- Highly selective conversion of glyceric acid to 3-iodopropionic acid by hydriodic acid mediated hydrogenation
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Glycerol, generated in abundance as the by-product in the process of biodiesel production and saponification, has seen attempts to convert it into value-added chemicals. However, due to the low selectivity of hydrogenolysis of the secondary hydroxyl group, valuable 1,3-substituted chemicals are difficult to obtain from glycerol by chemocatalysis. In this work, glyceric acid (GA), a renewable biomass from glycerol, was quantitatively converted to 3-iodopropionic acid (3-IPA) at 373 K in 3 h by hydroiodic acid mediated hydrogenation. As the reductant in this process, HI is oxidized to I2 and then regenerated in situ by metal catalysts and H2. The reaction pathway was proposed by intermediate identification and verified by a kinetics study and computational method. The catalytic system was shown to be stable and can be reused several times without loss in activity. As a 1,3-substituted chemical, 3-IPA is not only a potential monomer to form poly-3-hydroxypropionic acid, but also a good platform molecule to produce useful chemicals, e.g. 3-hydroxypropionic acid (3-HPA) and acrylic acid (AA), due to its highly reactive nature.
- Li, Teng,Liu, Shengqin,Wang, Bing,Long, Jingen,Jiang, Jun,Jin, Ping,Fu, Yao,Yu, Haizhu,Yang, Weiran
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- Synthesis of saturated fatty acids 11C (13C)-labelled in the ω-methyl position
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A method for the preparation of saturated fatty acids 11C (13C)-labelled in the ω-methyl position is described. A highly reactive zerovalent copper complex was prepared from lithium naphtalenide reduced lithium(2-thienyl)iodocuprate. The labelling precursors were obtained by addition of tert-butyl ω-iodocarboxylates to the organocuprate and these were reacted with [11C]methyl iodide to form 11C-labelled, protected intermediates. The tert-butyl ester protecting group was rapidly removed with trifluoroacetic acid, affording fatty acids 11C-labelled in the ω-methyl position. A solid phase extraction method was developed and preceded final HPLC purification. In a typical run starting with 2.75 GBq of [11C]methyl iodide, 375 MBq (66%) [16-11C]palmitic acid was obtained within 46 min from the end of radionuclide production.
- Neu, Henrik,Kihlberg, Tor,Langstroem, Bengt
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- 1,8-naphthalimide-based light-controlled fluorescent molecular switch compound bonded with bis-spilenpyran unit and synthesis method and application of compound
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The invention provides a 1,8-naphthalimide-based light-controlled fluorescent molecular switch compound bonded with a bis-spilenpyran unit and a synthesis method and application of the compound. Firstly, bis-spiropyran is modified to a 1,8-naphthylimide molecule through a covalent bond, the compound shows a good photochromic effect and light-controlled two-color fluorescent molecular switch performance in an organic solvent and a solid medium, the fluorescence resonance energy transfer efficiency of the compound is greatly improved, and the thermodynamic stability and photosensitivity of the compound are also high. The 1,8-naphthalimide-based light-controlled fluorescent molecular switch compound bonded with the bis-spilenpyran unit and the synthesis method and application of the compoundcan be used in the field of ion detection and photochemical imaging of biological systems.
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Paragraph 0040; 0046; 0047
(2019/04/30)
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- Method for using glyceric acid to prepare 3-hydroxypropionic acid
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The invention provides a method for using glyceric acid to prepare 3-hydroxypropionic acid. The method comprises the following steps that in a wild reaction condition, hydroiodic acid and glyceric acid are used for generating 3-iodopropionic acid in water; then 3-iodopropionic acid is extracted by using an organic solvent; and finally, a basic catalyst is used for catalyzing and hydrolyze 3-iodopropionic acid to be 3-hydracrylic acid. The reactants used in the method are cheap and easy to obtain, and the sources are green; the reaction time is short, efficient and energy saving effects are achieved; the amount of by-products is less, the yield rate of the first-step product 3-iodopropionic acid can reach 99%, and the yield rate of the second-step product 3-hydracrylic acid can reach 99%. The first-step product is separated by using the extraction method, and the extraction method is directly used in a two-phase system hydrolysis reaction in the second step. The product selectivity in the method is high, post-treatment is easy, and the method is easy to industrialize. The reaction system is simple, the reaction cost is low, and the preparation method has very important application value.
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Paragraph 0015; 0019-0020; 0024-0037
(2018/08/28)
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- Method for using glyceric acid to prepare 3-iodopropionic acid
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The invention provides a method for using glyceric acid to prepare 3-iodopropionic acid. The method comprises the following steps that glyceric acid and HI are added into a high temperature and high pressure reaction still at the mole ratio of 0.001 to 100, other catalysts are not added or a certain amount of metal catalyst is added, the reaction still is sealed, the reaction atmosphere is hydrogen or inert gas, the temperature is risen to be 20-250 DEG C while stirring is conducted, the temperature is rapidly cooled to be the room temperature after the reaction is conducted for a period of time, extraction is conducted by using an organic solvent, separation is conducted, and 3-iodopropionic acid is obtained. The reaction raw material used in the preparation method are green and regenerative; and the amount of by-products is less, and the yield rate of the product 3-iodopropionic acid can reach 99%. The product can be separated by using an extraction method. The product selectivity inthe method is high, post-treatment is easy, and the method is easy to industrialize. The reaction system is simple, the reaction cost is low, and the preparation method has very important applicationvalue.
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Paragraph 0015; 0019-0020; 0024-0037
(2018/08/28)
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- A glyceric acid preparation of acrylic acid (by machine translation)
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The invention relates to a method for the preparation of acrylic acid from the glyceric acid, under mild reaction conditions in the first, in water, hydrogen iodic acid and glyceric acid generating 3 - iodoproptonic acid; then, extracting with an organic solvent 3 - iodoproptonic acid; finally, alkaline catalyst or Lewis acid catalyst catalytic 3 - iodoproptonic acid generating cancels out the reaction producing the acrylic. The reactant used in the present invention is cheap, source green; the reaction time is short, high-efficiency energy-saving; very few [...], 1st step product 3 - iodoproptonic acid productive rate can reach 99%, 2nd step product acrylic acid yield can be up to 99%. This method for the method of extraction separation 1st step product, and directly used for 2nd step two-phase system cancels out the reaction. This method high selectivity, after treatment is simple, easy industrialization; reaction system is simple, low in cost, has very important application value. (by machine translation)
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Paragraph 0020; 0021; 0031; 0033; 0035; 0037; 0039; 0041
(2019/01/07)
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- Catalytic formation of acrylate from carbon dioxide and ethene
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With regard to sustainability, carbon dioxide (CO2) is an attractive C1 building block. However, due to thermodynamic restrictions, reactions incorporating CO2 are relatively limited so far. One of the so-called "dream reactions" in this field is the catalytic oxidative coupling of CO2 and ethene and subsequent β-H elimination to form acrylic acid. This reaction has been studied intensely for decades. However up to this date no suitable catalytic process has been established. Here we show that the catalytic conversion of ethene and CO2 to acrylate is possible in the presence of a homogeneous nickel catalyst in combination with a "hard" Lewis acid. For the first time, catalytic conversion of CO2 and ethene to acrylate with turnover numbers (TON) of up to 21 was demonstrated.
- Hendriksen, Coen,Pidko, Evgeny A.,Yang, Gang,Sch?ffner, Benjamin,Vogt, Dieter
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supporting information
p. 12037 - 12040
(2015/03/31)
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- Iodine catalyzed conjugate addition of mercaptans to α,β- unsaturated carboxylic acids under solvent-free condition
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We have described herein molecular iodine catalyzed Michael addition of thiol to α,β-unsaturated carboxylic acids. This environmentally benign catalytic system (iodine) used under mild and solvent-free conditions to achieve the corresponding adducts in excellent yield.
- Gao, Shijay,Tzeng, Tingkai,Sastry,Chu, Cheng-Ming,Liu, Ju-Tsung,Lin, Chunchi,Yao, Ching-Fa
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p. 1889 - 1893
(2007/10/03)
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- Reactions of nucleophilic substitution involving solid organic halogen compounds under shear deformation at high pressure
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Under conditions of shear deformation and high pressures (SD + HP), reactions of nucleophilic substitution were studied: 1) the replacement of aliphatic halogen atom with alkaline metal halides (halo-substituted aliphatic carboxylic acids, 1-bromoadamantane); 2) the replacement of halogen atom in aromatic nucleus (halobenzoic acids, dihalobenzenes) with halogen of salt; 3) the replacement of aliphatic halogen with hydroxyl (hydrolysis in a solid phase); 4) the replacement of halogen with amino group under deformation of the samples of ammonium α-halocarboxylates to give the corresponding amino acids.It was found that the exchange of the halogen atoms bonded with aliphatic carbon is most intensive in the mixtures of alkaline metal iodides with bromo-substituted acetic acid and propionic acids: the exchange reaction in these mixtures is observed even during grinding in the mortar. Unlike the liquid phase, under conditions of SD + HP exchange of the halogen atom of the aromatic nucleus with alkaline metal halides, proceeds successfully, and the reactivity of halides increases in the series Na K Rb Cs.Under SD + HP, 1-Br-adamantane reacts with water to form 1-adamantanol.A high reactivity of the water adsorbed by the reagents is observed. - Key words: shear deformation, high pressure, halogen derivatives of carboxylic acids, dihalobenzenes, alkaline metal halides, ammonium salts of halogen derivatives of carboxylic acids, amino acids, halo-substituted adamantanes, adamantanol, nucleophilic substitution reaction, hydrolysis, ball mill.
- Zharov, A. A.,Chistotina, N. P.,Gaziev, R. G.,Yakovleva, I. I.
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p. 1050 - 1055
(2007/10/02)
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- Synthesis of 6H-benzopyren-6-one, a polar constituent of carbon black
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6H-Benzopyren-6-one (6), a potentionally carcinogenic constituent of carbon black, can be synthesized smoothly and in good overall yield (49percent) from pyrene (1), by using the reactivity of the pyrene dianion.
- Tintel, C.,Brugge, M. van der,Lugtenburg, J.,Cornelisse, J.
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p. 220 - 223
(2007/10/02)
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