- Sequential hydroaminomethylation/Pd-catalyzed hydrogenolysis as an atom efficient route to valuable primary and secondary amines
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The facile synthesis of valuable primary and secondary amines is reported using a sequential procedure of hydroaminomethylation and Pd-catalyzed hydrogenolysis. The hydroaminomethylation reaction was catalyzed by a cationic Rh(I) iminopyridyl complex and the N-alkylated benzylamines were produced with high chemoselectivity, albeit as mixtures of linear and branched products. Performing the hydrogenolysis reaction using 10% Pd/C, provided access to valuable primary and secondary amines which have applications in the surfactant, pharmaceutical and polymer industries.
- October, Jacquin,Mapolie, Selwyn F.
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supporting information
(2021/04/12)
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- METHOD FOR PRODUCING HEXAMETHYLENE DIAMINE
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To provide a method for producing hexamethylene diamine from 1,6-hexanediol and ammonia, under easy-to-control mild conditions.SOLUTION: A method for producing hexamethylene diamine includes reacting 1,6-hexanediol with ammonia in the presence of a solvent by means of a noble metal-supporting catalyst.SELECTED DRAWING: None
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Paragraph 0033-0055
(2021/02/13)
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- Method for preparing aliphatic amine compound
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The invention discloses a method for preparing an aliphatic amine compound, comprising the following steps: using furfuryl amine or a furfuryl amine derivative as a raw material, and carrying out hydrogenolysis in the presence of a supported metal catalyst to obtain the aliphatic amine compound. According to the method disclosed by the invention, the aliphatic amine compound is prepared by catalyzing hydrogenolysis of the biomass-based furfuryl amine and the derivative thereof for the first time. The catalyst has high activity and high product selectivity. According to the method, a biomass-based compound is used as a raw material to prepare the aliphatic amine compound, and the requirements of sustainable development and green chemistry are met. The aliphatic amine compound prepared by the method has high selectivity, and is convenient for separation and purification of products. After the reaction of the method is finished, the catalyst is easy to separate and can be recycled, so that the method has a good application prospect.
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Paragraph 0071-0073
(2020/05/14)
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- Synthesis method of 6-amino-1-hexanol
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The invention relates to a synthesis method of 6-amino-1-hexanol. The synthesis method comprises the following steps: adding toluene and caprolactam into a reaction vessel, stirring, adding alkali into the reaction vessel in the stirring process, cooling the reaction temperature to the room temperature to obtain a primary reaction solution; slowly dropwise adding a red aluminum solution into the primary reaction solution, heating to carry out a reaction after dropwise adding so as to obtain a secondary reaction solution; cooling the secondary reaction solution, dropwise adding a quenching solution, continuously stirring for 15 minutes after dropwise adding, adding diatomite into the reaction vessel, stirring, filtering, carrying out reduced pressure distillation on the filtrate, and collecting fractions, thereby obtaining 6-amino-1-hexanol. The method has the advantages that the 6-amino-1-hexanol is synthesized from caprolactam by using red aluminum as a reducing agent, compared with existing rhodium and silver catalysts, the catalyst has the characteristics of short reaction time, mild conditions, low cost, simple process and the like, the maximal yield can reach 87%, and large-scale production is easy to realize.
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Paragraph 0021-0056
(2020/09/30)
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- Synthetic method 6-amino-1-hexanol
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The invention discloses a synthetic method 6-amino-1-hexanol. According to the synthetic method 6-amino-1-hexanol, chlorosulphonyl isocyanate and 1, 6-hexanediol are taken as main raw materials, one-pot method is adopted to synthesize 6-amino-1-hexanol. The synthesis route comprises following steps: 1, under the catalyst effect of a tertiary amine, chlorosulphonyl isocyanate and a primary alcoholare reacted to generate a Burgess reagent, 1, 6-hexanediol is added to generate an intermediate 6-hydroxyhexyl carbamic acid; and 2, the intermediate 6-hydroxyhexyl carbamic acid synthesized in step is subjected to projecting group removing directly without separation so as to obtain target product 6-amino-1-hexanol. The synthetic method is low in cost, simple in reaction conditions, few in reaction steps, short in time, and high in purity and yield of finished product 6-amino-1-hexanol.
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Paragraph 0031; 0033-0034; 0036
(2019/10/23)
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- Highly efficient nitrobenzene and alkyl/aryl azide reduction in stainless steel jars without catalyst addition
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The mechanochemical and selective reduction of aryl nitro and aryl/alkyl azide derivatives, with either formate salts or hydrazine, to the corresponding, synthetically useful amines occurs in excellent yields in a planetary ball mill without the addition of a catalyst. This newly developed and solvent-free protocol is efficient, fast and does not require the addition of a metal hydrogenation catalyst as the stainless steel jar itself fulfils that role. The method has been applied to a broad range of compounds and excellent yields have been obtained. The formylation of alkyl amines has been successfully performed, by means of mechanochemical activation, in the presence of ammonium formate alone.
- Martina, Katia,Baricco, Francesca,Tagliapietra, Silvia,Moran, Maria Jesus,Cravotto, Giancarlo,Cintas, Pedro
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supporting information
p. 18881 - 18888
(2018/11/26)
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- Ruthenium-Pincer-Catalyzed Hydrogenation of Lactams to Amino Alcohols
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By using the commercially available ruthenium pincer complex (Ru-MACHO-BH) as a catalyst, the challenging direct hydrogenation of lactams and analogues has been successfully accomplished to deliver corresponding value-added amino alcohols in good-to-excellent yields under mild reaction conditions. Remarkably, in addition to N-protected lactams, unprotected ones could also be readily reduced in the presence of a catalytic amount of weak base or even under neutral reaction conditions, which further highlights the broad substrate scope and the protocol efficiency.
- Chen, Jiangbo,Wang, Jiaquan,Tu, Tao
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supporting information
p. 2559 - 2565
(2018/07/30)
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- Tris(2-carboxyethyl)phosphine promotes hydrolysis of iminoboronates
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Iminoboronates are stable and formed fast. Their B[sbnd]N bonds could be reverted by some endogenous biological molecules. The reversible characteristic attracts significant attention in biological and chemical fields. Although synthesis of iminoboronates is well-studied, less efforts have been devoted to disconnecting the units. Here, a series of selected compounds were screened to evaluate their hydrolytic capability of iminoboronates by 1H NMR or 11B NMR detection. Tris(2-carboxyethyl)phosphine (TCEP), was emerged as an excellent reagent, which decomposed most iminoboronates in short time with high yields. In addition, TCEP is also able to hydrolyze hydrazones and oximes with moderate yields.
- Liu, Xiaoyu,Li, Zhihong,Xu, Hongtao,Zhan, Yuexiong,Ma, Peixiang,Chen, Hongli,Jiang, Biao
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p. 3101 - 3106
(2017/07/18)
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- Reductive amination of 1,6-hexanediol with Ru/Al2O3 catalyst in supercritical ammonia
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Hexamethylenediamine (HMDA) is an important reagent for the synthesis of Nylon-6,6, and it is usually produced by the hydrogenation of adiponitrile using a toxic reagent of hydrocyanic acid. Herein, we developed an environmental friendly route to produce HMDA via catalytic reductive amination of 1,6-hexanediol (HDO) in the presence of hydrogen. The activities of several heterogeneous metal catalysts such as supported Ni, Co, Ru, Pt, Pd catalysts were screened for the present reaction in supercritical ammonia without any additives. Among the catalysts examined, Ru/Al2O3 presented a high catalytic activity and highest selectivity for the desired product of HMDA. The high performance of Ru/Al2O3 was discussed based on the Ru dispersion and the surface properties like the acid-basicity. In addition, the reaction parameters such as reaction temperature, time, H2 and NH3 pressure were examined, and the reaction processes were discussed in detail.
- Li, Yan,Cheng, Haiyang,Zhang, Chao,Zhang, Bin,Liu, Tong,Wu, Qifan,Su, Xinluona,Lin, Weiwei,Zhao, Fengyu
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p. 920 - 926
(2017/07/05)
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- Direct Hydrogenation of a Broad Range of Amides under Base-free Conditions using an Efficient and Selective Ruthenium(II) Pincer Catalyst
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The ruthenium(II) complex, [fac-PNHN]RuH(η1-BH4)(CO) (B; PNHN=8-(2-diphenylphosphinoethyl)aminotrihydroquinoline), is a highly versatile and effective catalyst (loadings of 0.1–1 mol %) for the hydrogenation of a multitude of amides, which include primary, secondary, and tertiary amides, to give their corresponding alcohols and amines in high yields under base-free conditions. All products were confirmed by using GC and GC–MS.
- Wang, Zheng,Li, Yong,Liu, Qing-Bin,Solan, Gregory A.,Ma, Yanping,Sun, Wen-Hua
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p. 4275 - 4281
(2017/12/02)
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- METHOD FOR PRODUCING ALKANOL AMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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PROBLEM TO BE SOLVED: To provide a method for producing alkanol amines by alcohol amination of diols using ammonia under elimination of water. SOLUTION: The invention relates to a method for producing alkanol amines which comprise a primary amino group (-NH2) and a hydroxyl group (-OH), by alcohol amination of diols comprising two hydroxyl groups (-OH) using ammonia under elimination of water. The reaction is homogeneously catalyzed in the presence of at least one complex catalyst which contains at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0088; 0103
(2016/10/27)
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- The preparation obtained by homogeneous catalysis mellow amination method of the primary amine
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The invention relates to a method for producing primary amines comprising at least one functional group of formula (-CH2-NH2), by alcohol amination of educts which comprise at least one functional group of formula (-CH2-OH), using ammonia, and elimination of water. The homogeneously catalyzed alcohol amination is carried out in the presence of at least one complex catalyst which contains at least one element selected from the groups 8 and 9 of the periodic table and at least one phosphorus donor ligand of general formula (I).
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Paragraph 0207-0208; 0214
(2017/02/28)
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- Method for preparing 6-amino-1-hexanol by ultrasonic wave liquid phase reduction
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The invention provides a method for preparing 6-amino-1-hexanol by ultrasonic wave liquid phase reduction. The method concretely comprises the following steps that (1) through being metered by volume ratio, one part of 6-aminocaproic acid is added into a reaction vessel containing 10 to 15 parts of solvents; under the constant-temperature stirring condition, 2 to 4 parts of sodium borohydride solution is fast injected; ultrasonic wave treatment is performed; then, 5 to 8 parts of ethylene glycol solution is dripped under the backflow condition; constant-temperature stirring reaction is performed to obtain a reaction coarse product; (2) the reaction coarse product prepared in the first step is added into water for hydrolysis; reduced pressure distillation is performed; 125 to 128 DEG C distillation is collected, and 6-amino-1-hexanol products are obtained. The 6-amino-1-hexanol prepared by the method is based on the original synthesis process; a strong reducing agent and a weak reducing agent are selected and combined, 6-aminocaproic acid is subjected to reduction hydrogenization to obtain products through preparation. The preparation method is simple; an ultrasonic technology is combined with liquid phase immersion, so that the reduction efficiency is high; the environment protection is combined with the economic performance; the method can be used for industrial popularization and use.
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Paragraph 0038; 0039; 0040
(2016/10/09)
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- Ligand, metal complex containing ligand, and reaction using metal complex containing ligand
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A hydrogen transfer reaction may be more efficiently promoted by using a metal complex represented by Formula (2): (wherein, R1 to R8 are the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group or the like; or wherein; R1 and R2, R2 and R3, R3 and R4, R4 and R5, and R5 and R6 are respectively bonded to each other to form a bivalent hydrocarbon group; R9 are the same or different, and each represents an alkyl group or cycloalkyl group; M is ruthenium (Ru) or the like; X is a ligand; and n is 0, 1 or 2). More specifically, the metal complex enables a hydrogenation reaction of various substrates having a stable carbonyl group or the like to be advanced with a high yield under mild conditions.
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Page/Page column 46-50
(2016/10/31)
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- Preparation method of 6-amino-1-hexanol by taking calcium carbonate as catalyst
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The invention discloses a preparation method of 6-amino-1-hexanol by taking calcium carbonate as a catalyst. Calcium carbonate serves as the catalyst of a reaction, 1,6-hexanediol, ammonia and hydrogen are mixed and react for 1.5-2 h in a heated and pressurized mode on the condition that the temperature ranges from 270 DEG C to 290 DEG C, and the pressure ranges from 150 Mpa to 180 Mpa, and 6-amino-1-hexanol is generated. According to the preparation method, calcium carbonate serves as the catalyst, the raw materials are easy to obtain, the cost is low, the catalytic efficiency is high, and the catalytic effect is stable; the finished product 6-amino-1-hexanol is high in purity and high in yield, the high economic benefit is achieved, and the preparation method can be widely applied and promoted.
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Paragraph 0029; 0035-0043
(2017/03/17)
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- CATALYSTS AND PROCESSES FOR THE HYDROGENATION OF AMIDES
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There is provided a process for the reduction of one or more amide moieties in a compound comprising contacting the compound with hydrogen gas and a transition metal catalyst in the presence or absence of a base under conditions for the reduction an amide bond. The presently described processes can be performed at low catalyst loading using relatively mild temperature and pressures, and optionally, in the presence or absence of a base or high catalyst loadings using low temperatures and pressures and high loadings of base to effect dynamic kinetic resolution of achiral amides.
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Paragraph 0252; 0253
(2014/06/24)
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- Hydrogenation of amides catalyzed by a combined catalytic system of a Ru complex with a zinc salt
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Addition of catalytic amounts of zinc salts facilitated the hydrogenation of amides catalyzed by a ruthenium complex bearing 2-(diphenylphosphino) ethanamine (L1). The combined catalytic system of the ruthenium complex [RuCl2(L1)2] with a zinc salt such as Zn(OCOCF 3)2 mediated hydrogenation of various amides under mild conditions to afford the corresponding primary alcohols.
- Kita, Yusuke,Higuchi, Takafumi,Mashima, Kazushi
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supporting information
p. 11211 - 11213
(2014/09/30)
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- PROTECTED LINKER COMPOUNDS
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The invention features protected linker compounds which comprise at one terminus a protected amino group and at another other terminus a phosphorous activating group, such as a phosphoramidite group. These protected linker compounds are introduced chemically at the 5'-end of oligonucleotides for the purpose of preparing 5'-amino modified oligonucleotides. After deprotection, the thereby introduced amino group then allows further modification (e.g. attachment of dyes) or immobilization (on surfaces or beads) of the oligonucleotide. Specifically, the presented amino protecting group is designed to provide such protected linker compounds in a solid form, which facilitates efficient purification by precipitation or crystallization and aliquoting for distribution and storage.
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Page/Page column 31; 33
(2013/07/05)
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- Direct deamination of primary amines by water to produce alcohols
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Just add water! The title reaction is catalyzed by an acridine-based pincer complex (1, see scheme). This one-step transformation uses water as the only reagent in the absence of additional bases, oxidants, or reductants. Cyclization of 1,4-diaminobutane and 1,6-diaminohexane catalyzed by 1 leads to the formation of pyrrolidine and azepane, respectively. Copyright
- Khusnutdinova, Julia R.,Ben-David, Yehoshoa,Milstein, David
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supporting information
p. 6269 - 6272
(2013/07/19)
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- Catalytic hydrogenation of unactivated amides enabled by hydrogenation of catalyst precursor
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A general method for catalytic hydrogenation of unactivated amides was achieved. During the catalyst induction period, a novel structural change was observed involving full hydrogenation of the interior unsaturated bonds of the pyridines of the Ru-containing catalyst precursor. Based on this observation, the mechanism of amide hydrogenation may involve a two-step pathway, wherein the Ru catalyst having an H-Ru-N-H functionality is generated in the first step, followed by the amide carbonyl group interacting with the outer, rather than the inner, sphere of the Ru catalyst.
- Miura, Takashi,Held, Ingmar E.,Oishi, Shunsuke,Naruto, Masayuki,Saito, Susumu
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supporting information
p. 2674 - 2678
(2013/06/26)
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- PROCESS FOR PREPARING ALKANOLAMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Process for preparing alkanolamines which have a primary amino group (—NH2) and a hydroxyl group (—OH) by alcohol amination of diols having two hydroxyl groups (—OH) by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.
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Page/Page column 13-14; 19
(2012/09/22)
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- PROCESS FOR THE PREPARATION OF PRIMARY AMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Process for the preparation of primary amines which have at least one functional group of the formula (—CH2—NH2) by alcohol amination of starting materials which have at least one functional group of the formula (—CH2—OH), with ammonia, with the elimination of water, where the alcohol amination is carried out under homogeneous catalysis in the presence of at least one complex catalyst which comprises at least one element selected from groups 8 and 9 of the Periodic Table of the Elements, and also at least one phosphorus donor ligand of the general formula (I).
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Page/Page column 10; 12
(2012/09/22)
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- PROCESS FOR PREPARING DI-, TRI- AND POLYAMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Process for preparing primary amines which have at least one functional group of the formula (—CH2—NH2) and at least one further primary amino group by alcohol amination of starting materials having at least one functional group of the formula (—CH2—OH) and at least one further functional group (—X), where (—X) is selected from among hydroxyl groups and primary amino groups, by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.
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Page/Page column 12; 16
(2012/09/22)
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- Photorelease of primary aliphatic and aromatic amines by visible-light-induced electron transfer
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Visible-light-absorbing tris(bipyridyl)ruthenium(II) has been used to mediate electron transfer to N-methylpicolinium carbamates that undergo C-O bond fragmentation followed by spontaneous carbon dioxide release to give free amines. Release of several aliphatic and aromatic primary amines has been demonstrated under mild conditions using visible light.
- Edson, Joseph B.,Spencer, Liam P.,Boncella, James M.
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supporting information; experimental part
p. 6156 - 6159
(2012/01/05)
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- A highly active catalyst for the hydrogenation of amides to alcohols and amines
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Amide-zing: The reaction between 2 equivalents of Ph2P(CH 2)2NH2 and cis-[Ru(CH3CN) 2(η3-C3H5)(cod)]BF4 (cod=1,5-cyclooctadiene) forms a highly active catalyst precursor for the selective hydrogenation of amides. The reaction proceeds with excellent atom economy, yield, and turnover numbers (TONs) under moderate reaction conditions. The technology offers a greener, practical approach to the use of metal hydride reagents commonly employed in both academia and industry. Copyright
- John, Jeremy M.,Bergens, Steven H.
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supporting information; experimental part
p. 10377 - 10380
(2011/12/04)
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- Synthesis and biological activity of dialkylphosphocholines
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A series of dialkylphosphocholines were prepared and evaluated for their biological activity. The antiprotozoal activity was determined against Acanthamoeba lugdunensis. Compound 15 exhibited excellent trophocidal activity. None of the tested dialkylphosphocholines exhibited better fungicidal activity against Candida albicans than miltefosine. The antineoplastic activity was determined against HeLa. The most cytotoxic was compound 10, which was more active against tumor cells as against normal cells.
- Lukac, Milos,Mrva, Martin,Fischer-Fodor, Eva,Lacko, Ivan,Bukovsky, Marian,Miklasova, Natalia,Ondriska, Frantisek,Devinsky, Ferdinand
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scheme or table
p. 6346 - 6349
(2010/06/11)
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- Selective cleavage of O-(dimethoxytrityl) protecting group with sodium periodate
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Sodium periodate in aqueous organic solvents selectively removes, under mild reaction conditions, the O-(dimethoxytrityl) protecting group. Selectivity of the cleavage was studied using the nucleoside derivatives protected by various types of groups commonly used in nucleoside and nucleotide chemistry.
- Rejman, Dominik,Kralikova, Sarka,Tocik, Zdenek,Liboska, Radek,Rosenberg, Ivan
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p. 502 - 508
(2007/10/03)
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- The Reactions of Amine, Polyamine and Amino Alcohol Corrosion Inhibitors in Water at High Temperatures
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A stainless steel reactor has been used to investigate the reactions of mono-, di-, tri- and tetraamines, amino alcohols and amino ethers in degassed aqueous solution at 240-300 deg C.The predominant reactions involved nucleophilic substitutions, where the amino nitrogen acts as the nucleophile, and not solvolyses.With α,ω-diamines, cyclic and bicyclic amines were formed by inter- or intra-molecular processes.Amino alcohols react by displacement of the hydroxy rather than the amino group.The material balance deficit, however, was generally significant, and it issuggested that the missing materials are polyamines arising from polymerisation that competes with cyclisation.The major product from 1,2-diaminoethane and related polyaminoethanes and ethanolamines is diazabicyclooctane.The kinetics of some of the cyclisations were studied.Reactions of α,ω-diamines and 5-aminopentan-1-ol are first order in reactant.Conversion of 1,4-diaminobutane to pyrrolidine occurs with high selectivity at 240 deg C; in contrast the reactions of the less reactive compounds were less selective, probably due to the formation of polymeric materials.The relative reactivity of the substrates is discussed in detail.
- Smith, John R. Lindsay,Smart, Alison U.,Twigg, Martyn V.
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p. 939 - 947
(2007/10/02)
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