- Volatile short-chain amphiphiles derived from isosorbide: Hydrotropic properties of esters vs. ethers
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Two series of short-chain isosorbide monoalkanoates, differing from the free hydroxyl position, were synthesized and evaluated as volatile non-ionic hydrotropes, also known as solvo-surfactants . Their aqueous solubilities, solubilizing efficiencies and volatilities were evaluated and compared to the corresponding 5-O-alkylisosorbides. Whatever the acylation position (5-O- or 2-O-), isosorbide monoalkanoates are poorly water-soluble for acyl chains longer than four carbons, whereas 5-O-alkylisosorbides are completely miscible with water up to a pentyl chain, which seems to indicate that an ether link brings more hydrophilicity than an ester bond for these types of molecules. The shorter isosorbide monoalkanoates are completely miscible with water and the butanoates are particularly efficient in terms of aqueous solubilization of hydrophobic compounds. In addition, all hydrotropes exhibit some volatility albeit being non-VOC and contrarily to their ethers homologues, isosorbide alkanoates are easily hydrolysed in basic medium, which suggests a good biodegradability.
- Lavergne, Aurelie,Moity, Laurianne,Molinier, Valerie,Aubry, Jean-Marie
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Read Online
- Method for preparing 2-acetic acid-5-isosorbide dinitrate from sorbitol
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The invention discloses a method for preparing 2-acetic acid-5-isosorbide dinitrate from sorbitol, which comprises the following steps of: contacting a material containing sorbitol, an acetylating agent and a nitrating agent with a solid acid catalyst, and carrying out acylation reaction and nitration reaction to obtain the 2-acetic acid-5-isosorbide dinitrate. According to the method, sorbitol is subjected to one-pot conversion to prepare 2-acetic acid-5-isosorbide dinitrate, so that the operation process is greatly simplified, and the synthesis efficiency is improved; the used solid acid catalyst has small corrosion to equipment and is easily separated from a product; and the reaction conditions are mild, and high-vacuum, high-temperature and other high-energy-consumption operations are avoided.
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Paragraph 0043-0056
(2021/05/08)
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- Method for synthesizing isohexitol ester
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The invention discloses a method for synthesizing isohexitol ester, which is characterized in that a material containing hexitol and an esterifying agent is contacted with a solid acid catalyst in the presence of an aprotic solvent, and the isohexitol ester is obtained through one-pot one-step reaction. The method is especially suitable for the reaction of directly synthesizing the isohexitol ester, especially isosorbide ester, from hexitol, especially sorbitol, the total yield of the obtained isohexitol ester is 80% or above, and the yield of the isosorbide dicarboxylate reaches 60% or above.
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Paragraph 0010; 0043-0050; 0055-0056
(2021/05/05)
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- COMPOUNDS AND COMPOSITIONS FOR USE IN TREATING PSORIASIS
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Compounds and pharmaceutical compositions for use in the treatment of psoriasis are disclosed. Preferred compounds have demonstrated efficacy in reducing skin scaling, erythema and skin thickness in the mouse model of Aldara-induced psoriasis.
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Paragraph 0084
(2018/10/19)
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- Selective Methylmagnesium Chloride Mediated Acetylations of Isosorbide: A Route to Powerful Nitric Oxide Donor Furoxans
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Isosorbide was functionalized with furoxan for the first time to give adducts that release nitric oxide up to 7.5 times faster than the commercial vasodilator, isosorbide-5-mononitrate (Is5N). The synthesis was facilitated by MeMgCl-mediated selective acetylation of isosorbide or selective deacetylation of isosorbide-2,5-diacetate, which was rationalized in terms of a more stable 5-alkoxide magnesium salt using DFT. Isosorbide-furoxans are safer to handle than Is5N due to greater thermal stability.
- Kielty, Patrick,Smith, Dennis A.,Cannon, Peter,Carty, Michael P.,Kennedy, Michael,McArdle, Patrick,Singer, Richard J.,Aldabbagh, Fawaz
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supporting information
p. 3025 - 3029
(2018/05/28)
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- Development of a Practical Enzymatic Synthesis of Isosorbide-2-acetate
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Using immobilized lipase, we developed an enzymatic synthesis of isosorbide-2-acetate (1), a key intermediate in the preparation of isosorbide-5-mononitrate. 1 was prepared in high yield (~92%) with excellent regioselectivity (>99.5% d.e.) through hydrolysis (Novozym 435) or alcoholysis (lipase PS IM) of isosorbide-2,5-diacetate. The conditions for the enzymatic process were optimized. The substrate concentration could be 400-500 g/L, and the enzyme to substrate ratio was 10 wt %. The feasibility of enzyme recycling was also demonstrated. In addition, the enzymatic process was carried out on a kilogram scale and was proved to be scalable, efficient, and economical.
- Zhu, Shi-Guo,Huang, Jia-Xin,Zhang, Gui-Min,Chen, Shao-Xin,Zhang, Fu-Li
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p. 1548 - 1552
(2018/11/25)
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- ISOSORBIDE-BASED POLYMETHACRYLATES
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A monomer comprises the structure wherein R1 comprises H or a substituted hydrocarbyl or unsubstituted hydrocarbyl, and wherein R2 comprises H, a halide, or a substituted or unsubstituted (C1-C4) hydrocarbyl. A method comprises (a) reacting a dianhydrohexitol precursor having the structure with an acyl-group containing compound having the structure wherein R1 comprises H or a substituted hydrocarbyl or unsubstituted hydrocarbyl, and X comprises a halide, a hydroxyl group, or an acyl group to form an acylated dianhydrohexitol ester intermediate having the structure and (b) reacting the acylated dianhydrohexitol ester intermediate with an acrylic-based compound having the structure wherein R2 comprises H, a halide, or a substituted or unsubstituted (C1-C4) hydrocarbyl, and Y comprises a halide, a hydroxyl group, or an acyl group, to form a dianhydrohexitol-based monomer having the structure
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Paragraph 0135-0136
(2016/09/12)
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- Isohexide hydroxy esters: Synthesis and application of a new class of biobased AB-type building blocks
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Here we present the synthesis of a new family of sugar derived 1,4:3,6-dianhydrohexitol based AB-type monomers, containing one methyl ester group and a secondary hydroxyl group in all four possible stereo isomers (RR, RS, SR, SS). Structural characterization of the monomers (5a-d) was established by 1D and 2D NMR analysis, which was further confirmed by single-crystal X-ray structure determination. The application of these monomers in step-growth polymerization afforded fully isohexide based stereo-regular polyesters. Homo polyesters based on the RR and RS monomers were obtained with reasonable molecular weights by melt polymerization (Mn 2400 and 2500 resp.). These materials showed unexpectedly low glass-transition temperatures of 20°C and 15°C respectively. In contrast, the monomers with SR and SS configuration yielded only low molecular weight oligomers. Surprisingly, copolymerization of the RR and SR monomers gave a polyester with higher molecular weight (Mn 4100) and a high Tg of 80°C. These preliminary results show that isohexide hydroxyesters are an intriguing new class of biobased building blocks with many potential applications.
- Thiyagarajan, Shanmugam,Wu, Jing,Knoop, Rutger J. I.,Van Haveren, Jacco,Lutz, Martin,Van Es, Daan S.
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p. 47937 - 47950
(2014/12/10)
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- PRODUCTION OF 5-MEMBERED AND 6-MEMBERED CYCLIC ESTERS OF POLYOLS
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Described herein are improved methods for the preparation of 5- and 6-membered cyclic mono and diesters of sugar alcohols and anhydrosugar alcohols by reaction with an organic acid RCOOH over a solid acidic substrate. The process is adaptable to a continuous process for simultaneously making and separating the cyclic esters from the sugar alcohols and anhydrosugar alcohols under mild conditions using the solid acid substrate as both the catalyst and a chromatographic bed for separation. The reactions are performed at mild temperatures of 700C to 10O0C and the formation of the cyclic esters is nearly quantitative. Also described is a method for making 5- and 6-membered cyclic mono and diesters of sugar alcohols and anhydrosugar alcohols using microwave irradiation in the presence of the organic acid.
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Page/Page column 10-11
(2010/01/12)
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- Asymmetric synthesis of β-lactams by [2+2] cycloaddition using 1,4:3,6-dianhydro-d-glucitol (isosorbide) derived chiral pools
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Highly diastereoselective synthesis of cis-β-lactams via [2+2] cycloaddition reactions of imines derived from a chiral bicyclic aldehyde and ketenes is described. The chiral bicyclic aldehyde as well as chiral acids were prepared from commercially available inexpensive isosorbide. The cycloaddition reaction was found to be highly diastereoselective; in some cases giving a single diastereomer of cis-azetidin-2-one in very good yields. A moderate diastereoselectivity was observed with chiral ketenes derived from isosorbide.
- Shaikh,Kale,Shaikh, Md. Abrar,Puranik, Vedavati G.,Deshmukh
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p. 3380 - 3388
(2007/10/03)
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- New preparative routes to isosorbide 5-mononitrate
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Three new methods for the preparation of the vasodilator isosorbide 5-mononitrate are described. In the first method enzymatic regioselective acetylation of isosorbide gave isosorbide 2-butyrate. Nitration and deprotection of this material afforded isomerically pure isosorbide 5-mononitrate in high overall yield. Secondly, regioselective hydrogenation of isosorbide dinitrate over platinum oxide (PtO2) furnished the 5-mononitrate in 45% yield. Similarly, regioselective reduction of the dinitrate was achieved using sodium borohydride (NaBH4) activated with cobalt or iron phthalocyanine. All three methods show advantages over existing procedures. The Royal Society of Chemistry 2000.
- Brown, Chris,Marston, Richard W.,Quigley, Paul F.,Roberts, Stanley M.
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p. 1809 - 1810
(2007/10/03)
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- Process for the enzymatic production of isomerically pure isosorbide-2 and 5-monoesters as well as their conversion into isosorbide-2- and 5-nitrate
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Process for the enzymatic production of isomerically pure compounds having the general formulae I and II STR1 in which the substituents R have the meanings stated in the claims, as well as their use for the production of isomerically pure isosorbide-2-nitrate having the formula V and isosorbide-5-nitrate having the formula VI, STR2 which are both important as therapeutic agents for coronary diseases.
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- Selective alkylations of 1,4:3,6-dianhydro-D-glucitol (isosorbide)
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Each of the two hydroxyl groups of isosorbide can be alkylated selectively, either by direct alkylation with benzyl chloride or allyl bromide according to the reaction conditions, or by a three-step procedure involving selective monoacetylation, alkylation with four different reagents, and finally deacetylation.Monobutyl and monomethyl derivatives from isosorbide are also described.
- Abenhaiem, D.,Loupy, A.,Munnier, L.,Tamion, R.,Marsais, F.,Queguiner, G.
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p. 255 - 266
(2007/10/02)
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- Hydrolases in organic synthesis: Preparation of enantiomerically pure compounds
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Esterhydrolases (Esterases, Lipases) are highly (chemo-, regio- and enantio-) selective biocatalysts for the transformation of racemic and achiral substrates into enantiomerically pure compounds.Numerous examples for their application in the preparation of synthetically useful chiral auxiliaries and building blocks for flavour compounds, pheromones and several pharmaceuticals including β-adrenergic blockers, antidepressants and ACE inhibitors are presented.
- Ader, U,Andersch, P,Berger, M,Goergens, U,Seemayer, R,Schneider, M
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p. 145 - 150
(2007/10/02)
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- Synthesis of New Chiral Auxiliaries Derived From Isosorbide
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Synthesis of both monobenzenesulfonates of isosorbide (1,4:3,6-dianhydrosorbitol) was regioselectively achieved in high yields via a three-step sequence.These monoesters were O-alkylated before being reacted with various primary amines to give the corresponding amino esters.The full control of regioselectivity led either to the exo-exo or endo-endo isomers.In an independent pathway, isosorbide derived amino ethers and amino alcohols with both amino and hydroxy functions in the endo position, were synthesized from isosorbide in a four-step procedure including selective monobenzylation, tosylation, substitution by amines and debenzylation.
- Tamion, R.,Marsais, F.,Ribereau, P.,Queguiner, G.,Abenhaim, D.,et al.
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p. 1879 - 1890
(2007/10/02)
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- Enzymatic preparation of isomerically pure 1,4:3,6-dianhydro-D-glucitol monoacetates - Precursors for isoglucitol 2- and 5-mononitrates
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Using a highly selective lipase from Pseudomonas sp. (SAM II) the isomerically pure title compounds 3 and 4 were prepared either by enzymatic hydrolysis (alcoholysis) of the diacetate 2 or by enzymatic esterification of the diol 1, respectively. They were further converted into the pharmaceutically important, isomerically pure 1,4:3,6-dianhydro-D-glucitol-2- and 5-nitrates 6 and 7.
- Seemayer,Bar,Schneider
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p. 1123 - 1126
(2007/10/02)
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- Some Applications of Isopropenyl Acetate to O-, N- and C-Acetylation
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New procedure for the preparation of drugs and drug intermediates (isosorbide-5-nitrate, diltiazem) and intermediates of potential drugs using isopropenyl acetate are described.
- Gizur, Tibor,Harsanyi, Kalman
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p. 2365 - 2371
(2007/10/02)
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- Selective Esterification of 1,4:3,6-Dianhydro-D-glucitol
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Esterification of 1,4:3,6-dianhydro-D-glucitol (1) with carboxylic acids in the presence of 4-dimethylaminopyridine and dicyclohexylcarbodiimide affords 2-exo-acylates 3 with high regioselectivity, in addition to small amounts of the isomeric 5-endo-acylates 4 and 2,5-diacylates 5.
- Cekovic, Zivorad,Tokic, Zorana
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p. 610 - 612
(2007/10/02)
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- ESTERIFICATIONS REGIOSELECTIVES DU DIANHYDRO-1,4:3,6-D-GLUCITOL
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The 1,4:3,6-dianhydro-D-glucitol was regioselectively esterified at the 2-exo position in order to obtain the 1,4:3,6-dianhydro-5-O-nitro-D-glucitol derivative after nitration and deprotection of the 2-position.Since usual esterification reactions are directed toward the 5-endo position of higher reactivity, due to intramolecular hydrogen bonding and/or chelation involvement with the acylating agent, the selectivity toward the 2-exo position was achieved by preliminary dialkoxidation of the carbohydrate followed by treatment with pivaloyl chloride.
- Le Lem, Gael,Boullanger, Paul,Descotes, Gerard,Wimmer, Eric
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p. 567 - 570
(2007/10/02)
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- Regioselective Acylation of 1,4:3,6-Dianhydro-D-glucitol
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Acylation of 1,4:3,6-dianhydro-D-glucitol with anhydrides in the presence of heavy metal salts affords 5-endo-acylates with high regioselectivity, without detectable amounts of the isomeric 2-acylates.Acyl group migration occurs with preference for the 2-exo-position, on heating an acylation mixture, which contains varying amounts of 1,4:3,6-dianhydro-D-glucitol, 2- and 5-monoacylate and 2,5-diacylate, in the presence of reesterification catalysts and whilst distilling off the lower boiling 2-acylate.
- Stoss, Peter,Merrath, Peter,Schlueter, Guenther
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p. 174 - 176
(2007/10/02)
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- Process for the preparation of isosorbide-5-nitrate
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In a process for preparing isosorbide-5-nitrate, isosorbide is reacted with an aliphatic carboxylic acid, with the formation of an acylation mixture. The acylation mixture is then nitrated, and the resulting nitration mixture is hydrolyzed and/or transesterified in order to split off acyl groups. The product is used in treatment of angina pectoris.
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- Process for the production of isosorbide-5-nitrate
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This invention relates to a process for the production of isosorbide-5-nitrate comprising (a) subjecting an acylation mixture of isosorbide containing varying proportions of isosorbide, isosorbide-2-acylate, isosorbide-5-acylate and/or isosorbide-2,5-diacylate, or pure isosorbide-5-acylate or an equimolar mixture of isosorbide-2,5-diacylate and isosorbide to a transacylation reaction in the presence of a catalyst and removing the isosorbide-2-acylate present from the reaction mixture by fractional distillation; (b) optionally subjecting the separated isosorbide-2-acylate to a further purification step; (c) esterifying the obtained isosorbide-2-acylate with nitric acid; and (d) partially hydrolyzing the obtained isosorbide-2-acylate-5-nitrate.
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