cas 42711-75-1, 3-Hydroxyadamantane-1-carboxylic acid

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An Efficient and Practical Method for the Synthesis of Saxagliptin Intermediate 2-(3-Hydroxy-1-adamantane)-2-oxoacetic Acid and Its Optimization
A mild and relatively simple way for preparation of 2-(3-hydroxy-1-adamantane)-2-oxoacetic acid (I) was reported. It was prepared from 1-adamantanecarboxylic acid (II) via sulfuric acid/nitric acid to get 3-hydroxy-1-adamantanecarboxylic acid (III); treated with the one-pot method through acylation, condensation, and decarboxylation to obtain 3-hydroxy-1-acetyladamantane (IV); and finally oxidized by potassium permanganate (KMnO4) to get the target compound (I). The overall yield was about 60%, which provides a new idea for commercial production of saxagliptin intermediate.
Liao, Qi,Jiang, Lan,Li, Cong,Shen, Yaling,Wang, Min,Cao, Chengkun,Hu, Xiangnan
(2019)
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Method for preparing non-natural amino acid
The invention relates to a preparation and chiral resolution method for unnatural amino acids. The method comprises the following steps: with adamantanecarboxylic acid as a raw material, preparing 3-hydroxy-adamantanecarboxylic acid; carrying out chlorination, oxidation and the like so as to obtain 2-(3-hydroxy-1-adamantyl)glyoxalic acid; reacting 2-(3-hydroxy-1-adamantyl)glyoxalic acid with hydroxylamine hydrochloride so as to obtain 3-hydroxyadamantyl-glyoxalic acid oxime; carrying out reduction with a reducing agent and protection with Boc acid anhydride so as to obtain N-tertbutyloxycarbonyl-3-hydroxyadamantylglycine; and carrying out resolution with organic base so as to obtain two unnatural amino acids, i.e., (S)-N-tertbutyloxycarbonyl-3-hydroxyadamantylglycine and (R)-N-tertbutyloxycarbonyl-3-hydroxyadamantylglycine. Compared with the prior art, the method provided by the invention has the following advantages: improved synthesis technology; mild reaction conditions; small environmental pollution; and applicability to industrial production.
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Paragraph 0056-0058

(2020/09/18)

ADAMANTANYL-SUBSTITUTED BENZAMIDE COMPOUNDS AND THEIR USE AS P2X7 RECEPTOR ANTAGONISTS
The present invention relates to adamantanyl-substituted benzamide compounds and their use as antagonists of the P2X7 purinoreceptor. The invention further relates to methods for the treatment of disease and conditions associated with the P2X7 purinoreceptor.
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Page/Page column 20

(2020/03/15)

Synthesis method of 3-hydroxy-1-adamantanecarboxylic acid
The invention discloses a synthetic method of 3-hydroxy-1-adamantanecarboxylic acid, which comprises the following steps: step 1, mixing and dispersing 1-adamantanecarboxylic acid and sulfuric acid toobtain a mixture, wherein the mass ratio of 1-adamantanecarboxylic acid to sulfuric acid is 1: 4-8; step 2, pumping the mixture obtained in the step 1 into a thin-tube reactor, and pumping a first batch of nitric acid to be mixed with the mixture, wherein the molar ratio of 1-adamantanecarboxylic acid in the mixture to nitric acid is 1: (0.85-0.95), and the reaction temperature is 50-60 DEG C; step 3, after a time period of t of pumping the mixture in the step 2, a second batch of nitric acid is pumped in the position 3/4 of the total length of the thin-tube reactor, wherein the molar ratio of 1-adamantanecarboxylic acid to the newly pumped nitric acid in the mixture in the step 2 is 1: 0.25-0.45, and the reaction temperature is 70-80 DEG C; and step 4, hydrolyzing, separating and purifying to obtain the 3-hydroxy-1-adamantanecarboxylic acid. The nitration reaction is carried out in two stages, the consumption of nitric acid and sulfuric acid is greatly reduced, the treatment amount of waste acid after the reaction is reduced, the impurity content of the reaction product is low, and separation and purification are easy.
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Paragraph 0022-0030

(2020/07/14)

Synthesis method of 3-hydroxy-1-adamantanecarboxylic acid
The invention belongs to the field of organic synthesis and particularly relates to a synthesis method of 3-hydroxy-1-adamantanecarboxylic acid. In the method, with 1-adamantanecarboxylic acid being araw material and triethyl benzyl ammonium chloride (TEBAC) being a phase transfer catalyst, the 3-hydroxy-1-adamantanecarboxylic acid is prepared under alkaline conditions through hydroxylation withKMnO4. The new preparation method not only is reduced in cost and protects environment, but also is simple in operation and convenient in post-treatment. The method is high in yield, is simple in synthesis and is suitable for industrial production.
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Paragraph 0011; 0012

(2019/05/15)

Azido-Adamantyl Tin Sulfide Clusters for Bioconjugation
We present a new versatile route toward biomolecule-functionalized tin sulfide clusters. A novel bifunctional orthogonal spacer was developed and used for the formation of a trifold azido-adamantyl-terminated cluster, serving as a building block for click reactions. The azido cluster was quantitatively bioconjugated via a strain-promoted 1,3-dipolar cycloaddition, affording a peptide-decorated cluster.
Berndt, Jan-Philipp,Engel, Annikka,Hrdina, Radim,Dehnen, Stefanie,Schreiner, Peter R.
supporting information
p. 329 - 335
(2019/02/01)

Aniline-Based Inhibitors of Influenza H1N1 Virus Acting on Hemagglutinin-Mediated Fusion
Two series of easily accessible anilines were identified as inhibitors of influenza A virus subtype H1N1, and extensive chemical synthesis and analysis of the structure-activity relationship were performed. The compounds were shown to interfere with low pH-induced membrane fusion mediated by the H1 and H5 (group 1) hemagglutinin (HA) subtypes. A combination of virus resistance, HA interaction, and molecular dynamics simulation studies elucidated the binding site of these aniline-based influenza fusion inhibitors, which significantly overlaps with the pocket occupied by some H3 HA-specific inhibitors, indicating the high relevance of this cavity for drug design.
Leiva, Rosana,Barniol-Xicota, Marta,Codony, Sandra,Ginex, Tiziana,Vanderlinden, Evelien,Montes, Marta,Caffrey, Michael,Luque, F. Javier,Naesens, Lieve,Vázquez, Santiago
supporting information
p. 98 - 118
(2018/02/10)

Synthesis of (3-Hydroxyadamantan-1-yl)methanols
A convenient procedure has been developed for the synthesis of (3-hydroxyadamantan-1-yl)-methanols on the basis of nitroxylation of adamantan-1-ylmethanols with fuming nitring acid and subsequent reduction of intermediate nitric acid esters with hydrazine hydrate. The title diols have also been obtained by the reduction of 1-nitroxy-3-(nitroxymethyl)adamantanes. The nitroxylation process is accompanied by oxidation with the formation of substituted adamantane-1-carboxylic acids.
Ivleva,Pogulyaiko,Klimochkin, Yu. N.
p. 1294 - 1300
(2018/11/21)

One-pot synthesis of cage alcohols
An efficient one-pot procedure has been developed for the synthesis of cage alcohols with hydroxy groups in the bridgehead positions. The procedure includes initial nitroxylation with nitric acid or a mixture of nitric acid with acetic acid and subsequent hydrolysis in the presence of urea.
Klimochkin, Yu. N.,Yudashkin,Zhilkina,Ivleva,Moiseev,Oshis, Ya. F.
p. 971 - 976
(2017/09/07)

Alkane oxidation catalysed by a self-folded multi-iron complex
A preorganised ligand scaffold is capable of coordinating multiple Fe(II) centres to form an electrophilic CH oxidation catalyst. This catalyst oxidises unactivated hydrocarbons including simple, linear alkanes under mild conditions in good yields with selectivity for the oxidation of secondary CH bonds. Control complexes containing a single metal centre are incapable of oxidising unstrained linear hydrocarbons, indicating that participation of multiple centres aids the CH oxidation of challenging substrates.
Mettry, Magi,Moehlig, Melissa Padilla,Gill, Adam D.,Hooley, Richard J.
p. 120 - 128
(2016/11/09)

MANUFACTURING METHOD OF HYDROXY ADAMANTANE CARBOXYLIC ACID COMPOUND
PROBLEM TO BE SOLVED: To provide a method for easier manufacturing a hydroxy adamantane carboxylic acid at higher yield. SOLUTION: There is provided a manufacturing method of 3-hydroxy adamantane-1-carboxylic acid represented by the formula (2) including Process 1: adamantanol represented by the formula (1) and carbon monoxide or a carbon monoxide source are mixed in a sulphuric acid solution with concentration of 90 mass% or more and Process 2:nitrate is added to the resulting solution. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0043-0045

(2017/03/28)

An improved synthetic method of Saxagliptin intermediate 3-hydroxy-1-acetyladamantane and its characterization
An improved method with high yield and simple steps for the synthesis of 3-hydroxy-1-acetyladamantane was reported. 3-Hydroxy-1-acetyladamantane is an important intermediate of Saxagliptin for type 2 diabetes mellitus (T2DM). Its synthetic method started from 1-adamantanecarboxylic acid via oxidation by sulfuric acid/nitric acid, then VHA reagent (SOCl2/DMF) and sodium diethyl malonate were used in one-pot through acylation, substitution, decarboxylation and alkalization to give the target compound. It is an improved method that VHA reagent (SOCl2/DMF) was used in the step of acylation which effectively enhanced the total yield up to 74%, and the operations were effectually simplified by the one-pot method. The synthesized target compound has been characterized by single-crystal X-ray diffraction. The single-crystal X-ray diffraction analysis demonstrates that the target compound has extensive intermolecular hydrogen bondings involving the hydroxyl and acetyl groups in the solid state and the structure of the target compound was proved as 3-hydroxy-1-acetyladamantane.
Gan, Run,Zhou, Jing,Li, Jie,Zhang, Ming,Jiang, Xue,Hu, Xiangnan
p. 514 - 518
(2016/11/19)

A facile and economic method for the synthesis of (S)-N-Boc-3′-hydroxyadamantylglycine
(S)-N-Boc-3′-hydroxyadamantylglycine (I) is an important intermediate of saxagliptin for type 2 diabetes mellitus (T2DM). It was prepared from 1-adamantanecarboxylic acid(1) via mild reaction with sulfuric acid/nitric acid, VHA reagent (SOCl2/DMF) and sodium diethyl malonate, then was treated with hydrolysis, decarboxylation, alkalization and oxidation to give 2-(3-hydroxy-1-adamantyl)-2-oxoacetic acid (4), then through oximation, reduction and (Boc)2O protection to give the N-Boc-3′-hydroxyadamantylglycine(6), then was treated with quinidine to get (S)- N-Boc-3′-hydroxyadamantylglycine(I) and quinine to get (R)–N-Boc-3′-hydroxyadamantylglycine(II). Finally, Compound II was racemized by dicyclohexylcarbodiimide (DCC) and sodium?hydride (NaH) to afford compound 6. In this route, the overall yield of preparing compound I was about 35?% and the enantiomeric excess (ee) reach to 99?%. This route provided a novel idea for the preparation of (S)-N-Boc-3′-hydroxyadamantylglycine.
Li, Jie,Jiang, Xue,Gan, Run,Zhang, Ming,Pan, Xinmei,Hu, Xiangnan
p. 5709 - 5721
(2016/06/01)

Process for producing hydroxy adamantane carboxylic acid compounds
The present invention can provide a process for producing a hydroxy adamantane carboxylic acid compound represented by the above formula (2), which comprises (i) reacting an adamantane compound represented by the above formula (1) with carbon monoxide or with a carbon monoxide source in a proton acid solution prepared at a concentration of 90% by mass or more to thereby cause carboxylation of the OX group(s), and then (ii) adding an oxidizing agent to the reaction mixture to cause oxidation of the bridgehead C—H bond to thereby generate a hydroxyl group.
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(2015/06/16)

PROCESS FOR THE PREPARATION OF SAXAGLIPTIN AND ITS INTERMEDIATES
The present invention provides intermediates of saxagliptin and processes for their preparation. The present invention also provides a process for the preparation of saxagliptin or salts or hydrates thereof by using the intermediates.
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Page/Page column 18; 19

(2015/06/25)

A manufacturing method of a carboxylic acids and polyadamantane hydroxyacid purification method
PROBLEM TO BE SOLVED: To provide an efficient manufacturing method of hydroxy adamantane carboxylic acids that have an adamantane skeleton, and that are the raw materials of a functional resin excellent in an optical characteristic and heat resistance or the like. SOLUTION: The manufacturing method of hydroxy adamantane carboxylic acids comprises as follows. Adamantane diols shown by general formula (1) is made to react with at most two equivalents of a carbon monoxide source based on one equivalent of a hydroxyl group of the adamantane diols in a liquid state protonic acid solvent, and then the crystal of hydroxy adamantane carboxylic acid shown by general formula (2) is filtered to be separated. COPYRIGHT: (C)2013,JPOandINPIT
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Paragraph 0032; 0033; 0036

(2017/01/02)

Selective hydroxylation of adamantane and its derivatives
A general method was developed for hydroxylation into the nodal position of adamantane and its 1- and 2-substituted derivatives employing systems H 2O-CBr4 (BrCCl3, CCl4) in the presence of complexes of Pd, Ni, Ru, Co, Mo, W, and Fe. The oxidants in the systems are hypochlorous (HOCl) or hypobromous (HOBr) acids generated from water and halomethanes under the reaction conditions.
Khusnutdinov,Shchadneva,Mukhametshina,Dzhemilev
scheme or table
p. 1137 - 1142
(2009/12/03)

γ-aminoadamantanecarboxylic acids through direct C-H bond amidations
Utilizing bromine-free, direct C-H bond amidations we have synthesized a large variety of adamantane amides. Depending on the precursors used these amides directly yield pharmaceutically active aminoadamantanes or γ-aminoadamantanecarboxylic acids after hydrolytic cleavage. These rigid analogues of γ-aminobutyric acid (GABA) were protected at the C- and N-termini and we synthesized a number of peptides incorporating γ-aminoadamantanecarboxylic acids in solution as well as via solid phase peptide synthesis. These peptides are promising scaffolds for applications in medicinal chemistry as well as in organocatalysis. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Wanka, Lukas,Cabrelle, Chiara,Vanejews, Maksims,Schreiner, Peter R.
p. 1474 - 1490
(2008/09/19)

Investigation of the gas phase reactivity of the 1-adamantyl radical using a distonic radical anion approach
The gas phase reactions of the bridgehead 3-carboxylato-1-adamantyl radical anion were observed with a series of neutral reagents using a modified electrospray ionisation linear ion trap mass spectrometer. This distonic radical anion was observed to undergo processes suggestive of radical reactivity including radical-radical combination reactions, substitution reactions and addition to carbon-carbon double bonds. The rate constants for reactions of the 3-carboxylato-1-adamantyl radical anion with the following reagents were measured (in units 10-12 cm3 molecule-1 s -1): 18O2 (85 ± 4), NO (38.4 ± 0.4), I2 (50 ± 50), Br2 (8 ± 2), CH 3SSCH3 (12 ± 2), styrene (1.20 ± 0.03), CHCl3 (H abstraction 0.41 ± 0.06, Cl abstraction 0.65 ± 0.1), CDCl3 (D abstraction 0.035 ± 0.01, Cl abstraction 0.723 ± 0.005), allyl bromide (Br abstraction 0.53 ± 0.04, allylation 0.25 ± 0.01). Collision rates were calculated and reaction efficiencies are also reported. This study represents the first quantitative measurement of the gas phase reactivity of a bridgehead radical and suggests that distonic radical anions are good models for the study of their elusive uncharged analogues. The Royal Society of Chemistry.
Harman, David G.,Blanksby, Stephen J.
p. 3495 - 3503
(2008/09/20)

NEW ADAMANTANE DERIVATIVES AS DIPEPTIDYL, PEPTIDASE IV INHIBITORS, PROCESSES FOR THEIR PREPARATION, AND PHARMACEUTICAL COMPOSITIONS CONTAINING THEM
The present invention relates to dipeptidyl peptidase IV (DPP-IV) inhibitors of the formula (A): wherein R1, R2, Y, and n are as defined herein, pharmaceutical compositions containing the same, processes for their preparation, and methods for treating disorders mediated by DPP-IV inhibition, such as diabetes, especially Type II diabetes, with them.
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Page/Page column 49-50

(2008/06/13)

Interaction between an amantadine analogue and the transmembrane portion of the influenza A M2 protein in liposomes probed by 1H NMR spectroscopy of the ligand
1H NMR spectroscopy of a fluoroamantadine ligand was used to probe the pH dependence of binding to the transmembrane peptide fragment of the influenza A M2 proton channel (M2TM) incorporated into 1,2-dimyristoyl-sn- glycero-3-phosphocholine liposomes. Above pH 7.5, when M2TM bound the ligand, fluoroamantadine resonances became too broad to be detected. Fluoroamantadine interacted weakly with the liposomes, indicating it may first bind to the bilayer and then block target channels after diffusion across the membrane surface.
Kolocouris, Antonios,Hansen, Raino K.,Broadhurst, R. William
p. 4975 - 4978
(2007/10/03)

Adamantanemethanol derivatives and production processes thereof
An adamantanemethanol derivative of the invention is represented by the following formula (1), wherein Rais a hydrogen atom or a hydrocarbon group; Rbis a hydrocarbon group having a carbon atom, to which carbon atom at least one hydrogen atom is bonded, at a bonding site with the adjacent carbon atom; Rc, Rdand Reare each a hydrogen atom, a hydroxyl group which may be protected by a protective group or the like; provided that a hydroxyl group protected by a protective group or the like is bonded to at least one carbon atom constituting the adamantane skeleton when Rais a hydrogen atom or a methyl group and Rbis a methyl group; and at least one substituent, in addition to the HO—C(Ra)(Rb)— group indicated in the formula (1), is bonded to the adamantane ring when one of Raand Rbis a methyl group and the other is an ethyl group.
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Example 4

(2008/06/13)

ACID-SENSITIVE COMPOUND AND RESIN COMPOSITION FOR PHOTORESIST
The photoresist resin composition comprises a polymer containing an acid-responsive compound unit of the following formula (e.g. an adamantane skeleton) and a photoactive acid precursor. R1 may be an alkyl group having a tertiary carbon atom in the 1-position and the Z ring is a bridged-ring hydrocarbon ring comprising 2 to 4 rings. ???wherein R1 and R2 are the same or different from each other and each represents a hydrogen atom, an alkyl group or a cycloalkyl group; R3 represents a hydrogen atom or a methyl group; R4 represents a hydrogen atom, a halogen atom, an alkyl group, an oxygen-containing group, an amino group or an N-substituted amino group; the Z ring represents a monocyclic or polycyclic alicyclic hydrocarbon ring; n represents an integer of not less than 1; with proviso that R4 does not concurrently represent a hydrogen atom, and may be different over n occurrences; in formula (1), R1 and R2 may, jointly and together with the adjacent carbon atom, form an alicyclic hydrocarbon ring. The above photoresist resin composition is high in etching resistance, can be solubilized by irradiation, and is capable of providing a finer line pattern.
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(2008/06/13)

POLYMERIZABLE ADAMANTANE DERIVATIVES AND PROCESS FOR PRODUCING THE SAME
A compound shown by the following formula: ???wherein each of R1a, R2a, R3aand R4arepresents a substituent selected from a non-reactive atom, a non-reactive group, a hydroxyl group and an amino group, and at least two members selected from R1a, R2a, R3aand R4aare a hydroxyl group, a carboxyl group or an amino group; is subjected to an esterification reaction or an amidation reaction with a polymerizable unsaturated compound (e.g., an alcohol, a carboxylic acid, an amine) in the presence of a catalyst comprising an element selected from the Group 3 elements, such as a samarium compound, to obtain a polymerizable adamantane derivative having at least one polymerizable unsaturated group in high yield.
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(2008/06/13)

Linear Free Energy Relationship Studies of the Dimethyldioxirane C-H Bond Insertion Reaction
The relative rates of reaction of a series of p-substituted cumenes with dimethyldioxirane have been studied.The products are the corresponding cumyl alcohols.Treatment of the rate data with the Hammett substituent constants reveals that the insertion reaction is an electrophilic process with ρ = -2.76.Similar tretment of the data with the Brown-Okamoto substituent constants gives ρ+ = -1.61.The second-order rate constants for the reaction of a series of substituted adamantanes with dimethyldioxirane were also determined.Again, the products are the corresponding adamantanols.The rate constants were correlated with several types of substituent constants.The best correlations were obtained with the Taft ?* and ?I constants which gave ρ* = -1.08 and ρI = -2.39, respectively.Thus, the insertion reaction in this aliphatic system is also electrophilic.
Murray, Robert W.,Gu, Hong
p. 5673 - 5677
(2007/10/03)

FUNCTIONALIZATION OF CARBOXYLIC ACIDS OF THE ADAMANTANE AND BICYCLONONANE SERIES IN LIQUID BROMINE
Carboxylic acids of the adamantane and bicyclononane series react with nucleophilic reagents such as water or acetic acid in liquid bromine to give the corresponding hydroxy, acetoxy, and bromino derivatives.
Baklan, V. F.,Khil'chevskii, A. N.,Sologub, L. S.,Kukhar, V. P.
p. 1680 - 1683
(2007/10/02)

NOVEL SYNTHESIS OF 3-FLUORO-1-AMINOADAMANTANE AND SOME OF ITS DERIVATIVES
The title compound, 3-fluoro-1-aminoadamantane, isolated as the hydrochloride, has been synthesized in a three-step reaction sequence which is both convenient and rapid.Three derivatives of the amine, 3-fluoro-1-(N-adamantyl)-p-toluenesulfonamide, 3-fluoro-1-(N-adamantyl) benzamide, and 3-fluoro-1-methyl-(N-adamantyl) carbamate, have also been prepared.All compounds were characterized by usual methods.
Anderson, Gloria L.,Burks, Winifred A.,Harruna, Issifu I.
p. 1967 - 1974
(2007/10/02)

OXYGENDIFLUORIDE: A FLUORINATING AND OXYDATING AGENT IN ADAMANTAN CHEMISTRY
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Bolte, G.,Haas, A.
p. 502
(2007/10/02)

Oxy-Functionalization of Adamante-1-acetic Acid and Adamantane-1-carboxylic Acid by the Ferrous Iron-Molecular Oxygen System in Aqueous Solution
Oxygenation reactions of adamantanes with ferrous iron-molecular oxygen in phosphate buffer were investigated and the structures of the products were elucidated.In the reaction of adamantane-1-acetic acid (1a), five oxygenated products, the C(2)-oxo, C(4)-oxo, C(2),C(6)-dioxo, C(4)-ol, and C(3)-ol derivatives, were obtained.Similar oxygenation also occurred in the reaction of adamantane-1-carboxylic acid (2a) to give three products, the C(4)-oxo, C(4)-ol, and C(3)-ol derivatives.The oxy-functionalization of 1a and 2a in 0.5M phosphate buffer (pH 6.8) was found to occur almost quantitatively on addition of an appropriate amount of ferrous iron.
Miura, Toshiaki,Shibata, Kunihiko,Sawaya, Takuji,Kimura, Michiya
p. 67 - 73
(2007/10/02)

Herstellung und Solvolyse von 3-substituierten p-Toluolsulfonsaeure-(1-adamantyl)estern
Methods for the preparation of some hitherto unknown 3-substituted 1-adamantyl toluenesulfonates are evaluated.Their solvolysis products in dioxane/water 70:30 are reported.
Bielman, Rolf,Grob, Cyril A.,Schaub, Bruno
p. 1728 - 1733
(2007/10/02)