The effect of L-proline as a promoter on the condensation reaction of salicylaldehyde or its derivatives with ethyl acetoacetate in neutral ionic liquid [emim]BF4 was studied. All reactions were carried out under mild reaction conditions and achieved high yields. Moreover, the ionic liquid containing L-proline could be recycled and reused for several times without noticeably decreasing in productivity. The results show that the L-proline-[emim]BF4 system has a potential in contribution to the development of environmentally friendly and inexpensive processes in organic syntheses.
Coumarins ; chemical synthesis ; Ionic Liquids ; chemistry ; Proline ; chemistry

OBJECTIVETo study the chemical constituents of the dried roots of Zanthoxylum dimorphophyllumr. spinifolium and to find out the active constituents of the plant.

METHODModern chromatography was used to purify chemical constituents, and their structures were identified by various spectral methods.

RESULTFour compounds were isolated and identified as isopimpinellin (I), xanthoxyletin (II), 6-(2', 3'-dihydroxy-3'-methyl-butyl)-7-hydroxy-2H-1-benzopyran-2-one (III), 6-(2'-O-beta-D-glucopyranosyloxy, 3'-dihydroxy-3'-methybutyl)-7-hydroxy-2H-1-benzopyran-2-one (IV).

CONCLUSIONAll of the above compounds were isolated from the above mentioned plant for the first time.

Coumarins ; chemistry ; isolation & purification ; Furocoumarins ; chemistry ; isolation & purification ; Plant Roots ; chemistry ; Plants, Medicinal ; chemistry ; Zanthoxylum ; chemistry

OBJECTIVETo study the chemical constituents in roots of Heracleum rapula.

METHODThe constituents were isolated by column chromatography on silica gel and ODS, and identified by spectroscopic methods.

RESULTNine compounds, osthol ( I ), bergapten (II), xanthotoxin (III), isopimpinellin (IV), imperatorin (V), isoimperatorin (VI), cnidilin (VII), phellopterin (VIII), rivulobirin A (IX) were isolated and identified.

CONCLUSIONCompounds VI, VII, VIII, IX were isolated from this plant for the first time.

Coumarins ; chemistry ; isolation & purification ; Furocoumarins ; chemistry ; isolation & purification ; Heracleum ; chemistry ; Plant Roots ; chemistry ; Plants, Medicinal ; chemistry

Scopoletin is a coumarin compound with various biological activities including detumescence and analgesic, insecticidal, antibacterial and acaricidal effects. However, interference with scopolin and other components often leads to difficulties in purification of scopoletin with low extraction rates from plant resource. In this paper, heterologous expression of the gene encoding β-glucosidase An-bgl3 derived from Aspergillus niger were carried out. The expression product was purified and characterized with further structure-activity relationship between it and β-glucosidase analyzed. Subsequently, its ability for transforming scopolin from plant extract was studied. The results showed that the specific activity of the purified β-glucosidase An-bgl3 was 15.22 IU/mg, the apparent molecular weight was about 120 kDa. The optimum reaction temperature and pH were 55 ℃ and 4.0, respectively. Moreover, 10 mmol/L metal ions Fe²⁺ and Mn²⁺ increased the enzyme activity by 1.74-fold and 1.20-fold, respectively. A 10 mmol/L solution containing Tween-20, Tween-80 and Triton X-100 all inhibited the enzyme activity by 30%. The enzyme showed affinity towards scopolin and tolerated 10% methanol and 10% ethanol solution, respectively. The enzyme specifically hydrolyzed scopolin into scopoletin from the extract of Erycibe obtusifolia Benth with a 47.8% increase of scopoletin. This demonstrated that the β-glucosidase An-bgl3 from A. niger shows specificity on scopolin with good activities, thus providing an alternative method for increasing the extraction efficiency of scopoletin from plant material.
Aspergillus niger/genetics* ; beta-Glucosidase/chemistry* ; Scopoletin ; Polysorbates ; Coumarins

Saposhnikovia divaricata (Turcz.) Schischk (S. divaricata, Fangfeng) is a herb in the Apiaceae family, and its root has been used since the Western Han Dynasty (202 B.C.). Chromones and coumarins are the pharmacologically active substances in S. divaricata. Modern phytochemical and pharmacological studies have demonstrated their antipyretic, analgesic, anti-inflammatory, antioxidant, anti-tumor, and anticoagulant activities. Technological and analytical strategy theory advancements have yielded novel results; however, most investigations have been limited to the main active substances-chromones and coumarins. Hence, we reviewed studies related to the chemical composition and pharmacological activity of S. divaricata, analyzed the developing trends and challenges, and proposed that research should focus on components' synergistic effects. We also suggested that, the structure-effect relationship should be prioritized in advanced research.
Drugs, Chinese Herbal/pharmacology* ; Coumarins/pharmacology* ; Apiaceae/chemistry* ; Chromones

The root of Peucedanum harry-smithii var. subglabrum was extracted with methanol, then separated with solvents at different polarity into four fractions: aqueous (H2O), ethyl acetate (AcOEt), chloroform (CHCl3) and petroleum ether (DAB-6). From AcOEt psoralen, bargapten, xanthotoxin, marmesin, umbelliferone, scopoletin, (+/-) peuformosin, Pd-I b, (+/-) selinidin, praeruptorin D were isolated by column chromatography on silica gel, using petroleum ether/ethyl acetate as eluent. The structures of the coumarins were identified by 1H-NMR and 13C-NMR.
Apiaceae ; chemistry ; Coumarins ; chemistry ; isolation & purification ; Magnetic Resonance Spectroscopy ; methods ; Plant Roots ; chemistry ; Umbelliferones ; chemistry

AIMTo investigate the chemical constituents of the roots of Daphne genkwa.

METHODSSilica gel and Sephadex LH-20 column chromatographic techniques were employed for the isolation and purification. The structure was elucidated by a combination of spectroscopic analyses.

RESULTSA new dicoumarin named isodaphnoretin was isolated and the structure was established as 7-hydroxy-6-methoxy-4-[(2-oxo-2H-1-benzopyran-7-yl)-oxyl]-2H-1-benzopyran-2-one.

CONCLUSIONIsodaphnoretin is a new compound.

Coumarins ; chemistry ; isolation & purification ; Daphne ; chemistry ; Molecular Conformation ; Molecular Structure ; Plant Roots ; chemistry ; Plants, Medicinal ; chemistry

OBJECTIVETo develop a quantitative analysis of multi-components by single marker(QAMS) method for simultaneous determination of three coumarins in Angelica dahurica var. formosana, by using one standard substance.

METHODWith imperatorin as internal reference standard, and 2 relative correction factors (RCF) to imperatorin were calculated within certain ranges. Their contents in 20 batches of samples, collected from different areas, were determined by both external standard method and QAMS. The method was evaluated by comparison of the quantitative results between the two methods.

RESULTNo significant differences were found in the quantitative results of three coumarins in 20 batches of A. dahurica var. formosana determined by the two methods (RSD < 5%).

CONCLUSIONQAMS is feasible and suitable for quality control of A. dahurica var. formosana.

Angelica ; chemistry ; Chromatography, High Pressure Liquid ; Coumarins ; chemistry ; Drugs, Chinese Herbal ; chemistry ; Furocoumarins ; chemistry ; Reference Standards

OBJECTIVETo study the chemical components from dried roots of Zanthoxylum dimorphophyllum var. spinifoliun.

METHODThe chemical components were isolated by low pressure column chromatography and their structures were identified by spectroscopic methods.

RESULTFive compounds were isolated and identified as 6-(2', 3'-dihydroxy-3'-methyl-butyl)-7-hydroxy-5-methoxy-2H-1-benzopyran-2-one (I), 6-(2',3'-dihydroxy-3'-methyl-butyl)-7-methoxy-8-(3'-methyl-but-2'-enyl)-2H-1-benzopyran-2-one (II),6-(2',3'-dihydroxy-3'-methyl-butyl)-7-hydroxy-2H-1-benzopyran-2-one (III), 6-(2', 3'-oxiranyl-3'-methyl-butyl)-7-methoxy-8- (3-methyl-but-2-enyl)-2H-1-benzopyran-2-one (IV), 7-methoxy-8-(3'-methyl-but-2'-enyl)-2H-1-benzopyran-2-one (V).

CONCLUSIONThese compounds were isolated from the plant for the first time.

Coumarins ; chemistry ; isolation & purification ; Plant Roots ; chemistry ; Plants, Medicinal ; chemistry ; Zanthoxylum ; chemistry

OBJECTIVETo isolate and determine the chemical constituents from Ranunculus japonicus.

METHODCompounds were isolated by column chromatography, and identified by MS, NMR data.

RESULTNine compounds were obtained andelucidated as scoparone (1), tricin (2), protocatechuic acid (3), luteolin (4), anemonin (5), scopoletin (6), 5-hydroxy-6, 7-dimethoxyflavone (7), 5-hydroxy-7, 8-dimethoxyflavone (8), ternatolide (9), respectively.

CONCLUSIONCompounds 1-9 were isolated from R. japonicus for the first time while compounds 7, 8 were separated from Ranunculus genus first time.

Coumarins ; chemistry ; isolation & purification ; Flavonoids ; chemistry ; isolation & purification ; Plants, Medicinal ; chemistry ; Ranunculus ; chemistry