Study On The Chemical Constituents And Biological Activities Of Barks And Leaves Of Cinnamomum Cassia

The dried barks of Cinnamomum cassia Presl (Lauraceae) are widely applied in traditional Chinese medicine to treat tussis, gastrointestinal neurosis, diarrhea, amenorrhea, dysmenorrhea, impotency, arthralgia, edema, and cardiac palpitation. Its chemical ingredients are volatile oils, tannins, alkaloids, lignans, flavonoids, polysaccharides, terpenes (including sesquiterpenes, diterpenes) and so on. The research about pharmacological effects and chemical composition of dried leaves of Cinnamomum cassia Presl (Lauraceae) were rarely reported.Four parts of cinnamon barks and leaves were screened for the immunomodulatory activity, and the result showed that EtOAc part and n-BuOH prat of cinnamon barks exhibited significant immunosuppressive activity. The T cell inhibitory rate of EtOAc part was more than85%, and the B cell inhibitory rate of n-BuOH part was more than100%at the concentration of40μg/ml. Meanwhile, the EtOAc part and n-BuOH prat of cinnamon leaves showed weak immunosuppressive activities.Repeated extensive column chromatographies (silica gel, YMC gel, Sephadex LH-20, HPLC) on the EtOAc part and n-BuOH prat of the barks of C. cassia had resulted in40compounds. Based on the detailed MS, IR, NMR, HRESIMS, ECD spectroscopic analysis and X-ray diffraction analysis, these compounds were identified as cinncassiol F (1), cinncassiol Gi (2),19-deoxycinncassiol Gi16-0-β-D-glucopyranoside (3),18-hydroxy perseanol (4), perseanol (5), cinncassiol D1(6), cinncassiol D1glucoside (7), cinncassiol D2(8), cinncassiol D3(9), cinncassiol D4glucoside (10), cinnacaslol (11), cinnacasolide D (12),3,4,5-trimeth-oxyphenol-β-D-apiofuranosyl-(1â†'6)-O-β-D-glucopyranoside (13),3,4-dimethoxyphenyl1-O-β-D-apiofuranosyl-(1â†'6)-β-D-glucopyranoside, phenol-β-D-apiofuranosyl-(1â†'6)-O-β-D-glucopyranoside (15),(7S,8R)-dihy-drodehydrodiconiferyl alcohol9’-O-β-D-apiofuranosyl-(1â†'6)-O-β-D-glucopyranoside (16),1,2,3-propanetriol,1-[4-[(1R,2R)-2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3-me thoxyphenyl]-(1R,2R)-(17),(6R,7R,8R)-7a-[(β-D-glucopyranosyl)oxy] lyoniresinol (18), (6S,7R,8R-7a-[(β-D-glucopryanosyl)oxy]lyoniresinol (19),(6R,7S, glucopyranosyl)oxy]lyoniresinol (20), cinnacasside G (21), cinnacasside F (22), cinnacasside A (23), cinnacasside B (24), cinnacasside C (25), erythro-guaiacy lglycerol (26),(E)-3-(3-methoxyphenyl)acrylaldehyde (27), O-methoxy cinnamaldehyde (28),(7R,8S)-syringoylglycerol(29),(7S,8S)-syringoylglycerol (30),4-methoxy guaiacyl glycerol7-O-β-D-glucopyranoside (31), rosavin(32), cinnamyl(33),2-phenylethyl-1-O-a-L-arabinopyranosyl(1â†'6)-β-D-glucopyranoside (34),(R)-3-hydroxybutanolide (35), theobroxide (36),(2S,3R,4R,5R)-5-(hydroxymethyl)-2-(methoxymethyl)tetrahydrofuran-2,3,4-triol (37),5a-carba-β-D-altr (38),4-(2-hydroxyethyl)phenol (39),2H-1-benzopyran-3-ol,5,7-dimethoxy-3’,4’-methylene dioxyflavan-3-ol (40). Among them, compounds1,2,3,4,12,16,21,22were new compounds, compounds1possesses an unprecedented novel isoryanodane diterpenoid skeleton bearing a ketal and a hemiketal, and2possesses an unprecedented11,12-seco-isoryanodane diterpenoid skeleton with a lactone bridge,3and4were new isoryanoid diterpenoids,12was a new phenolic glycoside,16was a new lignan,21and22were new geranylphenylacetate glycosides.With the similar procedures,20compounds were isolated from the EtOAc part and n-BuOH prat of cinnamon leaves, and were identified as cinncassiol G2(41), aglycon (42), badounoid B (43), tsangane L (44), wilsonl B (45), lasianthionoside A (46), aromadendrane-4β,10β-diol (47), pumilaside A (48), cinnamoside (49),(+)-lariciresinol (50),(-)-4-epi-lyoniresinol (51),2,6-dimethoxy-p-hydroquinone1-O-β-D-glucopyranside (52), cinnacasolide A (53), canthoside C (54),1-(4-hydroxyphenyl) ethanone (55), fareanol (56),3-(4-Hydroxy-3-methoxyphenyl) propan-1,2-dio (57),2,3-dihydroxy-l-(3,4-dihydroxyphenyl)-1-propanone (58), dihydrocinnacasside (59),(S)-ethyl4-hydroxy-pentanoate (60). Among them,41was a new isoryanoid diterpenoid, compounds42-49were known sesquiterpenes.Selected compounds were evaluated for there immunosuppressive activity, cytotoxicity, antifeedant activity, respectively. In the test of immunosuppressive activity, selected compounds showed non-toxic effects on the spleen cells, and compounds2-7,9-11,13,21,42and43showed inhibitory activity on ConA-induced proliferation. Particularly,2and11exhibited very significant immunosuppressive activity, the inhibitory rate of compound2was more than85%at the selected concentration, and the inhibitary effect of2was similar as the positive control CsA. Diterpenes1and5were tested for their cytotoxicity, however, none of them exhibited significant activity. Compounds1,2,4,5,6,7,8were evaluated for their antifeedant activities against two generalist insect herbivores, the cotton bollworm (H. migerd) and the beet armyworm (S. exigua). Meanwhile, these compounds were selected to observe the growth inhibition on H. migera. The results revealed that compounds1,2,4,6and8exhibited obvious antifeedant activity against S. exigua, and the EC50of compound6was0.66μg/cm2; compounds1,4,6,8and9showed obvious antifeedant activity against H. migera, and compound2exhibited EC503.5μg/cm2; and all the diterpenoids showed significant growth inhibition of H. miger.