 h and 1 h (Fig. 1) after administration of com- action is the concomitant dehydration of the secondary pound 4 (60 mg kg−1) indicating that the sulfonamide alcohol under the reaction conditions, which was not is psychoactive. In the evaluation of the antinocicep- entirely unexpected with the temperature used. tive profile, 4 (30, 60, 90 mg kg−1) significantly de- The pharmacological effects of the sulfonamide 4 on creased the incidence of acetic acid-induced writhing the CNS were then evaluated. The toxicological evalu- (Fig. 2). Compound 4 at 90 mg kg−1 produced a near- ation of compound 4 did not induce mortality up to a maximal inhibition of the writhing response, similar − dose of 1000 mg/kg in mice, and no significant toxic to3mgkg 1 of morphine. In comparison with the re- effect was found during the observation period. sults found for unprotected terpenes, such as (R)-(−)- On the basis of animal observation, 4 (60 mg kg−1) carvone (1) [6, 9], compound 4 was more potent and did not affect the motoric coordination and mus- less toxic. The LD50 value reported for (R)-(−)-carv- − cle tone. However, the parameters of the behav- one is 426.6 (389.0 – 478.6) mg kg 1 [6]. Fig. 2 shows Note 353 that a sulfonamide group in the structure of 4 enhances (1S,2S,4R,6S)-6-Aminomethyl-8-p-menthen-2-ol (3a) and the pharmacological effect and reduces the toxicity. (1S,2R,4R,6S)-6-aminomethyl-8-p-menthen-2-ol (3b) A dry, nitrogen-purged, 100 mL three-necked flask with a Conclusions magnetic stirrer was charged with a suspension of lithium aluminum hydride (1.189 g, 31.3 mmol) in anhydrous The data reported in this paper demonstrate the psy- tetrahydrofuran (76 mL). A solution of 8.0 g (45.19 mmol) chopharmacological activity of compound 4 in mice. of nitrile 2 in tetrahydrofuran (12.5 mL) was added drop- The study shows that 4 has a CNS-depressant effect wise over 20 min to this suspension and the stirring con- similar to some commonly used drugs. This effect of tinued for a further 1 h. Destruction of the excess lithium the sulfonamide was not different from that observed aluminum hydride was effected by cautious dropwise ad- for other psychoactive terpenes [8, 9, 17]. However, 4 dition of water (10 mL), followed by dropwise addition showed low toxicity, fewer side effects, and an im- of 15 % NaOH (10 mL), and subsequent addition of water proved pharmacological profile. Our experimental re- (30 mL). Stirring was continued until a granular white pre- sults also suggest that by appropriate structural modifi- cipitate was formed. Filtration yielded a clear tetrahydrofu- cation of monoterpenes it should be possible to develop ran solution which was dried over anhydrous sodium sulfate. novel analgesic drugs. The aminoalcohols 3a and 3b, in a 95 : 5 ratio according to gas chromatographic analysis, were isolated as free amines by removal of the tetrahydrofuran under reduced pressure Experimental Section (7.341 g, 40.11 mmol, 89 % yield). The 3a/3b mixture (1.0 g) General was subjected to column chromatography over neutral alu- mina, eluting with hexane-EtOAc (1 : 1) to afford aminoal- GLC analyses were performed on a Shimadzu GC-17A cohol 3a (0.792 g, 79 % yield). Compound 3a: M. p. 72.8 – instrument equipped with a flame-ionization detector, us- ◦ α 30 + . ν 73.5 C. – [ ]D = 7 0(c =1.0;CHCl3). – IR (film): = ing a DB-1 (30 m × 0.25 mm) glass column. Column chro- 3489, 2933, 1647, 1037, 993, 887 cm−1.–1HNMR:δ = matography was performed on silica gel 60 (70 – 230 mesh 4.73 (2H, s), 3.75 (1H, q, J = 3.2 Hz), 2.92 (2H, s), 2.84 (2H, ASTM Merck). Radial thin-layer chromatography was car- d, J = 3.4 Hz), 2.35 (1H, tt, J = 3.6 Hz; 11.6 Hz), 2.00 – ried out on a Chromatotron model 8924 (silica gel 60PF274 1.93 (1H, m), 1.92 – 1.89 (1H, m), 1.87 – 1.84 (1H, m), 1.74 Merck). Melting points were determined on a Microqu´ımica (3H, s), 1.68 (1H, s), 1.65 – 1.59 (1H, m), 1.46 – 1.20 (2H, MQWAPF-301 apparatus and are uncorrected.
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