4478-93-7Relevant articles and documents
Anti-inflammatory and anti-apoptotic effects of (RS)- glucoraphanin bioactivated with myrosinase in murine sub-acute and acute MPTP-induced Parkinson's disease
Galuppo, Maria,Iori, Renato,De Nicola, Gina Rosalinda,Bramanti, Placido,Mazzon, Emanuela
, p. 5532 - 5547 (2013)
This study was focused on the possible neuroprotective role of (R S)-glucoraphanin, bioactivated with myrosinase enzyme (bioactive RS-GRA), in an experimental mouse model of Parkinson's disease (PD). RS-GRA is one of the most important glucosinolates, a thiosaccharidic compound found in Brassicaceae, notably in Tuscan black kale seeds. R S-GRA was extracted by one-step anion exchange chromatography, further purified by gel-filtration and analyzed by HPLC. Following, pure R S-GRA was characterized by 1H and 13C NMR spectrometry and the purity was assayed by HPLC analysis of the desulfo-derivative according to the ISO 9167-1 method. The obtained purity has been of 99%. To evaluate the possible pharmacological efficacy of bioactive RS-GRA (administrated at the dose of 10 mg/kg, ip +5 μl/mouse myrosinase enzyme), C57BL/6 mice were used in two different sets of experiment (in order to evaluate the neuroprotective effects in different phases of the disease), according to an acute (2 injections·40 mg/kg MPTP) and a sub-acute (5 injections·20 mg/kg MPTP) model of PD. Behavioural test, body weight changes measures and immunohistochemical localization of the main PD markers were performed and post-hoc analysis has shown as bioactive R S-GRA is able to reduce dopamine transporter degradation, tyrosine hydroxylase expression, IL-1β release, as well as the triggering of neuronal apoptotic death pathway (data about Bax/Bcl-2 balance and dendrite spines loss) and the generation of radicalic species by oxidative stress (results focused on nitrotyrosine, Nrf2 and GFAP immunolocalization). These effects have been correlated with the release of neurotrophic factors, such as GAP-43, NGF and BDNF, that, probably, play a supporting role in the neuroprotective action of bioactive RS-GRA. Moreover, after PD-induction mice treated with bioactive RS-GRA are appeared more in health than animals that did not received the treatment both for phenotypic behaviour and for general condition (movement coordination, presence of tremors, nutrition). Overall, our results suggest that bioactive RS-GRA can protect neurons against the neurotoxicity involved in PD via an anti-apoptotic/anti-inflammatory action.
Cytotoxic and antioxidant activity of 4-methylthio-3-butenyl isothiocyanate from Raphanus sativus L. (Kaiware Daikon) sprouts
Papi, Alessio,Orlandi, Marina,Bartolini, Giovanna,Barillari, Jessica,Iori, Renato,Paolini, Moreno,Ferroni, Fiammetta,Fumo, Maria Grazia,Pedulli, Gian Franco,Valgimigli, Luca
, p. 875 - 883 (2008)
There is high current interest in the chemopreventive potential of Brassica vegetables (cruciferae), particularly due to their content in glucosinolates (GL), which upon myrosinase hydrolysis release the corresponding isythiocyanates (ITC). Some ITCs, such as sulforaphane (SFN) from broccoli (Brassica oleacea italica), have been found to possess anticancer activity through induction of apoptosis in selected cell lines, as well as indirect antioxidant activity through induction of phase II detoxifying enzymes. Japanese daikon (Raphanus sativus L.) is possibly the vegetable with the highest per capita consumption within the Brassicaceae family. Thanks to a recently improved gram scale production process, it was possible to prepare sufficient amounts of the GL glucoraphasatin (GRH) as well as the corresponding ITC 4-methylthio-3-butenyl isothiocyanate (GRH-ITC) from its sprouts. This paper reports a study on the cytotoxic and apoptotic activities of GRH-ITC compared with the oxidized counterpart 4-methylsulfinyl-3-butenyl isothiocyanate (GRE-ITC) on three human colon carcinoma cell lines (LoVo, HCT-116, and HT-29) together with a detailed kinetic investigation of the direct antioxidant/radical scavenging ability of GRH and GRH-ITC. Both GRH-ITC and GRE-ITC reduced cell proliferation in a dose-dependent manner and induced apoptosis in the three cancer cell lines. The compounds significantly (p -1 s-1, respectively (at 298 K in methanol), whereas the corresponding value measured here for the reference antioxidant α-tocopherol was 425 ± 40 M-1 s-1. GRH reacted with H2O2 and tert-butyl hydroperoxide in water (pH 7.4) at 37°C, with rate constants of 1.9 ± 0.3 × 10-2 and 9.5 ± 0.3 × 10-4 M -1 s-1 (paralleling recently developed synthetic antioxidants) being quantitatively (>97%) converted to GRE. It is demonstrated that GRH-ITC has interesting antioxidant/radical scavenging properties, associated with a selective cytotoxic/apoptotic activity toward three human colon carcinoma cell lines, and very limited toxicity on normal human T-lymphocytes.
A new and effective approach to the synthesis of sulforaphane
Vo, Duy-Viet,Truong, Van-Dat,Tran, Thanh-Dao,Do, Van-Thanh-Nhan,Pham, Ngoc-Tuan-Anh,Thai, Khac-Minh
, p. 7 - 10 (2016)
Background: Sulforaphane [1-isothiocyanato-(4-methylsulfinyl)butane] identified from appears to possess health benefits such as activities against breast, skin and prostate cancer and diabetes. and studies provide evidence that it can provide protection at every stage of cancer progression. Sulforaphane was firstly synthesized by Von Schmidt and P.Karrer in 1948 via phthalimide route but after Zhang and co-worker reported its bioactivity in 1992, the chemical synthesis of sulforaphane by alternate route has attracted several research groups in the past 20 years . Methods: The synthesis started with the preparation of-methylthiolanium tetrafluoroborate by sonication of thiolane (1) with methyl iodide followed by anionic metathesis with NaBF4 in-butanol to give thiolanium tetrafluorborate (2). The ring opening of 2 by SN2 is conducted in 16 hours at 60 oC (as indicated by TLC) to obtain 1-Azido-(4-methylsulfinyl)butane (3). Conversion 3 into Erucin (4) was successfully obtained by Staudinger reaction, followed by oxidation of 4 in transition metal-free condition (H2O2/ glacial acetic acid) to give sulforaphane in racemic form. Results: Sulforaphane was obtained with 41% yield overall via only four steps with high purity without column chromatography. The approach not only opened up a new synthetic pathway to this naturally occurring isothiocyanate and its analogues, but also suggested a possible solution for converting by-products in petroleum refining processes into useful compounds. Conclusion: Sulforaphane was successfully synthesized from thiolane, a waste product in petroleum processing in a simpler and more efficient fashion, eco-friendy approach. All products were obtained in high yield and high purity. In comparison with previously reported strategies, this new approach is believed to be the shortest and the most efficient synthetic route to date.
Direct antioxidant activity of purified glucoerucin, the dietary secondary metabolite contained in rocket (Eruca sativa Mill.) seeds and sprouts
Barillari, Jessica,Canistro, Donatella,Paolini, Moreno,Ferroni, Fiammetta,Pedulli, Gian Franco,Iori, Renato,Valgimigli, Luca
, p. 2475 - 2482 (2005)
Rocket (Eruca sativa Mill, or Eruca vesicaria L.) is widely distributed all over the world and is usually consumed fresh (leafs or sprouts) for its typical spicy taste. Nevertheless, it is mentioned in traditional pharmacopoeia and ancient literature for several therapeutic properties, and it does contain a number of health promoting agents including carotenoids, vitamin C, fibers, flavonoids, and glucosinolates (GLs). The latter phytochemicals have recently gained attention as being the precursors of isothiocyanates (ITCs), which are released by myrosinase hydrolysis during cutting, chewing, or processing of the vegetable. ITCs are recognized as potent inducers of phase II enzymes (e.g., glutathione transferases, NAD(P)H:quinone reductase, epoxide hydrolase, etc.), which are important in the detoxification of electrophiles and protection against oxidative stress. The major GL found in rocket seeds is glucoerucin, GER (108 ±5 μmol g-1 d.w.) that represents 95% of total GLs. The content is largely conserved in sprouts (79% of total GLs), and GER is still present to some extent in adult leaves. Unlike other GLs (e.g., glucoraphanin, the bio-precursor of sulforaphane), GER possesses good direct as well as Indirect antioxidant activity. GER (and its metabolite erucin, ERN) effectively decomposes hydrogen peroxide and alkyl hydroperoxides with second-order rate constants of k2 = 6.9 ± 0.1 × 10-2 M -1 s-1 and 4.5 ± 0.2 × 10-3 M -1 s-, respectively, in water at 37 °C, thereby acting as a peroxide-scavenging preventive antioxidant. Interestingly, upon removal of H2O2 or hydroperoxides, ERN is converted into sulforaphane, the most effective inducer of phase II enzymes among ITCs. On the other hand, ERN (and conceivably GER), like other ITCs, does not possess any chain-breaking antioxidant activity, being unable to protect styrene from its thermally (37 °C) initiated autoxidation in the presence of AMVN. The mechanism and relevance of the antioxidant activity of GER and ERN are discussed.
Antioxidant activity of two edible isothiocyanates: Sulforaphane and erucin is due to their thermal decomposition to sulfenic acids and methylsulfinyl radicals
Cedrowski, Jakub,D?browa, Kajetan,Przybylski, Pawe?,Krogul-Sobczak, Agnieszka,Litwinienko, Grzegorz
, (2021/03/30)
Sulforaphane (SFN) and erucin (ERN) are isothiocyanates (ITCs) bearing, respectively, methylsulfinyl and methylsulfanyl groups. Their chemopreventive and anticancer activity is attributed to ability to modulate cellular redox status due to induction of Phase 2 cytoprotective enzymes (indirect antioxidant action) but many attempts to connect the bioactivity of ITCs with their radical trapping activity failed. Both ITCs are evolved from their glucosinolates during food processing of Cruciferous vegetables, therefore, we studied antioxidant behaviour of SFN/ERN at elevated temperature in two lipid systems. Neither ERN nor SFN inhibit the oxidation of bulk linolenic acid (below 100 °C) but both ITCs increase oxidative stability of soy lecithin (above 150 °C). On the basis of GC-MS analysis we verified our preliminary hypothesis (Antioxidants 2020, 9, 1090) about participation of sulfenic acids and methylsulfinyl radicals as radical trapping agents responsible for the antioxidant effect of edible ITCs during thermal oxidation of lipids at elevated temperatures (above 140 °C).
Selective Late-Stage Oxygenation of Sulfides with Ground-State Oxygen by Uranyl Photocatalysis
Li, Yiming,Rizvi, S. Aal-e-Ali,Hu, Deqing,Sun, Danwen,Gao, Anhui,Zhou, Yubo,Li, Jia,Jiang, Xuefeng
supporting information, p. 13499 - 13506 (2019/08/21)
Oxygenation is a fundamental transformation in synthesis. Herein, we describe the selective late-stage oxygenation of sulfur-containing complex molecules with ground-state oxygen under ambient conditions. The high oxidation potential of the active uranyl cation (UO22+) enabled the efficient synthesis of sulfones. The ligand-to-metal charge transfer process (LMCT) from O 2p to U 5f within the O=U=O group, which generates a UV center and an oxygen radical, is assumed to be affected by the solvent and additives, and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late-stage oxygenation in an atom- and step-efficient manner.
Sulfoxide and sulfone compounds, as well as selective synthesis method and application thereof
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Paragraph 0045-0048; 0201-0204, (2019/12/02)
The invention discloses a method for selectively synthesizing a sulfoxide compound shown as a formula (II) and a sulfone compound shown as a formula (III). In a reaction solvent, thioether (I) is usedas a reaction raw material and oxygen as an oxidation reagent, under the catalytic action of visible light and a photosensitive reagent; under the assistance of an additive, when a large-polarity proton-containing additive such as an acid and an alcohol or a solvent or an additive with excellent electron donating ability is used, a sulfoxide compound (II) is selectively generated; and when a small-polarity aprotic additive or a solvent is used, a sulfone compound (III) is selectively generated. The synthesis method has the advantages of easily available and cheap raw materials, simple reaction operation, mild reaction conditions, high yield and excellent functional group tolerance. According to the invention, synthesis and modification of some medicines are realized, and an efficient method for selectively constructing sulfoxide and sulfone compounds is provided for medicinal chemistry research.
Conversion synthetic method of sulforaphane
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Page/Page column 8-10, (2019/08/30)
The invention relates to a conversion synthetic method of sulforaphane and belongs to the field of organic compound synthesis technology. In order to solve the problem that existing sulforaphane preparation methods have disadvantages of low yield, high cost, toxic raw materials, etc., the invention provides a conversion synthetic method of sulforaphane. The method of the invention comprises the following steps: dimethyl sulfoxide and sodium hydride react according to a certain molar ratio to synthesize methylsulfinyl sodium; 1-bromo-3-chloropropane and thiocyanate react according to a certainmolar ratio to synthesize 3-chloroisothiocyanopropane; and 3-chloroisothiocyanopropane and methylsulfinyl sodium react according to a certain molar ratio to synthesize sulforaphane. By directly bridging two intermediates, one-step synthesis of sulforaphane is realized. The raw materials are safe and stable, and yield is higher. In addition, reaction conditions in the sulforaphane synthesis steps are mild; the reactions can be rapidly carried out in a normal-temperature or low-temperature environment; the synthetic product is avoided from being decomposed by heating; and purity and environmental stability of the product are enhanced. The above beneficial effects are all beneficial to practical application of sulforaphane.
Chemical synthesis method for sulforaphane
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Paragraph 0017, (2017/11/16)
The invention discloses a chemical synthesis method for sulforaphane. The method is characterized by including the steps of: (a) taking sodium iodide as the catalyst, reacting 4-chloro-1-butanol with sodium methyl mercaptide to obtain 4-methylthio-1-butanol; (b) in the presence of alkali, reacting 4-methylthio-1-butanol with methylsufonyl chloride to obtain 4-methylthio-1-butylmethysulfonate; (c) reacting4-methylthio-1-butylmethysulfonate with sodium azide in the presence of a phase transfer catalyst to obtain 1-azido-4-methylthiobutane; (d) reacting 1-azido-4-methylthiobutane with triphenylphosphine, and then carrying out reaction with carbon disulfide under a room temperature condition to obtain 1-isothiocyano-4-methylthiobutane; and (e) oxidizing1-isothiocyano-4-methylthiobutane with m-CPBA under a low temperature condition to obtain sulforaphane. The method provided by the invention has the advantages of simple technological process, easy treatment and high total yield (75%), and can achieve effective large-scale production of sulforaphane.
A radish muonium chemical synthesis method
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Paragraph 0015; 0022; 0032; 0034-0036, (2017/08/25)
The invention discloses a chemical synthetic method for raphanin and belongs to the technical field of drug synthesis. The chemical synthetic method for raphanin comprises the following three steps of: (1) reacting sodium methyl mercaptide with 1-bromo-4-chlorobutane to generate 1-chloro-4-methyl butyl sulfide; (2) in the presence of a phase transfer catalyst, reacting sodium thiocyanate with 1-chloro-4-methyl butyl sulfide, performing dichloromethane extraction after reaction, and performing rotary evaporation on an organic layer to obtain 1-isothiocyano-4-methyl butyl sulfide; and (3) dissolving 1-isothiocyano-4-methyl butyl sulfide in dichloromethane, performing oxidation by m-chloroperoxybenzoic acid, producing a reaction, and performing purification to obtain a product, namely raphanin. The chemical synthetic method is simple and convenient to operate, requires a few steps, and is high in yield and suitable for large-scale production.
