- Mechanistic insight into the synergistic Cu/Pd-catalyzed carbonylation of aryl iodides using alcohols and dioxygen as the carbonyl source
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Pd-catalyzed carbonylation, as an efficient synthetic approach to the installation of carbonyl groups in organic compounds, has been one of the most important research fields in the past decade. Although elegant reactions that allow highly selective carbonylations have been developed, straightforward routes with improved reaction activity and broader substrate scope remain long-term challenges for new practical applications. Here, we show a new type of synergistic Cu/Pd-catalyzed carbonylation reaction using alcohols and dioxgen as the carbonyl sources. A broad range of aryl iodides and alcohols are compatible with this protocol. The reaction is concise and practical due to the ready availability of the starting materials and the scalability of the reaction. In addition, the reaction affords lactones and lactams in an intermolecular fashion. Moreover, DFT calculations have been performed to study the detailed mechanisms. [Figure not available: see fulltext.]
- Li, Junxuan,Zhou, Jinlei,Wang, Yumei,Yu, Yue,Liu, Qiang,Yang, Tilong,Chen, Huoji,Cao, Hua
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- Palladium-Catalyzed Butoxycarbonylation of Polybromo(hetero)arenes: A Practical Method for the Preparation of (Hetero)arenepolycarboxylates and -carboxylic Acids
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The palladium-catalyzed alkoxycarbonylation of polybromo (hetero)arenes was investigated systematically. The results show that cheap and readily available in situ Pd(OAc) 2/ rac -BINAP catalyst can catalyze the butoxycarbonylation of various polybromo(hetero)arenes efficiently, and gave (hetero)arenepolycarboxylates with moderate to high yield (59-94%). Using this method, two new compounds, 4,4'-bis(butoxycarbonyl)-1,1'-bi-2-naphthol and dibutyl [2,2'-bipyrimidine]-5,5'-dicarboxylate, are reported for the first time. In addition, the gram-scale preparation of carboxylate and carboxylic acids was successful performed by butoxycarbonylation followed by hydrolysis. This shows the wide scope of substrates and practical applications of the Pd(OAc) 2/ rac -BINAP catalytic system. Moreover, these carboxylic acids and carboxylates can be used as ligands or structural units to construct MOFs, metal complexes, and COFs etc.
- Wu, Weilong,Jing, Yongkang,Zhang, Deyi,Yan, Xianghe,Liang, Rong,Lu, Zhiqiang,Ji, Baoming
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p. 403 - 410
(2021/10/12)
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- PLASTICIZER COMPOSITION AND RESIN COMPOSITION INCLUDING THE SAME
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A plasticizer composition and a resin composition including the same. The plasticizer composition includes a terephthalate-based material including a mixture of dibutyl terephthalate, butyl(2-ethylhexyl) terephthalate and di(2-ethylhexyl) terephthalate; and a glyceride-based material. The plasticizer composition has improved physical properties such as tensile strength, elongation rate and modulus and also has excellent properties attributable to the inclusion of a terephthalate-based material, such as excellent transmittance, transparency and migration loss properties.
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Paragraph 0068
(2021/05/07)
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- A METHOD FOR MANUFACTURING TEREPHTHALATE-BASED COMPOSITION COMPRISING APPLYING PRESSURE
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Provided is a method for manufacturing a terephthalate-based composition, the method comprising: a step (S1) of flowing in a dialkyl terephthalate in which alkyl has 7 to 10 carbon atoms and a primary alcohol with a low boiling point having 4 or 5 carbon atoms into a reactor and performing transesterification of the dialkyl terephthalate and the primary alcohol with a low boiling point anda step (S2) of extracting in a reduced pressure an unreacted material and a by-product from the reactor after finishing the transesterification,wherein the step S1 comprises a pressure-applying step in which the pressure of the reactor is 1.5 to 2.5 bar.
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Page/Page column title page; 2; 3
(2021/10/15)
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- Synthesis of Esters from Stable and Convenient Sulfoxonium Precursors under Catalyst- And Additive-Free Conditions
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A convenient and efficient procedure for the construction of esters from stable sulfoxonium ylides and alcohols has been developed. This protocol presents a broad substrate scope and good yields of the desired esters can be isolated. Notably, no catalyst, oxidant, base or any other additive is required.
- Wu, Xiao-Feng,Yuan, Yang
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p. 1820 - 1824
(2019/09/09)
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- METHOD OF PREPARING ESTERS OF TEREPHTHALIC ACID
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?The present invention relates to the field of preparing esters of terephthalic acid, used as plasticizers for the manufacture of plasticizers for polyvinyl chloride plastic materials. The invention discloses a method according to which the step of esterification of the acid with an alcohol comprises the use of two catalysts of different nature, in particular a metal-containing catalyst and an acid catalyst, which are added sequentially. The technical result of the present invention is to increase conversion of terephthalic acid up to 100% and to reduce the amount of by-products formed during the production of a dicarboxylic acid ester. The obtained ester is characterized by a low acid number and a low value of color.
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Page/Page column 14-20
(2019/04/26)
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- PLASTICIZER COMPOSITION AND RESIN COMPOSITION INCLUDING THE SAME
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The present invention relates to a plasticizer composition and a resin composition including the same, and can provide a plasticizer composition in which three types of terephthalate-based materials and three types of cyclohexane 1,4-diester-based materials are mixed, and by which environmental friendliness can be secured, mechanical properties such as tensile strength and an elongation rate, physical properties such as migration properties and volatile loss can be improved to levels equal to or higher than those of existing products, and effects of improving processability and plasticizing efficiency can be expected, and a resin composition including the same.
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Paragraph 0080; 0081
(2019/02/24)
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- ESTER-BASED COMPOUND, COMPOSITION COMPRISING THE SAME, METHOD FOR PREPARING THE SAME AND RESIN COMPOSITION COMPRISING THE SAME (AS AMENDED)
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The present invention relates to an ester-based plasticizer composition, a method for preparing the same and a resin composition comprising the same. The ester-based plasticizer composition according to one embodiment of the present invention is a novel terephthalate-based ester compound for a plasticizer prepared through transesterification. When the ester-based plasticizer composition is used in a resin composition, it is capable of providing excellent resistance for stress, and excellent physical properties such as migration resistance and volatility resistance as well as tensile strength and elongation rate.
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Paragraph 0021; 0025
(2018/02/03)
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- DBU-Based Dicationic Ionic Liquids Promoted Esterification Reaction of Carboxylic Acid with Primary Chloroalkane Under Mild Conditions
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Abstract: A series of DBU-based (DBU = 1, 8-diazabicyclo [5.4.0] undec-7-ene) dicationic ionic liquids with different anions were successfully synthesized by the reaction of DBU and 1, 6-dichlorohexane. Therein, the dicationic ionic liquid 1, 1′-(hexane-1, 6-diyl)bis(1, 8-diazabicyclo [5.4.0]undec-7-enium) dichlorine (IL-1) was successfully employed as an efficient catalyst in esterification reaction of carboxylic acids with primary chloroalkanes under mild conditions without any additional basic reagents. Moreover, the optimum catalyst could be efficiently reused for five times without any significant change on the catalytic effect. The improved protocol is not only efficient, but also green and pollution-free.
- Liu, Yang,Mao, Guijie,Zhao, Hongyan,Song, Jinyi,Han, Huatao,Li, Zhuofei,Chu, Wenyi,Sun, Zhizhong
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p. 2764 - 2771
(2017/09/14)
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- Preparation method of low-melting-point mixture of diesters of terephthalic acid
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The invention relates to a preparation method of terephthalate n-butyl.isobutyl ester and a preparation method of low-melting-point mixture of diesters of terephthalic acid. According to the preparation method, dimethyl terephthalate and mixed liquor of n-butanol and isobutanol are used as raw materials, and high-temperature-resistant acidic resin is used as a catalyst. The disadvantage that a product is hard to separate, separation processes are many, and there are lots of waste liquids in the prior art is overcome. Instruments and equipment used in the process by the method are simple. In addition, operation steps are simple, and yield of the target product is high.
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Paragraph 0048; 0049; 0050; 0074
(2016/11/24)
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- Synthesis, biological evaluation of 1,3,4-oxadiazole, triazole and uracil derivatives from poly (ethylene terephthalate) waste
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POLY(ethylene terephthalate) (PET) was hydrolyzed in aqueous NaOH using solar energy. PET is used as versatile reagent for the synthesis of a variety of heterocyclic compounds. Uracil (6a, b), 1,3,4-oxadiazole (9, 12a, b), 1,3,4-triazole (10, 14), thiadiazole (11a, b and 15) derivatives were synthesized from PET. The antimicrobial and antioxidant activities of the synthesized compounds were evaluated and showed significant activities.
- Fahim, Asmaa M.,Yakout, El-Sayed M.A.,Ragab, Eman A.,Farag, Ahmad M.,Nawwar, Galal A. M.
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p. 285 - 303
(2017/02/26)
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- METHOD OF PREPARING ESTER PLASTICIZER AND ESTER PLASTICIZER PREPARED THEREFROM
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Provided is a method of preparing an ester plasticizer, more particularly, a method of preparing an ester plasticizer including conducting a transesterification reaction of a compound of Chemical Formula 1 with a first alcohol of Chemical Formula 2. According to the preparation method according to an embodiment of the present invention, an ester plasticizer having high purity, yield, and process efficiency as well as excellent plasticizer properties such as processability and absorption rate may be easily prepared even under no catalyst.
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Paragraph 0089; 0099; 0100; 0101
(2014/11/27)
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- An improved protocol for palladium-catalyzed alkoxycarbonylations of aryl chlorides with alkyl formates
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The palladium-catalyzed alkoxycarbonylation of aryl and heteroaryl halides using butyl formate has been investigated. In the presence of palladium (II) acetate/n-butylbis(1-adamantyl)phosphine (L1), and l,8-diazabicyclo[5.4.0]undec- 7-ene (DBU) as base fo
- Schareina, Thomas,Zapf, Alexander,Cotte, Alain,Gotta, Matthias,Beller, Matthias
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experimental part
p. 1205 - 1209
(2010/07/04)
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- Low-melting mixtures of di-n-butyl and diisobutyl terephthalate
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Mixtures of terephthalate diesters having lowered freezing points and methods of making the terephthalic acid diesters. The method includes contacting a first alcohol, a second different alcohol and dimethyl terephthalate in the presence of a catalyst to thereby form the terephthalate diesters.
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Page/Page column 3; 4; 5; 6
(2008/06/13)
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- Preparation of monoalkyl terephthalates: An overview
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Terephthalic acid can be readily converted to the corresponding monoalkyl terephthalate in high yield, via a two-step procedure. This method is advantageously compared to the more representative methods described in the literature. The purification of the expected monoester, a crucial problem for this synthetic pathway, is discussed, and an original procedure has been developed. Copyright Taylor & Francis Group, LLC.
- Chenot, Elodie-Denise,Bernardi, Dan,Comel, Alain,Kirsch, Gilbert
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p. 483 - 490
(2007/10/03)
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- Process for the preparation of bis(amidocarboxylic acids)
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A process is reported for the preparation of bis(amidocarboxylic acid) involving reacting an ester with an aminocarboxylate compound, the latter being formed from lactams or aminocarboxylic acids and salts thereof. The ester and aminocarboxylate compound are present in a weight ratio of about 1:1 to about 1:4, and reaction is conducted in a mono- or polyhydric alcohol solvent.
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- Unsymmetrical dicarboxylic esters as bleach precursors
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A bleach precursor compound, its peroxygen derivative, and detergent compositions containing these materials are disclosed herein. The bleach precursors structurally comprise a pair of different diesters, one ester containing an electrically-charged functional group. Perhydrolysis of the precursor in the presence of hydrogen peroxide and a basic aqueous media generates a peroxycarboxylic acid.
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- The Esterification of Carboxylic Acid with Alcohol over Hydrous Zirconium Oxide
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The esterification of carboxylic acids with alcohols proceeded efficienly with hydrous zirconium oxide to give the corresponding esters in the vapor phase, in the liquid phase, and in an autoclave.The steric hindrance of carboxylic acids and alcohols affected the esterification by lowering the reactivity.With a rise in the reaction temperature, the conversion of the carboxylic acid increased.The dehydration of alcohols was prevented by using hydrous zirconium oxide in spite of the high reaction temperature.The reaction rate is first-order with respect to the concentration of the catalyst and an alcohol and is inversely proportional to thta of the carboxylic acid.Transesterification also proceeded efficiently.
- Takahashi, Kyoko,Shibagaki, Makoto,Matsushita, Hajime
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p. 2353 - 2361
(2007/10/02)
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