Vol.35, No.3 (1986) 157

報 文

Synthesis of cis-12-Nonaecen-9-one, cis-13-Icosen- 10-one , the Pheromone of Peach Fruit Moth, and cis-5-Undecen-2-one, a Biologically Active Molecule from the Pedal Gland of the Bontebok

Tetsuo MIYAKOSHI Department of Industrial , Faculty of Engineering, Meiji University (Higashimita, Tama-ku, Kawasaki)

A convenient synthesis of cis-12-nonadecen-9-one (4a), cis-13-icosen-10-one (4b), the pheromone of peach fruit moth, and cis-5-undecen-2-one (4c), the principal volatile component of the pedal glant exudate of the bontebok is described. (4a) was synthesized starting from 1-nitrononance (1a) and acrolein via three steps. The synthetic route is shown in Scheme-1. (4b) was easily prepared starting from 1-nitrodecane (1b) in good yield. Similarly, (4c) could be obtained by the Michael reaction of nitroethane (1c) with acrolein.

(1) (2)

(3) (4) 1, 2, 3, a: R1=C8H17; b: R1=C9H19; c: R1=CH3 4, a: R1=C8H17, R2=C6H13; b: R1=C9H19, R2=C6H13; c: R1=CH3, R2=C5H11 I: TBP, II: glycohol, p-Toluenesulfonic acid III: CH3COOK, CH3OH, e-IV : HCl V: Wittig reaction Scheme-1

synthesis have been reported7)•`9) 1 Introduction

. However, an attempt to prepare these unsa-

The sex pheromone emitted by the Japanese turated (4a)•`(4c) by similar methods peach fruit moth (Carposia niponensis Walsing- has not been reported. As an extension of ham), was identified as cis-12-nonadecen-9-one our research on the synthesis of natural pro-

(4a), cis-13-icosen-10-one (4b) by Tamai ducts using aliphatic nitro compounds, we and co-workers in 19771). Since then, several report here a convenient synthesis of these methods for the synthesis of these pheromones pheromones by the Michael addition of nitroal- have been reported1)•`5). kanes.

cis-5-Undecen-2-one (4c) was isolated as the Aliphatic nitro compounds play important principal volatile component of the pedal gland roles in the development of new synthetic exudate of the bontebok, Damaliscus dorcas methodology in organic synthesis10),11). We dorcas6). Since the above mentioned recently reported the Michael addition of nitro-

(4c) has strong biological activity as a mam- to ƒ¿, ƒÀ-unsaturated ketones catalyzed by malian pheromone, various methods for its tertialy phosphine. This is convenient proce-

7 158 J. Jpn. Oil Chem. Soc. (YUKAGAKU)

4 -nitropentane (2c) dure for the preparation of ƒÁ-nitro ketones12)•`14). In the present study, we demonstrate the syn- To a stirred solution of acrolein (2.8g, 50 thetic applicability of this method, thus showing mmol) and 1-nitrononane (1a) (43.3g, 0.25 it to be a convenient synthesis of (4a), (4b), mol) in benzene (50ml), tributylphosphine (40 and (4c) starting from readily available nitro- mg, 0.2mmol) dissolved in benzene (1ml) was (1) and acrolein. added with moderately strong stirring. Follow- ing this addition the temperature reached 45•` 2 Experimental 50•Ž and the mixture was cooled. Stirring

2•E1 Analytical Apparatus was continued for 20min followed by the addi- No correction was made for melting and tion of a solution of p-toluenesulf onic acid boiling points. Melting points were taken on monohydrate (200mg, 1mmol) in ethylene glycol Yanagimoto micro melting point apparatus. (3.7g, 60mmol) with stirring for 10min. The The GLC analysis was carried out using a mixture was then refluxed for 5h, and washed Hewlet Packard 5890 A research chromatograph with solution of 5% sodium hydrogen carbonate

(column 0.20mm•~12.5m, cross-linked methyl and saturated sodium chloride. silicone). The IR spectra were recorded on a The organic solution was concentrated to give Shimadzu IR-27G spectrophotometer. The 1, 1-ethylenedioxy-4-nitrododecane (2a). (2a) 1H -NMR spectra were recorded on a Varian was purified by column chromatography over

EM-390 spectrometer at 90MHz, using TMS silica gel (60•`80 mesh) with benzene-hexane

(ƒÂ=0.00ppm) as the internal standard; Ab- (30:1) as the eluent, giving 9.6g (70% yield) breviations: s=singlet, d=doublet, t=triplet, of pure (2a) as a colorless liquid.

q=quartet, m=multiplet, and br=broad. IR (neat): 1540, 1140cm-1. 1H-NMR(CCl4): Chemical shifts are given in ppm; spin-spin 0.95 (deformed t, 3H, CH3), 1.3•`2.1 (m, 18 coupling constants J are given in Hz. H, CH2), 3.8 (m, 4H, CH2), 4.4 (m, 1H,

2•E2 1-Nitrononane (1a) and 1-nitrodecane CH), 4.80 (t, J=4.2Hz, 1H, CH). Found: (1b) C, 61.63%; H, 9.99%. Calcd for C14H27O4N: 1-Bromononane (20.7g, 0.1mol) was poured C, 61.51; H, 9.96%. into a stirred mixture of 80ml dimethyl sulf- 1, 1-Ethylenedioxy-4-nitrotridecane (2b) was oxide (DMSO), 0.5g of benzyltriethylammo- obtained from acrolein (2.8g, 50mmol) and 1- nium chloride as a catalyst, and 17.0g of potas- nitrotridecane (1b) (46.8g, 0.25mol) by the sium nitrite (0.2mol) contained in a 200ml same procedure in a 70% yield. IR (neat): flask immersed in a water bath held at room 1540, 1140cm-1. 1H-NMR(CCl4): 0.97 (de- temperature. Stirring was continued for 4h. formed t, 3H, CH3), 1.3•`2.1 (m, 20H, CH2), The reaction mixture was then poured into 200 3.8 (m, 4H, CH2), 4.4 (m, 1H, CH), 4.80 ml of ice water and extracted with ethyl acetate. (t, J=4.2Hz, 1H, CH). Found: C, 62.81; The usual workup gave 1-nitrononane (1a) H, 10.47%. Calcd for C15H29O4N: C, 62.68;

(10.4g, 60% yield) following distillation, bp H, 10.17%. 126•Ž/16mmHg, IR (neat): 1545cm-1. 1H- 1, 1-Ethylenedioxy-4-nitropentane (2c) was NMR(CCl4): 0.97 (deformed t, 3H, CH3), 1.3 obtained from acrolein (2.8g, 50mmol) and •` 2.1 (m, 14H, CH2), 4.35 (t, J=6.8Hz, 2H, nitroethane (18.8g, 0.25mol) in a manner si- CH2NO2). Found: N, 8.15%. Calcd for milar to the above in a 72% yield, bp 95•`97 C9H19O2N: N, 8.09%. •Ž/2mmHg. IR (neat): 1540, 1140cm-1. 1H- 1-Nitrodecane (1b) was prepared from 1- NMR(CCl4): 1.53 (d, J=6Hz, 3H, CH3), 1.7 bromodecane (22.1g, 0.1mol) and potassium •` 2.3 (m, 4H, CH2), 3.9 (m, 4H, CH2), 4.6 nitrite (17.0g, 0.2mol) by a manner similar (m, 1H, CH), 4.82 (t, J=4.2Hz, 1H, CH). to that described above in a 62% yield, bp 136 Found: C, 47.85; H, 7.59%. Calcd for C7H13 •Ž/16mmHg (lit.15) bp 107•Ž/2mmHg). O4N: C, 47.99; H, 7.48%. 2•E3 1, 1-Ethylenedioxy-4-nitrododecane 2•E4 4-Oxododecanal(3a), 4-oxotridecanal (2a), 1, 1-ethylenedioxy-4-nitrotri- (3b), and 4-oxopentanal (3c) ecane (2b), and 1, 1-etylenedioxy- Potassium acetate (0.5g, 5mmol) was added

8 Vol.35, No.3 (1986) 159

to a stirred solution of 1, 1-ethylenedioxy-4- ing. Stirring was continued at this tempera- nitrododecane (2a) (2.7g, 10mmol) in me- ture for 8h followed by heating under reflux thanol (40ml) at 25•Ž. The mixture was for 4h. Benzene was evaporated under reduced

electrolyzed in a Beaker type cell at a constant pressure and hexane was poured onto the residue. current (0.18A, 8V) using platinum electrodes The mixture was extracted with hexane and the

(1cm2) for 4F/mol. The methanol was then extract washed with water and then dried over removed on a rotary evaporator and the residue anhydrous sodium sulfate. The hexane was added to 4% hydrochloric acid (100ml). The concentrated to give a crude product. This in mixture was stirred at 40•`45•Ž for 5h under turn was chromatographed over silica gel (60•` nitrogen, cooled and extracted with ethyl acetate 80 mesh) with benzene-hexane (8:2) as the elu-

(3•~30ml). ent to give a 0.87g (60% yield) of cis-12- The combined organic layers were washed nonadecen-9-one (4a) as a colorless liquid. IR with 5% sodium hydrogen carbonate (50ml) (neat): 1710cm-1. 1H-NMR(CCl4): 0.90 (de- and dried with sodium sulfate. The solvent formed t, 6H, CH3), 1.1•`1.7 (br s, 20H, was evaporated and the residue purified by CH2), 1.9•`2,15 (m, 2H, CH2), 2.2•`2.45 (m, column chromatography over silica gel (60•`80 6H, CH2), 5. 1•`5.4 (m, 2H, CH=CH). The mesh) with benzene-hexane (9:1) as the eluent, product was identified by a comparison of the to give 1.6g (81% yield) of pure 4-oxopentanal NMR spectrum with the one reported5).

(3a) as white crystals, mp 74•Ž, IR (KBr): cis-13-Icosen-10-one (4b) was obtained in 2710, 1715, 1705cm-1. 1H-NMR (CCl4): 0.90 the same manner from 1, 1-ethylenedioxy-4-

(deformed t, 3H, CH3), 1.3•`1.8 (m, 12H, nitrotridecane (3b) in a 60% yield. IR (neat): CH2), 2.38 (t, J=7Hz, 2H, CH2), 2.55 (br 1710cm-1. 1H-NMR(CCl4): 0.90 (deformed s, 4H, CH2), 9.70 (s, 1H, CHO). Found: C, t, 6H, CH3), 1.1•`1.7 (br s, 22H, CH2), 1.9 72.78; H, 11.31%. Calcd for C12H22O2: C, •` 2.15 (m, 2H, CH2), 2.2•`2.45 (m, 6H, 72.68; H, 11.18%. CH2), 5.1•`5.4 (m, 2H, CH=CH). The pro- 4-Oxotridecanal (3b) was obtained from 1, duct was identified by comparing its NMR 1-ethylenedioxy-4-nitrotridecane (2b) by the spectrum with that in the literature4). same procedure in an 85% yield, mp 67.0•Ž. cis-5-Undecen-2-one (4c) was obtained from IR (KBr): 2710, 1715, 1705cm-1. 1H-NMR 4-oxopentanal (3c) using hexyltriphenylphos-

(CCl4): 0.90 (deformed t, 3H, CH3), 1.3•`1.8 phonium ylide by the same procedure in a 58% (m, 14H, CH2), 2.38 (t, J=7Hz, 2H, CH2), yield, bp 80•`81•Ž/2mmHg (lit.9) bp 79•`80•Ž/ 2.55 (br s, 4H, CH2), 9.70 (s, 1H, CHO). 0.8mmHg). IR (neat): 1710cm-1; 1H-NMR Found: C, 73.71; H, 11.57%. Calcd for C13 (CCl4): 0.90 (deformed t, 3H, CH3), 1.1•`1.7 H24O2: C, 73.53; H, 11.39%. (m, 6H, CH2), 2.10 (s, 3H, CH3), 2.2•`2.45 4-Oxopentanal (3c) was synthesized from 1, (m, 6H, CH2), 5.1•`5.4 (m, 2H, CH=CH). 1-ethylenedioxy-4-nitropentane (2c) by a pro- 3 Results and Discussion cedure similar to that described above in a 54%

yield, bp 70•Ž/16mmHg (lit.16) bp 64•`65•Ž/11 3•E1 Michael reaction of nitroalkanes (1) mmHg). IR (neat): 2750, 1715, 1710 cm-1. with acrolein 1 H-NMR (CCl4): 2.13 (s, 3H, CH3), 2.63 (s, Michael reactions of nitroalkanes (1) with 4H, CH2), 9.83 (s, 1H, CHO). acrolein were carried out using various tertiary-

2•E5 cis-12-Nonadecen-9-one (4a), cis-13- phosphines as catalysts in benzene at room tem- icosen-10-one (4b), and cis-5-un- perature. The results are shown in Table-1. d ecen-2-one (4c) The Michael reaction products of nitroalkane

To a solution of heptyltriphenylphosphorane with ƒ¿, ƒÀ-unsaturated have been in benzene, prepared from heptyltriphenylphos- reported to decompose on heating17),18). The

phonium bromide (2.3g, 5.2mmol) and sodium conversion of ƒÁ-nitro into ethylenedioxy (0.2g, 5.3mmol), was added solution acetale in the present research was thus carried of 4-oxododecanal (3a) (1g, 5.2mmol) in out using ethylene glycol. In so doing, ƒÁ- benzene (70ml) at room temperature with stirr- ethylenedioxy nitroalkanes (2) were obtained by

9 160 J. Jpn. Oil Chem. Soc. (YUKAGAKU)

Table-1 Preparation of 1, 1-ethylenedioxy-4- The Michael reaction of 1-nitrononane (1a)

nitroalkane (2) with acrolein catalyzed by TBP in benzene

followed by acetalization gave 1, 1-ethylene- (1) dioxy-4-nitrododecane (2a) in a 70% yield.

(2a) was subjected to the Nef reaction with

the electrochemical oxidation in methanol in the (2) presence of potassium acetate. The product, without being isolated, was then acid hydrolyzed

so as to undergo deactalization to 4-oxodode-

canal (3a) in good yield, 81%. 4-Oxotridecanal

(3b) was also prepared in the same manner

from 1, 1-ethylenedioxy-4-nitrotridecane (2b).

4-Oxopentanal (3c) was obtained by the same

procedure from 1, 1-ethylenedioxy-4-nitropen-

tane (2c) in a low yield, 54%.

The salt-free Wittig reagent prepared from

heptyltriphenylphosphonium bromide and sodium

amide was added to a solution of (3a) in

benzene to give cis-12-nonadecen-9-one (4a) TCP: Tricyclohexylphosphine in a 60% yield. cis-13-Icosen-10-one (4b) TBP: Tributylphosphine TPP: Triphenylphosphine. was synthesized from (3b) by the same pro- cedure. Similarly, cis-5-undecen-2-one (4c) distillation. Whenever the nitroalkane (1) was obtained by the Wittig reaction of hexyl-

possess more than one hydrogen on the carbon triphenylphosphonium ylide with (3c). The ƒ¿ of the nitro group, multiple Michael additions resulting products, (4a), (4b), and (4c) can occur, leading to undesirable products. To showed no infrared absorption bands in the

provent the occurrence of such reactions as neighborhood of 970cm-1 due to disubstituted much as possible, a reactant ratio of 5•`3: 1 trans-. The structures of these products of (1) to acrolein was used. When (1a) and were identified by a comparison of their IR and acrolein reacted in benzene in the presence of NMR spectra with those reported4),5),7). tributylphosphine (TBP), the primary product In conclusion, the methods described above was 1, 1-ethylenedioxy-4-nitrododecane (2a). were found to be convenient procedures for The yield of product (2a) was found to be easily preparing (4a), (4b) and (4c). Par- influenced by the concentrations of TBP, corres- ticulaly, ƒÁ-oxoaldehydes (3) are obtainable from

ponding to the type of tertiaryphospoine [e.g., 1, 1-ethylenedioxy-4-nitroalkanes (1). The uti- tricyclohexylphosphine, TBP, triphenylphosphine lization of 1, 1-ethylenedioxy-4-nitroalkanes (2)

(TPP)], and to relative concentration of (1a) and ƒÁ-oxoaldehydes (3) for the synthesis of corresponding to acrolein and time. The yields perfumes and insect pheromones is now under were best at lower concentrations of TBP further investigation. (0.004 equivalents) and with stronger base Acknowledgments (TBP in place of TPP). The yields varied from 52•`70% and were not optimal. The author wishes to thank Professor S. Saito for Similarly, 1, 1-ethylenedioxy-4-nitrotridecane his critical comments and the Institute of Science and Technology of Meiji University for providing (2b) and 1, 1-ethylenedioxy-4-nitropentane (2 financial support. (Received Sept. 24, 1985) c) were obtained from 1-nitrotridecane (1b)

and nitroethane (1c) in 70 and 72% yields, References

respectively. 1) Y. Tamaki, K. Honma, and K. Kawasaki,

3•E2 Synthesis of cis-12-nonadecen-9-one Appl. Entmol. Zool., 12, 60 (1977). (4a), cis-13-icosen-10-one (4b), and 2) S. Tamada, K. Mori, and M. Matsui, Agric.

cis-5-undecen-2-one (4c) Biol. Chem., 42, 191 (1978).

10 Vol.35, No.3 (1986) 161

3) Y. Naoshima, M. Kawakubo, S. Wakabayashi, 15) N. Kornblum, H.O. Larson, R.K. Blackwood, and S. Hayashi, Agric. Biol. Chem., 45, 439 D.D. Mooberry, E.P. Oliveto, and G.E. Gra- (1981). ham, J. Am. Chem. Soc., 78, 1497 (1956). 4) T. Yoshida and S. Saito, Bull. Chem. Soc. 16) A. Mondon, Angew. Chemie., 64, 224 (1952). Jpn., 55, 3047 (1982). 17) H. Shecheter, D.E. Ley, L. Zoldin, J. Am. 5) S. Ito, N. Saito, K. Hatakeda, T. Goto, Y. Chem. Soc., 74, 3664 (1952). Ikushima, and T. Asano, Bull. Chem. Soc. 18) D.T. Warner, O.A. Moe, J. Am. Chem. Soc., Jpn., 57, 2015 (1984). 74, 1064 (1952). 6) B.V. Burger, M. leRoux, C.F. Garbers, H.S.C. Spies, R.G. Bigalke, K.G.R. Pachler, P.L.

Wessels, V. Christ, and K.H. Maurer, Z. ニ ト ロ ア ル カ ン を 用 い る 昆 虫 フ ェ ロ モ Naturforsch, 31C, 21 (1976). 7) K. Mori, T. Ara, and M. Matsui, Agric. Biol. ンcis-12-ノ ナ デ セ ン-9-オ ン,cis-13-イ Chem., 41, 2295 (1977). コ セ ン-10-オ ン 及 びcis-5-ウ ン デ セ ン- 8) Jpn. Pat. 7,908,652 (1979), Chem. Abstr., 91, 2-オ ン の 簡 便 な 合 成 56373 (1979).

9) H.C. Brown, U.S. Racherla, and D. Basavaiah, 宮 腰 哲 雄 Synthesis, 1984, 303. 明 治 大 学工 学部 工 業 化 学 科(川 崎 市 多 摩 区 東 三 田1-1-1) 10) D. Seebach, E.W. Colvin, F. Lehr, and T. Weller, Chimia, 33, 1 (1979). cis-12-ノ ナ デ セ ン-9-オ ン(4a), cis-13-イ コ セ ン- 11) N. Ono and A. Kaji, Yuki Gosei Kagaku 10-オ ン(4b)及 びcis-5-ウ ン デ セ ン-2-オ ン(4c)の

Kyokai Shi, 38, 115 (1980). 簡 便 な 合 成 を報 告 す る 。(4a)は1-ニ ト ロ ノ ナ ン(1a) 12) T. Miyakoshi and S. Saito, Yukagaku, 31, 35 と ア ク ロ レ イ ン のMichael反 応 を 利 用 し て 三 段 階 で, (1982). 目的 の フ ェ ロ モ ン を 合 成 す る こ と が で き た 。(4b)は 13) T. Miyakoshi and S. Saito, Yukagaku, 31, 231 (1982). 1-ニ トロ デ カ ン(1b)を 出 発 物 質 に し て,収 率 よ く得 る 14) T. Miyakoshi and S. Saito, Yukagaku, 32, こ と が で き た 。 同 様 に(4c)は ニ ト ロ エ タ ン と ア ク ロ レ 749 (1983). イ ン のMichael反 応 を利 用 し て 合 成 す る こ と が で き た 。

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