Chen, Yao-zu

He, Lan

Li, Bo-gang

Pan, Xuan

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Indian Journal of ChemistryVol. 37B, June 1998, pp. 612 - 614Tongolenine C and tongolenine D, two newditerpenoid alkaloids from Delphiniumtongolense F.Lan Het, Xuan Pan*t, Bo-gang Li§, Yao-zu Chen!tThe Department.of Pharmacy of Lanzhou Medical College,Lanzhou 730 000, China; tThe Chemistry Department of Zhe-jian Univ., Hangzhou 310 027, China; §The Chengdu Instituteof Biology, Academia Sinica, Chengdu 610 041, ChinaReceived 17 June 1997; accepted (revised) 2 February 1998The phytochemical investigation of Delphiniumtongolense F. yields two new diterpenoid alkaloids ton-golenine C and tongolenine D. Their structures havebeen elucidated by spectroscopical methods.Delphinium tongolense F., distributing in the Northof Yunnan Province and the West of SichuanProvince of China, is antipyretic'. In the previousstudy two new diterpenoid alkaloids tongolenineand tongolenine have been isolated". In conti-nuation to the above studies another two new diter-penoid alkaloids were obtained from the wholeplants. Their structures were established as Ia,14a, 16/3-trimethoxy-7,8-diol-4-methoxy-methy-lene-LlI9(N)lycoctonate (tongolenine C, 1) and la,6/3, 16/3-trimethoxy-14a-ol-4-methyl-19-one-7,8-methylenedioxylycoctonate (tongolenine D,. 2) bymeans of spectroscopic method.Results and DiscussionTongolenine C (1) was isolated as white powder.The molecular ion peak at mJz 421.2503 in itsHREIMS revealed the molecular formulaC23H35N06. The lHNMR spectrum exhibited foursignals for the protons of four methoxy groups at 83.12,3.34,3.42 and 3.51 (each 3H, s), besides C18-Orne, other three methoxy groups should be locatedto C-I, C-14 and C-163. All of which indicatedtongolenine C is a Cje-diterpenoid alkaloids. Ac-cording to the HREIMS (mJz 421.2503, M\C23H35N06), I3CNMR (DEPT, Table I) signals at 877.2 (s) and 86.6 (s) as well as the absorptions at3450 and 3446 cm-l in IR indicated the presence oftwo hydroxy groups which could be assigned toC-8 and C-74. There are no evidences for the ex-NoteTongo1e~ C (I) Tongo1enneD (2)istences of NCH2CH3 and Ca-Me (CI8), but a me-thine (C-19) with a chemical shift of 180.1 ppm(d) and a methane at 8 80.4 ppm (t), thus the moie-ties -N=CH- (absorption at 1645 cm-l in IR) and-CH2-OMe rather than 4-Me (C-18) could bepostulated. The above mentioned spectral data en-abled us to elucidate the structure is 1a, 14a, 16f3-trirnethoxy-7,8-diol-4-methoxymethylene-LlI9(N)1y-coctonate.Tongolenine D (2) was obtained as colorlessneedles. The molecular ion peak at mJz 435.2262(~, C23H33N07) in HREIMS was observed.Twenty three signals in I3CNMR (DEPT, Table I)were recognized as (9xCH, 5xCH2, 4xCH3 and5xC. The signals at 85.23 and 5.15 (each IH, s) inlHNMR along with signal at 8 93.9 (t) in l3CNMRindicated the existence of 7,8-0CH20. ThelHNMR spectrum exhibited a sigrial for the protonsof three methoxy groups at 8 3.28, 3.39, 3.41.These evidences showed that tongolenine D is be-longing tolycoctonine type diterpenoid alkaloidwith 7,8-methylenedioxy. The signal at 8 176.1 Cand the lack of a signal at about 857.0 (CH2) for C-19 in 1.3CNMR, the ion peak at mJz 404[M-CO-He r in ElMS as well as the absorption at1720 cm-l in iR suggested the presence of a car-bonyl group (C-19), which is something like thatin thaliesessine. CI9=O causes downfield shift ofCrMe (I8-H), which resonate at 8 1.29 (3H, s). Inview of the fragment at mJz 418 (M+-·OH), themolecular ion peak in ElMS and the twenty threesignals in '13CNMR (DEPT) one hydroxy groupcould be resumed. By comparing the NMR data oftongolenine D with those of delelatine6 and del-NOTES 613Table I-IJCNMR data oftongolenine C (I) and tongolenine D (2)C-atom Tongolenine C# Tongolenine D~ C-atom Tongolenine C# Tongolenine D~I 82.5, d 81.8, d 14 84.0, d 74.1, d2 28.8, t 26.3, t 15 33.0, t 34.1, t3 33.1, t 29.7, t 16 83.6, d 81.7,d4 38.5, s 34.1, s 17 66.3, d 59.4, d5 53.0, d 45.9, d 18 80.4, t 22,0, q6 31.3, t 91.5, d 19 180.1, d 176.1, s7 86.6, d 91.0, s -OCH2- 94.4, t8 77.2, s 79.9, s I-OMe 57.6, q 55.7, q9 42.2, d 47.8, d 6-0Me 58.9, q10 46.0, d 42.2, d 14-0Me 56.3, qII 49.0, s 47.2, s 16-0Me 56.2, q 56.7, q12 24.7, d 26.7, t 18-0Me 58.9, q13 37.7, d 35.2, d*s, d, t and q refer to C, CH, CH2 and CH), respectively.# and !'J. recorded at 100 MHz and 75 MHz, respectively.brunine", two signals for quaternary carbons at 891.0 and 79.9 ppm could be tentatively assigned toC-7 and C-8, respectively. Because of the signalsat 8 91.6 (C-6), 81.8 (C-l) and 81.7 (C-16) ppmin '3CNMR (DEPT), the three methoxy groupsshould be located to C-I, C-6 and C-166. The hy-droxy group was determined as C'4-0H due to theresonance at 874.1 (d) in 13CNMR and at 8 4.03 in'HNMR6. Consequently, the structure of tongo-lenine D was elucidated as 1a, 613,1613-trimethoxy-14a-ol-4-methyl-19-one-7,8-methylenedioxy-Iycoctonate.Experimental SectionGeneral. Mps are uncorrected; 'HNMR weretaken in CDC13 using TMS as internal standard andHREIMS were taken at 70 eV.Plant material. Delphium tongolense F. wascollected in Sept. 1994, in Luding County, SichuanProvince, P.R. China, and identified by ProfessorS.-C. Xiao (Chengdu Institute of Biology, Acade-mia Sinica, P.R. China), where a specimen is de-posited.Extraction and isolation. The whole plant (1.3kg) of D. tongloense were powdered and soakedthree times with 95% EtOH at r.t. After removingsolvent in vacuo the extract was suspended in 2%H2S04 and filtrated. The acidic solution wasbasified to about pH 10 with ammonia (25%) andexhaustively extracted with CHCh to get 16 g ofalkaloidal extract after removing CHCh. The ex-tract was SUbjected to CC (550 g, A1203) and elutedwith Et20 to give fractions l~IV. From fraction 3,1 (2 mg) was obtained by CC on silica gel elutingwith cyclohexane : acetone : diethylamine=20 : 1 :1 drop ~ 1 : 1 : I drop, and then HPLC wotj C,s-reverse phase, methanol:water. From fraction IV 2(5.3 mg) was isolated by CC on silica gel elutingwith cyclo-hexane:acetone (l 0: I), and further puri-fication by recrystallization from acetone.Tongolenine C (1). White powder m.p.>350°C;[a];4 +44.4° (c=0.5, CHCI3) IR(KBr): 3450 and3446 (OH) 1645 cm" (-N=C( ); HREIMS: mlz421.2503 (M+, Calc. for: C23H3SN06, ,;21.2464);ElMS: mlz 421 (M+), 420 (M+-H), 358(M+-CH30H-CH30·), 404 (M--HOt, 390(M+-OMe), 376 (M+-CH20Me), 403 (M+-H20),402 (M+-H20-H), 374 (M+-CH30H-CH3);'HNMR (400 MHz): 8 3.66 (lH, br), 3.61 (lH, t,J=4.7 Hz, 1413-H), 3.12, 3.34, 3.42 and 3.51 (each3H, s, 4xOCH3); 13CNMR (100 MHz) data, seeTable I.Tongolenine D (2). Colorless needles, m.p.24310-311°C (acetone); [a]D+5.66 (c=0.27,CHCh); IR(KBr): 3350 (OH), 1720 (C=O); HRE-IMS: mlz 435. 2262 (M+, Calc. for C23H33N07:435.2257). ElMS: mlz 435 (~), 420 (M+-OMe),404 (M+-CO-H), 388 (M+-CO-H20-H); 'HNMR(300 MHz); 8 5.23 and 5.15 (each 1H, s,-OCH20-), 4.03 (lH, br, 1413-H), 3.96 (IH, d,J=6.2, 6a-H), 3.78 (lH, t, J=3.7 Hz), 3.24 (IH, d,J=2.5 Hz, 113-H),3.28, 3.39 and 3.41 (each 3H, s,3xOMe), 1.40 (3H, t, J=7 Hz, NCH2CH3), 1.29(3H, s, 18-H).614 INDIAN J CHEM, SEC.B, JUNE 1998AcknowledgementThis work was supported by the Di-ao Founda-tion from the Di-ao Pharmaceutical Company ofthe Chinese Academy of Sciences.References1 De1ectis Florae Repupubaris Sinicae Agendae AcaderniaeSinicae Edita Flora Republica Popularis Sinicae, SciencePublisher, Beijing, 27, 1979, p. 405.2 He L, Chen L-S, Li B-G & Chen Y-Z, Chinese ChemicalLetters, 7, 1996, 556.3 Wada K, Yamamoto T, Bando H & Kawahara N, Phyto-chemistry, 31, 1992,2135.4 Sakai S-I, Shinma N, Hasegawa S & Okamoto T, Ya-kugaku Zashi, 98, 1978, 1376.5 Wu Y -C. Wu T -S, Niwa M, Lu S -T & Hirata Y, Phyto-chemistry, 27, 1988,3949.6 Ross S -A, Desai H -K, Joshi B -S, Srivastave S -K,Glinski J -A, Chern S -Y & Pelletier S -W, Phytochemis-try, 27, 1988,3719.7 Deng W & Sung W -L, Heterocycles, 24, 1986, 873.

Tongolenine C and tongolenine D, two new diterpenoid alkaloids from Delphinium tongolense F.

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Tongolenine C and tongolenine D, two new diterpenoid alkaloids from Delphinium tongolense F.

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