Studies On Chemical Constituents And Antiallergic Effects Of The Dry Flower Buds Of Magnolia Biondii Pamp

Magnolia Flos is derived from the dry flower buds of Magnolia biondii Pamp,Magnolia sprengeri Pamp and Magnolia denudate Desr,which is a common dispelling wind chinese herbs,like allergic pruritus,rhinitis and asthma.Based on the investigation of Nanzhao,Nanyang,Henan Province,the original county of Magnolia Flos,this paper has learned about the planting scale,variety,cultivation,harvesting,market circulation and production policy of Nanzhao Magnolia Flos,and selected the variety of Nanzhao(Magnolia biondii Pamp)for further research,including phytochemistry,pharmacology and the pharmacodynamic basis of antiallergic effects.Through antiallergic bioassay-guided procedures,seven compounds were isolated from the petroleum ether fraction of the Magnolia Flos(Magnolia biondii Pamp)and seventy-four compounds were isolated from the ethyl acetate fraction.On the basic of physico-chemical properties and spectroscopic analysis,their structures were identified as follows.(1R,2S,5R,6S)-isoeudesmin(1),(1R,2S,5R,6S)-isopinoresinol monomethylether(2),(1R,2S,5R,6S)-isomagnolin-12'-O-?-D-glucoside(3),(7R,8S,7?S)-3',4-O-dimethylcedrusin(4),9'-O-acetyl-(7R,8S,7'R,8'R)-fargesol(5),(7R,8S,7'R,8'R)-fargesol(6),(+)-syringaresinol(7),(+)-pinoresinol(8),medioresinol B(9),(+)-demethoxypinoresinol(10),(+)-de-4'-O-methylmagnolin(11),(+)-4''-de-Omethylmagnolin(12),de-4'-O-methylyangabin(13),(+)-eudesmin(14),lirioresinol B dimethyl ether(15),(+)-magnolin(16),epimagnolin B(17),(+)-piperitol(18),(+)-kobusin(19),(+)-aschantin(20),fargesin(21),icariside E7(22),magnolin-12'-O-?-Dglucoside(23),syringaresinol-12'-O-?-D-glucopyranoside(24),eucommin A(25),12,12'-dimethoxy-11-hydroxy-6,4: 2,8-diepoxylignan-11'-O-?-D-glucopyranoside(26),(±)-5'-methoxy-4'-O-methyllariciresinol(27),(+)-lariciresinol(28),lariciresinol-4-monome ether(29),3-furanmethanol-tetrahydro-2-(4-hydroxy-3',5'-dimethoxyphenyl)-4-[(3'',4'',5''-trimethoxyphenyl)methyl]-(2R,3S,4S)-rel-(30),lariciresinol dimethyl ether(31),7R,8S,7'S,8'R-3,4,3',4'-tetramethoxy-9,7'-dihydroxy-8.8',7.O.9'-lignan(32),7R,8S,7'S,8'R-3,4,5,3',4'-pentamethoxy-9,7'-dihydroxy-8.8',7.O.9'-lignan(33),7S,8R,7'S,8'R-3,4,3',4'-tetramethoxy-9,7'-dihydroxy-8.8',7.O.9'-lignan(34),rel-[7S,8S,8'S]-3,4,3',4'-tetra-methoxy-9,7'-dihydroxy-8.8',7.O.9'-lignan(35),(7S,8R,7S,8S)-(-)-fargesol(36),9'-O-acetyl-(7S,8R,7S,8S)-(-)-fargesol(37),mgnostellin A(38),biondinin E(39),3',4-Odimethylcedrusin(40),(7S,8R)-dihydrodehydrodiconiferyl alcohol(41),(7R,8S)-dihydrode-hydrodiconiferyl alcohol 9-O-?-D-glucopyranoside(42),glochidioboside(43),(+)-isolariciresinol(44),(7R,8S)-1-(3,4-dimethoxyphenyl)-2-O-(2-methoxy-4-omegahydroxypropylphenyl)propane-1,3-diol(45),erythro-guaiacylglycerol-8-O-4'-(coniferyl alcohol)ether(46),veraguensin(47),pressafonin A(48),pressafonin B(49),(-)-bornyl ferulate(50),(-)-bornyl isoferulate(51),geranyl caffeate(52),geranyl trans-p-hydroxycinnamate(53),p-menth-3-ene-1,2,8-triol(54),dihydrotagetone methyl alcohol(55),naphthalenetriol(56),(-)-1?,4?,6?-trihydroxy-eudesmane(57),t-cadinol(58),t-muurolol(59),?-cadinol(60),(-)-parthenolide(61),(+)-dehydroabietic acid(62),7S,10S-epoxy-3E,5E-farnesadien-1,2,11-triol(63),7R,10Sepoxy-3E,5E-farnesadien-1,2,11-triol(64),farnesol(65),3,4-dimethoxyphenyl-?-Dglucopyranoside(66),Syringin(67),coniferin(68),benzeneformic acid(69),phydroxybenzoic acid(70),4-ethoxybenzyl alcohol(71),ehyl-p-hydroxybenzoate(72),lthymidine(73),scopoletin(74),biondnoid I(75),N-trans-p-coumaroyltyramine(76),1,7-dicarboxyheptane(77),Sitosterol-3-O-?-D-glucopyranoside(78),linoleic acid(79),?-sitosterol(80),(6Z,9Z,12Z)-heptadecatriene(81)?Among them,compounds 1-6 were new compounds;compounds 10-13,22,23,25-31,42-46,50-55,57,63,64,66,71,73,76 were firstly isolated from Magnolia genus;compounds 7,8,18,24,32-34,36,41,56,61,62,68-70,72,77,78 including those compounds firstly isolated from Magnolia genus were firstly isolated from Magnolia Flos(Magnolia biondii Pamp).All of the isolated compounds were evaluated for antiallergic effects.The results suggested that lignans compounds 1,14-18,21,9,10,23,25,26,28,29,30,38,41,cinnamic acid monoterpenes ester compounds 50,51,52 and other compounds 62,63,73,74,77 displayed a certainly inhibitory effect on mast cell degranulation.After evaluating the results of bioactive test,contents and distributions of these active constituents in crude extracts of Magnolia Flos(Magnolia biondii Pamp),the key role of lignans in the treatment of allergic diseases caused by mast cells degranulation and the pharmacological basis of anti-allergy of Magnolia Flos(Magnolia biondii Pamp)were illustrated.Based on the antiallergic activity of cinnamic acid bornyl ester compounds,a series of derivatives of cinnamic acid bornyl ester compounds were obtained by chemical synthesis.Among them,seven synthetic compounds,including 3-hydroxycinnamic acid bornyl ester(S7),4-fluorocinnamate acid bornyl ester(S8),4-formylcinnamate acid bornyl ester(S9),4-dimethylaminocinnamate acid bornyl ester(S10),3-methoxycinnamate acid bornyl ester(S11),4-bromocinnamate acid bornyl ester(S12),3,4-difluorocinnamic acid bornyl ester(S13),exhibited stronger inhibitory effect on mast cell degranulation rather than the natural compounds from Magnolia Flos(Magnolia biondii Pamp).Because of the similarity between the structures of lignans or cinnamic acid bornyl ester derivatives and marked differences in their antiallergic effects,the structure–activity relationship between these lignans or cinnamic acid bornyl ester derivatives and their inhibition of mast cell degranulation was also discussed.Thus,it provided some references for the discovery of the antiallergic drugs.In addition,this paper firstly analyzed the chemical constituents of crude extracts and volatile oils of the petal & calyx of Magnolia biondii Pamp by HPLC fingerprint and GC-MS fingerprint.The results suggested that the chemical compositions of the petal & calyx had a high similarity to the flower buds.Furthermore,the content of the magnolin and the volatile oil were both in line with the standards of the 2015 edition of the Pharmacopoeia of the People's Republic of China.Therefore,it inferred that there was a certain rationality to regard the petal & calyx as the flower buds in clinical medication.